JP2001006632A - Packaging material for battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a packaging material for battery capable of manufacturing a battery vessel consisting of a soft packaging sack having extremely excellent characteristics to sustain practical use using a barrier functioning material having excellent traits including the water vapor barrier and/or oxygen gas barrier functions, resistance against electrolytic solution, etc., and also using a plastic film and/or any other material which are laminated in layers by the dry laminate method, extrusion laminate method, or the like. SOLUTION: A packaging material for a battery is composed of at least a base layer 1, barrier functioning layer 2 and a heat seal layer 3, or otherwise, such layers plus an intermediate layer, wherein the barrier functioning layer 2 should consist of an evaporative attachment film of inorganic oxide and a coating film made of a composition of polymeride/condensate produced through hydrolysis of silicon compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a packaging material for a battery, and more particularly, to a lithium ion secondary battery, particularly a solid electrolyte, which is excellent in water vapor barrier properties, oxygen gas barrier properties, electrolyte resistance and the like. The present invention relates to a battery packaging material useful for producing a battery container such as a polymer battery.

[0002]

2. Description of the Related Art In recent years, as electronic devices have become smaller, lighter and more portable, batteries used for them have also been required to have higher capacity, lighter weight, smaller size, more portable devices, and the like. Is growing. In particular, there is a strong demand for lithium secondary batteries.For example, metal cans and the like have conventionally been used as battery containers in order to achieve weight reduction of battery containers. Instead, it has been proposed to use a plastic film or the like and use a soft packaging bag or the like made of a packaging material having a multilayer structure. In order to use a soft packaging bag made of a packaging material such as a plastic film as a battery container for a lithium secondary battery or the like, the packaging material constituting the battery container is particularly required to have a water vapor barrier property and an oxygen gas barrier property. It is excellent in various conditions such as resistance to electrolytes and the like, and cannot be put to practical use unless the characteristics are sufficiently satisfied.
By the way, in order to satisfy the above conditions, in addition to a plastic film, etc., a barrier material having excellent properties such as water vapor barrier properties, oxygen gas barrier properties, and electrolytic solution resistance, etc. It is laminated by dry laminating method or extrusion laminating method, and is laminated to form a packaging material.The packaging material is formed into a bag or box, and is used as a battery container. It manufactures packaging bags. At present, as a barrier material that satisfies the above-mentioned conditions in a packaging material constituting a battery container, the solution is generally achieved by using aluminum foil. It is. In addition, as a material having an excellent barrier property, for example, it has been proposed to use a resin film having an excellent gas barrier property such as polyvinylidene chloride resin or polyvinyl alcohol or an ethylene-vinyl alcohol copolymer. I have. Further, in recent years, as a material having excellent gas barrier properties, for example, using a physical vapor deposition method such as a vacuum vapor deposition method, or a chemical vapor deposition method such as a low-temperature plasma chemical vapor deposition method or the like, silicon oxide, aluminum oxide, etc. It has been proposed to use a gas barrier film composed of an inorganic oxide vapor-deposited film.

[0003]

However, when the above-mentioned aluminum foil is used as a barrier material, the aluminum foil is extremely excellent in gas barrier properties and the like, but the corrosion and collection of the aluminum foil due to the generation of pinholes and the like. There is a problem such as elution of the aluminum foil due to the contact between the conductor and the aluminum foil, and further, there is a problem that the disposal treatment after use is not suitable for environmental protection. In the case of a barrier material made of a resin film such as the polyvinylidene chloride resin described above, if the battery container is disposed of by incineration after use, harmful substances such as chlorine gas are generated, and the environment is environmentally friendly. In addition, the gas barrier property is not always sufficient, and is not suitable when a high gas barrier property is required. Further, in the case of a barrier material composed of a resin film such as a polyvinyl alcohol or an ethylene-vinyl alcohol copolymer, it has relatively excellent gas barrier properties under absolute dry conditions, but has a water vapor gas barrier property. However, it is not sufficient, and the oxygen gas barrier property is remarkably deteriorated under the humidity condition. Therefore, there is a problem in practical use as a gas barrier material. In addition, in recent years, a gas barrier film composed of a deposited film of an inorganic oxide, which has attracted attention as a barrier material, is formed by stacking inorganic oxide particles, and because the film necessarily includes a defect structure, The gas barrier properties are limited, and the glassy film structure is inferior in bending resistance, causing cracks and the like in the film easily due to mechanical stress, etc., and the gas barrier properties are significantly deteriorated. It is pointed out. For this reason, in the gas barrier film composed of the above-mentioned inorganic oxide vapor-deposited film, the gas barrier film composed of a multi-stage vapor-deposited film composed of two or more layers, or the vapor deposition of the above-described inorganic oxide, using a multi-stage vapor deposition method or the like. A gas barrier film composed of a composite film composed of a film and the above-mentioned resin film having excellent gas barrier properties has also been proposed, but it is a fact that this cannot be said to be sufficiently satisfactory. . Therefore, the present invention uses a barrier material having excellent properties in various conditions such as water vapor barrier property, oxygen gas barrier property, and electrolytic solution resistance, and uses this with a plastic film and other materials. Provided is a useful battery packaging material which can be laminated by a dry lamination method or an extrusion lamination method, multilayered, and capable of producing a battery container comprising a soft packaging bag having extremely excellent properties that can withstand practical use. It is.

[0004]

Means for Solving the Problems The present inventor has conducted various studies on a battery packaging material to solve the above problems, and as a result, at least a base material layer, a barrier layer,
In a heat-sealing layer, or at least a base material layer, a barrier layer, an intermediate layer, and a battery packaging material comprising a heat-sealing layer, the barrier properties constituting the above-mentioned barrier layer As a material, a core of a composition comprising a deposited film of an inorganic oxide and a polycondensate obtained by hydrolysis of a silicon compound is used.
And a plastic film or the like, for example, by a dry laminating method or an extruding laminating method, to produce a packaging material for a battery. By using the battery packaging material, the heat-sealing layers are overlapped with each other facing each other, and heat-sealing ends of the three outer peripheries to produce a soft packaging bag. When a battery was manufactured by using as a battery container, water vapor barrier property, oxygen gas barrier property,
Manufactures battery containers consisting of flexible packaging bags that have excellent properties in various conditions such as electrolyte resistance, have no peeling phenomenon between layers, etc., have excellent durability, etc., and have extremely excellent properties that can withstand practical use. The present invention has been completed by finding out what can be done.

That is, the present invention provides at least a substrate layer, a barrier layer, and a heat-sealing layer,
In a battery packaging material comprising at least a substrate layer, a barrier layer, an intermediate layer, and a heat-sealing layer, as the barrier layer, a vapor-deposited inorganic oxide film and hydrolysis of a silicon compound are used. The present invention relates to a packaging material for batteries, characterized by using a barrier layer consisting of two layers with a coating film made of a composition consisting of a polycondensate of the above.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The above-mentioned present invention will be described below in more detail with reference to the drawings and the like. In the present invention, a sheet means any of a sheet-like material and a film-like material.
This means any of a film-like material and a sheet-like material. The layer configuration of the battery packaging material according to the present invention will be described more specifically with reference to drawings and the like. FIGS. 1 and 2 illustrate a few examples of the layer configuration of the battery packaging material according to the present invention. FIG. 3 and FIG. 4 illustrate an example of a battery using a battery container comprising a soft packaging bag manufactured using the battery packaging material according to the present invention shown in FIG. FIG.

First, the packaging material A for a battery according to the present invention.
As shown in FIG. 1, in a battery packaging material 4 comprising at least a base material layer 1, a barrier layer 2, and a heat-sealing layer 3, an inorganic oxide It has a basic structure of a structure using a barrier layer 7 composed of two layers, a deposited film 5 of a product and a coating film 6 of a composition composed of a polycondensate obtained by hydrolysis of a silicon compound. is there. Further, as another example of the battery packaging material according to the present invention, as shown in FIG. 2, as shown in FIG. 2, at least the base material layer 1a, the barrier layer 2a, the intermediate layer 8, and the heat sealing property. In the battery packaging material 4a composed of the layer 3a, the barrier layer 2a is composed of a deposited film 5a of an inorganic oxide and a coating film 6a of a composition composed of a polycondensate obtained by hydrolysis of a silicon compound. mention may be made of a battery packaging material a ₁ having the structure using the barrier layer 7a formed of the layer. The above-mentioned examples illustrate only 12 examples of the packaging material for a battery according to the present invention, and it is needless to say that the present invention is not limited thereto. For example, although not shown, in the present invention, the battery packaging material according to the present invention is not only a material having the above-described layer constitution, but also, if necessary, for strength reinforcement and other purposes. A material such as a plastic film and other materials can be arbitrarily combined and laminated. Further, for example, although not illustrated, in the present invention, the inorganic oxide deposited film includes not only a single-layer film composed of one layer of the inorganic oxide deposited film but also two or more inorganic oxide deposited films. Any one of a multi-layered film and a composite film composed of two or more layers of different types of inorganic oxide vapor-deposited films can be used.

Next, in the present invention, an example of a battery container made of the flexible packaging bag manufactured using the battery packaging material according to the present invention will be described with reference to FIG.
In the example using the battery packaging material A according to the present invention shown in FIG. 3, as shown in FIG. 3, a pair of battery packaging materials A according to the present invention shown in FIG. The battery packaging materials A, A according to the present invention are
The sealable layers 3 and 3 are superposed on each other with their surfaces facing each other, and then heat sealing is performed on the three peripheral edges, and heat seal portions 9, 9 and 9 are formed on the three sides. An opening 10 is formed on one side above the opening, and a soft packaging bag 11 is manufactured. Thus, in the present invention, as shown in FIG. 4, the soft packaging bag 11 produced above is used as a battery container 12, and the upper opening 10 of the battery container 12 made of the soft packaging bag 11 is used. (Shown in FIG. 3) from the battery power generation element 13
Then, the upper opening 10 is heat-sealed to form an upper heat-sealing portion 14 for use in the soft packaging manufactured using the battery packaging material 4 according to the present invention. A battery 15 using a battery container 12 composed of a bag 11 can be manufactured. In FIG. 4, 16
Represents a positive electrode terminal, and 17 represents a negative electrode terminal. The above examples illustrate one example of a battery using a battery container formed of a soft packaging bag manufactured using the battery packaging material according to the present invention, and the present invention is not limited thereto. is not. For example, although not shown, using the battery packaging material shown in FIG. 2 above, and using a battery container made of a soft packaging bag manufactured using the battery packaging material according to the present invention in the same manner as above It is possible to manufacture a battery with a reduced capacity. Further, although not shown, as the form of the battery container formed of the soft packaging bag manufactured using the battery packaging material according to the present invention, battery containers having various forms can be manufactured. For example, various packaging forms such as a two-sided heat seal type flexible packaging bag, a pillow type flexible packaging bag, a vacuum or pressure-formed tray type container, and the like can be adopted.

