WO2019031611A1 - Packaging material for battery, battery, production methods therefor, and method for improving printing suitability of ink for packaging material for battery - Google Patents

Abstract

It is composed of a laminate comprising at least a base material layer, a barrier layer, and a heat fusible resin layer in this order, and at least a fatty acid amide compound is present on the surface of the laminate on the base material layer side. The packaging material for batteries which the said fatty-acid amide compound melt | dissolves 1 g or more with respect to 100 g of methyl ethyl ketone in a 25 degreeC environment.

Description

Packaging material for battery, battery, method for producing them, and method for improving printability of the packaging material for battery with ink

The present invention relates to a battery packaging material, a battery, a method for producing them, and a method for improving the printability of the battery packaging material with ink.

Conventionally, various types of batteries have been developed, but in all batteries, a packaging material has become an indispensable member for sealing battery elements such as electrodes and electrolytes. Conventionally, metal packaging materials have been widely used as packaging for batteries, but in recent years, various shapes are required for batteries as the performance of electric vehicles, hybrid electric vehicles, personal computers, cameras, mobile phones, etc. is improved. Needs to be thinner and lighter. However, in the case of metal battery packaging materials that have been widely used in the past, it is difficult to follow the diversification of the shape, and there is also a drawback that there is a limit to weight reduction.

Therefore, as a packaging material for a battery that can be easily processed into various shapes and that can realize thinning and weight reduction, a film-like material in which a base material layer, an adhesive layer, a barrier layer, and a thermally adhesive resin layer are sequentially laminated A laminate has been proposed (see, for example, Patent Document 1). In such a film-like battery packaging material, the battery element can be sealed by heat-sealable resin layers facing each other and heat-sealing the peripheral portion by heat sealing.

In various packaging materials composed of the laminate as described above, the ink is printed on the surface of the base material layer to form a bar code, a handle, characters and the like, and adhesion is performed on the printed base material layer By the method of laminating the agent and the barrier layer, the method of printing on the packaging material (generally referred to as middle printing) is widely adopted. However, when such a printing surface is present between the base material layer and the barrier layer, the adhesion between the base material layer and the barrier layer is reduced, and delamination tends to occur between the layers. In particular, since high safety is required of a battery to which a battery packaging material is applied, the method of printing by such a middle printing is avoided in the battery packaging material. Therefore, conventionally, in the case of forming a print such as a bar code on the battery packaging material, generally, a method of sticking a seal on which the print is formed on the surface of the base material layer is employed.

JP 2008-287971A

However, when the seal on which the print is formed is attached to the surface of the base material layer, the thickness and weight of the battery packaging material increase. Therefore, the present inventors considered a method of printing directly by printing ink on the surface of the base material layer of the battery packaging material in consideration of the recent trend of further thinning and weight reduction of the battery packaging material. did.

As a method of printing by direct ink printing on the surface of the base material layer of the battery packaging material, for example, pad printing (also referred to as “tanpo printing”) or inkjet printing is known. Pad printing is the following printing method. First, the ink is poured into the concave portion of the flat plate where the pattern to be printed is etched. Next, the silicon pad is pressed from above the recess to transfer the ink to the silicon pad. Next, the ink transferred to the surface of the silicon pad is transferred to a print target to form a print on the print target. Such pad printing is easy to print on the surface of the formed battery packaging material because the ink is transferred to the printing object using an elastic silicon pad or the like, and the battery element is a battery packaging material. After sealing, it has the advantage of being able to print on the battery. Moreover, it has the same advantage also in inkjet printing.

However, when the present inventors examined, when the ink is printed on the surface of the base material layer side of the battery packaging material, the ink is repelled on the surface of the base layer side, the ink is difficult to be fixed, and the ink is It has become apparent that there may occur unformed parts.

Moreover, in the battery packaging material, in order to increase the volumetric energy density, generally, a recess is formed by cold forming, and the storage volume of the battery element is increased. In recent years, it has been required to further increase the storage volume by deep drawing. However, when pinholes or cracks occur in the battery packaging material during molding, the electrolyte may penetrate into the barrier layer to form a metal deposit, which may result in a short circuit. Because of this, there is a demand for packaging materials for batteries to have even better formability.

Under such circumstances, the main object of the present invention is to provide a battery packaging material having both excellent printability and excellent formability. Furthermore, the present invention also provides a method for producing the battery packaging material, a battery using the battery packaging material, a method for producing the battery, and a method for improving the printability of the battery packaging material with the ink. I assume.

The present inventors diligently studied to solve the above-mentioned problems. As a result, it is comprised from the laminated body provided with a base material layer, a barrier layer, and a heat-fusion resin layer in this order at least, and the fatty acid amide compound exists in the surface at the side of the base material layer of the said laminated body at least. Furthermore, it has been found that the battery packaging material, in which the fatty acid amide compound dissolves 1 g or more in 100 g of methyl ethyl ketone in a 25 ° C. environment, has both excellent printability and excellent formability. . The present invention has been completed by further studies based on these findings.

That is, the present invention provides a battery packaging material and a battery according to the aspects described below.
Item 1. It is comprised from the laminated body provided with a base material layer, a barrier layer, and a heat fusible resin layer at least in this order,
A fatty acid amide compound is present at least on the surface of the laminate on the substrate layer side,
The packaging material for batteries which said fatty-acid amide compound melt | dissolves 1 g or more with respect to 100 g of methyl ethyl ketone in a 25 degreeC environment.
Item 2. ^2. The battery packaging material according to item 1, wherein a fatty acid amide compound is present at 2.0 mg / m ² or more on the surface of the laminate on the base material layer side.
Item 3. 3. The battery packaging material according to item 1 or 2, which is used in applications where printing with ink is applied to the surface of the laminate on the side of the base material layer.
Item 4. The packaging material for a battery according to claim 3, wherein the ink contains at least one selected from the group consisting of methyl ethyl ketone, acetone, isopropyl alcohol, and ethanol.
Item 5. The packaging material for a battery according to any one of Items 1 to 4, wherein the wetting tension of the surface on the side of the base material layer is 32 mN / m or more.
Item 6. The fatty acid amide compound is at least one selected from the group consisting of erucic acid amide, ethylene bis oleic acid amide, oleyl stearic acid amide, stearyl oleic acid amide, stearyl erucic acid amide, oleic acid amide, and behenic acid amide The packaging material for a battery according to any one of Items 1 to 5, wherein
Item 7. 7. The battery packaging material according to any one of items 1 to 6, wherein a fatty acid amide compound is present on the surface on the heat fusible resin layer side.
Item 8. A battery, wherein a battery element comprising at least a positive electrode, a negative electrode, and an electrolyte is contained in a package made of the battery packaging material according to any one of Items 1 to 7.
Item 9. Item 9. The battery according to item 8, having a printed portion on the surface of the package on the side of the base material layer.
Item 10. 10. The battery according to item 8 or 9, wherein the surface of the package on the side of the base material layer has a printed part with ink.
Item 11. At least a step of laminating the base material layer, the barrier layer, and the heat fusible resin layer in this order;
A fatty acid amide compound is present at least on the surface of the laminate on the substrate layer side,
The manufacturing method of the packaging material for batteries using what melts 1 g or more with respect to 100 g of methyl ethyl ketone in a 25 degreeC environment as said fatty-acid amide compound.
Item 12. Item 12. The method for producing a battery packaging material according to Item 11, further comprising the step of subjecting at least one surface of the base material layer to a corona treatment.
Item 13. Item 8. A process of containing a battery element comprising at least a positive electrode, a negative electrode, and an electrolyte in a package made of the battery packaging material according to any one of items 1 to 7;
Printing with ink on the surface of the package on the substrate layer side;
A method of manufacturing a battery, comprising:
Item 14. 1 g or more dissolved in 100 g of methyl ethyl ketone in a 25 ° C. environment on the surface of the base material layer side of the battery packaging material comprising at least a base material layer, a barrier layer, and a heat-sealable resin layer in this order And a fatty acid amide compound is present to improve the printability of the packaging material for the battery with respect to the surface on the side of the substrate layer.

According to the present invention, a battery packaging material having both excellent printability and excellent formability can be provided. Furthermore, according to the present invention, a method for producing the battery packaging material, a battery using the battery packaging material, a method for producing the battery, and a method for improving the printability of the battery packaging material by the ink are provided. You can also.

It is a schematic diagram which shows an example of the cross-section of the packaging material for batteries of this invention. It is a schematic diagram which shows an example of the cross-section of the packaging material for batteries of this invention. It is a schematic diagram which shows an example of the cross-section of the packaging material for batteries of this invention. It is a schematic diagram which shows an example of the cross-section of the packaging material for batteries of this invention. It is a schematic diagram for demonstrating the measuring method of seal | sticker intensity | strength. It is a schematic diagram for demonstrating the measuring method of seal | sticker intensity | strength. It is a schematic diagram for demonstrating the measuring method of seal | sticker intensity | strength. It is a schematic diagram for demonstrating the measuring method of logarithmic attenuation factor (DELTA) E by rigid-body pendulum measurement. It is a schematic diagram for demonstrating the measuring method of seal | sticker intensity | strength. The temperature difference T ₁ and the temperature difference T ₂ in differential scanning calorimetry is a diagram schematically showing.

The battery packaging material of the present invention is composed of a laminate having at least a base layer, a barrier layer, and a heat fusible resin layer in this order, and at least on the surface of the laminate on the base layer side. Is characterized in that a fatty acid amide compound is present, and the fatty acid amide compound is dissolved in 1 g or more in 100 g of methyl ethyl ketone in a 25 ° C. environment.

In the present specification, a numerical range indicated by “to” means “above” or “below”. For example, the notation of 2 to 15 mm means 2 mm or more and 15 mm or less. Hereinafter, the battery packaging material of the present invention will be described in detail.

1. Laminated structure of battery packaging material The battery packaging material of the present invention comprises, as shown in FIG. 1, a laminate having at least a base layer 1, a barrier layer 3 and a heat-fusible resin layer 4 in this order. It is done. In the battery packaging material of the present invention, the base material layer 1 is the outermost layer side, and the heat-fusible resin layer 4 is the innermost layer. That is, when assembling the battery, the battery element is sealed by sealing the battery element by thermally fusing the heat-fusible resin layers 4 located on the peripheral edge of the battery element.

In the battery packaging material 10 of the present invention, as shown in FIG. 2, an adhesive layer 2 is provided between the base material layer 1 and the barrier layer 3 as needed for the purpose of enhancing the adhesiveness thereof. It may be done. In addition, as shown in FIG. 3, the battery packaging material 10 of the present invention is bonded between the barrier layer 3 and the heat fusible resin layer 4 as necessary for the purpose of enhancing the adhesiveness thereof. A layer 5 may be provided. Moreover, as shown in FIG. 4, the surface coating layer 6 may be formed on the surface on the base layer 1 side.

The thickness of the laminate constituting the battery packaging material 10 of the present invention is not particularly limited, but the battery packaging material having excellent formability while reducing the thickness of the battery packaging material to increase the energy density of the battery From the viewpoint of making it, for example, about 180 μm or less, preferably about 150 μm or less, more preferably about 60 to 180 μm, further preferably about 60 to 150 μm.

In the battery packaging material 10 of the present invention, a fatty acid amide compound is present on the surface on the base layer 1 side. Furthermore, the said fatty-acid amide compound melt | dissolves 1 g or more with respect to 100 g of methyl ethyl ketone (MEK) in a 25 degreeC environment. In the battery packaging material of the present invention, excellent printability and excellent formability are exhibited by the presence of the fatty acid amide compound having such specific solubility on the surface on the side of the base material layer 1 Can. The details of this mechanism are considered as follows. That is, when the fatty acid amide compound is present on the surface on the base layer 1 side, the slipperiness between the surface on the base layer side and the molding die is improved, and when drawing is performed with the die, Since the battery packaging material is easily drawn in, it is considered that deep draw forming is possible and pinholes and tears are less likely to occur. Furthermore, since the fatty acid amide compound is dissolved in a specific solvent such as methyl ethyl ketone by a predetermined amount, it is contained in the solvent contained in the ink when printing is performed on the surface of the substrate layer 1 by inkjet printing, for example. The fatty acid amide compound is dissolved in it, and the fixing of the dye or pigment contained in the ink on the surface of the substrate layer 1 side is less likely to be inhibited by the fatty acid amide compound, and it is considered that the excellent printability is exhibited. Be

That is, according to the present invention, the environment at 25 ° C. on the surface of the base material layer 1 side of the battery packaging material comprising the laminate including at least the base material layer 1, the barrier layer 3 and the heat fusible resin layer 4 in this order The fatty acid amide compound which dissolves 1 g or more with respect to 100 g of methyl ethyl ketone in the above can be provided to provide a method of improving the printability by the ink to the surface of the base material 1 side of the battery packaging material. That is, on the surface of the base material layer 1 side of the battery packaging material of the present invention, a fatty acid amide compound having a property of dissolving 1 g or more in 100 g of methyl ethyl ketone in a 25 ° C. environment is present.

