JP6402844B1 - Adhesive film for metal terminal and battery - Google Patents

Abstract

Provided is an adhesive film for a metal terminal that has high adhesion to a packaging material and a metal terminal, and further has excellent resistance to an electrolytic solution.
An adhesive film for metal terminals interposed between a metal terminal electrically connected to the electrode of the battery element and a packaging material for sealing the battery element,
The adhesive film for metal terminals is composed of a laminate comprising at least one polypropylene layer and at least one acid-modified polypropylene layer,
The acid-modified polypropylene layer constitutes a surface layer on at least one side of the adhesive film for metal terminals,
The polypropylene layer has a sea-island structure observed when the cross section is observed with an electron micrograph,
The adhesive film for metal terminals, wherein the total thickness of the polypropylene layer is in the range of 0.7 to 3.5, where the total thickness of the acid-modified polypropylene layer is 1.

Description

  The present invention relates to an adhesive film for a metal terminal and a battery.

  Conventionally, various types of batteries have been developed, and packaging materials are indispensable members for sealing battery elements such as electrodes and electrolytes in all batteries. Conventionally, metal packaging materials have been widely used as battery packaging, but in recent years, with the increasing performance of electric vehicles, hybrid electric vehicles, personal computers, cameras, mobile phones, etc., batteries are required to have various shapes. At the same time, there is a demand for reduction in thickness and weight. However, conventionally used metal packaging materials have the disadvantages that it is difficult to follow the diversification of shapes and that there is a limit to weight reduction.

  Therefore, in recent years, as a packaging material that can be easily processed into various shapes and can be made thinner and lighter, it is a film-like material in which a base layer / adhesive layer / barrier layer / heat-sealable resin layer are sequentially laminated. Laminates have been proposed. When such a film-shaped packaging material is used, the peripheral portion of the packaging material is heat-sealed by heat sealing with the heat-fusible resin layers positioned in the innermost layer of the packaging material facing each other. The battery element is sealed with the packaging material.

  A metal terminal protrudes from the heat seal portion of the packaging material, and the battery element sealed by the packaging material is electrically connected to the outside by a metal terminal electrically connected to the electrode of the battery element. That is, of the portion where the packaging material is heat-sealed, the portion where the metal terminal is present is heat-sealed in a state where the metal terminal is sandwiched between the heat-fusible resin layers. Since the metal terminal and the heat-fusible resin layer are made of different materials from each other, the adhesiveness tends to decrease at the interface between the metal terminal and the heat-fusible resin layer.

  For this reason, an adhesive film may be arranged between the metal terminal and the heat-fusible resin layer for the purpose of enhancing the adhesion between them.

Japanese Patent Laying-Open No. 2015-79638

  Such an adhesive film is required to have excellent resistance to an electrolytic solution sealed with the packaging material in addition to high adhesion to the packaging material and the metal terminal.

  Under such circumstances, the main object of the present invention is to provide an adhesive film for a metal terminal that has high adhesion to the packaging material and the metal terminal and that is also excellent in resistance to electrolyte. Another object of the present invention is to provide a battery using the metal terminal adhesive film.

  The inventors of the present invention have intensively studied to solve the above problems. As a result, an adhesive film for metal terminals interposed between a metal terminal electrically connected to the electrode of the battery element and a packaging material for sealing the battery element, the adhesive film for metal terminal Is composed of a laminate comprising at least one polypropylene layer and at least one acid-modified polypropylene layer, and the acid-modified polypropylene layer is a surface layer on at least one side of the adhesive film for metal terminals. The polypropylene layer has a sea-island structure when the cross section is observed with an electron micrograph, and when the total thickness of the acid-modified polypropylene layer is 1, the total thickness of the polypropylene layer is 0. It is seen that the adhesive film for metal terminals in the range of 0.7 to 3.5 has high adhesion to the packaging material and the metal terminals, and also has excellent resistance to electrolyte. It was. The present invention has been completed by further studies based on such knowledge.

That is, this invention provides the invention of the aspect hung up below.
Item 1. An adhesive film for metal terminals interposed between a metal terminal electrically connected to the electrode of the battery element and a packaging material for sealing the battery element,
The adhesive film for metal terminals is composed of a laminate comprising at least one polypropylene layer and at least one acid-modified polypropylene layer,
The acid-modified polypropylene layer constitutes a surface layer on at least one side of the adhesive film for metal terminals,
The polypropylene layer has a sea-island structure observed when the cross section is observed with an electron micrograph,
The adhesive film for metal terminals, wherein the total thickness of the polypropylene layer is in the range of 0.7 to 3.5, where the total thickness of the acid-modified polypropylene layer is 1.
Item 2. Item 2. The metal terminal adhesive film according to Item 1, wherein the polypropylene layer contains block polypropylene.
Item 3. Item 3. The metal terminal adhesive film according to Item 1 or 2, wherein the polypropylene layer is composed of unstretched polypropylene.
Item 4. The said polypropylene layer has a laminated structure by which the layer comprised by the random polypropylene, the layer comprised by the block polypropylene, and the layer comprised by the random polypropylene were laminated | stacked in this order. The adhesive film for metal terminals according to any one of the above.
Item 5. Item 5. The adhesive film for metal terminals according to any one of Items 1 to 4, wherein a melting peak is observed in the range of 150 ° C. or higher and 165 ° C. or lower when the adhesive film for metal terminals is measured with a differential scanning calorimeter. .
Item 6. Item 6. The adhesive film for metal terminals according to any one of Items 1 to 5, wherein the residual thickness ratio of the adhesive film for metal terminals, measured by the following measurement method, is 50% or more.
An aluminum plate having a thickness of 100 μm and the adhesive film for metal terminals are prepared.
The thickness A (μm) of the adhesive film for metal terminals is measured.
The adhesive film for metal terminals is overlapped on a central portion of the aluminum plate so that the length direction and the width direction of the aluminum plate and the adhesive film for metal terminals coincide with each other.
Two metal plates with a width of 7 mm longer than the length of the aluminum plate are prepared, and the temperature is measured from above and below the aluminum plate and the metal terminal adhesive film so as to cover the entire surface of the metal terminal adhesive film. The metal plate is heated and pressurized under the conditions of 190 ° C., surface pressure of 1.27 MPa, and time of 3 seconds to obtain a laminate of the aluminum plate and the metal terminal adhesive film.
The thickness B (μm) of the portion where the laminate is heated and pressed is measured.
The thickness residual ratio of the adhesive film for metal terminals is calculated by the following formula.
Residual thickness of metal terminal adhesive film (%) = (thickness B-100) / thickness A × 100
Item 7. Item 7. The adhesive film for metal terminals according to any one of Items 1 to 6, wherein a heat shrinkage rate in the flow direction of the adhesive film for metal terminals is 70 to 90%.
Item 8. The packaging material is composed of a laminate including at least a base material layer, a barrier layer, and a heat-fusible resin layer in this order,
Item 8. The metal terminal adhesive film according to any one of Items 1 to 7, wherein the metal terminal adhesive film is interposed between the heat-fusible resin layer and the metal terminal.
Item 9. A battery element including at least a positive electrode, a negative electrode, and an electrolyte, a packaging material that seals the battery element, and a metal terminal that is electrically connected to each of the positive electrode and the negative electrode and protrudes outside the packaging material A battery comprising:
Item 9. A battery in which the metal terminal adhesive film according to any one of Items 1 to 8 is interposed between the metal terminal and the packaging material.
Item 10. Use of a laminate comprising at least one polypropylene layer and at least one acid-modified polypropylene layer,
The acid-modified polypropylene layer constitutes a surface layer on at least one side of the adhesive film for metal terminals,
The polypropylene layer has a sea-island structure observed when the cross section is observed with an electron micrograph,
When the total thickness of the acid-modified polypropylene layer is 1, the total thickness of the polypropylene layer is in the range of 0.7 to 3.5,
Use of the laminate as an adhesive film for a metal terminal interposed between a metal terminal electrically connected to an electrode of a battery element and a packaging material for sealing the battery element.

  ADVANTAGE OF THE INVENTION According to this invention, the adhesiveness film for metal terminals which has high adhesiveness with a packaging material and a metal terminal, and was excellent also in electrolyte solution resistance can be provided. Furthermore, according to this invention, the battery using the said adhesive film for metal terminals can also be provided.

It is a schematic plan view of the battery of the present invention. FIG. 2 is a schematic cross-sectional view taken along line A-A ′ of FIG. 1. FIG. 2 is a schematic cross-sectional view taken along line B-B ′ in FIG. 1. It is a schematic sectional drawing of the adhesive film for metal terminals of this invention. It is a schematic sectional drawing of the adhesive film for metal terminals of this invention. It is a schematic sectional drawing of the packaging material used for the battery of this invention. It is a schematic diagram for demonstrating the measuring method of the seal strength in an Example. It is a schematic diagram for demonstrating the measuring method of the seal strength in an Example. It is a schematic diagram for demonstrating the measuring method of the seal strength in an Example. It is a schematic diagram for demonstrating the measuring method of the seal strength in an Example. "Polymer microphotographs: macroscopic macromolecules 1. Shape and function of molecular assembly" (editor: Polymer Society of Japan, publisher: Yamashin, publisher: Baifukan Co., Ltd., May 30, 1986, first edition) Issuance) is a transmission electron micrograph (scale bar is 5 μm) shown as “C” on page 29.

  The adhesive film for metal terminals of the present invention is an adhesive film for metal terminals interposed between a metal terminal electrically connected to an electrode of a battery element and a packaging material for sealing the battery element. The metal terminal adhesive film is composed of a laminate including at least one polypropylene layer and at least one acid-modified polypropylene layer, and the acid-modified polypropylene layer has the metal terminal adhesive property. A surface layer on at least one side of the film is formed, and the polypropylene layer has a sea-island structure when the cross-section is observed with an electron micrograph, and the total thickness of the acid-modified polypropylene layer is 1. The total thickness of the layers is in the range of 0.7 to 3.5. Hereinafter, the adhesive film for metal terminals of the present invention and the battery of the present invention using the same will be described in detail.