Next, in the present invention, the material constituting the battery packaging material according to the present invention, the manufacturing method thereof, and the like will be described in more detail. First, the barrier layer constituting the battery packaging material according to the present invention is formed. To explain the deposited film of the inorganic oxide to be described, as the deposited film of the inorganic oxide, for example, physical vapor deposition, or chemical vapor deposition, or a combination thereof, the inorganic oxide Manufacturing by forming a single-layer film consisting of one layer of a vapor-deposited film, a multilayer film consisting of two or more layers of an inorganic oxide vapor-deposited film, or a composite film consisting of two or more layers of different kinds of inorganic oxide-deposited films Is what you can do. The vapor-deposited film of the inorganic oxide by the physical vapor deposition method described above will be described in more detail. Physical vapor deposition method such as ion cluster beam method (Physical Vapor Deposition)
n method, PVD method) can be used to form a deposited film of an inorganic oxide. In the present invention, specifically, a metal oxide is used as a raw material, and this is heated and vapor-deposited on a plastic sheet, or a metal or a metal oxide is used as a raw material and oxygen is used. A vapor-deposited film can be formed by an oxidation reaction vapor deposition method of introducing and oxidizing and depositing on a plastic sheet, and a plasma-assisted oxidation reaction vapor deposition method of promoting an oxidation reaction by plasma.
In the above, as a heating method of the deposition material, for example,
Resistance heating method, high frequency induction heating method, electron beam
This can be performed by a system heating method (EB) or the like.

In the present invention, a specific example of a method for forming a thin film of an inorganic oxide by physical vapor deposition is shown in FIG. 5. FIG. 5 is a schematic structural diagram showing an example of a roll-up type vacuum evaporation apparatus. It is. As shown in FIG. 5, a plastic sheet 1 unwound from an unwinding roll 23 in a vacuum chamber 22 of a winding-type vacuum evaporation apparatus 21 includes:
It is guided to a cooled coating drum 26 via guide rollers 24 and 25. Thus, the plastic sheet guided on the cooled coating drum 26 can be used.
The evaporation source 28 heated by the crucible 27, for example, metal aluminum or aluminum oxide, is evaporated on the plate 1, and, if necessary, oxygen gas or the like is ejected from an oxygen gas outlet 29. While supplying the mask 3
Through 0 and 30, for example, a deposited film of an inorganic oxide such as aluminum oxide is formed, and then, in the above, the plastic sheet 1 on which a deposited film of an inorganic oxide such as aluminum oxide is formed is formed. , Guide roll 25 ', 2
By feeding the film through 4 'and winding it on a take-up roll 31, an inorganic oxide vapor-deposited film can be formed by physical vapor deposition according to the present invention. In the present invention, first, a first-layer inorganic oxide vapor-deposited film is formed using the above-mentioned roll-up type vacuum vapor-deposition apparatus,
Next, in the same manner, a vapor-deposited film of an inorganic oxide is further formed on the vapor-deposited film of the inorganic oxide, or the film is formed in a continuous manner using a roll-up vacuum vapor deposition apparatus as described above. By continuously forming a vapor-deposited film of an inorganic oxide, a vapor-deposited film of an inorganic oxide composed of a multilayer film of two or more layers can be formed.

In the above description, as the inorganic oxide deposited film, basically any thin film on which a metal oxide is deposited can be used. For example, silicon (Si), aluminum (Al), magnesium (Mg) , Calcium (C
a), potassium (K), tin (Sn), sodium (N
a), a vapor-deposited film of an oxide of a metal such as boron (B), titanium (Ti), lead (Pb), zirconium (Zr), and yttrium (Y) can be used. Thus, preferred are silicon (Si), aluminum (A
1) and the like.
Thus, the above-mentioned vapor-deposited film of a metal oxide can be referred to as a metal oxide, such as silicon oxide, aluminum oxide, and magnesium oxide. The notation is, for example, SiO _x , AlO _x MO such as MgO _X
X (wherein, M represents a metal element, and the value of X is
The range differs depending on the metal element. ). The range of the value of X is silicon (S
i) is 0-2, and aluminum (Al) is 0-1.
5. Magnesium (Mg) is 0-1, calcium (C
a) is 0-1, potassium (K) is 0-0.5, tin (Sn) is 0-2, and sodium (Na) is 0-0.
5, boron (B) is 0-1,5, titanium (Ti) is
0-2, lead (Pb): 0-1, zirconium (Zr)
Can have a value in the range of 0 to 2 and yttrium (Y) can have a value in the range of 0 to 1.5. In the above, when X = 0,
It is a perfect metal, is not transparent and cannot be used at all, and the upper end of the range of X is a fully oxidized value. In the present invention, generally, except for silicon (Si) and aluminum (Al), examples used are scarce. Silicon (Si) is 1.0 to 2.0, aluminum (A)
For l), a value in the range of 0.5 to 1.5 can be used. In the present invention, the thickness of the above-mentioned inorganic oxide vapor-deposited film varies depending on the type of the metal used or the metal oxide.
It is desirable to arbitrarily select and form it within the range of about 00 °, preferably about 100 to 1000 °. Further, in the present invention, as the deposited metal film of the inorganic oxide, the metal to be used, or as the oxide of the metal, used in one kind or a mixture of two or more kinds, and the inorganic oxide mixed with different materials is used. A vapor deposition film can also be formed.

Next, in the present invention, the vapor-deposited inorganic oxide film formed by the above-mentioned chemical vapor deposition method will be further described. Chemical vapor deposition (Ch) such as vapor deposition, thermochemical vapor deposition, photochemical vapor deposition, etc.
electrical Vapor Deposition method,
A deposited film of an inorganic oxide can be formed by using a CVD method or the like. In the present invention, specifically, a monomer gas for vapor deposition such as an organic silicon compound is used as a raw material on one surface of a plastic sheet, and an inert gas such as an argon gas or a helium gas is used as a carrier gas. Use, and
A vapor-deposited film of an inorganic oxide such as silicon oxide can be formed by using a low-temperature plasma-enhanced chemical vapor deposition method using an oxygen gas or the like as an oxygen supply gas and a low-temperature plasma generator or the like. In the above, as the low-temperature plasma generator, for example, a generator such as a high-frequency plasma, a pulse wave plasma, or a microwave plasma can be used. Thus, in the present invention, a highly active and stable plasma is obtained. For this purpose, it is desirable to use a generator using a high-frequency plasma method.

More specifically, an example of a method of forming a deposited film of an inorganic oxide by the above-described low-temperature plasma chemical vapor deposition method will be described. FIG. FIG. 1 is a schematic configuration diagram of a low-temperature plasma chemical vapor deposition apparatus showing an outline of a method of forming an oxide deposition film. As shown in FIG. 6, in the present invention, the vacuum chamber of the plasma enhanced chemical vapor deposition apparatus 41 is used.
The plastic sheet 1 is unwound from an unwinding roll 43 disposed in the inside of the plastic sheet 1 and the plastic sheet 1 is further fed.
Is transported on the peripheral surface of the cooling / electrode drum 45 at a predetermined speed via the auxiliary roll 44. In the present invention, oxygen gas, an inert gas, a monomer gas for vapor deposition such as an organic silicon compound, and the like are supplied from the gas supply devices 46 and 47 and the raw material volatile supply device 48 and the like. While adjusting the gas mixture composition for vapor deposition, the gas mixture composition for vapor deposition was introduced into the vacuum chamber 42 through the raw material supply nozzle 49, and the above-mentioned cooling / electrode drum 45
Plasma is generated by the glow discharge plasma 50 on the plastic sheet 1 conveyed on the peripheral surface, and the plasma is irradiated to form a deposited film of an inorganic oxide such as silicon oxide, thereby forming a film. I do. In the present invention, at that time,
A predetermined power is applied to the electrode drum 45 from a power source 51 disposed outside the chamber, and a magnet 52 is disposed near the cooling / electrode drum 45 to promote generation of plasma. Then, a plastic screen on which a deposited film of an inorganic oxide such as silicon oxide is formed as described above.
The roll 1 can be wound on a winding roll 54 via an auxiliary roll 53 to produce a deposited film of an inorganic oxide by a plasma enhanced chemical vapor deposition method according to the present invention. In the figure, 55 represents a vacuum pump. The above exemplification is merely an example, and it goes without saying that the present invention is not limited thereby. Although not shown, in the present invention, the inorganic oxide deposited film is not limited to one layer of the inorganic oxide deposited film, but may be a multilayer film in which two or more layers are stacked. The materials may be used alone or as a mixture of two or more types, and a vapor-deposited film of an inorganic oxide mixed with different materials may be used. In the present invention, a low-temperature plasma-enhanced chemical vapor deposition apparatus as described above is used to first form a first layer of an inorganic oxide vapor-deposited film. On the film, an inorganic oxide vapor-deposited film is further formed, or by using a low-temperature plasma-enhanced chemical vapor deposition apparatus as described above, this is connected in series, and the inorganic oxide is continuously formed. By forming a vapor deposition film of above, a vapor deposition film of an inorganic oxide composed of a multilayer film of two or more layers can be formed.

In the above description, as a monomer gas for vapor deposition of an organic silicon compound or the like which forms a vapor deposition film of an inorganic oxide such as silicon oxide, for example, 1.1.3.3-tetramethyldisiloxane, hexamethyldisiloxane Siloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane,
Phenyltrimethoxysilane, methyltriethoxysilane, octamethylcyclotetrasiloxane, and the like can be used. In the present invention, among the organic silicon compounds as described above, the use of 1.1.3.3-tetramethyldisiloxane or hexamethyldisiloxane as a raw material is advantageous in terms of handleability and formed deposited film. It is a particularly preferable raw material in view of its properties and the like. In the above, for example, an argon gas, a helium gas, or the like can be used as the inert gas.

In the present invention, in the silicon oxide deposited film formed above, a monomer gas such as an organic silicon compound and an oxygen gas are chemically reacted, and the reaction product is closely adhered to the plastic sheet. wear, and dense, it is possible to form a thin film rich in flexibility or the like, usually, the general formula SiO _X (where
X represents a number from 0 to 2), and is a continuous vapor-deposited film mainly composed of silicon oxide. Thus, the above silicon oxide vapor-deposited film is represented by the general formula SiO _X (where X represents a number from 1.3 to 1.9) in terms of transparency, barrier properties, and the like. It is preferably a thin film mainly composed of a deposited silicon oxide film. In the above, the value of X changes depending on the molar ratio of the monomer gas to the oxygen gas, the energy of the plasma, etc. In general, the gas permeability decreases as the value of X decreases, but the film itself has It has a yellow color and poor transparency. Further, the above-described deposited film of silicon oxide has silicon (Si) and oxygen (O) as essential constituent elements, and furthermore, one of carbon (C) and hydrogen (H), or both elements Consisting of a deposited film of silicon oxide containing as a trace constituent element, and having a thickness of 50 °
In the range of 500 °, the composition ratio of the essential constituent elements and the trace constituent elements is continuously changed in the film thickness direction. Further, when the silicon oxide vapor-deposited film contains a compound composed of carbon, the content of carbon is reduced in the depth direction of the film thickness. Thus, in the present invention, the above-mentioned deposited film of silicon oxide is, for example, an X-ray photoelectron spectrometer (Xray Photoelectron Spe)
troscopy, XPS), secondary ion mass spectrometer (Secondary Ion Mass Spec)
The above physical properties are confirmed by performing elemental analysis of the deposited silicon oxide film using a method of performing ion etching in the depth direction or the like using a surface analysis device such as Troscopy (SIMS). can do. In the present invention, the thickness of the deposited silicon oxide film is desirably about 50 to 2000 °, and specifically, the thickness is 100 to 1000.
Å is desirable, so in the above, 1000Å,
Further, if the thickness is more than 2000 °, cracks and the like are likely to occur in the film, which is not preferable.
If it is less than 50 °, it is not preferable because it is difficult to exhibit the barrier effect. In the above description, the film thickness can be measured by a fundamental parameter method using, for example, a fluorescent X-ray analyzer (model name: RIX2000) manufactured by Rigaku Corporation. Further, in the above, as a means for changing the thickness of the deposited film of silicon oxide, increasing the volume velocity of the deposited film, that is, a method of increasing the amount of the monomer gas and the oxygen gas or the rate of the deposition. It can be performed by a method of slowing down.