In the present invention, from the viewpoint of achieving both excellent printability and excellent moldability, the amount of the fatty acid amide compound present on the surface on the substrate layer 1 side is preferably about 2.0 mg / m ² or more for the lower limit. More preferably about 4.0 mg / m ² or more, more preferably about 5.0 mg / m ² or more, more preferably about 6.5 mg / m ² or more, still more preferably about 7.0 mg / m ² or more. is, the upper limit is preferably about 20.0 mg / m ² or less, more preferably about 15.0 mg / m ² or less, more preferably 14.5 mg / m ² or less, more preferably 14.0 mg / m ² or less and examples of the preferred range 2.0 to 20.0 mg / m ² about 2.0 to 15.0 mg / m ² about 2.0 to 14.5 mg / m ² about, 2.0 to 14 .0mg / m ² approximately, 4.0 to 2 .0mg / m ² approximately, 4.0 ~ 15.0mg / m ² approximately, 4.0 ~ 14.5mg / m ² approximately, 4.0 ~ 14.0mg / m ² approximately, 5.0 ~ 20.0mg / m ² approximately, 5.0 ~ 15.0mg / m ² approximately, 5.0 ~ 14.5mg / m ² approximately, 5.0 ~ 14.0mg / m ² or so,
6.5 ~ 20.0mg / m ² approximately, 6.5 ~ 15.0mg / m ² approximately, 6.5 ~ 14.5mg / m ² approximately, 6.5 ~ 14.0mg / m ² approximately, 7. 0 ~ 20.0mg / m ² approximately, 7.0 ~ 15.0mg / m ² approximately, 7.0 ~ 14.5mg / m ² approximately, and about 7.0 ~ 14.0mg / m ^2.

If the amount of the fatty acid amide compound present on the surface of the base material layer 1 side of the battery packaging material is too large, the fatty acid amide compound adheres to the mold at the time of molding, thereby forming lumps and contaminating the mold. Problems can arise. When the other battery packaging material is molded while the mold is contaminated, a block of fatty acid amide compound deposited on the mold adheres to the surface of the battery packaging material, and the heat fusion of the heat fusible resin layer is carried out as it is To be served. As a result, when the heat-fusible resin layer is heat-fused, the manner in which the fatty acid amide compound adheres becomes uneven, so that sealing failure occurs. In order to prevent this, it is necessary to increase the cleaning frequency for removing the fatty acid amide compound attached to the mold, which may cause a problem that the continuous productivity of the battery is lowered. In the battery packaging material of the present invention, when the amount of the fatty acid amide compound present on the surface on the side of the base layer 1 is in the above range, the continuous productivity of the battery can be effectively improved.

From the same viewpoint, the amount of the fatty acid amide compound dissolved in 100 g of methyl ethyl ketone in a 25 ° C. environment is preferably about 1 to 16 g, more preferably about 1 to 14 g, and still more preferably about 5 to 12 g.

The fatty acid amide compound which dissolves 1 g or more in 100 g of methyl ethyl ketone in a 25 ° C. environment is not particularly limited, but preferably erucic acid amide, ethylene bis oleic acid amide, oleyl stearic acid amide, stearyl oleic acid amide, stearyl Erucic acid amide, oleic acid amide, behenic acid amide and the like can be mentioned. The fatty acid amide compound may be used alone or in combination of two or more. The amount of the fatty acid amide compound dissolved in 100 g of methyl ethyl ketone is determined by gradually adding the fatty acid amide compound to 100 g of methyl ethyl ketone stirred with a stirrer or the like in a 25 ° C. environment and measuring the amount dissolved maximally. It can confirm. More specifically, 1.0 g of a fatty acid amide compound is introduced into 100 g of methyl ethyl ketone at 25 ° C., sufficiently stirred by a stirrer, and allowed to stand. When the undissolved matter can not be visually confirmed in the obtained solution, 1.0 g of the fatty acid amide compound is further added, and the solution is sufficiently stirred with a stirrer each time. When the dissolution residue of the fatty acid amide compound is confirmed in the solution, 2.0 g of the fatty acid amide compound is further added, and the mixture is stirred with a stirrer and allowed to stand. The supernatant is sampled in a state where the undissolved matter has sedimented, and the concentration of the fatty acid amide compound in the solution is quantified by high performance liquid chromatography (HPLC) to obtain the amount of the fatty acid amide compound dissolved in 100 g of methyl ethyl ketone. The quantification is carried out by creating and interpolating a standard curve.

The amount of the fatty acid amide compound present on the surface of the base material layer 1 side of the battery packaging material is such that the predetermined area on the surface of the base material layer 1 side is washed away with an organic solvent and the fatty acid amide compound contained in the obtained cleaning liquid The amount can be quantified using a gas chromatography mass spectrometer (GC-MS).

In the battery packaging material of the present invention, the wet tension of the surface on the side of the substrate layer 1 is preferably about 32 mN / m or more, more preferably 35 to 46 mN, from the viewpoint of improving the printability while enhancing the formability. And preferably about 36 to 44 mN / m. In the present invention, the wetting tension of the packaging material for a battery is a value measured by a method according to the definition of JIS K 6768: 1999, and the specific method is as described in the examples.

The battery packaging material of the present invention can be suitably used in applications where printing with ink is performed on the surface of the laminate on the side of the base material layer 1. As printing by ink, the above-mentioned pad printing, inkjet printing, etc. are suitable, for example, and in particular, inkjet printing is suitable. Preferred examples of the solvent contained in the ink include methyl ethyl ketone, acetone, isopropyl alcohol and ethanol. The solvents may be used alone or in combination of two or more.

A printing portion may be formed on the surface of the base material 1 side of the battery packaging material of the present invention. In the present invention, the printing unit is a portion where printing is performed. The printing includes, for example, a bar code, a pattern, characters and the like, and the shape of the printing is not limited. The method for forming the print portion is not particularly limited, and the print portion can be formed by printing with ink, a pen using ink, or the like. When the battery packaging material of the present invention has a printing portion, the printing portion is preferably a printing portion in which printing is formed by printing of ink. That is, it is preferable that the packaging material for batteries of this invention has the printing part by ink on the surface at the side of the base material layer 1.

Furthermore, in the battery packaging material of the present invention, in a state where the heat fusible resin layers 4 are opposed to each other, a metal plate having a width of 7 mm is used, and the temperature is 190 ° C. in the lamination direction from both sides of the test sample. The heat fusible resin layer 4 is heat-sealed together by heating and pressurizing under a pressure of 2.0 MPa and a time of 3 seconds, as shown in FIGS. In a state of 140 ° C. environment, tensile speed 300 mm / min, peel angle 180 °, distance between chucks 50 mm, tensile strength 1.5 seconds from the start of tensile strength using a tensile tester. In the meantime, it is preferable that the maximum value of the tensile strength (seal strength) measured by peeling the heat-fused interface is, for example, 3.0 N / 15 mm or more, and more preferably 4.0 N / 15 mm or more. The upper limit of the tensile strength is, for example, about 5.0 N / 15 mm or less, and a preferable range is 3.0 to 5.0 N / 15 mm and 4.0 to 5.0 N / 15 mm. As described above, the heat resistance temperature of the separator inside the battery is generally around 120 to 140 ° C., so in the battery packaging material of the present invention, the tensile strength (seal strength) in a high temperature environment of 140 ° C. Preferably, the maximum value of x satisfies the above values. In addition, in order to set to such tensile strength, the kind, composition, molecular weight, etc. of resin which comprise a heat sealing | fusion resin layer are adjusted, for example.

As shown in Examples described later, the above tensile test at each temperature is carried out in a constant temperature bath, and the test sample is attached to the chuck in a constant temperature bath at a predetermined temperature (25 ° C. or 140 ° C.) for 2 minutes Hold and start measurement.

In the battery packaging material of the present invention, the electrolyte solution (the concentration of lithium hexafluorophosphate is 1 mol / l, and the volume ratio of ethylene carbonate: diethyl carbonate: dimethyl carbonate is 1: 1) in an environment of 85 ° C. After the battery packaging material is brought into contact with the solution of 1: 1 (a solution obtained by mixing ethylene carbonate, diethyl carbonate and dimethyl carbonate at a volume ratio of 1: 1: 1) for 72 hours, the heat fusion is performed The thermally fused resin layer is thermally fused under the conditions of a temperature of 190 ° C., a surface pressure of 2.0 MPa, and a time of 3 seconds while the electrolytic solution is attached to the surface of the conductive resin layer, and the thermally fused interface The seal strength when peeling off is preferably 80% or more (80% or more of the seal strength retention) of the seal strength when not contacting the electrolytic solution, and is 90% or more. It is more preferable, and more preferably 100%.

(Measurement method of retention rate of seal strength)
Using the seal strength before contact with the electrolyte measured by the following method as a reference (100%), the retention (%) of the seal strength after contact with the electrolyte is calculated.

<Measurement of seal strength before contact with electrolyte>
In the following <Measurement of seal strength after contact with electrolyte solution>, tensile strength (seal strength) is measured in the same manner except that the electrolyte is not injected into the test sample. The maximum tensile strength until the heat-sealed part is completely peeled off is taken as the seal strength before contact with the electrolyte.

<Measurement of seal strength after contact with electrolyte>
As shown in the schematic view of FIG. 9, the battery packaging material is cut into a rectangle of width (x direction) 100 mm × length (z direction) 200 mm to obtain a test sample (FIG. 9 a). The test sample is folded at the center in the z direction so that the heat fusible resin layer side is overlapped (FIG. 9 b). Next, both ends of the folded test sample in the x direction are sealed with a heat seal (temperature 190 ° C., surface pressure 2.0 MPa, time 3 seconds), and formed into a bag shape having one opening E (Fig. 9c). Next, from the opening E of the test sample formed into a bag shape, the electrolytic solution (the concentration of lithium hexafluorophosphate is 1 mol / l, and the volume ratio of ethylene carbonate: diethyl carbonate: dimethyl carbonate is 1: 1: 6 g of a solution of 1) is injected (FIG. 9 d), and the end of the opening E is sealed with a heat seal (temperature 190 ° C., surface pressure 2.0 MPa, time 3 seconds) (FIG. 9 e). Next, with the folded portion of the bag-like test sample facing down, the bag is left to stand for a predetermined storage time (time to be in contact with the electrolyte) in an environment at a temperature of 85 ° C. The end of the test sample is then cut (FIG. 9e) to drain all the electrolyte. Next, with the electrolyte adhering to the surface of the heat fusible resin layer, the upper and lower surfaces of the test sample are sandwiched between metal plates (7 mm wide), and the conditions of temperature 190 ° C., surface pressure 1.0 MPa, time 3 seconds The heat-sealable resin layers are heat-sealed together (FIG. 9f). Next, the test sample is cut to a width of 15 mm with a double-edged sample cutter so that the seal strength at a width (x direction) of 15 mm can be measured (Fig. 9f, g). Next, peel off the thermally fused interface under the conditions of a tensile speed of 300 mm / min, a peel angle of 180 °, and a distance between chucks of 50 mm in an environment of 25 ° C. using a tensile tester so that T-peel occurs. The tensile strength (seal strength) is measured (FIG. 7). The maximum tensile strength until the heat-fused part is completely peeled off is taken as the seal strength after electrolyte contact.

2. Each Layer Forming a Packaging Material for a Battery [Base Material Layer 1]
In the battery packaging material 10 of the present invention, the base material layer 1 is a layer located on the outermost layer side. About the raw material which forms the base material layer 1, it does not restrict | limit in particular that it is what is provided with insulation. As a material which forms base material layer 1, for example, polyester, polyamide, epoxy resin, acrylic resin, fluorine resin, polyurethane, silicon resin, phenol resin, polyether imide, polyimide, polycarbonate, and mixtures or copolymers thereof Etc. Among these, the base material layer 1 preferably has at least one of a layer formed of polyester and a layer formed of polyamide.

Specific examples of the polyester include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene isophthalate, copolymer polyester having ethylene terephthalate as the main component of the repeating unit, and butylene terephthalate as the main component of the repeating unit. Copolymerized polyesters and the like. Further, as a copolymerized polyester having ethylene terephthalate as the main component of the repeating unit, specifically, a copolymer polyester in which ethylene terephthalate is polymerized as the main component of the repeating unit with ethylene isophthalate (hereinafter, polyethylene (terephthalate / isophthalate) Polyethylene (terephthalate / isophthalate), polyethylene (terephthalate / adipate), polyethylene (terephthalate / sodium sulfoisophthalate), polyethylene (terephthalate / sodium isophthalate), polyethylene (terephthalate / phenyl-dicarboxylate) And polyethylene (terephthalate / decanedicarboxylate). Further, as a copolymerized polyester having butylene terephthalate as the main component of the repeating unit, specifically, a copolymer polyester in which butylene terephthalate is polymerized with butylene isophthalate as the main component of the repeating unit (hereinafter, polybutylene (terephthalate / isophthalate) And polybutylene (terephthalate / adipate), polybutylene (terephthalate / sebacate), polybutylene (terephthalate / decanedicarboxylate), polybutylene naphthalate and the like. These polyesters may be used alone or in combination of two or more. Polyester has an advantage that it is excellent in electrolytic solution resistance and is less likely to be whitened due to adhesion of the electrolytic solution, and is suitably used as a forming material of the base material layer 1.

Further, as polyamides, specifically, aliphatic polyamides such as nylon 6, nylon 66, nylon 610, nylon 12, nylon 46, and copolymers of nylon 6 and nylon 66; terephthalic acid and / or isophthalic acid Hexamethylenediamine-isophthalic acid-terephthalic acid copolymerized polyamide such as nylon 6 I, nylon 6 T, nylon 6 IT, nylon 6 I 6 T (I is isophthalic acid, T represents terephthalic acid) containing constitutional units derived from An aromatic polyamide such as pamide (MXD6); an alicyclic polyamide such as polyaminomethylcyclohexyl adipamide (PACM 6); and a copolymer of a lactam component and an isocyanate component such as 4,4'-diphenylmethane diisocyanate. Polya De, copolymerized polyamide and polyester and a copolymer of a polyalkylene ether glycol polyester amide copolymer and polyether ester amide copolymers; and copolymers thereof. These polyamides may be used alone or in combination of two or more. The stretched polyamide film is excellent in stretchability, can prevent the occurrence of whitening due to resin cracking of the base material layer 1 at the time of molding, and is suitably used as a forming material of the base material layer 1.