  In the present specification, the 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.

1. Metal terminal adhesive film The metal terminal adhesive film of the present invention is interposed between a metal terminal electrically connected to an electrode of a battery element and a packaging material for sealing the battery element. . Specifically, for example, as shown in FIGS. 1 to 3, the metal terminal adhesive film 1 of the present invention includes a metal terminal 2 electrically connected to an electrode of the battery element 4, and the battery element 4. It is interposed between the packaging material 3 to be sealed. The metal terminal 2 protrudes outside the packaging material 3, and is sandwiched between the packaging material 3 via the metal terminal adhesive film 1 at the peripheral edge 3 a of the heat-sealed packaging material 3. In the present invention, the heat at the time of heat-sealing the packaging material is usually in the range of about 160 to 220 ° C., and the pressure is usually in the range of about 0.5 to 2.0 MPa.

  The adhesive film 1 for metal terminals of the present invention is provided in order to enhance the adhesion between the metal terminals 2 and the packaging material 3. By improving the adhesion between the metal terminal 2 and the packaging material 3, the sealing performance of the battery element 4 is improved. As described above, when the battery element 4 is heat sealed, the battery element is sealed such that the metal terminal 2 electrically connected to the electrode of the battery element 4 protrudes outside the packaging material 3. . At this time, the metal terminal 2 formed of metal and the heat-fusible resin layer 34 (layer formed of a heat-fusible resin such as polyolefin) located in the innermost layer of the packaging material 3 are formed of different materials. Therefore, when an adhesive film is not used, the sealing performance of the battery element tends to be low at the interface between the metal terminal 2 and the heat-fusible resin layer 34. Even when an adhesive film is used, if the adhesive film has low electrolytic solution resistance, the sealing performance of the battery element tends to be low.

  For example, as shown in FIGS. 4 and 5, the metal terminal adhesive film 1 of the present invention is composed of a laminate including at least one polypropylene layer 11 and at least one acid-modified polypropylene layer 12. The acid-modified polypropylene layer 12 constitutes a surface layer on at least one side of the metal terminal adhesive film 1, and the polypropylene layer 11 has a sea-island structure when the cross section is observed with an electron micrograph. When the total thickness of the acid-modified polypropylene layer 12 is 1, the total thickness of the polypropylene layer 11 is set in the range of 0.7 to 3.5. Thereby, since the adhesive film 1 for metal terminals of this invention has high adhesiveness with a packaging material and a metal terminal, and also is excellent also in electrolyte solution resistance, it improves the sealing performance of a battery element effectively. be able to.

  As the total thickness of the polypropylene layer 11 when the total thickness of the acid-modified polypropylene layer 12 is 1, from the viewpoint of further improving the electrolytic solution resistance while further improving the adhesion between the packaging material and the metal terminal Is preferably in the range of about 0.75 to 3.2, more preferably in the range of about 0.8 to 2.0.

  In the adhesive film 1 for metal terminals of the present invention, the acid-modified polypropylene layer 12 constitutes a surface layer on at least one side of the adhesive film for metal terminals. The acid-modified polypropylene layer 12 made of acid-modified polypropylene has excellent adhesion to a metal material as compared with the polypropylene layer 11 made of polypropylene. For this reason, by disposing the adhesive film 1 for metal terminals of the present invention between the metal terminal 2 and the packaging material 3 so that the acid-modified polypropylene layer 12 is positioned on the metal terminal 2 side, The sealing performance can be effectively increased.

  The adhesive film 1 for metal terminals of the present invention only needs to have at least one polypropylene layer 11 and at least one acid-modified polypropylene layer 12 respectively. As a preferable laminated structure of the metal terminal adhesive film 1 of the present invention, for example, as shown in FIG. 4, a structure in which a polypropylene layer 11 and an acid-modified polypropylene layer 12 are laminated one by one, for example, in FIG. As shown, a structure in which acid-modified polypropylene layers 12 are laminated one on each side of the polypropylene layer 11 is exemplified. Note that, as will be described later, a single polypropylene layer 11 may be formed by continuously laminating a plurality of layers made of the same or different polypropylene, and the plurality of layers may constitute a single polypropylene layer 11. Good. Similarly, in one acid-modified polypropylene layer 12, a plurality of layers made of the same or different acid-modified polypropylene are continuously laminated, and the plurality of layers constitute one acid-modified polypropylene layer 12. It may be.

  Specific examples of a preferable laminated structure of the metal terminal adhesive film 1 of the present invention include a two-layer structure of acid-modified polypropylene layer 12 / polypropylene layer 11; acid-modified polypropylene layer 12 / polypropylene layer 11 / acid-modified polypropylene layer 12. A three-layer structure laminated in this order; a five-layer structure in which acid-modified polypropylene layer 12 / polypropylene layer 11 / acid-modified polypropylene layer 12 / polypropylene layer 11 / acid-modified polypropylene layer 12 are laminated in this order, etc. Among these, a two-layer structure of acid-modified polypropylene layer 12 / polypropylene layer 11; a three-layer structure in which acid-modified polypropylene layer 12 / polypropylene layer 11 / acid-modified polypropylene layer 12 are laminated in this order is more preferable.

  As for the adhesive film 1 for metal terminals of this invention, it is preferable that all the layers are comprised with polyolefin. More specifically, the adhesive film 1 for a metal terminal of the present invention is also preferably configured by only the acid-modified polypropylene layer 12 and the polypropylene layer 11, and further includes another polyolefin layer composed of polyolefin. The embodiment is also preferable. Specific examples of the polyolefin constituting the polyolefin layer include polyethylene and acid-modified polyethylene. In the acid-modified polyethylene, the acid-modifying component of ethylene is not particularly limited, and examples thereof include unsaturated carboxylic acids used in acid modification exemplified in the acid-modified polypropylene layer 12 described later or anhydrides thereof.

  Although it does not restrict | limit especially as thickness of the adhesive film 1 for metal terminals of this invention, From a viewpoint of improving electrolyte solution resistance further, further improving adhesiveness with a packaging material and a metal terminal, Preferably it is 40. About -200 micrometers, More preferably, it is about 55-150 micrometers, More preferably, about 60-110 micrometers is mentioned.

  Moreover, from the viewpoint of further improving the electrolytic solution resistance while further improving the adhesion between the packaging material and the metal terminal, when measuring the metal terminal adhesive film 1 of the present invention with a differential scanning calorimeter, It is preferable that a melting peak is observed in the range of 150 to 165 ° C.

  From the same viewpoint, the metal terminal adhesive film 1 of the present invention preferably has a thickness residual ratio of the metal terminal adhesive film measured by the following measuring method of about 50% or more, It is preferably about 55% or more, more preferably about 60% or more. The upper limit of the residual thickness rate is preferably about 90% or less, preferably about 85% or less, and preferably about 80% or less. The range of the thickness remaining ratio is preferably about 55 to 90%, about 55 to 85%, about 55 to 80%, about 60 to 90%, about 60 to 85%, and about 60 to 80%. It is done. By using the metal terminal adhesive film 1 having a residual rate of 50% or more, a short circuit between the barrier layer and the metal terminal contained in the packaging material can be effectively suppressed, and the packaging material and the metal It becomes possible to further improve the adhesiveness with the adhesive film for terminals. Moreover, by using the adhesive film 1 for a metal terminal having a residual rate of 90% or less, the shape of the step of the metal terminal can be suitably followed, and the end of the metal terminal can be suitably covered. Can do.

(Measurement of residual thickness of adhesive film for metal terminals)
A 100 μm thick aluminum plate (pure aluminum, JIS H4160-1994 A1N30H-O) and an adhesive film for metal terminals are prepared. The thickness A (μm) of the adhesive film for metal terminals is measured with a micro gauge. The adhesive film for metal terminals is stacked on the center portion of the aluminum plate so that the length direction and the width direction of the aluminum plate and the adhesive film for metal terminals coincide with each other. At this time, it arrange | positions so that the acid-modified polypropylene layer and aluminum plate of the adhesive film for metal terminals may contact | connect. Prepare two metal plates that are longer than the aluminum plate and have a width of 7 mm. Cover the entire surface of the adhesive film for the metal terminal and cover the entire surface of the adhesive film for the metal terminal. Heating and pressing are performed under the conditions of a pressure of 1.27 MPa and a time of 3 seconds to obtain a laminate of an aluminum plate and an adhesive film for metal terminals. The thickness B (μm) of the heated and pressurized portion of the laminate is measured with a micro gauge. The thickness residual ratio of the adhesive film for metal terminals is calculated by the following formula.
Residual thickness of metal terminal adhesive film (%) = (thickness B-100) / thickness A × 100
The length direction is a longitudinal direction corresponding to the long side of the object in plan view, and the width direction is a short direction corresponding to the short side of the object in plan view. When the size in the length direction and the width direction match (square), either may be used as the length direction or the width direction.

In the measurement of the residual rate, depending on the area of the adhesive film for metal terminals, it can be measured by applying a pressure load so that the surface pressure becomes 1.27 MPa. Specifically, it can be converted by the following formula: [Pressure load by metal plate (N)] / [Area to pressurize metal terminal adhesive film (mm ² )] = Surface pressure (MPa). In addition, the pressurization load (N) by a metal plate can be adjusted with the diameter and air pressure of the cylinder which adjust the pressure of a metal plate.