In the present invention, as a vapor-deposited film of the inorganic oxide constituting the battery packaging material according to the present invention, for example, different types of inorganic oxide are used by using both physical vapor deposition and chemical vapor deposition. It is also possible to form and use a composite film composed of two or more layers of an oxide deposited film. As a composite film composed of two or more layers of the above-mentioned different inorganic oxide vapor-deposited films, first, a plastic sheet is dense and flexible by chemical vapor deposition on a plastic sheet. An inorganic oxide deposited film capable of relatively preventing the occurrence of cracks is provided, and then an inorganic oxide deposited film formed by physical vapor deposition is provided on the inorganic oxide deposited film to form two layers. It is desirable to form an inorganic oxide vapor-deposited film composed of the above composite film. Of course, in the present invention,
Contrary to the above, an inorganic oxide deposited film is first provided on a plastic sheet by physical vapor deposition, and then dense and flexible by chemical vapor deposition. It is also possible to provide an inorganic oxide vapor deposition film composed of a composite film composed of two or more layers by providing an inorganic oxide vapor deposition film which can relatively prevent the occurrence of cracks.

Next, in the present invention, as a plastic sheet for holding the above-mentioned inorganic oxide vapor-deposited film, basically, when forming an inorganic oxide vapor-deposited film or a coating film, etc. Withstand deposition conditions, coating conditions, etc.
In addition, they have excellent adhesion to the inorganic oxide vapor-deposited film or the coating film and the like, and can be favorably retained without impairing the characteristics of those films. Various resin films or sheets excellent in strength, durability and the like as a material can be used.
Specifically, examples of the film or sheet of the above various resins include polyethylene resin, polypropylene resin, cyclic polyolefin resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile Ru-butadiene-styrene copolymer (ABS resin), polyvinyl chloride resin, fluorine resin, poly (meth) acrylic resin, polycarbonate resin, polyethylene terephthalate, polyethylene naphthalate Polyester resins such as nylon, polyamide resins such as various nylons, polyimide resins, polyamide imide resins, polyaryl phthalate resins, and silicone resins.
Use films or sheets of various resins such as resin, polysulfone resin, polyphenylene sulfide resin, polyethersulfone resin, polyurethane resin, acetal resin, cellulose resin and others. be able to. In the present invention, among the resin films or sheets described above, a fluorine-based resin sheet, a cyclic polyolefin-based resin sheet, and a polycarbonate-based resin sheet are used.
It is preferable to use a poly (meth) acrylic resin sheet, a polyamide resin sheet, or a polyester resin sheet.

In the present invention, as the film or sheet of the above-mentioned various resins, for example, one or more of the above-mentioned various resins are used, and are extruded, cast-molded, T-die-processed, and cut. A method of forming the above various resins alone using a film forming method such as an inflation method, an inflation method, or the like, or a multi-layer coextrusion film forming using two or more kinds of various resins. A film or sheet of various resins is manufactured by a method of forming two or more resins, and a method of mixing and forming a film before forming a film. For example, various resin films or sheets stretched in a uniaxial or biaxial direction using a tenter method or a tuber method can be used. In the present invention, the film thickness of various resin films or sheets is 6 to 300 μm.
And more preferably about 10 to 200 μm.

In the above, one or more of the above-mentioned various resins are used, and when forming the film, for example, the processability, heat resistance, weather resistance, mechanical properties, dimensional stability, Antioxidant, slippery, mold release, flame retardant,
Various plastic compounding agents and additives can be added for the purpose of improving or modifying the antifungal property, electric properties, etc., and the amount of addition can be from a very small amount to several tens%. They can be arbitrarily added according to the purpose.
In the above, common additives include, for example, lubricants, crosslinking agents, antioxidants, ultraviolet absorbers, light stabilizers, fillers, reinforcing agents, reinforcing agents, antistatic agents, flame retardants, flame retardants , A foaming agent, a fungicide, a pigment, and the like can be used, and further, a modifying resin and the like can be used.

In the present invention, the surface of various resin films or sheets may be prepared in advance, if necessary, in order to improve the tight adhesion with an inorganic oxide deposited film or the like.
A desired surface treatment layer can be provided. In the present invention, as the surface treatment layer, for example, a corona discharge treatment, an ozone treatment, a low-temperature plasma treatment using an oxygen gas or a nitrogen gas, a glow discharge treatment, an oxidation treatment using a chemical or the like, Arbitrarily perform pretreatment such as other,
For example, a corona treatment layer, an ozone treatment layer, a plasma treatment layer, an oxidation treatment layer, and the like can be formed and provided. The above-mentioned surface pretreatment may be performed in a separate step, and, for example, in the case of a surface pretreatment such as a low-temperature plasma treatment or a glow discharge treatment, before forming the above-mentioned inorganic oxide vapor-deposited film or the like. The processing can be performed in pre-processing by in-line processing, and in such a case, there is an advantage that the manufacturing cost can be reduced. The above-mentioned surface pretreatment is carried out as a method for improving the tight adhesion between the film or sheet of various resins and the deposited film of the inorganic oxide or the like. As another method, for example, a primer coat agent layer, an undercoat or the like may be previously provided on the surface of various resin films or sheets.
A coating agent layer, an anchor coating agent layer, an adhesive layer, a vapor-deposited anchor coating agent layer, or the like may be arbitrarily formed to be a surface treatment layer. Examples of the coating agent layer of the above pretreatment include polyester resin, polyamide resin, polyurethane resin, epoxy resin, and phenol resin.
Resin, (meth) acrylic resin, polyvinyl acetate resin, polyolefin resin such as polyethylene aliha polypropylene or a copolymer or modified resin thereof,
A resin composition containing a cellulose-based resin or the like as a main component of the vehicle can be used.

Further, in the present invention, the plastic sheet is protected on one side of the above-mentioned plastic sheet against vapor deposition conditions when an inorganic oxide vapor-deposited film is formed, and the like. For example, its yellowing, deterioration or shrinkage, or suppresses cohesive failure or the like in the film surface layer or inner layer, and further, on one surface of the plastic sheet, a deposited film of an inorganic oxide is satisfactorily formed, In addition, in order to improve the tight adhesion between the plastic sheet and the deposited film of the inorganic oxide, etc., one surface of the plastic sheet is
As the surface pretreatment layer, for example, a chemical vapor deposition method (Chemical Vapor Depo) such as the aforementioned plasma chemical vapor deposition method, thermal chemical vapor deposition method, or photochemical vapor deposition method.
or a physical vapor deposition method such as a vacuum evaporation method, a sputtering method, or an ion plating method.
An evaporation-resistant protective film can be provided by forming a vapor-deposited thin film of an inorganic oxide using an evaporation method (PVD method). Note that, in the present invention, the thickness of the deposition-resistant protective film made of silicon oxide or the like is a thin film, and further, a non-barrier film having no barrier property against water vapor gas, oxygen gas, or the like is sufficient. Specifically, the thickness is desirably less than 150 °, specifically, the thickness is about 10 to 100 °, preferably 20 to 100 °.
It is desirable to be at about 80 °, more preferably at about 20 to 60 °. In the above, when the thickness is more than 150 °, specifically, more than 100 °, furthermore, 80 °, further more than 60 °, the deposition conditions and the like become severe, and the plastic seal
Yellowing or deterioration, and furthermore, causing cohesive failure,
It is difficult to form a good deposition-resistant protective film, and it is not preferable because cracks and the like are easily generated in the film. If the thickness is less than 10 °, furthermore, 20 ° or 60 °, the deposition-resistant protective film becomes less. This is not preferable because the function as a protective layer is lost, and it is difficult to achieve the effect.

Next, in the present invention, a coating film made of a composition comprising a polycondensate obtained by hydrolysis of a silicon compound which forms a barrier layer constituting the battery packaging material according to the present invention will be described. In order to form a coating film, first, a silicon compound is used as a main component,
The raw material can be used as such or dissolved in a suitable solvent such as ethanol or isopropanol and contacted with the stoichiometrically necessary water, preferably one or several parts excess of water. Hydrolysis is carried out to prepare a composition comprising a polycondensate obtained by the hydrolysis. The above hydrolysis is generally
-20 to 130C, preferably a temperature of 0C to 30C,
Alternatively, it is preferable to carry out the reaction at the boiling point of the solvent used selectively. In the above, the best method for bringing into contact with water depends on, among other things, the reactivity of the raw materials used. Therefore, for example, the dissolved raw material can be slowly dropped into excess water, or
The water can be added to the raw material in which the water is selectively dissolved at once or in several portions. It is also advantageous to use an organic or inorganic solvent containing water instead of adding water as it is, and to introduce water into the reaction mixture. Often, it is particularly advisable to introduce water into the reaction mixture using adsorbents containing water, for example molecular sieves, and organic solvents containing water, for example ethanol at 30% strength. I know. Further, water can be added by a reaction for forming water, for example, a reaction for forming an ester from an acid and an alcohol. When a solvent is used, ketones, preferably lower dialkyl ketones such as acetone and methyl isobutyl ketone, esters, and preferably diethyl ether, in addition to the above-mentioned effectively usable lower aliphatic alcohols. Suitable are lower dialkyl ethers such as ter, tetrahydrofuran (THF), amides, esters, especially ethyl acetate, dimethylformamide and mixtures thereof.

The polycondensation by hydrolysis can be optionally carried out by adding a catalyst, for example, a compound which releases protons or hydroxyl ions, or amines. Suitable catalysts include organic or inorganic acids such as hydrochloric acid and acetic acid, ammonia, alkali and alkaline earth metal hydroxides, for example, sodium hydroxide, potassium hydroxide, or calcium hydroxide. And organic or inorganic salts, and amines soluble in the reaction medium, such as lower alkylamines or altanolamines. Volatile acids and bases, especially
Hydrochloric acid, ammonia and triethylamine are particularly preferred. The total concentration of the catalyst may be, for example, up to 3 moles per liter. All raw material compounds are hydrolyzed (polycondensation)
It need not be already present at the start, in fact, in certain cases it may be advantageous to bring only some of these compounds into contact with water first and the remaining compounds to be added later. is there. In order to avoid precipitation as much as possible during the polycondensation by hydrolysis, it is preferred to add the water in several stages, for example in three stages. In the first step, for example, one-half to one-tenth of the stoichiometrically required amount of water by hydrolysis is added. After brief stirring, add one-fifth to one-tenth of the stoichiometric amount of water. Add water. The polycondensation time by hydrolysis varies depending on the specific raw material components and their quantitative ratios, the catalyst to be selectively used, the reaction temperature, and the like. Generally, polycondensation by hydrolysis is carried out at atmospheric pressure, but can also be carried out under pressure or under reduced pressure. When the addition of water is completed, the mixture is stirred, preferably for a long time, for example, 2 to 3 hours at room temperature or slightly higher temperature, to prepare a composition comprising a polycondensate obtained by hydrolysis of a silicon compound.