The base material layer 1 may be formed of a uniaxially or biaxially stretched resin film, or may be formed of an unstretched resin film. Among them, a uniaxially or biaxially stretched resin film, in particular a biaxially stretched resin film, is suitably used as the substrate layer 1 because its heat resistance is improved by orientation crystallization. Further, the base material layer 1 may be formed by coating the above-described material on the barrier layer 3.

Among these, as a resin film which forms the base material layer 1, Preferably nylon, polyester, More preferably, biaxially stretched nylon, biaxially stretched polyester, Especially preferably biaxially stretched nylon is mentioned.

The base material layer 1 can also be laminated (multilayer structure) of at least one of a resin film and a coating of different materials in order to improve pinhole resistance and insulation when forming a battery package. is there. Specifically, a multilayer structure in which a polyester film and a nylon film are laminated, a multilayer structure in which a plurality of nylon films are laminated, a multilayer structure in which a plurality of polyester films are laminated, and the like can be mentioned. When the base material layer 1 has a multilayer structure, a laminate of a biaxially stretched nylon film and a biaxially stretched polyester film, a laminate of a plurality of biaxially stretched nylon films laminated, and a laminate of a plurality of biaxially stretched polyester films laminated Body is preferred. For example, in the case where the base material layer 1 is formed of a resin film of two layers, a polyester resin and a polyester resin are laminated, a polyamide resin and a polyamide resin are laminated, or a polyester resin and a polyamide resin are laminated. It is more preferable to use a structure in which polyethylene terephthalate and polyethylene terephthalate are laminated, a structure in which nylon and nylon are laminated, or a structure in which polyethylene terephthalate and nylon are laminated. In addition, the biaxially oriented polyester has a multilayer structure of a laminate of a biaxially stretched nylon film and a biaxially stretched polyester film, for example, because it is difficult to discolor when the electrolytic solution adheres to the surface, etc. The base material layer 1 is preferably a laminate having a biaxially stretched nylon and a biaxially stretched polyester in this order from the barrier layer 3 side. When the base material layer 1 has a multilayer structure, the thickness of each layer is preferably about 3 to 25 μm.

When the base material layer 1 has a multilayer structure, each resin film may be bonded via an adhesive, or may be directly laminated without using an adhesive. In the case of bonding without using an adhesive, for example, a method of bonding in a hot melt state such as coextrusion lamination method, sandwich lamination method, thermal lamination method and the like can be mentioned. Moreover, when making it adhere | attach through an adhesive agent, the adhesive agent to be used may be a 2 liquid curing adhesive, and may be a 1 liquid curing adhesive. Furthermore, the adhesion mechanism of the adhesive is not particularly limited, and may be any of a chemical reaction type, a solvent volatilization type, a heat melting type, a heat pressure type, an electron beam curing type, an ultraviolet ray curing type, and the like. Specific examples of the adhesive include those similar to the adhesive exemplified in the adhesive layer 2 described later. Further, the thickness of the adhesive can be the same as that of the adhesive layer 2.

The surface on the substrate layer 1 side may be a corona-treated surface. Since the surface on the substrate layer 1 side is corona-treated, the printability of the surface of the substrate layer 1 can be improved. The conditions for the corona treatment are not particularly limited. For example, by treating the surface on the base layer 1 side at a velocity of 10 m / min at an irradiation output of 1 Kw or more, the wetting tension of the surface on the base layer 1 side can be increased.

The thickness of the base material layer 1 is preferably 4 μm or more, more preferably about 10 to 75 μm from the viewpoint of forming the battery packaging material 10 having excellent formability while reducing the thickness of the battery packaging material 10. And more preferably about 10 to 50 μm.

[Adhesive layer 2]
In the battery packaging material 10 of the present invention, the adhesive layer 2 is a layer provided between the substrate layer 1 and the barrier layer 3 as needed in order to firmly bond the substrate layer 1 and the barrier layer 3.

The adhesive layer 2 is formed of an adhesive capable of adhering the base layer 1 and the barrier layer 3. The adhesive used to form the adhesive layer 2 may be a two-component curable adhesive, may be a one-component curable adhesive, or may be a resin without a curing reaction. Furthermore, the adhesion mechanism of the adhesive used to form the adhesive layer 2 is not particularly limited, and may be any of a chemical reaction type, a solvent volatilization type, a heat melting type, a heat pressure type, and the like.

Specific examples of the adhesive component that can be used to form the adhesive layer 2 include polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene isophthalate, copolyester, etc .; Adhesives; Polyurethane adhesive; Epoxy resin; Phenolic resin resin; Polyamide resin such as nylon 6, nylon 66, nylon 12, copolymerized polyamide; Polyolefin resin such as polyolefin, carboxylic acid modified polyolefin, metal modified polyolefin Resin, polyvinyl acetate resin; cellulose adhesive; (meth) acrylic resin; polycarbonate; polyimide resin; amino resin such as urea resin, melamine resin; chloroprene rubber, nitrile - arm, styrene rubbers such as butadiene rubber; and silicone resins. These adhesive components may be used alone or in combination of two or more. Among these adhesive components, a polyurethane adhesive is preferably mentioned. Moreover, resin used as these adhesion components can improve adhesive strength together with a suitable hardening | curing agent. The curing agent is appropriately selected from polyisocyanate, polyfunctional epoxy resin, oxazoline group-containing polymer, polyamine resin, acid anhydride and the like according to the functional group of the adhesive component.

The polyurethane adhesive includes, for example, a polyurethane adhesive containing a main compound containing a polyol compound and a curing agent containing an isocyanate compound. Preferred examples include two-component polyurethane adhesives of which curing agents are aromatic or aliphatic polyisocyanates with polyols such as polyester polyols, polyether polyols, and acrylic polyols as main components. Further, as the polyol compound, it is preferable to use a polyester polyol having a hydroxyl group in the side chain in addition to the hydroxyl group at the end of the repeating unit. By forming the adhesive layer 2 with a polyurethane adhesive, excellent electrolytic solution resistance is imparted to the battery packaging material, and peeling of the base layer 1 is suppressed even if the electrolytic solution adheres to the side surface.

The adhesive layer 2 may allow addition of other components as long as the adhesive property is not impaired, and may contain a colorant, a thermoplastic elastomer, a tackifier, a filler and the like. When the adhesive layer 2 contains a coloring agent, the battery packaging material can be colored. As the colorant, known ones such as pigments and dyes can be used. Moreover, only one type of colorant may be used, or two or more types may be mixed and used.

The type of pigment is not particularly limited as long as the adhesion of the adhesive layer 2 is not impaired. Examples of the organic pigment include pigments such as azo pigments, phthalocyanine pigments, quinacridone pigments, anthraquinone pigments, dioxazine pigments, indigothioindigo pigments, perinone-perylene pigments, isoindolenine pigments, and benzimidazolone pigments, and the like. Examples of the pigment include pigments of carbon black type, titanium oxide type, cadmium type, lead type, chromium oxide type, iron type and the like, and further, fine powder of mica (mica), fish scale foil and the like can be mentioned.

Among the colorants, carbon black is preferable, for example, in order to make the appearance of the battery packaging material black.

The average particle size of the pigment is not particularly limited, and, for example, about 0.05 to 5 μm, preferably about 0.08 to 2 μm. In addition, let the average particle diameter of a pigment be the median diameter measured by laser diffraction / scattering type particle diameter distribution measuring apparatus.

The content of the pigment in the adhesive layer 2 is not particularly limited as long as the battery packaging material is colored, and may be, for example, about 5 to 60% by mass, preferably 10 to 40% by mass.

The thickness of the adhesive layer 2 is not particularly limited as long as it exhibits a function as an adhesive layer, and for example, about 1 to 10 μm, preferably about 2 to 5 μm.

[Barrier layer 3]
In the battery packaging material, the barrier layer 3 is a layer having a function to prevent water vapor, oxygen, light and the like from invading the inside of the battery, in addition to the strength improvement of the battery packaging material. The barrier layer 3 is preferably a metal layer, that is, a layer formed of a metal. Specifically as a metal which comprises the barrier layer 3, aluminum, stainless steel, titanium etc. are mentioned, Preferably aluminum is mentioned. The barrier layer 3 can be formed of, for example, a metal foil, a metal vapor deposition film, an inorganic oxide vapor deposition film, a carbon-containing inorganic oxide vapor deposition film, a film provided with these vapor deposition films, or the like. It is more preferable to form by aluminum alloy foil. From the viewpoint of preventing the occurrence of wrinkles and pinholes in the barrier layer 3 during the production of the battery packaging material, the barrier layer is made of, for example, annealed aluminum (JIS H4160: 1994 A8021 H-O, JIS H4160: It is more preferable to use a soft aluminum alloy foil such as 1994 A8079 H-O, JIS H4000: 2014 A8021 P-O, JIS H 4000: 2014 A8079 P-O).

The thickness of the barrier layer 3 is not particularly limited as long as it exhibits a function as a barrier layer such as water vapor, but from the viewpoint of reducing the thickness of the battery packaging material, it is preferably about 100 μm or less, more preferably about 10 to 100 μm. More preferably, about 10 to 80 μm can be mentioned.

In addition, it is preferable that at least one surface, preferably both surfaces, of the barrier layer 3 be subjected to chemical conversion treatment in order to stabilize adhesion, to prevent dissolution or corrosion, and the like. Here, the chemical conversion treatment means a treatment for forming an acid resistant film on the surface of the barrier layer. As the chemical conversion treatment, for example, chromate chromate treatment using a chromium compound such as chromium nitrate, chromium fluoride, chromium sulfate, chromium acetate, chromium borate, chromium biphosphate, chromium acetate acetyl acetate, chromium chloride, potassium chromium sulfate and the like Phosphoric acid treatment using phosphoric acid compounds such as sodium phosphate, potassium phosphate, ammonium phosphate and polyphosphoric acid; aminated phenol polymers having repeating units represented by the following general formulas (1) to (4) And chromate treatment with In the aminated phenol polymer, repeating units represented by the following general formulas (1) to (4) may be contained singly or in any combination of two or more. It is also good.

In the general formulas (1) to (4), X represents a hydrogen atom, a hydroxy group, an alkyl group, a hydroxyalkyl group, an allyl group or a benzyl group. Further, R ¹ and R ² are the same or different and each represents a hydroxy group, an alkyl group or a hydroxyalkyl group. In the general formulas (1) to (4), examples of the alkyl group represented by X, R ¹ and R ² include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and an isobutyl group, Examples thereof include linear or branched alkyl groups having 1 to 4 carbon atoms such as a tert-butyl group. Also, examples of the hydroxyalkyl group represented by X, R ¹ and R ² include, for example, hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3- A linear or branched C1-C4 straight-chain or branched one having one hydroxy group such as hydroxypropyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group etc. An alkyl group is mentioned. In the general formulas (1) to (4), the alkyl group and the hydroxyalkyl group represented by X, R ¹ and R ² may be identical to or different from each other. In the general formulas (1) to (4), X is preferably a hydrogen atom, a hydroxy group or a hydroxyalkyl group. The number average molecular weight of the aminated phenol polymer having repeating units represented by the general formulas (1) to (4) is, for example, preferably about 500 to 1,000,000, and about 1,000 to 20,000. More preferable.

In addition, as a chemical conversion treatment method for imparting corrosion resistance to the barrier layer 3, a coating in which fine particles of aluminum oxide, titanium oxide, cerium oxide, metal oxide such as tin oxide, or barium sulfate are dispersed in phosphoric acid is coated; A method of forming an acid resistant film on the surface of the barrier layer 3 can be mentioned by carrying out the baking treatment at 150 ° C. or higher. In addition, on the acid resistant film, a resin layer may be further formed by crosslinking the cationic polymer with a crosslinking agent. Here, as the cationic polymer, for example, polyethylene imine, an ionic polymer complex composed of polyethylene imine and a polymer having a carboxylic acid, primary amine graft acrylic resin obtained by graft polymerizing a primary amine on an acrylic main skeleton, polyallylamine Or derivatives thereof, aminophenol and the like. As these cationic polymers, only 1 type may be used and you may use combining 2 or more types. Moreover, as a crosslinking agent, the compound which has an at least 1 sort (s) of functional group chosen from the group which consists of an isocyanate group, a glycidyl group, a carboxyl group, and an oxazoline group, a silane coupling agent etc. are mentioned, for example. As these crosslinking agents, only one type may be used, or two or more types may be used in combination.