In the measurement of the residual thickness ratio of the adhesive film for metal terminals described above, the length of the adhesive film for metal terminals and the length of the aluminum plate can be determined by measuring at a temperature of 190 ° C., a surface pressure of 1.27 MPa, and a time of 3 seconds. The width and the width are not limited. For example, in the case where measurement is possible with a metal terminal adhesive film having a length of 70 mm and a width of 5 mm (a method such as cutting may be adopted), this size of the metal terminal adhesiveness is used. Using the film and an aluminum plate having a length of 60 mm and a width of 25 mm, the thickness residual ratio of the adhesive film for metal terminals can be suitably measured. [Area to pressurize the metal terminal adhesive film (mm ² )] is an area of the portion where the aluminum plate and the metal terminal adhesive film overlap, for example, the metal terminal adhesive for these sizes. In the case of using a film and an aluminum plate, the area is 60 mm × 5 mm. Moreover, the thickness of the said aluminum plate does not change substantially by the heating and pressurization at the time of obtaining the laminated body of an aluminum plate and the adhesive film for metal terminals. Even if the size of the metal terminal adhesive film to be measured is different, the size of the aluminum plate may not be changed as long as the above measurement can be performed.

  The melt mass flow rate (MFR) of the entire adhesive film for metal terminal 1 of the present invention is not particularly limited, but the viewpoint of further improving the electrolytic solution resistance while further improving the adhesion between the packaging material and the metal terminal. Is preferably about 1 to 15, more preferably about 2 to 12, and still more preferably about 3 to 10. The melt mass flow rate (MFR) of the metal terminal adhesive film 1 as a whole is a value measured using a melt indexer with a measurement temperature of 230 ° C. and a load of 2.16 kg according to a method in accordance with the provisions of JIS K7210: 2014. It is.

  Moreover, as a heat shrinkage rate (%) of the flow direction (MD) of the adhesive film 1 for metal terminals of this invention, a minimum becomes like this. Preferably it is about 70% or more, More preferably, it is about 75% or more, More preferably, about The upper limit is preferably about 95% or less, more preferably about 92% or less, and still more preferably about 90% or less. In addition, the range of the heat shrinkage rate (%) is preferably about 70 to 95%, about 70 to 92%, about 70 to 90%, about 75 to 95%, about 75 to 92%, 75 to 90. %, 80 to 95%, 80 to 92%, and 80 to 90%. The measurement method of the thermal shrinkage rate (%) is as follows.

(Measurement method of heat shrinkage rate (%))
The metal terminal adhesive film is cut into a size of 50 mm in length (MD) × 4 mm in width (TD) to obtain a test piece. Next, the length M (mm) of the test piece is measured with a metal scale. Next, the end in the length direction of the test piece is fixed to the wire mesh with tape, and the test piece is suspended from the wire mesh. In this state, after placing it in an oven heated to 190 ° C. for 120 seconds, the test piece is taken out together with the wire mesh and naturally cooled in a room temperature (25 ° C.) environment. Next, the length N (mm) of the test piece naturally cooled to room temperature is measured with a metal ruler. The thermal contraction rate of the adhesive film for metal terminals is calculated by the following formula.
Thermal contraction rate (%) = (length N / length M) × 100

  When sealing the battery element, when the metal terminal adhesive film is heat-sealed while being sandwiched between the metal terminal and the packaging material, the pressure from the metal plate used for heat sealing In addition, there are a portion where the dimension of the adhesive film for metal terminal does not change, and a portion where the pressure is not applied because the distance from the metal plate is large, and the portion contracts. At this time, even in a portion where no pressure is applied, the thickness of the portion where the pressure is applied can be effectively suppressed by being appropriately thermally contracted toward the portion where the pressure is applied. On the other hand, when the thermal shrinkage of the metal terminal adhesive film is too large, the metal terminal adhesive film 1 is placed on the metal terminal and bonded to the metal terminal in a preheating stage before being subjected to heat sealing. There is a possibility that the conductive film moves due to heat shrinkage and the positional relationship between the metal terminal and the adhesive film for metal terminal is shifted. For this reason, it is desirable that the adhesive film 1 for metal terminals of the present invention has an appropriate heat shrinkage rate. In addition, as a moderate thermal contraction rate of the adhesive film 1 for metal terminals of this invention, it is mentioned that the lower limit of the thermal contraction rate (%) of the above-mentioned flow direction (MD) is 70% or more, for example. It is done.

(Polypropylene layer 11)
In the present invention, the polypropylene layer 11 is a layer made of polypropylene. The polypropylene layer 11 has a sea-island structure when the cross section is observed with an electron micrograph. The observation of the sea-island structure in the cross-section of the polypropylene layer 11 means that the sea part and the island part are observed as in, for example, an electron micrograph shown in FIG. Fig. 11 shows “Polymer microphotographs: Macromolecules as seen in the eye 1. Shape and function of molecular assembly” (editor: Polymer Society of Japan, publisher: Yamashin, publisher: Baifukan Co., Ltd., May 1986) This is a transmission electron micrograph (scale bar is 5 μm) shown as “C” on page 29 of the first edition issued on May 30). The sea-island structure in the cross section of the polypropylene layer 11 can be confirmed by observing an electron micrograph by staining the cross section of the polypropylene layer with osmium tetroxide (OsO ₄ ) as shown in FIG. In FIG. 11, the sea portion is brighter than the island portion, but depending on the measurement method and conditions, the sea portion may appear darker than the island portion. In any case, if the sea portion and the island portion can be distinguished, the ratio of the area of the island portion in the sea-island structure can be measured.

  In the sea-island structure of the polypropylene layer 11, the ratio of the area of the island part is not particularly limited, but from the viewpoint of further improving the electrolytic solution resistance while further improving the adhesion with the packaging material and the metal terminal, Preferably about 10 to 50%, more preferably about 20 to 40%. The measuring method of the ratio of the area of the island part in the sea island structure of the polypropylene layer 11 is as follows. In addition, when the ratio of the area of an island part is 2% or less, it is evaluated that it does not have a sea island structure substantially.

(Measurement method of the ratio of the area of the island part in the sea island structure)
An adhesive film for metal terminals is embedded in a thermosetting epoxy resin and cured. A commercially available rotating microtome (UC6 manufactured by LEICA) and a cross section in the target direction (cross section along TD) were prepared using a diamond knife, and at that time, a cryomicrotome using liquid nitrogen was −70. Cross section is prepared at ° C. The embedding resin is stained overnight with ruthenium tetroxide. Since the polypropylene expands when dyed, the expanded portion is trimmed with a microtome, and a portion further cut by about 1 to 2 μm with a thickness of about 100 nm is observed as follows. The stained section is observed with a field emission scanning electron microscope (for example, S-4800 TYPE1, manufactured by Hitachi High-Technologies Corporation, measurement condition: 3 kV 20 mA High WD 6 mm detector (Upper)) and an image (magnification is 10,000 times). get. Next, image processing software that can binarize the image (for example, image analysis software WinROOF (Ver 7.4) manufactured by Mitani Corporation) is used to binarize the island portion and the ocean portion of the sea-island structure for the image. The ratio of the area occupied by the island portion (the total area of the island portion / the area of the measurement range of the image) is obtained, for example, the conditions described in the embodiment are adopted as specific image processing conditions.

  By observing the sea-island structure when the cross section of the polypropylene layer 11 is observed with an electron micrograph, the cold resistance strength is enhanced while maintaining the excellent heat resistance of the adhesive film for metal terminals. Moreover, adhesiveness with a packaging material and a metal terminal is improved, and also electrolyte solution resistance improves.

  In the present invention, the polypropylene layer 11 is preferably composed of unstretched polypropylene. It can be confirmed that the polypropylene layer 11 is composed of unstretched polypropylene and is not composed of stretched polypropylene by analyzing the polypropylene layer 11 by the X-ray diffraction method. Specifically, when the wide-angle X-ray diffraction of the polypropylene layer 11 made of unstretched polypropylene is measured, it corresponds to the 110 plane of the polypropylene crystal with respect to the peak intensity corresponding to the 040 plane calculated from the diffraction pattern of the polypropylene crystal. The ratio of peak intensities (040-plane peak intensity / 110-plane peak intensity) is in the range of 0.5 to 1.5, and the polypropylene layer composed of stretched polypropylene is outside this range. That is, in the present invention, when the wide-angle X-ray diffraction is measured, the polypropylene layer 11 has a ratio of the peak intensity corresponding to the 110 plane of the polypropylene crystal to the peak intensity corresponding to the 040 plane calculated from the diffraction pattern of the polypropylene crystal ( 040 plane peak intensity / 110 plane peak intensity) is made of polypropylene that falls within a range of 0.5 to 1.5.

  The peak corresponding to the 110 plane appears near 2θ = 14 °, and the peak corresponding to the 040 plane appears near 2θ = 17 °. The measurement conditions by wide-angle X-ray diffraction are: Soller / PCS (opening angle of incident parallel slit): 5.0 deg, IS length (length of length limiting slit): 10.0 mm, PSA open (opening angle of light receiving PSA is open) ), Soller (opening angle of the light receiving parallel slit): 5.0 deg, 2θ / θ: 2 to 40 deg, step is 0.04 deg.

Moreover, it can confirm that the polypropylene layer 11 is comprised with the unstretched polypropylene and is not comprised with the stretched polypropylene by analyzing the polypropylene layer 11 by a Raman spectroscopy. Specifically, when analyzed polypropylene layer by Raman spectroscopy, approximately the height of crystalline peak intensity appearing 809cm ^-1 "A", the amorphous peak intensity appearing at about 842cm ^-1 high When the ratio (A / B) of the length “B” is 1.6 or less, it can be confirmed that the polypropylene layer 11 is composed of unstretched polypropylene. The measurement conditions were a laser wavelength of 633 nm, a grating of 600 gr / mm, a confocal hole of 100 μm, a microscope lens of 10 times, an exposure time of 15 sec, an integration count of 1 time, and a cross section parallel to the MD (Machine Direction) of the polypropylene layer 11. The Raman spectrum was measured so that the MD and the incident laser polarization plane were parallel. A straight line connecting 710 cm ⁻¹ and 925 cm ⁻¹ was used as a baseline. Analysis conditions, the time of the baseline correction, the peak height at 809cm ^-1 and 842cm ^-1, was calculated as the peak intensity. The above-described “A” peak intensity of crystallinity appearing at about 809 cm ⁻¹ is a peak attributed to a combination mode of main chain CC expansion and contraction and CH3 bending vibration. Further, the height “B” of the amorphous peak intensity appearing at about 842 cm ⁻¹ is a peak attributed to the CH3 bending vibration mode.