Next, in the present invention, the composition prepared as described above is used, for example, by a floating knife coating method, a knife over roll coating method, an inverted knife coating method, and a square coating method. Roll coat method, reverse roll coat method, roll coat method, gravure roll coat method, kiss roll coat method, air blade coat method, dip coat method Coating methods such as, for example, a flow coating method, a spin coating method, a spray coating method, a bar coating method, a curtain coating method, and others, or gravure printing, offset printing, Using a printing method such as silk screen printing, transfer printing, or the like, apply or print on the surface of the above-described inorganic oxide vapor-deposited film, and then perform drying and further aging treatment. The coating film according to the present invention can be formed. . In the above, the thickness of the coating film is about 0.1 to 75 g / m ² (dry state),
More preferably, it is about 1.0 to 50 g / m ² (dry state).

In the present invention, the co-condensation of a composition comprising a polycondensate obtained by hydrolysis of the silicon compound is performed.
When the heating film is cured by irradiating with thermal means or ionizing radiation, it is preferable to add an initiator or the like in advance to the composition comprising the polycondensate obtained by hydrolysis of the silicon compound. It is. As the initiator, a commercially available photopolymerization reaction initiator can be used.
Examples of these initiators include, for example, Irgacure 185 (1-hydroxycyclohexyl phenyl ketone), Irgacure 500 manufactured by Ciba Geigy, Switzerland.
(1-hydroxycyclohexyl phenyl ketone +
Benzophenone) and other Irgacure-type photoinitiators, Glocur 1173, 1116, 139
6, 1174 and 1020 (Merck, Switzerland);
Benzophenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone,
Benzoin, 4.4'-dimethoxybenzoin, benzoin ethyl ether, benzoin isopropyl
Ether, benzoin dimethyl ether, 1.1.
1-Trichloroacetophenone, diethoxyacetophenone and dibenzosuberone can be used.
Suitable thermal initiators can use, in particular, organic peroxides in the form of diacyl peroxides, peroxydicarbonates, alkyl peresters, dialkyl peroxides, perketals, ketone peroxides and alkyl peroxides. .
As specific and preferred examples of thermal initiators, dibenzoyl peroxide, tert-butyl perbenzoate and azobisisobutyronitrile can be used. Of course, it is also possible to use an initiator for initiating the ionic polymerization reaction. In particular, it includes a group R 'having an epoxy group (eg, glycidyloxypropyltrimethoxysilane),
It has been found that a UV initiator that initiates a cationic polymerization reaction is effective for the compound represented by the general formula (1) described below. In these cases, the curing results with cations under the same conditions are often better than those with free radical initiators. The reaction initiator can be added to the composition in a usual amount, for example, 30 to 50% by weight.
The initiator can be added in an amount of 0.5 to 2% by weight (based on the total amount) in compositions containing solids of

Further, in the present invention, the coating film is cured by drying after coating or printing. The coating film can then be cured in a known manner, either thermally or by irradiation (e.g. using an ultraviolet lamp, laser, etc.), depending on the form of the initiator used. . In the case of a coating film containing a group R 'having an epoxy group to be described later, thermal curing is particularly advantageous. On the other hand, in the case of a coating film containing a group R' having an unsaturated CC bond, It has been found that curing by irradiation is usually more advantageous.

In the present invention, the above silicon
The compound represented by the general formula R'SiR _Three(However, in the formula,
R ′ is stable to hydrolysis, and is heat and / or
R represents an OH group
Represents a group and / or a group susceptible to hydrolysis. )so
Use one or more of the silicon compounds represented
be able to. In the above, the general formula R'SiR_ThreeIn
R ′ represents an epoxy atom group or a C—C double bond
It is preferable that the
You. Specific examples of the above-mentioned group containing an epoxy atom group include:
Is a glycidyloxyalkyl group, especially an alkyl moiety
Is a group having 1 to 4 carbon atoms, and is particularly preferable.
As an example, use the γ-glycidyloxypropyl group.
Can be. In the above, the general formula R'SiR_Three
A group containing an atomic group having a CC double bond,
Is optionally substituted alkenyl and alkynyl
Group, for example, 2 to 20, preferably 2 to 10
Having at least one carbon atom and at least one CC double bond
Straight, side chain or cyclic groups, especially vinyl, 1- and
And 2-propenyl, butenyl, isobutenyl, styrene
And lower alkenyl groups such as propargyl, and
And alkynyl or methacrylic or
It is particularly preferred to use groups containing groups containing
It is a new thing.

Next, in the above, the general formula R'SiR
Examples of R in ₃ include, for example, hydrogen, halogen, alkoxy, hydroxyl, alkynylcarbonyl and the like. In the present invention, particularly preferred specific examples include, for example, methoxy, ethoxy, n- and i-propoxy, n-, sec- and tert-butoxy, isobutoxy, β-methoxyethoxy, acetyloxy, propionyloxy, monomethylamino, Monoethylamino, dimethylamino, diethylamino, N-
Examples include ethylanilino, methylcarbonyl, ethylcarbonyl, methoxycarbonyl, ethoxycarbonyl, and the like. In the present invention, the R group in the general formula R′SiR ₃ is not present in the final product, but is lost by hydrolysis, and the hydrolysis product is immediately or later obtained by an appropriate method. And has no substituent, and produces a low molecular weight hydrolyzate such as lower alcohols such as methanol, ethanol, propanol and butanol. The R groups are particularly preferred.

In the present invention, the silicon compound represented by the general formula R'SiR ₃ may be entirely or partially preliminarily condensed, that is, a part of the silicon compound represented by the general formula R'SiR ₃ Compound generated by the hydrolyzate alone,
Alternatively, it can be used by mixing with another hydrolyzable compound such as an organometallic compound represented by a general formula described below. Such oligomers are preferably soluble in the reaction medium, linear or cyclic, of low molecular weight, having a degree of condensation of, for example, 2-100, in particular about 2-6, partial condensates (poly) It is preferred to use (organosiloxane). In the present invention, the general formula R'S used effectively
Specific examples of the silicon compound represented by iR ₃ include γ
-(Meth) acryloxypropyltrimethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane and vinyltris (β
-Methoxyethoxy) silane, and γ-glycidyloxypropyltrimethoxysilane.

Next, in the present invention, the silicon compound represented by the above general formula R'SiR ₃ is preferably not used alone, but is used generally for forming glass or ceramics. MR _n (wherein, M represents an element selected from silicon, aluminum, titanium, zirconium, vanadium, boron, or tin;
Represents an OH group and / or a group susceptible to hydrolysis, and n represents a valence of a metal element. ) Can be used by mixing one or more of the organometallic compounds represented by the formula (1), and converting these compounds to hydrates of the corresponding oxides by hydrolysis, preferably complete hydrolysis. . In the organometallic compounds represented by the general formula MR _n,
As the metal element, for example, silicon, aluminum, titanium, zirconium, vanadium, boron, tin, and the like can be used. Of course, in the present invention, compounds of other elements not described herein may also be used. Can be. In the organic metal compound represented by the general formula MR _n, as the R, may be the same or different, silicon represented, including the meaning of the preferred embodiment in the general formula R'SiR ₃ described above Compound R in the case of
Can be defined in the same way as In the present invention,
Organometallic compounds represented by the general formula MR _n is a silicon compound represented by the general formula R'SiR ₃ described above, in a molar ratio of 1: 99 to 99: is preferably mixed for use at a ratio of 1 It is possible.

Further, in the present invention, in order to form the coating film according to the present invention, the above-mentioned general formula R'Si
In addition to the silicon compound represented by R ₃ and the organometallic compound represented by the general formula MR _n , one or more resins having a hydrogen bond-forming group are added as a binder component,
They can also be mixed. Examples of the resin having a hydrogen bond forming group include polymers having a hydroxyl group and derivatives thereof, for example, polyvinyl alcohol, polyvinyl acetal, ethylene-vinyl alcohol copolymer, and phenol resin. , A methylol melamine resin or the like and a derivative thereof, a polymer having a carboxyl group and a derivative thereof, for example, a polymer containing a unit of a polymerizable unsaturated acid such as poly (meth) acrylic acid, maleic anhydride, itaconic acid or the like. Coalescing and esterification of these polymers,
For example, homo- or copolymers containing units such as vinyl esters such as vinyl acetate, (meth) acrylates such as methyl methacrylate, polymers having an ether bond,
For example, in addition to polyalkylene oxide, polyoxyalkylene glycol, polyvinyl ether and the like, and polymers having an amide bond such as silicon resin, for example,> N (CO
R) -polyoxazoline or polyalkyleneimine having a bond (wherein R represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent) -Acylated products, polyvinylpyrrolidone having> NC (O) -bonds and derivatives thereof, polyurethane having urethane bonds, polymers having urea bonds, polymers having amide bonds, and the like can be used. Thus,
In the present invention, a resin having a hydrogen bond forming groups mentioned above, to a mixture of an organic metal compound represented by the silicon compound of the general formula MR _n represented by the general formula R'SiR ₃ described above, the weight ratio It is possible to mix and use them at a ratio of 1:99 to 99: 1, preferably at a ratio of 5 to 30.

Next, in the present invention, the base material layer constituting the battery packaging material according to the present invention will be described. Since the base material layer serves as the base material constituting the battery container, weather resistance, Heat resistance, light resistance, water resistance, chemical resistance,
Has various properties such as moisture resistance, stain resistance, insulation properties, moldability, pinhole resistance, etc., and has excellent mechanical, physical or chemical strength, toughness, etc., and is extremely durable. And
In order to protect the battery element, it is necessary to have excellent scratch resistance, shock absorption and the like. Specific examples of the base material layer include a fluorine-based resin, a polyamide-based resin (various nylon resins), a polyester-based resin such as polyethylene terephthalate, a polyethylene-based resin, a polypropylene-based resin, and a cyclic polyolefin. Use films or sheets of various resins such as resin, polystyrene resin, (meth) acrylic resin, polycarbonate resin, acetal resin, cellulose resin, etc. Can be. As the above resin film or sheet, for example, a biaxially stretched resin film or sheet can also be used. Further, in the above resin film or sheet, the film thickness is about 6 to 200 μm, more preferably 10 to 150 μm.
μm is desirable. In the present invention, as the base material layer, two or more resin films or sheets as described above may be laminated and used.

Next, the heat-sealing layer constituting the battery packaging material according to the present invention will be described. The heat-sealing layer is melted by heat and mutually melted. Any material can be used as long as it can be attached, for example, low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear (linear) low-density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene- Ethyl acrylate copolymer, ethylene-
Acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-propylene copolymer, methylpentene polymer, polyethylene, polyolefin resins such as polypropylene, acrylic acid, methacrylic acid, maleic acid,
Films or sheets of resins composed of one or more of resins such as acid-modified polyolefin resins modified with unsaturated carboxylic acids such as maleic anhydride, fumaric acid, itaconic acid, etc. A thin film can be used. The resin film or sheet described above can be used in a single layer or a multilayer,
As a barrier material for oxygen, water vapor and the like, for example, aluminum,
A metal film such as silicon oxide or aluminum oxide, or a vapor-deposited film of an inorganic oxide or the like can also be provided. The thickness of the resin film or sheet is about 5 μm to 300 μm,
Preferably, about 10 μm to 100 μm is desirable.