Moreover, as a method of specifically providing an acid resistant coating, for example, at least the surface on the inner layer side of an aluminum alloy foil is first subjected to an alkaline dipping method, an electrolytic cleaning method, an acid cleaning method, an electrolytic acid cleaning method as one example. Degreasing treatment by a known treatment method such as acid activation method, and then the degreasing surface is treated with metal phosphate such as chromium phosphate, titanium phosphate, zirconium phosphate, zinc phosphate and the like Treatment solution (aqueous solution) mainly composed of a mixture of metal salts, or treatment solution (aqueous solution) mainly composed of a mixture of nonmetal phosphate and nonmetal salts thereof, or acrylic resin with these Or a treatment solution (aqueous solution) composed of a mixture with a water-based synthetic resin such as a phenolic resin or a urethane resin is applied by a known coating method such as roll coating, gravure printing, or immersion. And it makes it possible to form the acid-resistant coating. For example, when treated with a chromium phosphate salt treatment liquid, it becomes an acid-resistant film composed of chromium phosphate, aluminum phosphate, aluminum oxide, aluminum hydroxide, aluminum fluoride, etc., and is treated with a zinc phosphate salt treatment liquid In the case of an acid resistant coating, the coating is made of zinc phosphate hydrate, aluminum phosphate, aluminum oxide, aluminum hydroxide, aluminum fluoride and the like.

Moreover, as another example of the specific method of providing an acid resistant film, for example, at least the surface on the inner layer side of an aluminum alloy foil is first subjected to an alkaline dipping method, an electrolytic cleaning method, an acid cleaning method, an electrolytic acid cleaning method, an acid An acid resistant film can be formed by degreasing treatment by a known treatment method such as activation method and then applying known anodic oxidation treatment to the degreasing treatment surface.

Moreover, phosphate-based and chromic acid-based films are mentioned as another example of the acid resistant film. Examples of phosphates include zinc phosphate, iron phosphate, manganese phosphate, calcium phosphate and chromium phosphate. Examples of chromic acid include chromium chromate.

Moreover, as another example of the acid resistant coating, by forming an acid resistant coating such as phosphate, chromate, fluoride, triazine thiol compound, etc., between the aluminum and the substrate layer at the time of embossing and forming Anti-delamination, hydrogen fluoride generated by the reaction between electrolyte and water prevents dissolution and corrosion of the aluminum surface, especially dissolution and corrosion of aluminum oxide present on the aluminum surface, and adhesion of the aluminum surface The properties (wettability) are improved, and the effect of preventing the delamination of the base layer and aluminum during heat sealing and the prevention of the delamination of the base layer and aluminum during press molding are shown in the embossed type. Among the substances forming the acid resistant film, an aqueous solution composed of three components of a phenol resin, a chromium (III) fluoride compound, and phosphoric acid is applied to the aluminum surface, and the treatment of dry baking is good.

The acid resistant film further comprises a layer having cerium oxide, phosphoric acid or phosphate, an anionic polymer, and a crosslinking agent for crosslinking the anionic polymer, wherein the phosphoric acid or phosphate is any of the above-mentioned. It may be blended in an amount of 1 to 100 parts by mass with respect to 100 parts by mass of cerium oxide. It is preferable that the acid resistant coating be a multilayer structure further including a layer having a cationic polymer and a crosslinking agent for crosslinking the cationic polymer.

Furthermore, it is preferable that the said anionic polymer is a copolymer which has poly (meth) acrylic acid or its salt, or (meth) acrylic acid or its salt as a main component. Moreover, it is preferable that the said crosslinking agent is at least 1 sort (s) chosen from the group which consists of a compound which has a functional group in any one of an isocyanate group, glycidyl group, a carboxyl group, and an oxazoline group, and a silane coupling agent.

Moreover, it is preferable that the said phosphoric acid or phosphate is condensed phosphoric acid or condensed phosphate.

For the chemical conversion treatment, only one type of chemical conversion treatment may be performed, or two or more types of chemical conversion treatments may be performed in combination. Furthermore, these chemical conversion treatments may be performed using one type of compound alone, or may be performed using two or more types of compounds in combination. Among the chemical conversion treatments, a chromate chromate treatment, a chemical conversion treatment in which a chromium compound, a phosphoric acid compound, and an aminated phenol polymer are combined, and the like are preferable. Among the chromium compounds, chromic acid compounds are preferred.

Specific examples of the acid resistant coating include those containing at least one of phosphate, chromate, fluoride, and triazine thiol. In addition, an acid resistant film containing a cerium compound is also preferable. As a cerium compound, cerium oxide is preferable.

Moreover, as a specific example of an acid resistant film, a phosphate type film, a chromate type film, a fluoride type film, a triazine thiol compound film, etc. are mentioned. The acid resistant coating may be one of these or a combination of two or more. Furthermore, as an acid resistant coating, after degreasing the surface of the aluminum alloy foil on the chemical conversion treatment, a treatment liquid comprising a mixture of a metal phosphate and an aqueous synthetic resin, or a mixture of a nonmetallic phosphate and an aqueous synthetic resin It may be formed of a treatment liquid comprising

The analysis of the composition of the acid-resistant film can be performed using, for example, time-of-flight secondary ion mass spectrometry. Analysis of the composition of the acid-resistant film using time-of-flight secondary ion mass spectrometry detects, for example, a peak derived from at least one of Ce ⁺ and Cr ⁺ .

It is preferable that the surface of the aluminum alloy foil is provided with an acid resistant film containing at least one element selected from the group consisting of phosphorus, chromium and cerium. In addition, it is confirmed using X-ray photoelectron spectroscopy that at least one element selected from the group consisting of phosphorus, chromium and cerium is contained in the acid-resistant film on the surface of the aluminum alloy foil of the packaging material for batteries. can do. Specifically, first, in the battery packaging material, the heat fusible resin layer, the adhesive layer and the like laminated on the aluminum alloy foil are physically peeled off. Next, the aluminum alloy foil is placed in an electric furnace, and the organic components present on the surface of the aluminum alloy foil are removed at about 300 ° C. for about 30 minutes. Thereafter, X-ray photoelectron spectroscopy of the surface of the aluminum alloy foil is used to confirm that these elements are contained.

The amount of acid-resistant coatings to be formed on the surface of the barrier layer 3 in the chemical conversion treatment is not particularly limited, for example, in the case of performing the above-mentioned chromate treatment, the surface 1 m ² per barrier layer 3, the chromium compound is chromium 0.5 to 50 mg or so, preferably 1.0 to 40 mg or so, the phosphorus compound is 0.5 to 50 mg or so, preferably 1.0 to 40 mg, and the aminated phenol polymer is 1.0 or more It is desirable that the content be about 200 mg, preferably about 5.0 to 150 mg.

The thickness of the acid-resistant coating is not particularly limited, but is preferably about 1 nm to 10 μm, more preferably about 1 to 100 nm, from the viewpoint of the cohesion of the coating and the adhesion to the aluminum alloy foil and the heat-fusion resin layer. More preferably, it is about 1 to 50 nm. The thickness of the acid resistant coating can be measured by a transmission electron microscope or a combination of an observation by a transmission electron microscope and energy dispersive X-ray spectroscopy or electron beam energy loss spectroscopy.

In the chemical conversion treatment, the temperature of the barrier layer is 70 after the solution containing the compound used for forming the acid resistant coating is applied to the surface of the barrier layer by the bar coating method, roll coating method, gravure coating method, immersion method or the like. It is carried out by heating to about 200 ° C. In addition, before the chemical conversion treatment is performed on the barrier layer, the barrier layer may be subjected in advance to a degreasing treatment by an alkaline immersion method, an electrolytic cleaning method, an acid cleaning method, an electrolytic acid cleaning method or the like. By performing the degreasing treatment in this manner, the chemical conversion treatment on the surface of the barrier layer can be performed more efficiently.

[Heat-fusible resin layer 4]
In the battery packaging material of the present invention, the thermally fusible resin layer 4 corresponds to the innermost layer, and is a layer that thermally fuses the thermally fusible resin layers when the battery is assembled to seal the battery element.

The resin component used for the heat fusible resin layer 4 is not particularly limited as long as heat fusible is possible, and examples thereof include polyolefin, cyclic polyolefin, acid-modified polyolefin, and acid-modified cyclic polyolefin. That is, the resin constituting the heat-fusible resin layer 4 may or may not contain a polyolefin skeleton, and preferably contains a polyolefin skeleton. The resin constituting the heat-fusible resin layer 4 can be analyzed by, for example, infrared spectroscopy, gas chromatography-mass spectrometry, etc., as long as it contains a polyolefin skeleton, and the analysis method is not particularly limited. Moreover, when the resin which comprises the heat sealing | fusion resin layer 4 is analyzed by an infrared spectroscopy, it is preferable that the peak originating in maleic anhydride is detected. For example, when measuring the infrared spectroscopy at a maleic anhydride-modified polyolefin, a peak derived from maleic acid is detected in the vicinity of the wave number of 1760 cm ^-1 and near the wave number 1780 cm ^-1. However, if the acid denaturation degree is low, the peak may be small and not detected. In that case, analysis is possible by nuclear magnetic resonance spectroscopy.

Specific examples of the polyolefin include polyethylenes such as low density polyethylene, medium density polyethylene, high density polyethylene and linear low density polyethylene; homopolypropylene, block copolymers of polypropylene (for example, block copolymers of propylene and ethylene), polypropylene Polypropylenes such as random copolymers of (for example, random copolymers of propylene and ethylene); terpolymers of ethylene-butene-propylene and the like. Among these polyolefins, preferably polyethylene and polypropylene are mentioned.

The cyclic polyolefin is a copolymer of an olefin and a cyclic monomer, and examples of the olefin which is a constituent monomer of the cyclic polyolefin include ethylene, propylene, 4-methyl-1-pentene, butadiene, isoprene and the like. . Moreover, as a cyclic monomer which is a constituent monomer of the cyclic polyolefin, for example, cyclic alkenes such as norbornene; specifically, cyclic dienes such as cyclopentadiene, dicyclopentadiene, cyclohexadiene, norbornadiene, and the like can be mentioned. Among these polyolefins, preferred are cyclic alkenes, more preferably norbornene. As a constituent monomer, styrene is also mentioned.

The acid-modified polyolefin is a polymer obtained by modifying the polyolefin by block polymerization or graft polymerization with an acid component such as a carboxylic acid. Examples of the acid component used for modification include carboxylic acids such as maleic acid, acrylic acid, itaconic acid, crotonic acid, maleic anhydride, itaconic anhydride, or anhydrides thereof.

The acid-modified cyclic polyolefin is prepared by copolymerizing part of the monomers constituting the cyclic polyolefin with an α, β-unsaturated carboxylic acid or an anhydride thereof, or α, β- to the cyclic polyolefin. It is a polymer obtained by block polymerization or graft polymerization of unsaturated carboxylic acid or its anhydride. The cyclic polyolefin to be carboxylic acid modified is the same as described above. Moreover, as a carboxylic acid used for modification | denaturation, it is the same as that of what is used for modification | denaturation of the said polyolefin.

Among these resin components, preferred are polyolefins such as polypropylene, carboxylic acid-modified polyolefins, and more preferably polypropylene and acid-modified polypropylenes.

The heat fusible resin layer 4 may be formed of one type of resin component alone, or may be formed of a blend polymer in which two or more types of resin components are combined. Furthermore, although the heat fusible resin layer 4 may be formed of only one layer, it may be formed of two or more layers of the same or different resin components.

A fatty acid amide compound may be present on the surface of the heat-fusible resin layer 4. The fatty acid amide compound is not particularly limited, and examples thereof include saturated fatty acid amides, unsaturated fatty acid amides, substituted amides, methylolamides, saturated fatty acid bisamides, unsaturated fatty acid bisamides and the like. Specific examples of the saturated fatty acid amide include lauric acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, hydroxystearic acid amide and the like. Specific examples of the unsaturated fatty acid amide include oleic acid amide and erucic acid amide. Specific examples of the substituted amide include N-oleyl palmitic acid amide, N-stearyl stearic acid amide, N-stearyl oleic acid amide, N-oleyl stearic acid amide, N-stearyl erucic acid amide and the like. In addition, specific examples of methylolamide include methylol stearic acid amide and the like. Specific examples of the saturated fatty acid bisamide include methylenebisstearic acid amide, ethylenebiscapric acid amide, ethylenebislauric acid amide, ethylenebisstearic acid amide, ethylenebishydroxystearic acid amide, ethylenebisbehenic acid amide, hexamethylene bisstearin Acid amide, hexamethylene bisbehenamide, hexamethylene hydroxystearic amide, N, N'-distearyl adipamide, N, N'-distearyl sebacate amide and the like can be mentioned. Specific examples of unsaturated fatty acid bisamides include ethylene bis oleic acid amide, ethylene bis erucic acid amide, hexamethylene bis oleic acid amide, N, N'-dioleyl adipic acid amide, N, N'-dioleyl sebacic acid amide Etc. Specific examples of fatty acid ester amides include stearoamidoethyl stearate and the like. Further, specific examples of the aromatic bisamides include m-xylylene bis-stearic acid amide, m-xylylene bis-hydroxystearic acid amide, N, N'-distearyl isophthalic acid amide and the like. The fatty acid amide compounds may be used alone or in combination of two or more.

The thickness of the heat fusible resin layer 4 is not particularly limited as long as it exhibits the function as a heat fusible resin layer, but preferably about 60 μm or less, more preferably about 15 to 40 μm.

When a fatty acid amide compound is present on the surface of the heat-fusible resin layer 4, the amount thereof is not particularly limited, but preferably 3 mg / m ² or more, more preferably at a temperature of 24 ° C. and a relative humidity of 60%. Is about 10 to 50 mg / m ² , more preferably about 15 to 40 mg / m ² .