  In this invention, the confirmation method of MD of the polypropylene layer 11 is as follows. About each cross section (total of 10 cross sections) up to the direction perpendicular to the cross section in the length direction by changing the angle by 10 degrees from the cross section in the length direction of the polypropylene layer 11 and the direction parallel to the cross section in the length direction. In each case, the sea-island structure is confirmed by observation with an electron micrograph. Next, the shape of each island is observed in each cross section. With respect to the shape of each island, a straight line distance connecting the leftmost end in the direction perpendicular to the thickness direction of the polypropylene layer 11 and the rightmost end in the vertical direction is defined 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. The direction parallel to the cross section where the average of the diameter y of the island shape is the largest is determined as MD.

  The polypropylene contained in the polypropylene layer 11 is preferably crystalline such as homopolypropylene, block copolymer of polypropylene (for example, block copolymer of propylene and ethylene), random copolymer of polypropylene (for example, random copolymer of propylene and ethylene) or the like. Amorphous polypropylene is mentioned. Examples of the composition in which the polypropylene layer 11 has the above-described sea-island structure include, for example, a composition in which the polypropylene layer 11 contains a polypropylene block copolymer, a composition containing a polypropylene block copolymer and a polypropylene random copolymer, and homopolypropylene and random polypropylene. Examples include a composition containing a polyethylene component. Among these, it is more preferable that the polypropylene layer 11 contains block polypropylene, and it is more preferable that the polypropylene layer 11 is composed of block polypropylene. In addition, as a ratio of the propylene contained in block polypropylene, Preferably it is about 10-90 mass%, More preferably, about 30-80 mass% is mentioned.

  In the adhesive film 1 for metal terminals of the present invention, the polypropylene layer 11 may be a single layer or two or more layers. In addition, one polypropylene layer 11 may be formed by successively laminating a plurality of layers made of the same or different polypropylene, and the plurality of layers may constitute one polypropylene layer 11. The polypropylene layer 11 preferably includes a layer made of block polypropylene.

  A preferred embodiment of the single polypropylene layer 11 is preferably a laminate of a layer composed of random polypropylene and a layer composed of block polypropylene, and in particular, a layer composed of random polypropylene and block polypropylene. It is preferable to have a laminated structure (three-layer structure) in which a layer constituted by the above and a layer constituted by random polypropylene are laminated in this order.

  In the present invention, when a plurality of layers made of polypropylene are continuously laminated, these layers are collectively referred to as a single polypropylene layer 11. Similarly, when a plurality of layers composed of acid-modified polypropylene are continuously laminated, these layers are collectively referred to as one acid-modified polypropylene layer 12.

  The thickness of one polypropylene layer 11 is not particularly limited as long as the total thickness of the polypropylene layer 11 is within a range of 0.7 to 3.5 when the total thickness of the acid-modified polypropylene layer 12 is 1. However, from the viewpoint of further improving the electrolytic solution resistance while further improving the adhesion between the packaging material and the metal terminal, it is preferably about 15 to 80 μm, more preferably about 20 to 70 μm. The details of the mechanism are not clear, but if the thickness of the acid-modified polypropylene layer is too large, the acid-modified polypropylene layer tends to cause cohesive failure and the adhesiveness of the adhesive film for metal terminals tends to decrease. It is in.

  From the viewpoint of further improving the electrolytic solution resistance while further improving the adhesion between the packaging material and the metal terminal, the polypropylene layer 11 has the thickness of the metal terminal adhesive film 1 in the metal terminal adhesive film 1. Preferably, it occupies about 40% or more, more preferably occupies about 45% or more. As an upper limit, the polypropylene layer 11 preferably occupies about 85% or less of the thickness of the metal terminal adhesive film 1, More preferably, it occupies 80% or less. A preferable range of the thickness of the polypropylene layer 11 in the thickness of the metal terminal adhesive film 1 is about 40 to 85% and about 45 to 80%.

  Although it does not restrict | limit especially as a melting peak temperature of the polypropylene layer 11, From a viewpoint of improving electrolyte solution resistance further, further improving adhesiveness with a packaging material and a metal terminal, Preferably it is about 140-165 degreeC, More preferably, about 150-160 degreeC is mentioned. In the present invention, the melting peak temperature of the polypropylene layer 11 is a value measured using a differential scanning calorimeter (DSC), the heating rate is 10 ° C./min, and the temperature measurement range is −50 to 200 ° C. Measured using an aluminum pan as the sample pan.

(Acid-modified polypropylene layer 12)
In the present invention, the acid-modified polypropylene layer 12 is a layer made of acid-modified polypropylene. The acid-modified polypropylene layer 12 also preferably has a sea-island structure when the cross section is observed with an electron micrograph. The confirmation method of the sea-island structure in the acid-modified polypropylene layer 12 is the same as the confirmation method in the polypropylene layer 11 described above.

  In the sea-island structure of the acid-modified polypropylene layer 12, the ratio of the area of the island portion is not particularly limited, but from the viewpoint of further improving the electrolytic solution resistance while further improving the adhesion with the packaging material and the metal terminal. Is preferably about 10 to 50%, more preferably about 20 to 40%. The method for measuring the ratio of the area of the island portion in the sea-island structure of the acid-modified polypropylene layer 12 is the same as the measurement method for the polypropylene layer 11 described above, except that the measurement target is the acid-modified polypropylene layer 12. In addition, when the ratio of the area of an island part is 2% or less, it is evaluated that it does not have a sea island structure substantially.

  The acid-modified polypropylene is not particularly limited as long as it is an acid-modified polypropylene, and preferably a polypropylene graft-modified with an unsaturated carboxylic acid or an anhydride thereof. Examples of the unsaturated carboxylic acid or anhydride thereof used for acid modification include maleic acid, acrylic acid, itaconic acid, crotonic acid, maleic anhydride, itaconic anhydride and the like.

The acid-modified polypropylene is preferably crystalline or amorphous, such as homopolypropylene, polypropylene block copolymer (eg, propylene and ethylene block copolymer), and polypropylene random copolymer (eg, propylene and ethylene random copolymer). May be mentioned. Among these, it is preferable to contain a polypropylene block copolymer (block polypropylene) or a random copolymer of polypropylene (random polypropylene). The acid-modified polypropylene layer 12 can be analyzed by infrared spectroscopy, gas chromatography mass spectrometry, or the like, and the analysis method is not particularly limited. For example, when measuring the infrared spectroscopy at a maleic anhydride-modified polypropylene, 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 modification degree is low, the peak may be small and may not be detected. In that case, it can be analyzed by nuclear magnetic resonance spectroscopy.

  In the adhesive film 1 for metal terminals of the present invention, the acid-modified polypropylene layer 12 may be only one layer or two or more layers. In addition, one acid-modified polypropylene layer 12 is formed by continuously laminating a plurality of layers made of the same or different acid-modified polypropylene, and the plurality of layers constitute one acid-modified polypropylene layer 12. May be.

  A preferred embodiment of the single acid-modified polypropylene layer 12 is a layer composed of maleic anhydride-modified polypropylene.

  The thickness of the single acid-modified polypropylene layer 12 is particularly as long as the total thickness of the polypropylene layer 11 is within a range of 0.7 to 3.5 when the total thickness of the acid-modified polypropylene layer 12 is 1. Although not limited, from the viewpoint of further improving the electrolytic solution resistance while further improving the adhesion between the packaging material and the metal terminal, preferably about 10 μm or more, more preferably about 15 μm or more, the upper limit is, Preferably it is about 40 micrometers or less, More preferably, it is about 35 micrometers or less, More preferably, it is about 30 micrometers or less.

  The melting peak temperature of the acid-modified polypropylene layer 12 is not particularly limited, but is preferably 130 to 165 ° C. from the viewpoint of further improving the electrolytic solution resistance while further improving the adhesion between the packaging material and the metal terminal. Degree, more preferably about 140 to 160 ° C. In the present invention, the melting peak temperature of the acid-modified polypropylene layer 12 is a value measured in the same manner as the method for measuring the melting peak temperature of the polypropylene layer 11.

  From the viewpoint of improving the sealing strength while suppressing crushing of the adhesive film for metal terminals during heat sealing, in the adhesive film 1 for metal terminals of the present invention, the softening point of the polypropylene layer 11 and the acid-modified polypropylene layer 12 The absolute value of the difference between the softening points is preferably about 40 ° C. or lower, more preferably about 30 ° C. or lower, more preferably about 20 ° C. or lower, and the lower limit is preferably about 0 ° C. or higher. Preferably about 5 degreeC or more, More preferably, about 10 degreeC or more is mentioned. The softening points of the polypropylene layer 11 and the acid-modified polypropylene layer 12 are values measured as follows.

(Measurement method of softening point)
Using a scanning thermal microscope (NanoTA manufactured by Anasys), the cantilever model of the thermal probe is a value measured under conditions of EX-AN2-200 and a heating rate of 5 ° C./s. The softening point was the peak top temperature.

  The metal terminal adhesive film 1 of the present invention may contain various additives such as a lubricant, an antioxidant, an ultraviolet absorber, and a light stabilizer, if necessary. In addition, depending on the kind of additive, content, etc., the adhesive film 1 for metal terminals may discolor.

  The content of the lubricant contained in the entire metal terminal adhesive film 1 is preferably about 0 to 2000 ppm.

(Measurement of lubricant amount)
The content of the lubricant contained in the entire metal terminal adhesive film 1 is a value measured using a gas chromatograph mass spectrometer (GC-MS). Specifically, in boiling refluxed methanol, the additive in the adhesive film for metal terminals was extracted into methanol, and the obtained methanol extract was analyzed by GC-MS for metal terminals. The amount of lubricant contained in the entire adhesive film is measured.