Next, in the present invention, the intermediate layer constituting the battery packaging material according to the present invention will be described. As the intermediate layer, an insulating resin film or sheet can be used. Furthermore, similarly to the above-mentioned base material layer, it has various properties such as weather resistance, heat resistance, light resistance, water resistance, chemical resistance, moisture resistance, stain resistance, moldability, pinhole resistance, etc. It has excellent mechanical, physical or chemical strength, toughness, etc., is extremely durable, and has excellent scratch resistance, shock absorption, etc. because it protects battery elements. Films or sheets can be used. Specifically, for example, polyamide resins (various nylon resins), polyester resins such as polyethylene terephthalate, polyethylene resins, polypropylene resins, cyclic polyolefin resins, polystyrene resins, polycarbonates Films or sheets of various resins such as a resin, an acetal resin, a cellulose resin, a (meth) acrylic resin, a fluorine resin and others can be used. Film or sheet of the above resin
As the sheet, for example, a biaxially stretched resin film or sheet can be used. In the above resin film or sheet, the film thickness is 6
The thickness is preferably about 200 to 200 μm, more preferably about 10 to 150 μm.

In the present invention, when producing the battery packaging material according to the present invention, its strength, weather resistance,
Other materials, such as low-density polyethylene, medium-density polyethylene, etc., in order to improve various robustness such as scratch resistance, insulation, pinhole resistance, sealing (heat seal), etc. High-density polyethylene, linear low-density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate copolymer, ethylene-
Acrylic acid or methacrylic acid copolymer, methylpentene polymer, polybutene resin, polyvinyl chloride resin, polyvinyl acetate resin, polyvinylidene chloride resin, vinyl chloride-vinylidene chloride copolymer, poly (meth) acryl Resin, polyacrylonitrile resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyester resin, polyamide resin, polycarbonate Resin, polyvinyl alcohol resin, saponified ethylene-vinyl acetate copolymer, fluororesin, diene resin, polyacetal resin, polyurethane resin, nitrocellulose
And any other known resin film or sheet. In the present invention, the above-mentioned film or sheet may be any of unstretched and uniaxially or biaxially stretched. The thickness is arbitrary,
It can be used by selecting from the range of several μm to 300 μm. Further, in the present invention, the film or sheet may be any film such as an extruded film, an inflation film, or a coating film.

Next, in the present invention, a method for producing the packaging material for a battery according to the present invention using the above-mentioned materials will be described. Examples of the production method include laminating with a laminating adhesive. A dry lamination method in which the layers are laminated via an adhesive layer for heat transfer, an extrusion lamination method in which the layers are laminated through a melt-extruded resin layer made of a melt-extruded adhesive resin, or a film or sheet of a heat-meltable resin. It can be performed by a method such as a hot-melt lamination method in which the layers are laminated through an intervening method or the like. In the above, as the adhesive for laminating, for example, a one-part or two-part curing or non-curing type vinyl-based adhesive,
(Meth) acrylic, polyamide, polyester,
Adhesives for laminating such as solvent type, aqueous type, emulsion type and the like such as polyether type, polyurethane type, epoxy type, rubber type and the like can be used.
As the coating method of the above-mentioned adhesive for laminating, for example, a direct gravure roll coating method,
Gravure roll coating, kiss coating, reverse slot
Lucote method, Fonten method, Transfer roll coating
Can be applied by a method such as
The amount of ting is about 0.1 to 10 g / m ² (dry state), more preferably 1 to 6 g / m ² (dry state).
Position is desirable. In the present invention, for example, an adhesion promoter such as a silane coupling agent can be arbitrarily added to the adhesive for laminating.

Next, in the above, as the melt-extruded adhesive resin, for example, low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear (linear)
Low-density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-propylene copolymer, Methylpentene polymer, polyethylene, polyolefin resin such as polypropylene, acrylic acid,
An acid-modified polyolefin resin modified with an unsaturated carboxylic acid such as methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid and others can be used as an adhesive resin for extrusion. Thus, in the present invention, it is preferable to use low-density polyethylene, particularly linear low-density polyethylene, acid-modified polyethylene or polypropylene, as the melt-extruded adhesive resin. The thickness of the melt-extruded resin layer of the melt-extruded adhesive resin is 5 to
About 100 μm, more preferably about 10 to 50 μm is desirable. In the present invention, when it is necessary to obtain a stronger adhesive strength when laminating by the extrusion lamination method, for example, an anchor coating agent or the like may be applied to the coating thin film surface. Can be coated. As the above-mentioned anchor coating agent, specifically, for example, organic titanium-based anchor coating agents such as alkyl titanate, isocyanate-based anchor coating agents, polyethyleneimine-based anchor coating agents Various aqueous or oil-based anchor coating agents, such as a coating agent, a polybutadiene-based anchor coating agent, and the like, can be used. Thus, in the present invention, the above-mentioned anchor coating agent may be used, for example, a roll coat, a gravure coat, a knife coat, a dip coat, a spray coat, and other coats.
An anchor coating agent layer can be formed by coating with a coating method and drying the solvent, diluent and the like. In the above, the coating amount of the anchor coating agent is 0.1
-5 g / m ² (dry state) is desirable.

In the above description, the heat-meltable resin film or sheet may be any one that can be melted by heat and fused to each other. Examples thereof include low-density polyethylene, medium-density polyethylene, and high-density polyethylene. , Linear (linear) low-density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene
Ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-propylene copolymer, methylpentene polymer, polyethylene, polyolefin resin such as polypropylene, acrylic acid, methacrylic acid, Maleic acid, maleic anhydride,
An acid-modified polyolefin resin modified with an unsaturated carboxylic acid such as fumaric acid, itaconic acid or the like, or a resin film or sheet made of one or more resins such as the others can be used. The thickness is arbitrary, but can be selected from a range of several μm to 300 μm.

In the present invention, when the above-mentioned lamination is performed, if necessary, a (meth) acryl-based resin, an olefin-based resin, a vinyl-based resin, A heat-melt adhesive, a solvent-based adhesive, a photo-curable adhesive, or the like containing a resin, such as a resin, as a main component of the vehicle can be used. Further, in the above-mentioned lamination, on each lamination facing surface, in order to improve the tight adhesion, if necessary, for example, corona discharge treatment, ozone treatment, low-temperature plasma treatment using oxygen gas or nitrogen gas, Pretreatment such as glow discharge treatment, oxidation treatment using a chemical agent or the like, and other treatments can be optionally performed. Further, in the above-mentioned lamination, a primer coat agent layer, an undercoat agent layer, an adhesive layer, an anchor coat agent layer, or the like is arbitrarily formed on each of the laminated opposing surfaces in advance. Then, surface pretreatment can be performed. As the coating agent layer of the above pretreatment, for example, polyester-based resin, polyamide-based resin, polyurethane-based resin, epoxy-based resin,
Phenol-based resin, (meth) acrylic resin, polyvinyl acetate-based resin, polyolefin-based resin such as polyethylene aliha polypropylene or copolymers or modified resins thereof, cellulose-based resin, etc. Can be used. In the above, as a method of forming the coating agent layer, for example, a coating agent such as a solvent type, an aqueous type, or an emulsion type is used, and a roll coating method, a gravure roll coating is used. Law,
The coating can be performed by using a coating method such as a kiss coating method or the like.

Next, in the present invention, a soft packaging bag manufactured by using the above-described battery packaging material will be described. The soft packaging bag is manufactured by the above-described laminating method. Using a material, the surfaces of the heat-sealing resin layer are superimposed on each other, and then the outer peripheral edge is heat-sealed to form a seal portion. A battery container comprising the flexible packaging bag according to the invention can be manufactured. Thus, as the bag making method, the battery packaging material manufactured by the above-described laminating method is folded or overlapped, the inner layer surfaces thereof are opposed to each other, and the peripheral edge portion is, for example, Side seal type, two-way seal type, three-way seal type, four-way seal type, envelope-attached seal type,
Heat seal according to heat seal forms such as gasoline-sealed seal type (pyro-seale type), pleated seal type, flat bottom seal type, square bottom seal type, etc. As a result, it is possible to manufacture battery containers comprising the flexible packaging bags of various forms according to the present invention. In the above, the heat sealing method is as follows.
For example, bar seals, rotary roll seals, belt seals
A known method such as a seal, an impulse seal, a high-frequency seal, or an ultrasonic seal can be used.

Next, in the present invention, various batteries such as a current collector constituting a lithium secondary battery and others are formed from the opening of the battery container formed of the soft packaging bag manufactured as described above. The battery power generation element is filled, and then the opening is heat-sealed to form a seal portion, thereby manufacturing various batteries using the battery container comprising the flexible packaging bag according to the present invention. be able to. Thus, the above-mentioned battery can be reduced in weight, reduced in size, made portable, etc., and further improved in water vapor barrier property, oxygen gas barrier property, electrolyte solution resistance, delamination resistance, pinhole resistance, etc. Excellent, and has various properties such as weather resistance, heat resistance, light resistance, water resistance, chemical resistance, moisture resistance, stain resistance, insulation, etc., and mechanical, physical or chemical strength. , Excellent in toughness, extremely durable,
In addition, because of the protection of the battery element, it satisfies various functions such as impact resistance, environmental stress cracking resistance, seal stability, storage stability, etc., and has extremely excellent characteristics that can withstand practical use. Things.

[0042]