In the battery packaging material of the present invention, by the following method, in the case of measuring the temperature difference between T ₁ and the temperature difference T _2, the value obtained by dividing the temperature difference T ₂ at a temperature difference T ₁ (ratio T ₂ It is preferable that / T ₁ ) is, for example, 0.55 or more, and further preferably 0.60 or more. As understood from the measurement contents of the temperature differences T ₁ and T ₂ below, the heat fusible resin layer contacts the electrolyte as the ratio T ₂ / T ₁ approaches the upper limit value of 1.0. This means that the change in the width between the start point (extrapolation melting start temperature) and the end point (extrapolation melting end temperature) of the melting peak before and after is small (see the schematic diagram of FIG. 10). That is, the value of T ₂ are, is usually of T ₁ values below. Low-molecular-weight resin contained in the resin forming the heat-fusible resin layer is brought into contact with the electrolyte as a factor that increases the change in the width between the extrapolation melting start temperature and the extrapolation melting end temperature of the melting peak. The elution peak temperature and the extrapolation end temperature of the melting peak of the heat fusible resin layer after being dissolved in the electrolyte by contact with the electrolyte are measured before the electrolyte is brought into contact with the electrolyte. To be smaller. Proportion of low molecular weight resin contained in the resin forming the heat-fusible resin layer as one of methods for reducing the change in the width between the extrapolation melting start temperature and the extrapolation melting end temperature of the melting peak There is a way to adjust the

(Measurement of temperature difference T ₁ )
According to the definition of JIS K7121: 2012, a differential scanning calorimetry (DSC) is used to obtain a DSC curve for polypropylene used for the heat-sealable resin layer of each of the above-mentioned battery packaging materials. From the obtained DSC curve, measuring the temperature difference T ₁ of the extrapolation melting start temperature of the melting peak temperature of the heat-fusible resin layer and the extrapolated ending melting temperature.

(Measurement of temperature difference T ₂ )
The concentration of lithium hexafluorophosphate is 1 mol / l and the volume ratio of ethylene carbonate: diethyl carbonate: dimethyl carbonate is 1: 1: After standing for 72 hours in the electrolyte solution which is the solution of 1, it is sufficiently dried. Next, a differential scanning calorimetry (DSC) is used to obtain a DSC curve for the dried polypropylene, in accordance with JIS K7121: 2012. Next, from the obtained DSC curve, measuring the temperature difference T ₂ of the extrapolation melting start temperature of the melting peak temperature of the heat-fusible resin layer after drying and extrapolated ending melting temperature.

A commercial item can be used as a differential scanning calorimeter to measure the extrapolation melting start temperature and the extrapolation melting end temperature of the melting peak temperature. In addition, as a DSC curve, after holding the test sample at -50 ° C for 10 minutes, the temperature is raised to 200 ° C at a heating rate of 10 ° C / min (first time), and after holding for 10 minutes at 200 ° C, the temperature lowering rate The temperature is lowered to -50 ° C at -10 ° C / min and held at -50 ° C for 10 minutes, then the temperature is raised to 200 ° C at a heating rate of 10 ° C / min (second time) and held at 200 ° C for 10 minutes, The DSC curve at the time of temperature rising to 200 ° C. for the second time is used. Also, when measuring the temperature difference T ₁ and the temperature difference T _2, in each of the DSC curve, of the melting peak appearing in the range of 120 ~ 160 ° C., analyzed the melting peak difference between the input of thermal energy is maximized Do. Even when two or more peaks overlap and are present, analysis is performed only on the melting peak where the difference in thermal energy input is the largest.

The extrapolation melting start temperature means the starting point of melting peak temperature, and the difference between the heat energy input and the straight line extending the baseline on the low temperature (65 to 75 ° C) side to the high temperature side is the largest. The curve on the cold side of the peak is taken as the temperature at the point of intersection with the tangent drawn at the point where the slope is maximum. Extrapolation end temperature means the end point of melting peak temperature, a straight line extending the baseline on the high temperature (170 ° C) side to the low temperature side, and the high temperature side of the melting peak where the difference between the thermal energy input is maximum The temperature at the point of intersection with the tangent drawn at the point where the slope is maximum is taken as the curve of.

In the battery packaging material of the present invention, the thermally fusible resin layers are thermally fused in a state where the electrolytic solution is in contact with the thermally fusible resin layer in a high temperature environment and the electrolytic solution adheres to the thermally fusible resin layer. has been in the case, by heat sealing, from the viewpoint of exhibiting a still higher sealing strength, a value obtained by dividing the temperature difference T ₂ at a temperature difference T ₁ (the ratio T ₂ / T _1), for example 0.55 or more, preferably 0.60 or more, more preferably 0.70 or more, further preferably 0.75 or more, and a preferable range is about 0.55 to 1.0, 0.60 to 1 0: about 0.70 to about 1.0, about 0.75 to about 1.0. The upper limit is, for example, 1.0. In order to set such a ratio T ₂ / T _1, for example, the kind of the resin constituting the thermally adhesive resin layer 4, the composition, for adjusting the molecular weight.

[Adhesive layer 5]
In the battery packaging material of the present invention, the adhesive layer 5 is a layer optionally provided between the barrier layer 3 and the heat-fusible resin layer 4 in order to firmly bond the barrier layer 3 and the heat-fusible resin layer 4.

The adhesive layer 5 is formed of a resin capable of adhering the barrier layer 3 and the heat fusible resin layer 4. As resin used for formation of adhesion layer 5, the thing of the adhesion mechanism, the kind of adhesive agent component, etc. can use the thing similar to the adhesive illustrated by adhesive agent layer 2. Moreover, as resin used for formation of the contact bonding layer 5, polyolefin resin, such as polyolefin mentioned above-mentioned heat-fusion resin layer 4, cyclic polyolefin, carboxylic acid modified polyolefin, carboxylic acid modified cyclic polyolefin, can also be used. . As the polyolefin, a carboxylic acid-modified polyolefin is preferable, and a carboxylic acid-modified polypropylene is particularly preferable, from the viewpoint of excellent adhesion between the barrier layer 3 and the heat-fusible resin layer 4. That is, the resin constituting the adhesive layer 5 may or may not contain a polyolefin skeleton, and preferably contains a polyolefin skeleton. It is possible to analyze that the resin constituting the adhesive layer 5 contains a polyolefin skeleton, for example, by infrared spectroscopy, gas chromatography mass spectrometry, etc., and there is no particular limitation on the analysis method. Moreover, when the resin which comprises the contact bonding layer 5 is analyzed by an infrared spectroscopy, it is preferable that the peak originating in maleic anhydride is detected. For example, when measuring the infrared spectroscopy at a maleic anhydride-modified polyolefin, a peak derived from maleic acid is detected in the vicinity of the wave number of 1760 cm ^-1 and near the wave number 1780 cm ^-1. However, if the acid denaturation degree is low, the peak may be small and not detected. In that case, analysis is possible by nuclear magnetic resonance spectroscopy.

Furthermore, from the viewpoint of making the battery packaging material excellent in shape stability after molding while reducing the thickness of the battery packaging material, the adhesive layer 5 cures the resin composition containing the acid-modified polyolefin and the curing agent. It may be a thing. As the acid-modified polyolefin, preferably, the same ones as the carboxylic acid-modified polyolefin and the carboxylic acid-modified cyclic polyolefin exemplified in the heat fusible resin layer 4 can be exemplified.

The curing agent is not particularly limited as long as it cures acid-modified polyolefin. Examples of the curing agent include epoxy-based curing agents, polyfunctional isocyanate-based curing agents, carbodiimide-based curing agents, oxazoline-based curing agents, and the like.

The epoxy curing agent is not particularly limited as long as it is a compound having at least one epoxy group. Examples of the epoxy curing agent include epoxy resins such as bisphenol A diglycidyl ether, modified bisphenol A diglycidyl ether, novolak glycidyl ether, glycerin polyglycidyl ether, polyglycerin polyglycidyl ether and the like.

The polyfunctional isocyanate-based curing agent is not particularly limited as long as it is a compound having two or more isocyanate groups. Specific examples of the polyfunctional isocyanate-based curing agent include isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), those obtained by polymerizing or denating these, or the like Mixtures and copolymers with other polymers may be mentioned.

The carbodiimide curing agent is not particularly limited as long as it is a compound having at least one carbodiimide group (-N = C = N-). As a carbodiimide type | system | group hardening | curing agent, the polycarbodiimide compound which has a carbodiimide group 2 or more at least is preferable.

The oxazoline-based curing agent is not particularly limited as long as it is a compound having an oxazoline skeleton. Specific examples of the oxazoline curing agent include Epocross series manufactured by Nippon Shokubai Co., Ltd.

From the viewpoint of, for example, enhancing the adhesion between the barrier layer 3 and the thermally fusible resin layer 4 by the adhesive layer 5, the curing agent may be composed of two or more types of compounds.

The content of the curing agent in the resin composition forming the adhesive layer 5 is preferably in the range of about 0.1 to 50% by mass, and more preferably in the range of about 0.1 to 30% by mass, More preferably, it is in the range of about 0.1 to 10% by mass.

The thickness of the adhesive layer 5 is not particularly limited as long as it exhibits the function as an adhesive layer, but in the case of using the adhesive exemplified in the adhesive layer 2, it is preferably about 1 to 10 μm, more preferably 1 to There is about 5 μm. Further, in the case of using the resin exemplified for the heat fusible resin layer 4, it is preferably about 2 to 50 μm, more preferably about 10 to 40 μm. In the case of a cured product of an acid-modified polyolefin and a curing agent, it is preferably 30 μm or less, more preferably about 0.1 to 20 μm, and still more preferably about 0.5 to 5 μm. When the adhesive layer 5 is a cured product of a resin composition containing an acid-modified polyolefin and a curing agent, the adhesive layer 5 can be formed by applying the resin composition and curing it by heating or the like.

In the battery packaging material of the present invention, the adhesive layer 5 preferably has a logarithmic attenuation factor ΔE at 120 ° C. in a rigid pendulum measurement of, for example, 2.5 or less, and more preferably 2.0 or less. In the present invention, when the battery element is sealed with the battery packaging material by setting the logarithmic attenuation factor ΔE at 120 ° C. to, for example, 2.5 or less, or 2.0 or less, the heat fusible resin layer Crushing of the adhesive layer when heat-sealing each other is effectively suppressed, and high seal strength in a high temperature environment is exhibited.

The logarithmic attenuation factor at 120 ° C. in rigid pendulum measurement is an index showing the hardness of the resin in a high temperature environment of 120 ° C., and the smaller the logarithmic attenuation factor, the higher the hardness of the resin. In the rigid pendulum measurement, the damping rate of the pendulum when the temperature of the resin is raised from a low temperature to a high temperature is measured. In rigid pendulum measurement, generally, the edge portion is brought into contact with the surface of the object to be measured, and the pendulum motion is performed in the lateral direction to apply vibration to the object to be measured. In the battery packaging material of the present invention, the hard adhesive layer 5 having a logarithmic attenuation factor of, for example, 2.5 or less, and further 2.0 or less in a high temperature environment of 120 ° C. By disposing between them, crushing (thinning) of the adhesive layer 5 at the time of heat sealing of the battery packaging material can be suppressed, and furthermore, high seal strength can be exhibited in a high temperature environment.

The logarithmic attenuation rate ΔE is calculated by the following equation.
ΔE = [ln (A1 / A2) + ln (A2 / A3) +... Ln (An / An + 1)] / n
A: Amplitude n: Wave number

In the battery packaging material of the present invention, from the viewpoint of effectively suppressing the crush of the adhesive layer 5 when the heat fusible resin layers 4 are thermally fused to each other, and further exhibiting high seal strength in a high temperature environment. The logarithmic attenuation factor ΔE at 120 ° C. is, for example, about 1.4 to 2.5, preferably about 1.4 to 2.0, and more preferably about 1.4 to 1.6. In addition, in order to set to the said logarithmic attenuation factor (DELTA) E, the kind, composition, molecular weight, etc. of resin which comprise the contact bonding layer 5 are adjusted, for example.

In measuring the logarithmic attenuation rate ΔE, using a commercially available rigid pendulum physical property tester, a cylindrical cylinder edge as an edge portion pressed against the adhesive layer 5, an initial amplitude of 0.3 degree, and a temperature of 30 ° C. to 200 ° C. A rigid-body pendulum physical-property test is performed with respect to the contact bonding layer 5 on the conditions of the temperature increase rate of 3 degrees C / min. Then, based on the logarithmic attenuation factor at 120 ° C., the standard of the improvement effect of the seal strength by the suppression of the collapse exerted by the adhesive layer 5 and the thermal fusion of the high temperature environment was determined. In addition, about the contact bonding layer which measures logarithmic attenuation factor (DELTA) E, the packaging material for batteries was immersed in 15% hydrochloric acid, the base material layer and the aluminum foil were dissolved, and it became only the contact bonding layer and the heat fusible resin layer. Allow the sample to dry thoroughly and make it a measurement target.

In addition, it is also possible to obtain the battery packaging material from the battery and measure the logarithmic attenuation factor ΔE of the adhesive layer 5. When the battery packaging material is obtained from the battery and the logarithmic attenuation factor ΔE of the adhesive layer 5 is measured, a sample is cut out from the top surface portion that is less affected by the molding of the battery packaging material to be stretched.