  Although it does not restrict | limit especially as a lubricant, Preferably an amide type lubricant is mentioned. Specific examples of the amide-based lubricant include saturated fatty acid amide, unsaturated fatty acid amide, substituted amide, methylolamide, saturated fatty acid bisamide, unsaturated fatty acid bisamide, and the like. Specific examples of the saturated fatty acid amide include lauric acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, hydroxy stearic 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. Specific examples of methylolamide include methylol stearamide. Specific examples of saturated fatty acid bisamides include methylene bis stearamide, ethylene biscapric amide, ethylene bis lauric acid amide, ethylene bis stearic acid amide, ethylene bishydroxy stearic acid amide, ethylene bisbehenic acid amide, hexamethylene bis stearic acid amide. Examples include acid amide, hexamethylene bisbehenic acid amide, hexamethylene hydroxystearic acid amide, N, N′-distearyl adipic acid amide, N, N′-distearyl sebacic acid amide, and the like. Specific examples of unsaturated fatty acid bisamides include ethylene bisoleic acid amide, ethylene biserucic acid amide, hexamethylene bisoleic acid amide, N, N′-dioleyl adipic acid amide, N, N′-dioleyl sebacic acid amide Etc. Specific examples of the fatty acid ester amide include stearoamidoethyl stearate. Specific examples of the aromatic bisamide include m-xylylene bis stearic acid amide, m-xylylene bishydroxy stearic acid amide, N, N′-distearyl isophthalic acid amide and the like. One type of lubricant may be used alone, or two or more types may be used in combination.

  Moreover, the adhesive film 1 for metal terminals of this invention may contain the filler as needed. When the adhesive film 1 for a metal terminal contains a filler, the filler functions as a spacer, so that a short circuit between the metal terminal 2 and the barrier layer 33 of the packaging material 3 can be more effectively performed. It becomes possible to suppress. The particle size of the filler is about 0.1 to 35 μm, preferably about 5.0 to 30 μm, and more preferably about 10 to 25 μm. Moreover, when adding a filler to the adhesive film 1 for metal terminals, it is preferable to contain in the polypropylene layer 11 and / or the acid-modified polypropylene layer 12, and as content of a filler, the polypropylene layer 11 and an acid-modified polypropylene are included. About 100 to 30 parts by mass of the resin component forming the layer 12, about 5 to 30 parts by mass, and more preferably about 10 to 20 parts by mass, respectively.

  As the filler, either inorganic or organic can be used. Examples of inorganic fillers include carbon (carbon, graphite), silica, aluminum oxide, barium titanate, iron oxide, silicon carbide, zirconium oxide, zirconium silicate, magnesium oxide, titanium oxide, calcium aluminate, and calcium hydroxide. , Aluminum hydroxide, magnesium hydroxide, calcium carbonate and the like. Examples of organic fillers include fluorine resin, phenol resin, urea resin, epoxy resin, acrylic resin, benzoguanamine / formaldehyde condensate, melamine / formaldehyde condensate, polymethyl methacrylate cross-linked product, polyethylene cross-linked product, etc. Can be mentioned. Aluminum oxide, silica, fluororesin, acrylic resin, and benzoguanamine / formaldehyde condensate are preferable from the viewpoint of shape stability, rigidity, and content resistance, and spherical aluminum oxide and silica are more preferable among them. As a method of mixing the filler into the resin component that forms the polypropylene layer 11 and / or the acid-modified polypropylene layer 12, a method of melt-blending both in advance with a Banbury mixer or the like to obtain a master batch with a predetermined mixing ratio A direct mixing method with a resin component can be employed.

  Moreover, the adhesive film 1 for metal terminals may each contain the pigment as needed. As the pigment, various inorganic pigments can be used. As a specific example of the pigment, carbon (carbon, graphite) exemplified for the filler can be preferably exemplified. Carbon (carbon, graphite) is a material generally used in the battery, and there is no risk of elution from the electrolyte. In addition, a sufficient coloring effect can be obtained with an addition amount that has a large coloring effect and does not impair adhesiveness, and the apparent melt viscosity of the added resin can be increased without melting by heat. Furthermore, it is possible to prevent the pressure portion from becoming thin during thermal bonding (sealing), and to prevent a decrease in seal strength.

  When a pigment is added to the metal terminal adhesive film 1, it is preferably contained in the polypropylene layer 11 and / or the acid-modified polypropylene layer 12, and the amount added is, for example, carbon black having a particle size of about 0.03 μm. Is used, the resin component forming 100 parts by weight of the polypropylene layer 11 and the acid-modified polypropylene layer 12 is about 0.05 to 0.3 parts by weight, preferably 0.1 to 0.2 parts by weight. Degree. By adding a pigment to the metal terminal adhesive film 1, the presence or absence of the metal terminal adhesive film 1 can be detected by a sensor, or can be visually inspected. In addition, when the filler and the pigment are added to the polypropylene layer 11 and / or the acid-modified polypropylene layer 12, the filler and the pigment may be added to the same polypropylene layer 11 and / or the acid-modified polypropylene layer 12, From the viewpoint of not inhibiting the heat-fusibility of the metal terminal adhesive film 1, the filler and the pigment are preferably added separately to the polypropylene layer 11 and the acid-modified polypropylene layer 12.

  The adhesive film 1 for metal terminals of the present invention can be produced by laminating at least one polypropylene layer and at least one acid-modified polypropylene layer. A method for laminating at least one polypropylene layer and at least one acid-modified polypropylene layer is not particularly limited, and for example, a thermal lamination method, a sandwich lamination method, an extrusion lamination method, or the like can be used.

  The method for interposing the metal terminal adhesive film 1 between the metal terminal 2 and the packaging material 3 is not particularly limited. For example, the metal terminal 2 is sandwiched by the packaging material 3 as shown in FIGS. The metal terminal adhesive film 1 may be wound around the metal terminal 2 in the portion to be formed. Although not shown, the metal terminal adhesive film 1 is disposed on both sides of the metal terminal 2 so that the metal terminal adhesive film 1 crosses the two metal terminals 2 at the portion where the metal terminal 2 is sandwiched by the packaging material 3. May be.

[Metal terminal 2]
The metal terminal adhesive film 1 of the present invention is used by being interposed between the metal terminal 2 and the packaging material 3. The metal terminal 2 (tab) is a member that is electrically connected to the electrode (positive electrode or negative electrode) of the battery element 4 and is made of a metal material. The metal material constituting the metal terminal 2 is not particularly limited, and examples thereof include aluminum, nickel, and copper. For example, the metal terminal 2 connected to the positive electrode of a lithium ion battery is usually made of aluminum or the like. Moreover, the metal terminal connected to the negative electrode of a lithium ion battery is normally comprised with copper, nickel, etc.

  The surface of the metal terminal 2 is preferably subjected to chemical conversion treatment from the viewpoint of improving the resistance to electrolytic solution. For example, when the metal terminal 2 is made of aluminum, specific examples of the chemical conversion treatment include known methods for forming an acid-resistant film such as phosphate, chromate, fluoride, and triazine thiol compound. . Among the methods for forming an acid-resistant film, a phosphoric acid chromate treatment using a phenol resin, a chromium (III) fluoride compound, and phosphoric acid is preferably used.

  What is necessary is just to set the magnitude | size of the metal terminal 2 suitably according to the magnitude | size etc. of the battery used. As thickness of the metal terminal 2, Preferably it is about 50-1000 micrometers, More preferably, about 70-800 micrometers is mentioned. Moreover, as length of the metal terminal 2, Preferably it is about 1-200 mm, More preferably, about 3-150 mm is mentioned. The width of the metal terminal 2 is preferably about 1 to 200 mm, more preferably about 3 to 150 mm.

[Packaging material 3]
Examples of the packaging material 3 include those having a laminated structure including at least a base material layer 31, a barrier layer 33, and a heat-fusible resin layer 34 in this order. FIG. 6 shows an example in which a base material layer 31, an adhesive layer 32, a barrier layer 33, an adhesive layer 35, and a heat-fusible resin layer 34 are laminated in this order as an example of a cross-sectional structure of the packaging material 3. . The adhesive layer 32 is a layer provided as necessary for the purpose of improving the adhesion between the base material layer 31 and the barrier layer 33. The adhesive layer 35 is a layer provided as necessary for the purpose of improving the adhesion between the barrier layer 33 and the heat-fusible resin layer 34.

  In the packaging material 3, the base material layer 31 is the outermost layer side, and the heat-fusible resin layer 34 is the innermost layer. When the battery is assembled, the battery element 4 is hermetically sealed by bringing the heat-fusible resin layers 34 positioned at the periphery of the battery element 4 into contact with each other and heat-welding them, thereby sealing the battery element 4. 1 to 3 show the battery 10 when the embossed packaging material 3 formed by embossing or the like is used, the packaging material 3 may be a pouch type that is not molded. Good. The pouch type includes a three-side seal, a four-side seal, and a pillow type, but any type may be used.

[Base Material Layer 31]
In the packaging material 3, the base material layer 31 is a layer that functions as a base material of the packaging material, and is a layer that forms the outermost layer.

  The material for forming the base material layer 31 is not particularly limited as long as it has insulating properties. Examples of the material for forming the base material layer 31 include polyester, polyamide, polyolefin, epoxy resin, acrylic resin, fluorine resin, polyurethane, silicon resin, phenol resin, polyetherimide, polyimide, and mixtures and copolymers thereof. Etc.

  About the thickness of the base material layer 31, about 10-50 micrometers is mentioned, for example, Preferably about 15-30 micrometers is mentioned.

[Adhesive layer 32]
In the packaging material 3, the adhesive layer 32 is a layer that is disposed on the base material layer 31 as necessary in order to impart adhesion to the base material layer 31. That is, the adhesive layer 32 is provided between the base material layer 31 and the barrier layer 33 as necessary.

  The adhesive layer 32 is formed of an adhesive capable of bonding the base material layer 31 and the barrier layer 33. The adhesive used for forming the adhesive layer 32 may be a two-component curable adhesive or a one-component curable adhesive. Further, the adhesive used for forming the adhesive layer 32 is not particularly limited, and may be any of a chemical reaction type, a solvent volatilization type, a heat melting type, a hot pressure type, and the like.