EXAMPLES The present invention will be described below more specifically with reference to examples. Example 1 (1). A biaxially stretched polyethylene terephthalate film (manufactured by Teijin Limited, trade name, NSC, single-sided corona treatment) having a thickness of 25 μm was used, and was mounted on a delivery roll of a plasma chemical vapor deposition apparatus under the following conditions 120Å film thickness
Was formed on the corona-treated surface. (Evaporation conditions) Mixing ratio of reaction gas: hexamethyldisiloxane: oxygen gas: helium = 1: 10: 10 (unit: slm) Degree of vacuum in vacuum chamber: 5.5 × 10 ⁻⁶ mbar In evaporation chamber Degree of vacuum: 6.5 × 10 ^-2 mbar Cooling / electrode drum supply power: 18 kW Film transfer speed: 80 m / min Evaporation surface: Corona treated surface Next, a silicon oxide evaporation film having a thickness of 120 ° was formed as described above. Immediately after the vapor deposition of the biaxially stretched polyethylene terephthalate film, a corona discharge treatment is performed on the surface of the silicon oxide film at an output of 10 kW and at a processing speed of 100 m / min, and the surface tension of the film surface is reduced from 35 dyne. A corona treated surface improved to 60 dyne was formed. (2). Next, 25 mol% of aluminum sec-butyrate was slowly added dropwise to a mixture of 45 mol% of methacryloxypropyltrimethoxysilane and 30 mol% of methyltrimethoxysilane while stirring at room temperature. After the addition, the mixture was stirred for a further 5 minutes and then 15 minutes.
Cooled to ° C. One of the amount of water required for complete hydrolysis rubbing
One-fifth was gradually added dropwise with stirring. After stirring for another 5 minutes, the mixture was cooled to 8 ° C. Next, two-sixteenths of the amount of water required for complete hydrolysis was slowly added dropwise with stirring. Stir for another 15 minutes. Finally, the hydrolysis was completed and a composition for coating was prepared. Next, the coating composition prepared above was used, and this was used in the above (2).
The coated surface of the silicon oxide vapor-deposited film manufactured by the above method is coated by a gravure roll coating method.
After drying at 20 ° C. for 1 hour, a coating amount of 2.0 g / m ²
A coating material (dry state) was formed to produce a barrier material. (3). Next, a two-component curable polyurethane-based laminating adhesive was coated on one surface of a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm by a gravure roll coating method. 0.0 g / m ² (dry state)
To form a laminating adhesive layer of
The barrier material produced above is superimposed on the adhesive layer surface with its biaxially stretched polyethylene terephthalate film surface facing the other, and both are dry-laminated to produce a first laminate. did. Then, another thickness 1
On one surface of a 2 μm biaxially stretched polyethylene terephthalate film, a two-part curable polyurethane-based laminating adhesive is coated by a gravure roll coating method,
A first laminate manufactured by forming a laminate adhesive layer having a thickness of 2.0 g / m ² (dry state) and then dry laminating the laminate on the adhesive layer surface of the laminate. The coating film surfaces of the barrier material constituting the above were superposed on each other, and both were dry-laminated to produce a second laminate. Next, a two-part curable polyurethane-based adhesive for laminating is applied to the surface of the biaxially stretched polyethylene terephthalate film having a thickness of 12 μm constituting the second laminate produced above by the gravure roll coating method. To form an adhesive layer for lamination having a thickness of 2.0 g / m ² (dry state). Then, an acid-modified polypropylene film having a thickness of 50 μm is formed on the surface of the adhesive layer for lamination. Was subjected to dry lamination to produce a battery packaging material according to the present invention. (4) Next, a pair of the battery packaging materials produced above is prepared, and the 50 μm thick acid-modified polypropylene film surfaces of the pair of battery packaging materials are superimposed on each other, and then the three sides are overlapped. A heat seal was applied to the end around the outer periphery to produce a three-sided heat seal-type soft packaging bag to produce a battery container. Next, a lithium secondary battery power generating element having a positive electrode terminal and a negative electrode terminal is filled from the opening of the battery container manufactured as described above, and then the opening is heat-sealed to form a lithium secondary battery. Was manufactured. The lithium secondary battery produced as described above was excellent in water vapor barrier properties, oxygen gas barrier properties, resistance to electrolytes, and the like, did not peel off between the layers, and had extremely high durability.

Embodiment 2 (1). A 25 μm-thick biaxially stretched polyethylene terephthalate film (manufactured by Teijin Limited, trade name, NSC, single-sided corona treatment) was used, and this was mounted on a delivery roll of a roll-up type vacuum evaporation apparatus. This was fed out onto a coating drum, and under the following conditions, using aluminum as an evaporation source and supplying oxygen gas, the above-mentioned two by the reactive vacuum evaporation method using an electron beam (EB) heating method. On the surface of the axially stretched polyethylene terephthalate film, a deposited film of aluminum oxide having a thickness of 220 ° was formed. (Evaporation conditions) Evaporation source: Aluminum Degree of vacuum in vacuum chamber: 7.5 × 10 ⁻⁶ mbar Degree of vacuum in evaporation chamber: 2.1 × 10 ⁻⁶ mbar EB output: 25 kW Film transport speed: 480 m / Next, immediately after the biaxially stretched polyethylene terephthalate film on which the 220-nm-thick aluminum oxide vapor-deposited film was formed, a glow discharge plasma generator was used on the aluminum oxide vapor-deposited film surface. Then, using a mixed gas of plasma output of 1500 W, oxygen gas (O ₂ ): argon gas (Ar) = 19: 1, mixed gas pressure of 6 × 10 ⁻⁵ Toor, processing speed of 420 m / mi
Then, an oxygen / argon mixed gas plasma treatment was performed at n to form a plasma treated surface. (2). 25 g of ethyl silicate, 25 g of ethanol,
Mix 1.86 g of 2N hydrochloric acid and 1.51 g of water,
For 1-2 hours. At this time, the molar ratio of ethyl silicate to water in the above mixture was 1: 1.51. Next, 2.5 g of epoxysilane (manufactured by Toray Dow Corning Co., Ltd., trade name, SH6040) was added and stirred. Polyvinyl alcohol (Kuraray Co., Ltd.)
1.7 g of an aqueous solution containing 10% of a polymerization degree of 2000) was added, and the mixture was further stirred for 1 to 2 hours. 0.1 g of a 32% by weight N-dimethylbenzylamine ethanol solution was added to prepare a coating composition. Next, the coating composition prepared as described above was used, and this was coated on the plasma-treated surface of the aluminum oxide vapor-deposited film produced in the above (1) by a gravure roll coating method. And then dried at 120 ° C. for 1 hour,
A coating film having a coating amount of 2.0 g / m ² (dry state) was formed to produce a barrier material. (3). Next, a two-component curable polyurethane-based laminating adhesive was coated on one surface of a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm by a gravure roll coating method. 0.0 g / m ² (dry state)
To form a laminating adhesive layer of
The barrier material produced above is superimposed on the adhesive layer surface with its biaxially stretched polyethylene terephthalate film surface facing the other, and both are dry-laminated to produce a first laminate. did. Then, another thickness 1
On one surface of a 2 μm biaxially stretched polyethylene terephthalate film, a two-part curable polyurethane-based laminating adhesive is coated by a gravure roll coating method,
A first laminate manufactured by forming a laminate adhesive layer having a thickness of 2.0 g / m ² (dry state) and then dry laminating the laminate on the adhesive layer surface of the laminate. The coating film surfaces of the barrier material constituting the above were superposed on each other, and both were dry-laminated to produce a second laminate. Next, a two-part curable polyurethane-based adhesive for laminating is applied to the surface of the biaxially stretched polyethylene terephthalate film having a thickness of 12 μm constituting the second laminate produced above by the gravure roll coating method. To form an adhesive layer for lamination having a thickness of 2.0 g / m ² (dry state). Then, an acid-modified polypropylene film having a thickness of 50 μm is formed on the surface of the adhesive layer for lamination. Was subjected to dry lamination to produce a battery packaging material according to the present invention. (4) Next, a pair of the battery packaging materials produced above is prepared, and the 50 μm thick acid-modified polypropylene film surfaces of the pair of battery packaging materials are superimposed on each other, and then the three sides are overlapped. A heat seal was applied to the end around the outer periphery to produce a three-sided heat seal-type soft packaging bag to produce a battery container. Next, a lithium secondary battery power generating element having a positive electrode terminal and a negative electrode terminal is filled from the opening of the battery container manufactured as described above, and then the opening is heat-sealed to form a lithium secondary battery. Was manufactured. The lithium secondary battery produced as described above was excellent in water vapor barrier properties, oxygen gas barrier properties, resistance to electrolytes, and the like, did not peel off between the layers, and had extremely high durability.

Embodiment 3 (1). A biaxially stretched polyethylene terephthalate film (manufactured by Teijin Limited, trade name: NSC, single-sided corona treatment) having a thickness of 25 μm was used, and was mounted on a delivery roll of a plasma chemical vapor deposition apparatus under the following conditions. An evaporated thin film of silicon oxide having a thickness of 35 ° was formed on the corona treated surface to provide an anti-evaporation protective film. (Evaporation conditions) Reaction gas mixture ratio: hexamethyldisiloxane: oxygen gas: helium = 5: 5: 5 (unit: slm) Degree of vacuum in vacuum chamber: 7.0 × 10 ⁻⁶ mbar In evaporation chamber Degree of vacuum: 3.8 × 10 ^-2 mbar Cooling / electrode drum supply power: 15 kW Sheet transfer speed: 100 m / min (2). Next, a thickness of 25 μm provided with the above-described evaporation-resistant protective film.
m of biaxially stretched polyethylene terephthalate film, and in the same manner as described above, this was mounted on a delivery roll of a plasma enhanced chemical vapor deposition apparatus, and a silicon oxide deposited film having a thickness of 120 mm was formed under the following conditions. The biaxially stretched polyethylene terephthalate film was formed on the surface of the deposition-resistant protective film. (Evaporation conditions) Reaction gas mixture ratio: hexamethyldisiloxane: oxygen gas: helium = 1: 10: 10 (unit: slm) Degree of vacuum in vacuum chamber: 5.5 × 10 ⁻⁶ mbar In evaporation chamber Degree of vacuum: 6.5 × 10 ^-2 mbar Cooling / electrode drum power supply: 18 kW Film transport speed: 80 m / min Next, the above-mentioned biaxially stretched polyethylene terephthalate on which a silicon oxide deposited film having a thickness of 120 ° was formed. -Immediately after the vapor deposition, the surface tension of the vapor-deposited film was increased from 35 dyne to 60 dyne by performing corona discharge treatment on the silicon oxide vapor-deposited film surface at an output of 10 kW and at a processing speed of 100 m / min. A corona treated surface was formed. (3). Next, the coating composition prepared in Example 1 was used, and the composition was applied to the corona-treated surface of the silicon oxide vapor-deposited film prepared in the above (2) by a gravure roll coating method. Then, the coating was dried at 120 ° C. for 1 hour to form a coating film having a coating amount of 2.0 g / m ² (dry state), thereby producing a barrier material. (4). Next, a two-component curable polyurethane-based laminating adhesive was coated on one surface of a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm by a gravure roll coating method. 0.0 g / m ² (dry state)
To form a laminating adhesive layer of
The barrier material produced above is superimposed on the adhesive layer surface with its biaxially stretched polyethylene terephthalate film surface facing the other, and both are dry-laminated to produce a first laminate. did. Then, another thickness 1
On one surface of a 2 μm biaxially stretched polyethylene terephthalate film, a two-part curable polyurethane-based laminating adhesive is coated by a gravure roll coating method,
A first laminate manufactured by forming a laminate adhesive layer having a thickness of 2.0 g / m ² (dry state) and then dry laminating the laminate on the adhesive layer surface of the laminate. The coating film surfaces of the barrier material constituting the above were superposed on each other, and both were dry-laminated to produce a second laminate. Next, a two-part curable polyurethane-based adhesive for laminating is applied to the surface of the biaxially stretched polyethylene terephthalate film having a thickness of 12 μm constituting the second laminate produced above by the gravure roll coating method. To form an adhesive layer for lamination having a thickness of 2.0 g / m ² (dry state). Then, an acid-modified polypropylene film having a thickness of 50 μm is formed on the surface of the adhesive layer for lamination. Was subjected to dry lamination to produce a battery packaging material according to the present invention. (5) Next, a pair of the battery packaging materials produced above is prepared, and the 50 μm thick acid-modified polypropylene film faces of the pair of battery packaging materials are superposed on each other, and then the three sides are overlapped. A heat seal was applied to the end portion around the outer periphery to produce a three-sided heat seal type soft packaging bag, and a battery container was produced. Next, a lithium secondary battery power generating element having a positive electrode terminal and a negative electrode terminal is filled from the opening of the battery container manufactured as described above, and then the opening is heat-sealed to form a lithium secondary battery. Was manufactured. The lithium secondary battery produced as described above was excellent in water vapor barrier properties, oxygen gas barrier properties, resistance to electrolytes, and the like, did not peel off between the layers, and had extremely high durability.