Further, in the battery packaging material of the present invention, the heat fusible resin layers of the laminates constituting the battery packaging material are opposed to each other, and the temperature is 190 ° C., the surface pressure is 0.5 MPa, and the condition is 3 seconds. After heating and pressing in the laminating direction, the residual ratio of the thickness of the adhesive layer is preferably 70% or more, preferably 80% or more, and preferably 70 to 95%, 80 to 95%. Can be mentioned. The upper limit of the residual ratio of the thickness is, for example, about 95%. The residual ratio of the thickness is a value measured by the following method. In order to set the remaining ratio of the thickness, for example, the type, composition, molecular weight and the like of the resin constituting the adhesive layer 5 are adjusted.

<Measurement of Remaining Ratio of Adhesive Layer Thickness>
The battery packaging material is cut into a length of 150 mm and a width of 60 mm to prepare a test sample. Next, the heat fusible resin layers of the test sample are made to face each other. Next, in this state, using a metal plate having a width of 7 mm, heat fusion is performed under the conditions of a temperature of 190 ° C., a surface pressure of 0.5 MPa, and a time of 3 seconds in the stacking direction from both sides of the test sample. Heat-sealable resin layers. Next, the heat-sealed portion of the test sample is cut in the stacking direction using a microtome, and the thickness of the adhesive layer is measured on the exposed cross section. The test sample before heat fusion is similarly cut in the laminating direction using a microtome, and the thickness of the adhesive layer is measured on the exposed cross section. The ratio of the thickness of the adhesive layer after the thermal fusion to the thickness of the adhesive layer before the thermal fusion is calculated to measure the remaining ratio (%) of the thickness of the adhesive layer.

Moreover, the packaging material for batteries can be acquired from a battery, and the residual ratio of the thickness of the contact bonding layer 5 can also be measured. When the battery packaging material is obtained from the battery and the residual ratio of the thickness of the adhesive layer 5 is measured, a sample is cut out from the top surface portion having little influence of stretching of the battery packaging material by molding to be a measurement target.

The logarithmic attenuation factor ΔE of the adhesive layer 5 can be adjusted, for example, by the melt mass flow rate (MFR), the molecular weight, the melting point, the softening point, the molecular weight distribution, and the crystallinity of the resin constituting the adhesive layer 5.

[Surface covering layer 6]
In the battery packaging material of the present invention, the outer side of the base material layer 1 (the barrier layer of the base material layer 1 as needed) for the purpose of improving designability, electrolytic solution resistance, abrasion resistance, moldability, etc. If necessary, a surface covering layer 6 may be provided on the side opposite to 3).

The surface coating layer 6 can be formed of, for example, polyvinylidene chloride, polyester resin, urethane resin, acrylic resin, epoxy resin or the like. Among these, the surface coating layer 6 is preferably formed of a two-component curable resin. Examples of the two-component curable resin that forms the surface covering layer 6 include a two-component curable urethane resin, a two-component curable polyester resin, and a two-component curable epoxy resin. Further, an additive may be blended in the surface coating layer 6.

Examples of the additive include fine particles having a particle diameter of about 0.5 nm to 5 μm. The material of the additive is not particularly limited, and examples thereof include metals, metal oxides, inorganic substances, and organic substances. Further, the shape of the additive is not particularly limited, and examples thereof include spheres, fibers, plates, indeterminate shapes, and balloons. As the additive, specifically, talc, silica, graphite, kaolin, montmorrroid, montmorillonite, synthetic mica, hydrotalcite, silica gel, zeolite, aluminum hydroxide, magnesium hydroxide, zinc oxide, magnesium oxide, aluminum oxide, Neodymium oxide, antimony oxide, titanium oxide, cerium oxide, calcium sulfate, barium sulfate, calcium carbonate, calcium silicate, lithium carbonate, calcium benzoate, calcium oxalate, magnesium stearate, alumina, carbon black, carbon nanotubes, high Melting point nylon, acrylate resin, crosslinked acrylic, crosslinked styrene, crosslinked polyethylene, benzoguanamine, gold, aluminum, copper, nickel and the like can be mentioned. These additives may be used alone or in combination of two or more. Among these additives, silica, barium sulfate and titanium oxide are preferably mentioned from the viewpoint of dispersion stability and cost. In addition, the surface may be subjected to various surface treatments such as insulation treatment, high dispersion treatment, and the like. In addition, a lubricant, an antiblocking agent, a matting agent, as needed, on at least one of the surface and the inside of the surface coating layer 6 according to the surface coating layer 6 and the functionality to be provided on the surface, etc. Additives such as a flame retardant, an antioxidant, a light stabilizer, a tackifier, an antistatic agent, and an elastomer resin may be included. Specific examples of the lubricant include, for example, the lubricants described above. Further, the above-mentioned fine particles may function as a lubricant, an antiblocking agent, and a matting agent.

Although it does not restrict | limit especially as a method to form the surface coating layer 6, For example, the method of apply | coating the two-component curable resin which forms the surface coating layer 6 on the surface of the outer side of the base material layer 1 is mentioned. In the case of blending the additive, the additive may be added to and mixed with the two-component curable resin and then applied.

The content of the additive in the surface coating layer 6 is not particularly limited, but preferably about 0.05 to 1.0% by mass, more preferably about 0.1 to 0.5% by mass.

The thickness of the surface coating layer 6 is not particularly limited as long as the above-described function as the surface coating layer 6 is exhibited, and for example, about 0.5 to 10 μm, preferably about 1 to 5 μm.

3. Method for Producing Battery Packaging Material The method for producing a battery packaging material of the present invention is not particularly limited as long as a laminate obtained by laminating each layer of a predetermined composition is obtained, at least a base material layer, a barrier layer, And a step of laminating the heat fusible resin layer in this order, and at least a fatty acid amide compound is present on the surface of the laminate on the substrate layer side, as a fatty acid amide compound, The method of using what melt | dissolves 1 g or more with respect to 100 g of methyl ethyl ketone in a 25 degreeC environment is mentioned. A lubricant may be applied to the surface of the base layer 1 as a method of causing the lubricant to be present on the surface of the base layer 1 side, or a layer on the base layer 1 side (for example, the base layer 1 or the surface coating layer) A lubricant may be included in the resin constituting 6) to bleed out the lubricant on the surface on the substrate layer 1 side.

As an example of the manufacturing method of the packaging material for batteries of this invention, it is as follows. First, a laminate (hereinafter sometimes referred to as “laminate A”) in which the base material layer 1, the adhesive layer 2, and the barrier layer 3 are sequentially laminated is formed. Specifically, the laminate A is formed by gravure coating an adhesive used for forming the adhesive layer 2 on the base layer 1 or on the barrier layer 3 whose surface has been subjected to a chemical conversion treatment if necessary. It can carry out by the dry lamination method which makes the barrier layer 3 or the substrate layer 1 concerned laminate, and hardens the adhesive layer 2 after applying and drying with application methods, such as a roll coat method.

Next, the heat fusible resin layer 4 is laminated on the barrier layer 3 of the laminate A. In the case where the heat fusible resin layer 4 is directly laminated on the barrier layer 3, the resin component constituting the heat fusible resin layer 4 is gravure-coated or roll-coated on the barrier layer 3 of the laminate A It may be applied by a method such as When the adhesive layer 5 is provided between the barrier layer 3 and the heat fusible resin layer 4, for example, (1) the adhesive layer 5 and the heat fusible resin layer on the barrier layer 3 of the laminate A Method of laminating 4 by coextrusion (co-extrusion laminating method), (2) Separately, a laminated body in which the adhesive layer 5 and the heat-fusible resin layer 4 are laminated is formed, (3) A method of laminating by thermal laminating method, (3) A method of extruding or solution coating an adhesive for forming the adhesive layer 5 on the barrier layer 3 of the laminated body A, drying at a high temperature, and baking Method of laminating the thermally fusible resin layer 4 formed in advance into a sheet on the adhesive layer 5 by the thermal laminating method, (4) the barrier layer 3 of the laminated body A and the sheet Melted adhesion between the film and the heat-bonding resin layer 4 While pouring 5, and a method of bonding a laminate A and the heat-welding resin layer 4 through the adhesive layer 5 (sandwich lamination method).

When the surface covering layer 6 is provided, the surface covering layer 6 is laminated on the surface of the base layer 1 opposite to the barrier layer 3. The surface coating layer 6 can be formed, for example, by applying the above-mentioned resin that forms the surface coating layer 6 on the surface of the base layer 1. The order of the process of laminating the barrier layer 3 on the surface of the base material layer 1 and the process of laminating the surface coating layer 6 on the surface of the base material layer 1 is not particularly limited. For example, after the surface covering layer 6 is formed on the surface of the base layer 1, the barrier layer 3 may be formed on the surface of the base layer 1 opposite to the surface covering layer 6.

As described above, surface covering layer 6 / base layer 1 / optional layer 1 / optional adhesive layer 2 / optional layer surface optionally treated / optional 3 / optional layer A laminate of the adhesive layer 5 / thermal adhesive resin layer 4 to be provided is formed, but in order to strengthen the adhesion of the adhesive layer 2 and the adhesive layer 5 to be provided if necessary, It may be subjected to heat treatment such as hot roll contact, hot air, near or far infrared rays and the like. The conditions for such heat treatment include, for example, at 150 to 250 ° C. for 1 to 5 minutes.

In the battery packaging material of the present invention, each layer constituting the laminate improves or stabilizes film forming ability, lamination processing, final product secondary processing (pouching, embossing) suitability, etc., as necessary. For this purpose, surface activation treatments such as corona treatment, blast treatment, oxidation treatment, and ozone treatment may be performed. For example, by subjecting at least one surface of the base material layer to corona treatment, film forming property, lamination processing, final product secondary processing suitability and the like can be improved or stabilized. Furthermore, for example, by subjecting the surface of the base layer 1 opposite to the barrier layer 3 to corona treatment, the printability of the ink on the surface of the base layer 1 can be improved.

4. Applications of Battery Packaging Material The battery packaging material of the present invention is used for a package for sealing and housing battery elements such as a positive electrode, a negative electrode, and an electrolyte. That is, the battery element provided with at least a positive electrode, a negative electrode, and an electrolyte can be accommodated in a package formed of the battery packaging material of the present invention to make a battery.

Specifically, a battery element provided with at least a positive electrode, a negative electrode, and an electrolyte is a battery packaging material of the present invention, in which the metal terminal connected to each of the positive electrode and the negative electrode protrudes outward. The battery is covered by forming flanges (areas in which the heat fusible resin layers are in contact with each other) on the periphery of the element, and heat sealing the heat fusible resin layers of the flanges to seal them. A battery using a packaging material is provided. When the battery element is housed in a package formed of the battery packaging material of the present invention, the sealant portion of the battery packaging material of the present invention is placed inside (the surface in contact with the battery element). Form a body.

In the present invention, the step of housing the battery element provided with at least the positive electrode, the negative electrode, and the electrolyte in the package formed of the battery packaging material of the present invention, and the surface of the substrate layer side by ink By the method including the steps of applying printing, a battery in which printing is applied to the surface on the substrate layer side can be manufactured. That is, the battery of the present invention can be a battery having a printing portion on the surface. Moreover, a fatty acid amide compound exists in the surface by the side of the said base material layer of the said laminated body at least, and it can also be set as the battery which has the printing part by ink in the surface by the side of a base material layer.

The battery packaging material of the present invention may be used for either a primary battery or a secondary battery, but is preferably a secondary battery. The type of secondary battery to which the battery packaging material of the present invention is applied is not particularly limited. For example, lithium ion battery, lithium ion polymer battery, lead storage battery, nickel hydrogen storage battery, nickel cadmium storage battery, nickel Iron storage batteries, nickel-zinc storage batteries, silver oxide-zinc storage batteries, metal air batteries, multivalent cation batteries, capacitors, capacitors and the like can be mentioned. Among these secondary batteries, lithium ion batteries and lithium ion polymer batteries are mentioned as a suitable application object of the packaging material for batteries of the present invention.

Hereinafter, the present invention will be described in detail by way of Examples and Comparative Examples. However, the present invention is not limited to the examples.

(Example 1-26 and Comparative Example 1-25)
<Manufacture of battery packaging materials>
An aluminum alloy foil (35 μm in thickness) as a barrier layer was laminated on the base material layer having the configuration and thickness shown in Table 1 by a dry lamination method. Specifically, a two-component urethane adhesive (polyol compound and aromatic isocyanate compound) was applied to one surface of an aluminum alloy foil to form an adhesive layer (3 μm in thickness) on the aluminum alloy foil. Next, the adhesive layer on the barrier layer and the base material layer were laminated by a dry lamination method, and then an aging treatment was performed to produce a laminate of base material layer / adhesive layer / barrier layer. In addition, the chemical conversion treatment was performed on both sides of the aluminum alloy foil. The chemical conversion treatment of aluminum alloy foil is carried out by roll coating method so that the coating amount of chromium becomes 10 mg / m ² (dry mass) of the treatment liquid consisting of phenol resin, chromium fluoride compound and phosphoric acid. It was done by applying and baking. Next, in Examples 1 to 7, 9 to 19, 21 to 26 and Comparative Examples 1 to 8, 10 to 20, 22 to 25, on the barrier layer of the obtained laminate, carboxylic acid modified polypropylene (barrier By laminating 20 μm on the layer side and 15 μm of a heat fusible resin layer (arranged on the innermost layer side) made of the resin described in Table 1, the adhesive layer and the heat fusible resin on the barrier layer The layers were laminated to obtain a battery packaging material in which a base material layer / adhesive layer / barrier layer / adhesive layer / heat sealable resin layer was sequentially laminated. On the other hand, in Examples 8 and 20 and Comparative Examples 9 and 21, a two-component epoxy adhesive is applied on the barrier layer of the obtained laminate, and an adhesive layer (3 μm in thickness) is formed on the aluminum alloy foil. Then, the adhesive layer on the barrier layer and the unstretched polypropylene film 30 μm are laminated by a dry lamination method, and then an aging treatment is performed to obtain a substrate layer / adhesive layer / barrier layer / adhesive layer / thermal The battery packaging material in which the fusible resin layer was laminated | stacked in order was obtained.