  About the thickness of the adhesive bond layer 32, about 2-50 micrometers is mentioned, for example, Preferably about 3-25 micrometers is mentioned.

[Barrier layer 33]
In the packaging material, the barrier layer 33 is a layer having a function of preventing water vapor, oxygen, light, and the like from entering the battery, in addition to improving the strength of the battery packaging material. Specific examples of the metal constituting the barrier layer 33 include aluminum, stainless steel, and titanium, and preferably aluminum. The barrier layer 33 can be formed by, for example, a metal foil, a metal vapor-deposited film, an inorganic oxide vapor-deposited film, a carbon-containing inorganic oxide vapor-deposited film, a film provided with these vapor-deposited films, etc. Is preferable, and it is more preferable to form with an aluminum alloy foil. From the viewpoint of preventing generation of wrinkles and pinholes in the barrier layer 33 during the production of the battery packaging material, the barrier layer is made of, for example, annealed aluminum (JIS H4160: 1994 A8021H-O, JIS H4160: (1994 A8079H-O, JIS H4000: 2014 A8021P-O, JIS H4000: 2014 A8079P-O) and the like, more preferably formed of a soft aluminum alloy foil.

  Although the thickness of the barrier layer 33 will not be restrict | limited especially if the function as barrier layers, such as water vapor | steam, is exhibited, For example, about 10-50 micrometers, Preferably it can be set to about 10-40 micrometers.

[Adhesive layer 35]
In the packaging material 3, the adhesive layer 35 is a layer provided as necessary between the barrier layer 33 and the heat-fusible resin layer 34 in order to firmly bond the heat-fusible resin layer 34.

  The adhesive layer 35 is formed of an adhesive that can adhere the barrier layer 33 and the heat-fusible resin layer 34. Although it does not restrict | limit especially about the composition of the adhesive agent used for formation of an contact bonding layer, For example, the resin composition containing acid-modified polyolefin is mentioned. Examples of the acid-modified polyolefin include the same as those described in the acid-modified polypropylene layer 12. In addition, polyethylene such as low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, and the like were acid-modified with unsaturated carboxylic acid or an anhydride thereof (for example, those exemplified in the acid-modified polypropylene layer 12). A thing can also be illustrated.

  About the thickness of the contact bonding layer 35, about 1-40 micrometers is mentioned, for example, Preferably about 2-30 micrometers is mentioned.

[Heat-fusion resin layer 34]
In the packaging material 3, the heat-fusible resin layer 34 corresponds to the innermost layer, and is a layer that heat-welds the heat-fusible resin layers to each other to seal the battery element when the battery is assembled.

  The resin component used for the heat-fusible resin layer 34 is not particularly limited as long as it can be heat-welded, and examples thereof include polyolefin and acid-modified polyolefin.

  Examples of the polyolefin include the same as those exemplified for the polypropylene layer 11 and polyethylene such as low density polyethylene, medium density polyethylene, high density polyethylene, and linear low density polyethylene. Examples of the acid-modified polyolefin include the same as those described for the adhesive layer 35.

  Further, the thickness of the heat-fusible resin layer 34 is not particularly limited, but is preferably about 2 to 2000 μm, more preferably about 5 to 1000 μm, and still more preferably about 10 to 500 μm.

2. Battery 10
The battery 10 of the present invention includes a battery element 4 including at least a positive electrode, a negative electrode, and an electrolyte; a packaging material 3 that seals the battery element 4; 3 and a metal terminal 2 projecting to the outside. The battery 10 of the present invention is characterized in that the metal terminal adhesive film 1 of the present invention is interposed between the metal terminal 2 and the packaging material 3.

  Specifically, the metal element of the present invention is formed by packaging the battery element 4 including at least the positive electrode, the negative electrode, and the electrolyte with the packaging material 3 and the metal terminals 2 connected to each of the positive electrode and the negative electrode protruding outward. The terminal adhesive film 1 is interposed between the metal terminal 2 and the heat-fusible resin layer 34, and the flange portion of the packaging material (in the region where the heat-fusible resin layers 34 are in contact with each other at the periphery of the battery element 4. The battery 10 using the packaging material 3 is provided by covering the peripheral edge portion 3a) of the packaging material so as to be formed and heat-sealing and sealing the heat-fusible resin layers 34 of the flange portion. The When the battery element 4 is accommodated using the packaging material 3, the packaging material 3 is used so that the heat-fusible resin layer 34 of the packaging material 3 is on the inner side (surface in contact with the battery element 4).

  The battery of the present invention may be either a primary battery or a secondary battery, but is preferably a secondary battery. The type of secondary battery is not particularly limited. For example, a lithium ion battery, a lithium ion polymer battery, a lead battery, a nickel / hydrogen battery, a nickel / cadmium battery, a nickel / iron battery, a nickel / zinc battery Examples include batteries, silver oxide / zinc livestock batteries, metal-air batteries, multivalent cation batteries, capacitors, capacitors, and the like. Among these secondary batteries, a lithium ion battery and a lithium ion polymer battery are preferable.

  In addition, when measuring the thickness of the packaging material, the metal terminal, and the adhesive film for the metal terminal constituting the battery, the thickness of the portion where the packaging material, the adhesive film for the metal terminal and the metal terminal are laminated, the packaging The preferred thickness of the material is about 10 to 65 μm, the thickness of the metal terminal is about 50 to 1000 μm, the preferred thickness of the metal terminal adhesive film is about 30 to 80 μm, About 40-145 micrometers is mentioned as a sum total of the preferable thickness of a packaging material, and the preferable thickness of the adhesive film for metal terminals.

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

  In Examples and Comparative Examples, measurement of melting peak temperature, measurement of heat shrinkage rate, measurement of seal strength, measurement of residual thickness rate, resistance to electrolyte, and measurement of ratio of area of island part in sea-island structure Was performed as follows. Each result is shown in Table 1.

(Measurement of melting peak temperature)
The adhesive film for metal terminals was measured using a differential scanning calorimeter (DSC). As the apparatus, “DSC-60 Plus” manufactured by Shimadzu Corporation was used. The measurement conditions were a heating rate of 10 ° C./min, a temperature measurement range of −50 to 200 ° C., and an aluminum pan was used as a sample pan.

(Measurement of heat shrinkage)
The adhesive film for metal terminals was cut into a size of 50 mm (MD) × 4 mm (TD) in width and used as a test piece. Next, the length M (mm) of the test piece was measured with a metal scale. Next, the end in the length direction of the test piece was fixed to the wire mesh with tape, and the test piece was suspended from the wire mesh. In this state, after placing in an oven heated to 190 ° C. for 120 seconds, the test piece was taken out together with the wire mesh, and naturally cooled in a room temperature (25 ° C.) environment. Next, the length N (mm) of the test piece naturally cooled to room temperature was measured with a metal ruler. The thermal contraction rate of the adhesive film for metal terminals was calculated by the following formula.
Thermal contraction rate (%) = (length N / length M) × 100

(Measurement of seal strength)
As shown in the schematic diagram of FIG. 7, the packaging material 3 was cut into a size of length 150 mm (MD) × width 60 mm (TD). Moreover, the adhesive film 1 for metal terminals was cut out to the size of length 75mm (MD) x width 60mm (TD). Moreover, the metal terminal 2 (Aluminum plate, length 60mm, width 25mm, thickness 0.1mm) was prepared. Next, as shown in the schematic diagram of FIG. 8, the packaging material 3 was folded in the longitudinal direction at the position of the center P of the MD so that the heat-fusible resin layer was inside. Next, the metal terminal adhesive film 1 and the metal terminal 2 (aluminum plate, length 60 mm, width 25 mm, thickness 0.1 mm) are overlapped and folded into two as shown in the schematic diagram of FIG. Inserted between Material 3. At this time, the acid-modified polypropylene layer of the metal terminal adhesive film 1 was disposed so as to be in contact with the metal terminal 2. A cross-sectional view from the side is shown in FIG. 8b. In this state, as shown in the schematic diagram of FIG. 9a, heat sealing is performed from both sides of the packaging material 3 under conditions of a seal width of 7.0 mm, a seal temperature of 190 ° C., a surface pressure of 1.0 MPa, and a seal time of 3 seconds. A laminate was obtained. In the heat-sealed portion S of FIG. 9, the direction of the seal width corresponds to the MD of the packaging material. Next, the sample was cut out from the laminated body at the position of the two-dot chain line in the schematic diagram of FIG. 9B so that the width of the heat-sealed portion S (TD of the packaging material) was 15 mm. The sample packaging material 3 and the metal terminal adhesive film 1 thus obtained were separated in the direction of 180 ° to the position of the heat-sealed portion S. A cross-sectional view of the sample in this state as viewed from the side is shown in FIG. 9c. Next, using a tensile testing machine (AG-Xplus manufactured by Shimadzu Corporation), the speed was 300 mm / min, the distance between chucks was 50 mm, and the peeling method was a T-shaped peeling method, and the seal strength (N / 15 mm) was measured. . At this time, as shown in FIG. 10, in the laminate in which the packaging material 3 / the adhesive film for metal terminal 1 / the metal terminal 2 / the packaging material 3 are laminated in order, “the adhesive film for metal terminal 1 / the metal terminal” 2 / Packaging material 3 ”is sandwiched between the lower chuck and the packaging material 3 separated in the 180 ° direction is sandwiched between the upper chucks, and the packaging material 3 and the metal terminal adhesive film 1 are peeled off. The seal strength was measured.