Embodiment 4 (1). A 25 μm-thick polyethylene terephthalate film provided with an anti-evaporation protective film produced in Example 1 above was used, and this was mounted on a delivery roll of a take-up type vacuum evaporator. -The above polyethylene terephthalate is fed out on a reactive drum by the reaction vacuum deposition method using an electron beam (EB) heating method while supplying oxygen gas while using aluminum as a deposition source under the following conditions. On the surface of the protective film, a deposited film of aluminum oxide having a thickness of 220 ° was formed. (Evaporation conditions) Evaporation source: Aluminum Degree of vacuum in vacuum chamber: 7.5 × 10 ⁻⁶ mbar Degree of vacuum in evaporation chamber: 2.1 × 10 ⁻⁶ mbar EB output: 25 kW Film transport speed: 480 m / Next, immediately after the biaxially stretched polyethylene terephthalate film on which the 220-nm-thick aluminum oxide vapor-deposited film was formed, a glow discharge plasma generator was used on the aluminum oxide vapor-deposited film surface. Then, using a mixed gas of plasma output of 1500 W, oxygen gas (O ₂ ): argon gas (Ar) = 19: 1, mixed gas pressure of 6 × 10 ⁻⁵ Toor, processing speed of 420 m / mi
Then, an oxygen / argon mixed gas plasma treatment was performed at n to form a plasma treated surface. (2). Next, the coating composition prepared in Example 2 was used, and the composition was applied to the plasma-treated surface of the aluminum oxide vapor-deposited film produced in the above (1) by a gravure roll coating method. Then, the coating was dried at 120 ° C. for 1 hour to form a coating film having a coating amount of 2.0 g / m ² (dry state), thereby producing a barrier material. (3). Next, a two-component curable polyurethane-based laminating adhesive was coated on one surface of a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm by a gravure roll coating method. 0.0 g / m ² (dry state)
To form a laminating adhesive layer of
The barrier material produced above is superimposed on the adhesive layer surface with its biaxially stretched polyethylene terephthalate film surface facing the other, and both are dry-laminated to produce a first laminate. did. Then, another thickness 1
On one surface of a 2 μm biaxially stretched polyethylene terephthalate film, a two-part curable polyurethane-based laminating adhesive is coated by a gravure roll coating method,
A first laminate manufactured by forming a laminate adhesive layer having a thickness of 2.0 g / m ² (dry state) and then dry laminating the laminate on the adhesive layer surface of the laminate. The coating film surfaces of the barrier material constituting the above were superposed on each other, and both were dry-laminated to produce a second laminate. Next, a two-part curable polyurethane-based adhesive for laminating is applied to the surface of the biaxially stretched polyethylene terephthalate film having a thickness of 12 μm constituting the second laminate produced above by the gravure roll coating method. To form an adhesive layer for lamination having a thickness of 2.0 g / m ² (dry state). Then, an acid-modified polypropylene film having a thickness of 50 μm is formed on the surface of the adhesive layer for lamination. Was subjected to dry lamination to produce a battery packaging material according to the present invention. (4) Next, a pair of the battery packaging materials produced above is prepared, and the 50 μm thick acid-modified polypropylene film surfaces of the pair of battery packaging materials are superimposed on each other, and then the three sides are overlapped. A heat seal was applied to the end around the outer periphery to produce a three-sided heat seal-type soft packaging bag to produce a battery container. Next, a lithium secondary battery power generating element having a positive electrode terminal and a negative electrode terminal is filled from the opening of the battery container manufactured as described above, and then the opening is heat-sealed to form a lithium secondary battery. Was manufactured. The lithium secondary battery produced as described above was excellent in water vapor barrier properties, oxygen gas barrier properties, resistance to electrolytes, and the like, did not peel off between the layers, and had extremely high durability.

Embodiment 5 (1). The same biaxially stretched polyethylene terephthalate film having a thickness of 25 μm as in Example 1 above was used, and this was mounted on a delivery roll of a plasma enhanced chemical vapor deposition apparatus.
Under the following conditions, a deposited film of silicon oxide having a thickness of 120 ° was formed on the corona-treated surface of the biaxially stretched polyethylene terephthalate film. (Evaporation conditions) Reaction gas mixture ratio: hexamethyldisiloxane: oxygen gas: helium = 1: 10: 10 (unit: slm) Degree of vacuum in vacuum chamber: 5.5 × 10 ⁻⁶ mbar In evaporation chamber Degree of vacuum: 6.5 × 10 ^-2 mbar Cooling / electrode drum supply power: 18 kW Film transfer speed: 80 m / min Evaporation surface: Corona treated surface Next, a silicon oxide evaporation film having a thickness of 120 ° was formed as described above. Immediately after the vapor deposition of the biaxially stretched polyethylene terephthalate film, a corona discharge treatment is performed on the surface of the silicon oxide film at an output of 10 kW and at a processing speed of 100 m / min, and the surface tension of the film surface is reduced from 35 dyne. It was improved to 60 dyne to form a corona treated surface. (2). Next, a biaxially stretched polyethylene terephthalate film on which a silicon oxide vapor-deposited film having been subjected to the above-described corona treatment was used, and this was mounted on a delivery roll of a take-up type vacuum vapor deposition apparatus. Is fed onto a coating drum, and under the following conditions, the above-described biaxial coating is performed by a reactive vacuum evaporation method using an electron beam (EB) heating method while supplying oxygen gas using aluminum as an evaporation source. On the corona-treated surface of the silicon oxide vapor deposition film of the stretched polyethylene terephthalate film, a 220 ° -thick aluminum oxide vapor deposition film was formed. (Evaporation conditions) Evaporation source: Aluminum Degree of vacuum in vacuum chamber: 7.5 × 10 ⁻⁶ mbar Degree of vacuum in evaporation chamber: 2.1 × 10 ⁻⁶ mbar EB output: 25 KW Film transport speed: 480 m / Next, immediately after the biaxially stretched polyethylene terephthalate film on which the 220-nm-thick aluminum oxide vapor-deposited film was formed, a glow discharge plasma generator was used on the aluminum oxide vapor-deposited film surface. Then, using a mixed gas of plasma output of 1500 W, oxygen gas (O ₂ ): argon gas (Ar) = 19: 1, mixed gas pressure of 6 × 10 ⁻⁵ Toor, processing speed of 420 m / mi
Then, an oxygen / argon mixed gas plasma treatment was performed at n to form a plasma treated surface. (3). Next, the coating composition prepared in Example 1 was used, and the composition was applied to the plasma-treated surface of the aluminum oxide vapor-deposited film produced in the above (2) by a gravure roll coating method. Then, the coating was dried at 120 ° C. for 1 hour to form a coating film having a coating amount of 2.0 g / m ² (dry state), thereby producing a barrier material. (4). Next, a two-component curable polyurethane-based laminating adhesive was coated on one surface of a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm by a gravure roll coating method. 0.0 g / m ² (dry state)
To form a laminating adhesive layer of
A 15 μm-thick biaxially stretched nylon film is opposed to the surface of the adhesive layer for
A first laminate was manufactured. Further, a two-component curable polyurethane-based laminating adhesive is coated on the biaxially stretched nylon film surface of the first laminate produced as described above by a gravure roll coating method, and a thickness of 2. An adhesive layer for lamination of 0 g / m ² (dry state) is formed, and the barrier material produced above is coated on the surface of the adhesive layer for lamination with the biaxially stretched polyethylene terephthalate film. The two surfaces are superposed on each other and the two
Then, a second laminate was manufactured. Next, a two-part curable polyurethane-based laminating adhesive was coated on one surface of another 12 μm-thick biaxially stretched polyethylene terephthalate film by a gravure roll coating method. An adhesive layer for lamination having a thickness of 2.0 g / m ² (dry state) is formed, and then the second laminate produced by dry laminating as described above is applied to the surface of the adhesive layer for lamination. The coating film surfaces of the constituent barrier materials were superposed on each other, and the two were dry-laminated to produce a third laminate. Next, a two-part curable polyurethane-based laminating adhesive is applied to the surface of the biaxially stretched polyethylene terephthalate film having a thickness of 12 μm constituting the third laminate produced above by a gravure roll coating method. In-
To form an adhesive layer for lamination having a thickness of 2.0 g / m ² (dry state). Then, a 50 μm-thick acid-modified polypropylene film was dried on the adhesive layer for laminating. Thus, a packaging material for a battery according to the present invention was manufactured. (5) Next, a pair of the battery packaging materials produced above is prepared, and the 50 μm thick acid-modified polypropylene film faces of the pair of battery packaging materials are superposed on each other, and then the three sides are overlapped. A heat seal was applied to the end portion around the outer periphery to produce a three-sided heat seal type soft packaging bag, and a battery container was produced. Next, a lithium secondary battery power generating element having a positive electrode terminal and a negative electrode terminal is filled from the opening of the battery container manufactured as described above, and then the opening is heat-sealed to form a lithium secondary battery. Was manufactured. The lithium secondary battery produced as described above was excellent in water vapor barrier properties, oxygen gas barrier properties, resistance to electrolytes, and the like, did not peel off between the layers, and had extremely high durability.

Embodiment 6 (1). On one surface of a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm, a two-component curable polyurethane-based laminating adhesive was coated by a gravure roll coating method, and a thickness of 2.0 g / An adhesive layer for lamination of m ² (dry state) is formed, and then a biaxially stretched nylon film having a thickness of 15 μm is opposed to the surface of the adhesive layer for lamination. Thus, a first laminate was manufactured. Further, a two-component curable polyurethane-based laminating adhesive is coated on the biaxially stretched nylon film surface of the first laminate produced as described above by a gravure roll coating method, and a thickness of 2. A laminating adhesive layer of 0 g / m ² (dry state) was formed, and then the barrier material produced in Example 1 was used on the laminating adhesive layer surface. The stretched polyethylene terephthalate film surfaces were overlapped with each other facing each other, and both were dry-laminated to produce a second laminate. Then, a two-part curable polyurethane-based laminating adhesive is coated on one surface of another biaxially stretched polyethylene terephthalate film having a thickness of 12 μm by a gravure roll coating method.
To form a laminating adhesive layer having a thickness of 2.0 g / m ² (dry state), and then dry laminating the second laminating layer on the surface of the laminating adhesive layer. The coating film surfaces of the barrier material constituting the laminate were superposed with each other facing each other, and both were dry-laminated to produce a third laminate. Next, a two-part curable polyurethane-based anchor coat was used on the surface of the biaxially stretched polyethylene terephthalate film having a thickness of 12 μm that constitutes the third laminate produced above, and this was gravure-coated.
Using a coating method, an anchor coating agent layer is formed by coating to a film thickness of 1 μm, and then polypropylene and an acid-modified polypropylene are used on the anchor coating agent layer surface. , Each of which is co-extruded to a thickness of 30 μm,
Further, a co-extruded film having a thickness of 60 μm is extruded and laminated so that the acid-modified polypropylene layer becomes the outer surface, and a heat-sealing resin layer made of the co-extruded film is formed, and the present invention is concerned. A battery packaging material was manufactured. (2) Next, a pair of battery packaging materials manufactured as described above is prepared, and the acid-modified polypropylene film layers of the pair of battery packaging materials are superimposed on each other, and then, the three peripheral ends are surrounded. Heat seal the part,
A toseal-type flexible packaging bag was manufactured to manufacture a battery container. Next, a lithium secondary battery power generating element having a positive electrode terminal and a negative electrode terminal is filled from the opening of the battery container manufactured as described above, and then the opening is heat-sealed to form a lithium secondary battery. Was manufactured. The lithium secondary battery produced above has excellent water vapor barrier properties, oxygen gas barrier properties, resistance to electrolytes, etc., without peeling between its layers,
It was extremely durable.