Next, a fatty acid amide compound was applied to the surface of the base material layer of each battery packaging material. However, no fatty acid amide was applied to the battery packaging material of Comparative Example 1. The amounts of various fatty acid amide compounds present on the surface of the base layer side are as described in Table 1, respectively. In addition, amounts (g) of various fatty acid amide compounds dissolved in 100 g of methyl ethyl ketone (MEK) at 25 ° C. are as described in Table 1. It is erucic acid amide that the dissolution amount with respect to 100 g of MEK was 6.30 g. Moreover, it is ethylene bis oleic acid amide that the amount of dissolution with respect to 100 g of MEK was 1.11 g. It is oleic acid amide that the dissolution amount with respect to 100 g of MEK was 11.64 g. It is a stearic acid amide that the amount of dissolution with respect to 100 g of MEK was 0.92 g. The amount dissolved of 0.07 g with respect to 100 g of MEK is ethylenebisstearic acid amide. The measurement of the dissolved amount (g) in 100 g of methyl ethyl ketone (MEK) of various fatty acid amide compounds in a 25 ° C. environment was performed by the method described above. As high performance liquid chromatograph (HPLC), high performance liquid chromatograph “LC-2000 Plus” manufactured by JASCO Corporation was used. Further, in Example 1-25 and Comparative Example 1-25, after a predetermined amount of erucic acid amide is contained in the heat-fusion resin layer, bleed-out is carried out to obtain Elka on the surface of the heat-fusion resin layer. The acid amide was present at 35.0 mg / m ² . On the other hand, in Example 26, no lubricant was present on the surface of the heat-fusion resin layer.

In the battery packaging materials of Examples 4 and 16 and Comparative Examples 5 and 17, the surface of the base material layer was subjected to corona treatment before the fatty acid amide compound was applied. For corona treatment, corona treatment was performed at a constant speed of 10 m / min at an output of 1.0 Kw using a corona surface treatment apparatus manufactured by Wedge Corporation.

(Measurement of wetting tension)
The wetting tension of the surface of the base material layer side of each of the battery packaging materials obtained above was measured by the method according to the definition of JIS K6768: 1999. Using the mixed solution for wetting tension test manufactured by Nacalai Tesque, apply the reagent contained in spherical absorbent cotton linearly to the surface on the substrate layer side of each battery packaging material so as to be 6 cm ² After 2 seconds, it was visually judged whether or not the liquid film was broken, and the wetting tension when it was not broken was taken as the wetting tension of the surface. The measurement of the wetting tension was performed in an environment of a temperature of 23 ° C. and a relative humidity of 50%. The results are shown in Table 1.

(Formability evaluation)
Each battery packaging material obtained above was cut into a rectangle of 80 mm × 120 mm to prepare a sample. These samples were molded into a mold of 30 mm × 50 mm in an environment with a temperature of 24 ° C and a relative humidity of 50% (female mold, surface JIS B 0659-1: 2002, Annex 1 (reference)) Rough surface for comparison The maximum height roughness (nominal value of Rz) specified in Table 2 of the standard piece is 3.2 μm, and the corresponding molding die (male mold, surface is JIS B 0 656-1): 2002 Annex 1 (Reference) The maximum height roughness (nominal value of Rz) specified in Table 2 of the surface roughness standard piece for comparison is 1.6 μm, and the pressure is 0 at a pressure of 0.4 MPa. Molding is performed by increasing the molding depth by 0.5 mm from the molding depth of 5 mm, and the sample depth is 0.5 mm shallower than the molding depth when pinholes are generated in the battery packaging material, Limit molding depth. From the limit forming depth, the formability of the battery packaging material was evaluated according to the following criteria. The results are shown in Table 1.
A: critical molding depth 6.0 mm or more B: critical molding depth 5.0 mm or more and 5.5 mm or less C: critical molding depth 4.0 mm or more and 4.5 mm or less D: critical molding depth 3.5 mm or less

(Evaluation of continuous productivity of battery)
Each battery packaging material obtained above was cut into a rectangle of 80 mm × 120 mm to prepare a sample. Next, in an environment of a temperature of 24 ° C. and a relative humidity of 50%, a molding die having these bores of 30 mm × 50 mm in an environment of 50% relative humidity (female mold, surface JIS B 0659-1: 2002 Annex 1 (reference) comparison Surface roughness standard piece specified in Table 2, maximum height roughness (nominal value of Rz) is 3.2 μm, and molding die corresponding to this (male mold, surface is JIS B 0659) -1: 2002 Annex 1 (Reference) Using the maximum height roughness (nominal value of Rz) specified in Table 2 of the surface roughness standard piece for comparison is 1.6 μm, pressing pressure 0. Each 1000 pieces were cold-formed at a molding depth of 5 mm at 4 MPa. Next, the corners of the mold after cold forming were visually observed, and the continuous formability of the battery packaging material was evaluated according to the following criteria. The results are shown in Table 1.
A: The fatty acid amide compound is not transferred to the male and female types, and the mold is not whitened, so that the continuous formability is high. B: The fatty acid amide compound is only one of the male type and the female type. Since the mold is slightly whitened, the continuous formability is somewhat high. C: The fatty acid amide compound is transferred to both the male and female molds, and the mold is whitened. Is low

(Evaluation of printability)
As ink jet printer, 9040 manufactured by Markem Image Inc. was used, and as ink, MB175 manufactured by Markem Image Inc. was used. After printing using the said inkjet printer and ink on the surface by the side of the base material layer of the packaging material for batteries obtained above, it was made to dry for 10 seconds in the environment of temperature 24 degreeC and 50% of relative humidity. Next, a tape (S600 manufactured by 3M) was attached on the printed pattern, and the printed pattern and the tape were adhered by causing one reciprocation of a 2 kg roller from the top of the tape. Next, the tape is peeled off in the direction perpendicular to the surface of the substrate layer, and the exposed printed pattern is observed with an optical microscope, whereby the entire area (100%) of the printed pattern of the printed pattern (the area of the peeled portion) The ratio of ()) was measured, and the following numerical values were scored. The printability was evaluated in an environment of a temperature of 24 ° C. and a relative humidity of 50%. The results are shown in Table 1.

10: No peeling of printed pattern 9: Peeling of printed pattern is more than 0% of the whole printed pattern 10% or less 8: Peeling of printed pattern is more than 10% of the whole printed pattern 20% or less 7: Peeling of printed pattern Is more than 20% of the whole printing pattern 30% or less 6: peeling of the printing pattern is more than 30% of the whole printing pattern 40% or less 5: peeling of the printing pattern is more than 40% of the whole printing pattern 50% Following 4: Peeling of the printed pattern is more than 50% of the entire printed pattern 60% or less 3: Peeling of the printed pattern is more than 60% of the entire printed pattern 70% or less 2: Peeling of the printed pattern is the entire printed pattern More than 70% 80% or less 1: Peeling of print pattern is more than 80% of whole print pattern 90% or less 0: Peeling of print pattern is more than 90% of entire print pattern 100% or less

* In Example 26, no lubricant was present on the surface of the heat-fusion resin layer.

In Table 1, ONy is biaxially stretched nylon, PET is polyethylene terephthalate, PBT is polybutylene terephthalate, and PET / ONy is PET opposite to the barrier layer, and polyethylene terephthalate (12 μm) and nylon are used. It is a laminated film by dry lamination with (15 μm). Moreover, PET.ONy forms a base material layer by the laminated film by co-extrusion of a polyethylene terephthalate (3 micrometers) and nylon (12 micrometers). Also, PP means polypropylene, PE means polyethylene, and CPP means unstretched polypropylene.

From the results shown in Table 1, the fatty acid amide compound is present on the surface of the base material layer side of the battery packaging material, and the fatty acid amide compound is 1 g or more per 100 g of methyl ethyl ketone in a 25 ° C. environment. It can be seen that the battery packaging materials of Examples 1 to 26, which are soluble, have both excellent printability and excellent moldability, and are also excellent in continuous productivity of batteries.

<Measurement of logarithmic attenuation factor ΔE of adhesive layer>
The packaging material for each battery obtained in Example 1 and Example 3 is cut into a rectangle of width (TD: Transverse Direction) 15 mm × length (MD: Machine Direction) 150 mm to be a test sample (packaging material for battery 10 ). The MD of the battery packaging material corresponds to the rolling direction (RD) of the aluminum alloy foil, and the TD of the battery packaging material corresponds to the TD of the aluminum alloy foil, and the rolling direction of the aluminum alloy foil (RD ) Can be determined by rolling. When MD of the packaging material for batteries can not be specified by the rolling eye of aluminum alloy foil, it can specify by the following method. As a method of confirming the MD of the packaging material for a battery, the cross section of the heat fusible resin layer of the packaging material for a battery is observed with an electron microscope to confirm the sea-island structure, and the direction perpendicular to the thickness direction of the heat fusible resin layer A direction parallel to the cross section in which the average diameter of the island shapes is largest can be determined as MD. Specifically, the angle is changed by 10 degrees from the cross section in the length direction of the heat-fusible resin layer and the direction parallel to the cross section in the length direction, and each direction up to the direction perpendicular to the cross section in the length direction The cross-sections (total of 10 cross-sections) are respectively observed by electron micrographs to confirm the sea-island structure. Next, in each cross section, the shapes of the individual islands are observed. With respect to the shape of each island, a linear distance connecting the leftmost end in the direction perpendicular to the thickness direction of the heat-fusible resin layer and the rightmost end in the vertical direction is taken as a diameter y. In each cross section, the average of the top 20 diameters y is calculated in descending order of the diameter y of the island shape. A direction parallel to the cross section in which the average of the diameter y of the shape of the island is the largest is determined as MD. The schematic diagram for demonstrating the measuring method of logarithmic attenuation factor (DELTA) E by rigid-body pendulum measurement is shown in FIG. A rigid pendulum type physical property tester (Model No .: RPT-3000W manufactured by A & D Co., Ltd.), FRB-100 for the frame of the pendulum 30, RBP-060 for the cylindrical cylinder edge 30a at the edge, cold heat In block 31, CHB-100, vibration displacement detector 32, and weight 33 were used, and the initial amplitude was 0.3 degree. Place the measurement surface (adhesion layer) of the test sample upward on the cooling block 31 so that the axial direction of the cylindrical cylinder edge 30a with the pendulum 30 is orthogonal to the MD direction of the test sample on the measurement surface. installed. In addition, in order to prevent the floating and warping of the test sample during measurement, a tape was attached to a portion having no influence on the measurement result of the test sample and fixed on the heating and cooling block 31. The cylindrical cylinder edge was in contact with the surface of the adhesive layer. Next, using the heating and cooling block 31, the logarithmic attenuation factor ΔE of the adhesive layer was measured at a temperature rising rate of 3 ° C./min in a temperature range of 30 ° C. to 200 ° C. The logarithmic attenuation factor ΔE in the state where the surface temperature of the adhesive layer of the test sample (battery packaging material 10) became 120 ° C. was employed. (The test sample measured once was not used, and the average value measured three times (N = 3) using freshly cut ones was used.) For the adhesive layer, the packaging material for each battery obtained above The test sample was immersed in 15% hydrochloric acid to dissolve the base material layer and the aluminum foil, and the test sample having only the adhesive layer and the heat fusible resin layer was sufficiently dried to measure the logarithmic attenuation factor ΔE. Log attenuation factors ΔE at 120 ° C. are shown in Table 2, respectively. (Note that the logarithmic attenuation factor ΔE is calculated by the following equation.
ΔE = [ln (A1 / A2) + ln (A2 / A3) +. . . + Ln (An / An + 1)] / n
A: Amplitude n: Frequency)

<Measurement of Remaining Ratio of Adhesive Layer Thickness>
Each of the battery packaging materials obtained in Example 1 and Example 3 was cut into a length of 150 mm × a width of 60 mm to prepare a test sample (a battery packaging material 10). Next, the heat-fusible resin layers of test samples of the same size prepared from the same battery packaging material were made to face each other. Then, in this state, using a metal plate having a width of 7 mm, heating was performed at a temperature of 190 ° C., a surface pressure (0.5 MPa) described in Table 2, and a time of 3 seconds in the stacking direction from both sides of the test sample. The pressure was applied to thermally fuse the thermally fusible resin layers. Next, the heat-sealed portion of the test sample was cut in the stacking direction using a microtome, and the thickness of the adhesive layer was measured on the exposed cross section. The test sample before heat fusion was also cut in the stacking direction using a microtome in the same manner, and the thickness of the adhesive layer was measured for the exposed cross section. The ratio of the thickness of the adhesive layer after heat fusion to the thickness of the adhesive layer before heat fusion was calculated, and the remaining ratio (%) of the thickness of the adhesive layer was measured. The results are shown in Table 2.