(Evaluation of electrolyte resistance)
The adhesive film for metal terminals was cut into a size of 15 mm (MD) × 100 mm (TD) to obtain a test piece. Next, the test piece was immersed in an electrolytic solution (1M LiPF ₆ solution (ethylene carbonate: dimethyl carbonate: diethyl carbonate = 1: 1: 1, volume ratio) and stored in an oven at 85 ° C. for 24 hours. The test piece was taken out and washed with water, and the test piece was visually observed.The case where the test piece was not peeled off was designated as “A”, and the case where the test piece was peeled off was designated as “C”. "

(Measurement of residual thickness of adhesive film for metal terminals)
An aluminum plate (pure aluminum type, JIS H4160-1994 A1N30H-O) having a length of 60 mm, a width of 25 mm, and a thickness of 100 μm, and the metal terminal adhesive film having a length of 70 mm and a width of 5 mm were prepared. Next, the thickness A (μm) of the adhesive film for metal terminals was measured with a micro gauge. Next, the adhesive film for metal terminals was overlapped on the center portion of the aluminum plate so that the length direction and the width direction of the aluminum plate and the adhesive film for metal terminals coincided. Next, two metal plates longer than the length of the aluminum plate and having a width of 7 mm are prepared. Next, the temperature is measured from above and below the metal terminal adhesive film so as to cover the entire surface of the metal terminal adhesive film. Heating and pressing were performed under the conditions of 190 ° C., surface pressure of 1.27 MPa, and time of 3 seconds to obtain a laminate of an aluminum plate and an adhesive film for metal terminals. Next, the thickness B (μm) of the portion where the laminate was heated and pressed was measured with a micro gauge. The thickness residual ratio of the adhesive film for metal terminals was calculated by the following formula. At this time, the thickness B is determined from the center of the laminate and both ends in the length direction of the laminate (both ends of the portion where the aluminum plate and the metal terminal adhesive film are laminated) from the center. It was set as the average value of a total of three places of two places of 10 mm toward the part.
Residual thickness of metal terminal adhesive film (%) = (thickness B-100) / thickness A × 100

<Measurement method of the ratio of the area of the island part in the sea island structure>
An adhesive film for metal terminals was embedded in a thermosetting epoxy resin and cured. A commercially available rotating microtome (UC6 manufactured by LEICA) and a cross section in the target direction (cross section along TD) were prepared using a diamond knife, and at that time, a cryomicrotome using liquid nitrogen was −70. A cross-section was prepared at ° C. The embedding resin was stained overnight with ruthenium tetroxide. Since the polypropylene expands when dyed, the expanded portion was trimmed with a microtome, and a portion further cut by about 1 to 2 μm with a thickness of about 100 nm was observed as follows. The stained section is observed with a field emission scanning electron microscope (for example, S-4800 TYPE1, manufactured by Hitachi High-Technologies Corporation, measurement condition: 3 kV 20 mA High WD 6 mm detector (Upper)) and an image (magnification is 10,000 times). I got it. Next, image processing software that can binarize the image (for example, image analysis software WinROOF (Ver 7.4) manufactured by Mitani Corporation) is used to binarize the island portion and the ocean portion of the sea-island structure for the image. The ratio of the area occupied by the island portion (the total area of the island portion / the area of the image measurement range) was determined.The specific image processing conditions are as follows. Since the area was stained more than the sea area, the island area was observed brighter than the sea area.
[Image processing conditions]
3 × 3 pix Averaging binarization: Automatic binarization Isolated point removal: Remove an object or background consisting of one pixel.
Deletion: Determining the shape feature value or concentration feature value and deleting particles (recognizing an area of 0.005 μm ² as noise)

<Manufacture of adhesive film for metal terminals>
Example 1
As a polypropylene layer, an unstretched polypropylene film (CPP, total thickness 50 μm, melting peak temperature 155) of a three-layer structure in which a random polypropylene layer (6 μm) / block polypropylene layer (38 μm) / random polypropylene layer (6 μm) are sequentially laminated. ° C) was prepared. Next, maleic anhydride-modified polypropylene is laminated on both sides of the unstretched polypropylene film by extrusion lamination, and the acid-modified polypropylene layer (25 μm) / polypropylene layer (50 μm) / acid-modified polypropylene layer (25 μm) are sequentially formed. A laminated adhesive film for metal terminals was produced. About the obtained adhesive film for metal terminals, when the heat shrinkage rate was measured, it showed a high value of 83.0%.

(Example 2)
As a polypropylene layer, a three-layer unstretched polypropylene film (CPP, total thickness 60 μm, melting peak temperature 155) in which a random polypropylene layer (8 μm) / block polypropylene layer (44 μm) / random polypropylene layer (8 μm) are sequentially laminated. ° C) was prepared. Next, maleic anhydride-modified polypropylene is laminated on both sides of the unstretched polypropylene film by extrusion lamination, and the acid-modified polypropylene layer (20 μm) / polypropylene layer (60 μm) / acid-modified polypropylene layer (20 μm) are sequentially formed. A laminated adhesive film for metal terminals was produced. About the obtained adhesive film for metal terminals, when the heat shrinkage rate was measured, it showed a high value of 81.3%.

(Example 3)
As a polypropylene layer, an unstretched polypropylene film (CPP, total thickness 50 μm, melting peak temperature 155) of a three-layer structure in which a random polypropylene layer (6 μm) / block polypropylene layer (38 μm) / random polypropylene layer (6 μm) are sequentially laminated. ° C) was prepared. Next, maleic anhydride-modified polypropylene is laminated on one side of the unstretched polypropylene film by extrusion lamination to produce an adhesive film for metal terminals in which an acid-modified polypropylene layer (16 μm) / polypropylene layer (50 μm) is laminated. did. About the obtained adhesive film for metal terminals, when the thermal contraction rate was measured, it showed a high value of 80.1%.

Example 4
As a polypropylene layer, a three-layer unstretched polypropylene film (CPP, total thickness 30 μm, melting peak temperature 155) in which a random polypropylene layer (4 μm) / block polypropylene layer (22 μm) / random polypropylene layer (4 μm) are sequentially laminated. ° C) was prepared. Next, maleic anhydride-modified polypropylene is laminated on one side of the unstretched polypropylene film by extrusion lamination to produce an adhesive film for metal terminals in which an acid-modified polypropylene layer (36 μm) / polypropylene layer (30 μm) is laminated. did. When the thermal contraction rate was measured about the obtained adhesive film for metal terminals, it showed a high value of 88.1%.

(Example 5)
As a polypropylene layer, a three-layer unstretched polypropylene film (CPP, total thickness 30 μm, melting peak temperature 155) in which a random polypropylene layer (4 μm) / block polypropylene layer (22 μm) / random polypropylene layer (4 μm) are sequentially laminated. ° C) was prepared. Next, maleic anhydride-modified polypropylene is laminated on both sides of the unstretched polypropylene film by extrusion lamination, and the acid-modified polypropylene layer (18 μm) / polypropylene layer (30 μm) / acid-modified polypropylene layer (18 μm) are sequentially formed. A laminated adhesive film for metal terminals was produced. When the thermal contraction rate was measured about the obtained adhesive film for metal terminals, it showed a high value of 88.1%.

(Example 6)
As the polypropylene layer, an unstretched polypropylene film (CPP, total thickness 60 μm, melting peak temperature 159 ° C.) of a block polypropylene layer (60 μm) was prepared. Next, maleic anhydride-modified polypropylene is laminated on both sides of the unstretched polypropylene film by extrusion lamination, and the acid-modified polypropylene layer (20 μm) / polypropylene layer (60 μm) / acid-modified polypropylene layer (20 μm) are sequentially formed. A laminated adhesive film for metal terminals was produced. About the obtained adhesive film for metal terminals, when the heat shrinkage rate was measured, it showed a high value of 81.7%.

(Example 7)
As a polypropylene layer, a three-layer unstretched polypropylene film (CPP, total thickness 30 μm, melting peak temperature 155) in which a random polypropylene layer (4 μm) / block polypropylene layer (22 μm) / random polypropylene layer (4 μm) are sequentially laminated. ° C) was prepared. Next, a metal in which maleic anhydride-modified polypropylene is laminated on both surfaces of an unstretched polypropylene film by extrusion lamination, and an acid-modified polypropylene layer (16 μm) / polypropylene layer (30 μm) / acid-modified polypropylene (16 μm) is laminated. An adhesive film for terminals was produced. When the thermal contraction rate was measured about the obtained adhesive film for metal terminals, it showed a high value of 88.7%.

(Comparative Example 1)
As a polypropylene layer, a three-layer unstretched polypropylene film (CPP, total thickness 30 μm, melting peak temperature 155) in which a random polypropylene layer (4 μm) / block polypropylene layer (22 μm) / random polypropylene layer (4 μm) are sequentially laminated. ° C) was prepared. Next, maleic anhydride-modified polypropylene is laminated on both sides of the unstretched polypropylene film by extrusion lamination, and the acid-modified polypropylene layer (35 μm) / polypropylene layer (30 μm) / acid-modified polypropylene layer (35 μm) are sequentially formed. A laminated adhesive film for metal terminals was produced.

(Comparative Example 2)
As a polypropylene layer, an unstretched polypropylene film (CPP, total thickness 25 μm, melting peak temperature 155) having a three-layer structure in which a random polypropylene layer (3 μm) / block polypropylene layer (3 μm) / random polypropylene layer (19 μm) are sequentially laminated. ° C) was prepared. Next, maleic anhydride-modified polypropylene is laminated on one side of the unstretched polypropylene film by extrusion lamination to produce an adhesive film for metal terminals in which an acid-modified polypropylene layer (41 μm) / polypropylene layer (25 μm) is laminated. did.

(Comparative Example 3)
As the polypropylene layer, an oriented polypropylene film (OPP, homopolypropylene, thickness 50 μm, melting peak temperature 165 ° C.) was prepared. Next, maleic anhydride-modified polypropylene is laminated on both sides of the stretched polypropylene film by extrusion lamination, and an acid-modified polypropylene layer (25 μm) / polypropylene layer (50 μm) / acid-modified polypropylene layer (25 μm) are sequentially laminated. An adhesive film for a metal terminal was manufactured.

When the cross sections of the unstretched polypropylene layers used in Examples 1 to 5 and Comparative Examples 1 and 2 were stained with ruthenium tetroxide (RuO ₄ ) and a scanning electron micrograph was observed, a sea-island structure was observed. On the other hand, when the stretched polypropylene layer used in Comparative Example 3 was observed in the same manner, the sea-island structure was not observed.

(Manufacture of packaging materials)
An aluminum foil (thickness 40 μm) was prepared by chemical conversion treatment (phosphoric acid chromate treatment) on both sides with a chemical conversion treatment solution composed of a phenol resin, a chromium fluoride (trivalent) compound, and phosphoric acid. Next, one surface of this aluminum foil and a biaxially stretched nylon film (thickness 25 μm) were laminated via a urethane adhesive. Next, the other surface of the aluminum foil and an unstretched polypropylene film (thickness 30 μm) are sandwich-laminated with an acid-modified polypropylene resin (thickness 15 μm, polypropylene graft-modified with unsaturated carboxylic acid), and the acid-modified polypropylene is heated with hot air. Packaging in which biaxially stretched nylon film (25 μm) / aluminum foil (thickness 40 μm) / acid-modified polypropylene resin (thickness 15 μm) / unstretched polypropylene film (15 μm) are laminated in order by heating to a temperature above the softening point of the resin The material was manufactured. Using the obtained packaging material, the above-described seal strength was measured.

  In Table 1, PP means polypropylene and PPa means acid-modified polypropylene.

  As shown in Table 1, it is composed of a laminate comprising at least one polypropylene layer and at least one acid-modified polypropylene layer, and the acid-modified polypropylene layer is at least one surface of the adhesive film for metal terminals. When the cross section of the polypropylene layer is observed with a scanning electron micrograph, the sea-island structure is observed. Further, when the total thickness of the acid-modified polypropylene layer is 1, the polypropylene layer As for the adhesive film for metal terminals of Examples 1 to 5 in which the total thickness is within the range of 0.7 to 3.5, the sealing strength (that is, the adhesion) between the packaging material and the metal terminals is all. It can be seen that it is high and also excellent in resistance to electrolyte. On the other hand, although the polypropylene layer has the above-mentioned sea-island structure, the total thickness of the polypropylene layer is outside the range of 0.7 to 3.5 when the total thickness of the acid-modified polypropylene layer is 1. The adhesive films for metal terminals of Examples 1 and 2 were inferior in adhesion to the packaging material and the metal terminals. In addition, for the adhesive film for metal terminals of Comparative Example 3 that satisfies the above range but does not have the above-mentioned sea-island structure in the polypropylene layer, the adhesiveness to the packaging material and the metal terminals and the electrolytic solution resistance It was inferior to. Moreover, in Examples 1-7, when the island part area was measured by binarization for the sea-island structure of the polypropylene layer, each had a large value of 28.0% or more, and the acid-modified polypropylene layer Also had a large value of 24.5% or more. On the other hand, in Comparative Example 3, when the island area was measured by binarization for the sea-island structure of the polypropylene layer, the ratio of the area was a very low value of 1.57%, substantially having a sea-island structure. It was confirmed that they did not.

DESCRIPTION OF SYMBOLS 1 Adhesive film for metal terminals 2 Metal terminal 3 Packaging material 3a Peripheral part 4 of packaging material Battery element 10 Battery 11 Polypropylene layer 12 Acid-modified polypropylene layer 31 Base material layer 32 Adhesive layer 33 Barrier layer 34 Heat-fusible resin layer 35 Adhesive layer P Center S Heat-sealed part

Claims (11)

An adhesive film for metal terminals interposed between a metal terminal electrically connected to the electrode of the battery element and a packaging material for sealing the battery element,
The adhesive film for metal terminals is composed of a laminate comprising at least one polypropylene layer and at least one acid-modified polypropylene layer,
The acid-modified polypropylene layer constitutes a surface layer on at least one side of the adhesive film for metal terminals,
The polypropylene layer has a sea-island structure observed when the cross section is observed with an electron micrograph,
When the total thickness of the acid-modified polypropylene layer is 1, the total thickness of the polypropylene layer is in the range of 0.7 to 3.5,
The polypropylene layer has a laminated structure in which a layer made of random polypropylene, a layer made of block polypropylene, and a layer made of random polypropylene are laminated in this order. the film. An adhesive film for metal terminals interposed between a metal terminal electrically connected to the electrode of the battery element and a packaging material for sealing the battery element,
The adhesive film for metal terminals is composed of a laminate comprising at least one polypropylene layer and at least one acid-modified polypropylene layer,
The acid-modified polypropylene layer constitutes a surface layer on at least one side of the adhesive film for metal terminals,
The polypropylene layer has a sea-island structure observed when the cross section is observed with an electron micrograph,
When the total thickness of the acid-modified polypropylene layer is 1, the total thickness of the polypropylene layer is in the range of 0.7 to 3.5,
An adhesive film for metal terminals in which a melting peak is observed in a range of 150 ° C. or more and 165 ° C. or less when the adhesive film for metal terminals is measured with a differential scanning calorimeter. An adhesive film for metal terminals interposed between a metal terminal electrically connected to the electrode of the battery element and a packaging material for sealing the battery element,
The adhesive film for metal terminals is composed of a laminate comprising at least one polypropylene layer and at least one acid-modified polypropylene layer,
The acid-modified polypropylene layer constitutes a surface layer on at least one side of the adhesive film for metal terminals,
The polypropylene layer has a sea-island structure observed when the cross section is observed with an electron micrograph,
When the total thickness of the acid-modified polypropylene layer is 1, the total thickness of the polypropylene layer is in the range of 0.7 to 3.5,
The adhesive film for metal terminals, wherein the residual thickness ratio of the adhesive film for metal terminals is 50% or more as measured by the following measurement method.
An aluminum plate having a thickness of 100 μm and the adhesive film for metal terminals are prepared.
The thickness A (μm) of the adhesive film for metal terminals is measured.
The adhesive film for metal terminals is overlapped on a central portion of the aluminum plate so that the length direction and the width direction of the aluminum plate and the adhesive film for metal terminals coincide with each other.
Two metal plates with a width of 7 mm longer than the length of the aluminum plate are prepared, and the temperature is measured from above and below the aluminum plate and the metal terminal adhesive film so as to cover the entire surface of the metal terminal adhesive film. The metal plate is heated and pressurized under the conditions of 190 ° C., surface pressure of 1.27 MPa, and time of 3 seconds to obtain a laminate of the aluminum plate and the metal terminal adhesive film.
The thickness B (μm) of the portion where the laminate is heated and pressed is measured.
The thickness residual ratio of the adhesive film for metal terminals is calculated by the following formula.
Residual thickness of metal terminal adhesive film (%) = (thickness B-100) / thickness A × 100 An adhesive film for metal terminals interposed between a metal terminal electrically connected to the electrode of the battery element and a packaging material for sealing the battery element,
The adhesive film for metal terminals is composed of a laminate comprising at least one polypropylene layer and at least one acid-modified polypropylene layer,
The acid-modified polypropylene layer constitutes a surface layer on at least one side of the adhesive film for metal terminals,
The polypropylene layer has a sea-island structure observed when the cross section is observed with an electron micrograph,
When the total thickness of the acid-modified polypropylene layer is 1, the total thickness of the polypropylene layer is in the range of 0.7 to 3.5,
The adhesive film for metal terminals, wherein the heat shrinkage rate in the flow direction of the adhesive film for metal terminals is 70 to 90%. The entire polypropylene layer is constituted by an unstretched polypropylene adhesive film for a metal terminal according to claim 1.   The said polypropylene layer has a laminated structure by which the layer comprised by the random polypropylene, the layer comprised by the block polypropylene, and the layer comprised by the random polypropylene were laminated | stacked in this order. The adhesive film for metal terminals according to any one of the above. The metal adhesive film terminals when measured by differential scanning calorimetry, the melting peak in the range of 0.99 ° C. or higher 165 ° C. or less is observed, the metal according to any one of claims 1,3,4～ 6 Adhesive film for terminals. The adhesive film for metal terminals according to any one of claims 1, 2, 4 to 7 , wherein the residual thickness ratio of the adhesive film for metal terminals, measured by the following measurement method, is 50% or more. .
An aluminum plate having a thickness of 100 μm and the adhesive film for metal terminals are prepared.
The thickness A (μm) of the adhesive film for metal terminals is measured.
The adhesive film for metal terminals is overlapped on a central portion of the aluminum plate so that the length direction and the width direction of the aluminum plate and the adhesive film for metal terminals coincide with each other.
Two metal plates with a width of 7 mm longer than the length of the aluminum plate are prepared, and the temperature is measured from above and below the aluminum plate and the metal terminal adhesive film so as to cover the entire surface of the metal terminal adhesive film. The metal plate is heated and pressurized under the conditions of 190 ° C., surface pressure of 1.27 MPa, and time of 3 seconds to obtain a laminate of the aluminum plate and the metal terminal adhesive film.
The thickness B (μm) of the portion where the laminate is heated and pressed is measured.
The thickness residual ratio of the adhesive film for metal terminals is calculated by the following formula.
Residual thickness of metal terminal adhesive film (%) = (thickness B-100) / thickness A × 100 The adhesive film for metal terminals according to any one of claims 1 to 3, 5 to 8 , wherein a heat shrinkage rate in the flow direction of the adhesive film for metal terminals is 70 to 90%. The packaging material is composed of a laminate including at least a base material layer, a barrier layer, and a heat-fusible resin layer in this order,
The metal terminal for adhesive film is interposed, the adhesive film for a metal terminal according to any one of claims 1 to 9 between the metal terminal and the heat-fusible resin layer. A battery element including at least a positive electrode, a negative electrode, and an electrolyte, a packaging material that seals the battery element, and a metal terminal that is electrically connected to each of the positive electrode and the negative electrode and protrudes outside the packaging material A battery comprising:
A battery in which the adhesive film for a metal terminal according to any one of claims 1 to 10 is interposed between the metal terminal and the packaging material.

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