<Measurement of seal strength in a 25 ° C. environment or a 140 ° C. environment>
Each of the battery packaging materials obtained in Examples 1 and 3 was cut into a rectangle of width 60 mm × length 150 mm to obtain a test sample (battery packaging material 10). Next, as shown in FIG. 5, the test sample was folded back at the center P in the lengthwise direction, and the heat fusible resin layers were made to face each other. Next, using a metal plate 20 of 7 mm in width, 7 mm (width of the metal plate) in the longitudinal direction of the test sample under the conditions of a contact pressure of 1.0 MPa and a time of 1 second and 190 ° C. The heat fusible resin layers were heat-fused to each other. Next, using a double-edged sample cutter, as shown in FIG. 6, the test sample was cut to a width of 15 mm. In FIG. 6, the heat-sealed area is indicated by S. Next, as shown in FIG. 7, the tensile speed is 300 mm / min, the peel angle is 180 ° in an environment of a temperature of 25 ° C. or an environment of a temperature of 140 ° C. using a tensile tester so as to be T-peel. The heat-sealed interface is peeled off under the condition of a distance between chucks of 50 mm, and the maximum value of peel strength (N / 15 mm) for 1.5 seconds from the start of tensile strength measurement is the seal strength in an environment of 25 ° C. , And seal strength in an environment of 140 ° C. The tensile test at each temperature was performed in a constant temperature bath, and the test sample was attached to the chuck in the constant temperature bath at a predetermined temperature and held for 2 minutes, and then the measurement was started. In addition, each seal strength is an average value (n = 3) which produced and measured three test samples similarly respectively. The results are shown in Table 2.

From the results shown in Table 2, in the battery packaging materials of Examples 1 and 3, the logarithm at 120 ° C. in the rigid pendulum measurement of the adhesive layer located between the barrier layer and the heat fusible resin layer It is understood that the damping ratio ΔE is 2.5 or less, the crushing of the adhesive layer when the heat fusible resin layers are thermally fused to each other is effectively suppressed, and high seal strength is exhibited in a high temperature environment. . In addition, the battery packaging material of Example 1 had a logarithmic attenuation factor ΔE at 120 ° C. of 2.0 in the rigid body pendulum measurement of the adhesive layer located between the barrier layer and the heat-fusible resin layer. Below, it can be seen that the crushing of the adhesive layer when the heat fusible resin layers are thermally fused is effectively suppressed, and particularly high seal strength is exhibited in a high temperature environment. In Examples 2, 5, 6, 9-18, and 21-26, the same maleic anhydride-modified polypropylene as in Example 1 was used for the adhesive layer, and these examples are the same as Example 2 in Table 2. It can be said that the result is the same as the result. In addition, since Examples 3 and 4 use the same maleic anhydride-modified polypropylene, it can be said that these examples give similar results.

<Measurement of extrapolation melting start temperature of melting peak temperature and extrapolation melting end temperature>
Regarding the polypropylene used for the heat fusible resin layer of the packaging material for each battery obtained in Example 1 and Example 3 according to the following method, extrapolation melting start temperature and extrapolation melting end temperature of melting peak temperature The temperature differences T ₁ and T ₂ between the extrapolation melting start temperature and the extrapolation melting end temperature are measured, and the values of the temperature differences T ₁ and T ₂ obtained indicate the ratio (T ₂ / T ₁ And the absolute value of the difference | T ₂ −T ₁ | was calculated. The results are shown in Table 3.

(Measurement of temperature difference T ₁ )
According to the definition of JIS K 712: 2012, differential scanning calorimetry (DSC) was used to obtain a DSC curve for polypropylene used for the heat-sealable resin layer of each of the above-described battery packaging materials. From the obtained DSC curve was measured temperature difference T ₁ of the extrapolation melting start temperature of the melting peak temperature of the heat-fusible resin layer and the extrapolated ending melting temperature.

(Measurement of temperature difference T ₂ )
The concentration of lithium hexafluorophosphate is 1 mol / l and the volume ratio of ethylene carbonate: diethyl carbonate: dimethyl carbonate is 1: 1: After being allowed to stand for 72 hours in the electrolytic solution which is the solution of 1, it was sufficiently dried. Next, a DSC curve was obtained for the polypropylene after drying using differential scanning calorimetry (DSC) in accordance with the definition of JIS K7121: 2012. Next, from the obtained DSC curve was measured temperature difference T ₂ of the extrapolation melting start temperature of the melting peak temperature of the heat-fusible resin layer after drying and extrapolated ending melting temperature.

For measurement of the extrapolation melting start temperature and the extrapolation melting end temperature of the melting peak temperature, Q200 manufactured by TA Instruments was used as a differential scanning calorimeter. In addition, as a DSC curve, after holding the test sample at -50 ° C for 10 minutes, the temperature is raised to 200 ° C at a heating rate of 10 ° C / min (first time), and after holding for 10 minutes at 200 ° C, the temperature lowering rate The temperature is lowered to -50 ° C at -10 ° C and held at -50 ° C for 10 minutes, then the temperature is raised to 200 ° C at a heating rate of 10 ° C / min (second time), held at 200 ° C for 10 minutes, 2 The DSC curve at the time of temperature rising to 200 ° C. was used. Also, when measuring the temperature difference T ₁ and the temperature difference T _2, in each of the DSC curve, of the melting peak appearing in the range of 120 ~ 160 ° C., analyzed the melting peak difference between the input of thermal energy is maximized went. Even in the case where two or more peaks were overlapped and were present, analysis was performed only for the melting peak where the difference in thermal energy input is the largest.

The extrapolation melting start temperature means the starting point of melting peak temperature, and the difference between the heat energy input and the straight line extending the baseline on the low temperature (65 to 75 ° C) side to the high temperature side is the largest. The curve on the cold side of the peak was taken as the temperature at the point of intersection with the tangent drawn at the point where the slope is maximum. Extrapolation end temperature means the end point of melting peak temperature, a straight line extending the baseline on the high temperature (170 ° C) side to the low temperature side, and the high temperature side of the melting peak where the difference between the thermal energy input is maximum The temperature of the point of intersection with the tangent drawn at the point where the slope is maximum was taken as the curve of.

<Measurement of seal strength before contact with electrolyte>
In the following <Measurement of seal strength after contact with electrolyte solution>, tensile strength (seal strength) was measured in the same manner except that the electrolyte was not injected into the test sample. The maximum tensile strength until the heat-sealed part is completely peeled off is taken as the seal strength before contact with the electrolyte. In Table 3, the seal strength before contact with the electrolyte is described as the seal strength when the contact time of the electrolyte at 85 ° C. is 0 h.

<Measurement of seal strength after contact with electrolyte>
As shown in the schematic view of FIG. 9, each of the battery packaging materials obtained in Example 1 and Example 3 is cut into a rectangle having a width (x direction) of 100 mm and a length (z direction) of 200 mm to be used as a test sample. (Packaging material 10 for batteries) (Fig. 9a). The test sample (battery packaging material 10) was folded at the center in the z direction so that the heat fusible resin layer side was overlapped (FIG. 9b). Next, both ends of the folded test sample in the x direction were sealed with a heat seal (temperature 190 ° C., surface pressure 2.0 MPa, time 3 seconds), and formed into a bag shape having one opening E (Fig. 9c). Next, from the opening E of the test sample formed into a bag shape, the electrolytic solution (the concentration of lithium hexafluorophosphate is 1 mol / l, and the volume ratio of ethylene carbonate: diethyl carbonate: dimethyl carbonate is 1: 1: 6 g of the solution 1) was injected (FIG. 9 d), and the end of the opening E was sealed with a heat seal (temperature 190 ° C., surface pressure 2.0 MPa, time 3 seconds) (FIG. 9 e). Next, with the folded portion of the bag-like test sample facing down, the bag was left to stand for a predetermined storage time (a time for contacting with the electrolyte, for 24 hours, 72 hours) in an environment at a temperature of 85 ° C. The end of the test sample was then cut (FIG. 9e) to drain all the electrolyte. Next, with the electrolyte adhering to the surface of the heat fusible resin layer, the upper and lower surfaces of the test sample are sandwiched between metal plates 20 (7 mm width), and the temperature 190 ° C., surface pressure 1.0 MPa, time 3 seconds The heat fusible resin layers were heat-fused together under the conditions (FIG. 9 f). Next, the test sample was cut into a width of 15 mm with a double-edged sample cutter so that the seal strength at a width (x direction) of 15 mm could be measured (FIG. 9 f, g). Next, using a tensile tester (manufactured by Shimadzu Corporation, AGS-xplus (trade name)) so that T-peel occurs, tensile speed 300 mm / min, peel angle 180 °, chuck at an environment of temperature 25 ° C. The thermally fused interface was peeled off under the condition of a distance of 50 mm, and the tensile strength (seal strength) was measured (FIG. 7). The maximum tensile strength until the heat-sealed portion was completely peeled (the distance until peeling was 7 mm, which is the width of the metal plate) was taken as the seal strength after contact with the electrolyte.

The retention ratio (%) of seal strength after being brought into contact with the electrolytic solution is shown in Table 4 based on the seal strength before contacting with the electrolytic solution (100%).

Table 4 From the results shown in, the battery packaging material of Example 1 and 3, a value obtained by dividing the temperature difference T ₂ at a temperature difference T ₁ is is 0.55 or more, heat in a high temperature environment Even when the thermally fusible resin layers are thermally fused in a state where the electrolytic solution is in contact with the adhesive resin layer and the electrolytic solution is attached to the thermally fusible resin layer, high seal strength is achieved by the thermal fusion. It is understood that it exerts. Also, the battery packaging material of Example 1, a value obtained by dividing the temperature difference T ₂ at a temperature difference T ₁ is is 0.60 or more, electrolyte heat-welding resin layer in a high temperature environment It is understood that particularly high seal strength is exhibited by the thermal fusion even when the thermal fusion resin layers are thermally fused in a state in which the electrolytic solution adheres to the thermal fusion resin layer in contact. In the heat fusible resin layer of each example, the melting peak temperature starting point of the heat fusible resin layer is measured by the method described later by adjusting the amount of low molecular weight components in polypropylene A value (T ₂ / T ₁ ) obtained by dividing the temperature difference T ₂ between the extrapolation melting start temperature) and the end point (the extrapolation melting end temperature) by the temperature difference T ₁ is adjusted. In Examples 2, 5, 6, 9-18 and 21-26, the same polypropylene as in Example 1 is used for the heat-fusible resin layer, and these examples are as shown in Tables 3 and 4. It can be said that the same result as the result of Example 1 is obtained. Moreover, since the same polypropylene is used for the heat-fusion-bonding resin layer also in Examples 3 and 4, it can be said that these examples give similar results.

DESCRIPTION OF SYMBOLS 1 Base material layer 2 Adhesive layer 3 Barrier layer 4 Heat-fusion resin layer 5 Adhesive layer 6 Surface coating layer 10 Packaging material for batteries

Claims (14)

It is comprised from the laminated body provided with a base material layer, a barrier layer, and a heat fusible resin layer at least in this order,
A fatty acid amide compound is present at least on the surface of the laminate on the substrate layer side,
The packaging material for batteries which said fatty-acid amide compound melt | dissolves 1 g or more with respect to 100 g of methyl ethyl ketone in a 25 degreeC environment. The battery packaging material according to claim 1, wherein a fatty acid amide compound is present at 2.0 mg / m ² or more on the surface of the laminate on the base material layer side. The packaging material for batteries of Claim 1 or 2 used for the use by which the printing by an ink is given with respect to the surface by the side of the said base material layer of the said laminated body. The battery packaging material according to claim 3, wherein the ink contains at least one selected from the group consisting of methyl ethyl ketone, acetone, isopropyl alcohol, and ethanol. The battery packaging material according to any one of claims 1 to 4, wherein the wetting tension of the surface on the substrate layer side is 32 mN / m or more. The fatty acid amide compound is at least one selected from the group consisting of erucic acid amide, ethylene bis oleic acid amide, oleyl stearic acid amide, stearyl oleic acid amide, stearyl erucic acid amide, oleic acid amide, and behenic acid amide The battery packaging material according to any one of claims 1 to 5. The battery packaging material according to any one of claims 1 to 6, wherein a fatty acid amide compound is present on the surface on the heat fusible resin layer side. A battery, wherein a battery element comprising at least a positive electrode, a negative electrode, and an electrolyte is contained in a package made of the battery packaging material according to any one of claims 1 to 7. The battery according to claim 8, further comprising a printed portion on the surface of the base body side of the package. The battery according to claim 8 or 9, further comprising a printed part by ink on the surface on the substrate layer side of the package. At least a step of laminating the base material layer, the barrier layer, and the heat fusible resin layer in this order;
A fatty acid amide compound is present at least on the surface of the laminate on the substrate layer side,
The manufacturing method of the packaging material for batteries using what melts 1 g or more with respect to 100 g of methyl ethyl ketone in a 25 degreeC environment as said fatty-acid amide compound. The method for producing a battery packaging material according to claim 11, further comprising the step of subjecting at least one surface of the substrate layer to a corona treatment. A process of containing a battery element comprising at least a positive electrode, a negative electrode, and an electrolyte in a package made of the battery packaging material according to any one of claims 1 to 7,
Printing with ink on the surface of the package on the substrate layer side;
A method of manufacturing a battery, comprising: 1 g or more dissolved in 100 g of methyl ethyl ketone in a 25 ° C. environment on the surface of the base material layer side of the battery packaging material comprising at least a base material layer, a barrier layer, and a heat-sealable resin layer in this order And a fatty acid amide compound is present to improve the printability of the packaging material for the battery with respect to the surface on the side of the substrate layer.

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