Embodiment 7 (1). On one surface of a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm, a two-component curable polyurethane-based laminating adhesive was coated by a gravure roll coating method, and a thickness of 2.0 g / An adhesive layer for lamination of m ² (dry state) is formed, and then a biaxially stretched nylon film having a thickness of 15 μm is opposed to the surface of the adhesive layer for lamination. Thus, a first laminate was manufactured. Further, a two-component curable polyurethane-based laminating adhesive is coated on the biaxially stretched nylon film surface of the first laminate produced as described above by a gravure roll coating method, and a thickness of 2. A laminating adhesive layer of 0 g / m ² (dry state) was formed, and then the barrier material prepared in Example 2 was used on the laminating adhesive layer surface. The stretched polyethylene terephthalate film surfaces were overlapped with each other facing each other, and both were dry-laminated to produce a second laminate. Then, a two-part curable polyurethane-based laminating adhesive is coated on one surface of another biaxially stretched polyethylene terephthalate film having a thickness of 12 μm by a gravure roll coating method.
To form a laminating adhesive layer having a thickness of 2.0 g / m ² (dry state), and then dry laminating the second laminating layer on the surface of the laminating adhesive layer. The coating film surfaces of the barrier material constituting the laminate were superposed with each other facing each other, and both were dry-laminated to produce a third laminate. Next, a two-part curable polyurethane-based anchor coat was used on the surface of the biaxially stretched polyethylene terephthalate film having a thickness of 12 μm that constitutes the third laminate produced above, and this was gravure-coated.
Using a coating method, an anchor coating agent layer is formed by coating to a film thickness of 1 μm, and then polypropylene and an acid-modified polypropylene are used on the anchor coating agent layer surface. , Each of which is co-extruded to a thickness of 30 μm,
In addition, a co-extruded film having a thickness of 60 μm is extruded and laminated so that the surface of the acid-modified polypropylene layer becomes an outer surface, and a heat-sealing resin layer formed of the co-extruded film is formed. The battery packaging material was manufactured. (2) Next, a pair of the battery packaging materials manufactured as described above is prepared, and the 50 μm thick acid-modified polypropylene film surfaces of the pair of battery packaging materials are superimposed on each other, and then the three sides are overlapped. A heat seal was applied to the end around the outer periphery to produce a three-sided heat seal-type soft packaging bag to produce a battery container. Next, a lithium secondary battery power generating element having a positive electrode terminal and a negative electrode terminal is filled from the opening of the battery container manufactured as described above, and then the opening is heat-sealed to form a lithium secondary battery. Was manufactured. The lithium secondary battery produced as described above was excellent in water vapor barrier properties, oxygen gas barrier properties, resistance to electrolytes, and the like, did not peel off between the layers, and had extremely high durability.

Embodiment 8 (1). Using the same biaxially stretched polyethylene terephthalate film having a thickness of 25 μm as in Example 1 above, a reaction vacuum by an electron beam (EB) heating method was formed on one surface thereof in the same manner as in Example 2 above. A 220 ° -thick aluminum oxide vapor-deposited film was formed by a vapor deposition method, and a plasma-treated surface was further formed. Further, the second embodiment described above
Similarly, on the plasma-treated surface of the 220-nm-thick aluminum oxide vapor-deposited film formed above,
A 20 ° aluminum oxide deposited film was formed, and a plasma treated surface was further formed. (2). Next, the coating composition prepared in Example 1 above was used, and the composition was coated on the plasma-treated surface of the aluminum oxide vapor-deposited film produced above using a gravure roll coating method. Then, the coating was dried at 120 ° C. for 1 hour to form a coating film having a coating amount of 2.0 g / m ² (dry state), thereby producing a barrier material. (3). Next, a two-component curable polyurethane-based laminating adhesive was coated on one surface of a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm by a gravure roll coating method. 0.0 g / m ² (dry state)
To form a laminating adhesive layer of
The barrier material produced above is superimposed on the adhesive layer surface with its biaxially stretched polyethylene terephthalate film surface facing the other, and both are dry-laminated to produce a first laminate. did. Then, another thickness 1
On one surface of a 2 μm biaxially stretched polyethylene terephthalate film, a two-part curable polyurethane-based laminating adhesive is coated by a gravure roll coating method,
A first laminate manufactured by forming a laminate adhesive layer having a thickness of 2.0 g / m ² (dry state) and then dry laminating the laminate on the adhesive layer surface of the laminate. The coating film surfaces of the barrier material constituting the above were superposed on each other, and both were dry-laminated to produce a second laminate. Next, a two-part curable polyurethane-based adhesive for laminating is applied to the surface of the biaxially stretched polyethylene terephthalate film having a thickness of 12 μm constituting the second laminate produced above by the gravure roll coating method. To form an adhesive layer for lamination having a thickness of 2.0 g / m ² (dry state). Then, an acid-modified polypropylene film having a thickness of 50 μm is formed on the surface of the adhesive layer for lamination. Was subjected to dry lamination to produce a battery packaging material according to the present invention. (4) Next, a pair of the battery packaging materials produced above is prepared, and the 50 μm thick acid-modified polypropylene film surfaces of the pair of battery packaging materials are superimposed on each other, and then the three sides are overlapped. A heat seal was applied to the end around the outer periphery to produce a three-sided heat seal-type soft packaging bag to produce a battery container. Next, a lithium secondary battery power generating element having a positive electrode terminal and a negative electrode terminal is filled from the opening of the battery container manufactured as described above, and then the opening is heat-sealed to form a lithium secondary battery. Was manufactured. The lithium secondary battery produced as described above was excellent in water vapor barrier properties, oxygen gas barrier properties, resistance to electrolytes, and the like, did not peel off between the layers, and had extremely high durability.

Embodiment 9 (1). A biaxially-stretched polyethylene terephthalate film having a thickness of 25 μm was used in the same manner as in Example 1 above, and a film thickness of 120 mm was formed on one surface thereof in the same manner as in Example 1 above.
Was formed, and a corona-treated surface was further formed. Further, in the same manner as in Example 1 above, on the corona-treated surface of the deposited silicon oxide film having a thickness of 120 ° formed above, a deposited silicon oxide film having a thickness of 120 ° was similarly formed. A treated surface was formed. (2). Next, the coating composition prepared in Example 2 was used, and the composition was coated on the corona-treated surface of the silicon oxide vapor-deposited film produced above using a gravure roll coating method. And dried at 120 ° C. for 1 hour.
A coating film having a coating amount of 2.0 g / m ² (dry state) was formed to produce a barrier material. (3). Next, a two-component curable polyurethane-based laminating adhesive was coated on one surface of a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm by a gravure roll coating method. 0.0 g / m ² (dry state)
To form a laminating adhesive layer of
The barrier material produced above is superimposed on the adhesive layer surface with its biaxially stretched polyethylene terephthalate film surface facing the other, and both are dry-laminated to produce a first laminate. did. Then, another thickness 1
On one surface of a 2 μm biaxially stretched polyethylene terephthalate film, a two-part curable polyurethane-based laminating adhesive is coated by a gravure roll coating method,
A first laminate manufactured by forming a laminate adhesive layer having a thickness of 2.0 g / m ² (dry state) and then dry laminating the laminate on the adhesive layer surface of the laminate. The coating film surfaces of the barrier material constituting the above were superposed on each other, and both were dry-laminated to produce a second laminate. Next, a two-part curable polyurethane-based adhesive for laminating is applied to the surface of the biaxially stretched polyethylene terephthalate film having a thickness of 12 μm constituting the second laminate produced above by the gravure roll coating method. To form an adhesive layer for lamination having a thickness of 2.0 g / m ² (dry state). Then, an acid-modified polypropylene film having a thickness of 50 μm is formed on the surface of the adhesive layer for lamination. Was subjected to dry lamination to produce a battery packaging material according to the present invention. (4) Next, a pair of the battery packaging materials produced above is prepared, and the 50 μm thick acid-modified polypropylene film surfaces of the pair of battery packaging materials are superimposed on each other, and then the three sides are overlapped. A heat seal was applied to the end around the outer periphery to produce a three-sided heat seal-type soft packaging bag to produce a battery container. Next, a lithium secondary battery power generating element having a positive electrode terminal and a negative electrode terminal is filled from the opening of the battery container manufactured as described above, and then the opening is heat-sealed to form a lithium secondary battery. Was manufactured. The lithium secondary battery produced as described above was excellent in water vapor barrier properties, oxygen gas barrier properties, resistance to electrolytes, and the like, did not peel off between the layers, and had extremely high durability.

Comparative Example 1 (1). A biaxially stretched polyethylene terephthalate film (manufactured by Teijin Limited, trade name, NSC, single-sided corona treatment) having a thickness of 25 μm was used, and was mounted on a delivery roll of a plasma chemical vapor deposition apparatus under the following conditions 120Å film thickness
Was formed on the corona-treated surface. (Evaporation conditions) Mixing ratio of reaction gas: hexamethyldisiloxane: oxygen gas: helium = 1: 10: 10 (unit: slm) Degree of vacuum in vacuum chamber: 5.5 × 10 ⁻⁶ mbar In evaporation chamber Degree of vacuum: 6.5 × 10 ^-2 mbar Cooling / electrode drum supply power: 18 kW Film transfer speed: 80 m / min Evaporation surface: Corona treated surface Next, a silicon oxide evaporation film having a thickness of 120 ° was formed as described above. Immediately after the biaxially stretched polyethylene terephthalate film, the surface of the deposited silicon oxide film was subjected to corona discharge treatment at an output of 10 kW and at a processing speed of 100 m / min, and the surface tension of the deposited film surface was increased from 35 dyne. Form a corona treated surface that has been improved to 60 dyne,
A barrier material was manufactured. (2). Next, a two-component curable polyurethane-based laminating adhesive was coated on one surface of a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm by a gravure roll coating method. 0.0 g / m ² (dry state)
To form a laminating adhesive layer of
The barrier material produced above is superimposed on the adhesive layer surface with its biaxially stretched polyethylene terephthalate film surface facing the other, and both are dry-laminated to produce a first laminate. did. Then, another thickness 1
On one surface of a 2 μm biaxially stretched polyethylene terephthalate film, a two-part curable polyurethane-based laminating adhesive is coated by a gravure roll coating method,
A first laminated body manufactured by forming a laminating adhesive layer having a thickness of 2.0 g / m ² (dry state) and then dry laminating on the laminating adhesive layer surface Were laminated with the corona-treated surfaces of the silicon oxide vapor deposited films of the barrier materials facing each other, and both were dry-laminated to produce a second laminate. Next, a two-part curable polyurethane-based adhesive for laminating is applied to the surface of the biaxially stretched polyethylene terephthalate film having a thickness of 12 μm constituting the second laminate produced above by the gravure roll coating method. And thickness 2.0 g / m ² (dry state)
To form a laminating adhesive layer of
A 50 μm-thick acid-modified polypropylene film was dry-laminated on the surface of the adhesive layer for a battery, thereby producing a battery packaging material according to the present invention. (3) Next, a pair of the battery packaging materials manufactured as described above is prepared, and the 50 μm thick acid-modified polypropylene film surfaces of the pair of battery packaging materials are superimposed on each other, and then the three sides are overlapped. A heat seal was applied to the end around the outer periphery to produce a three-sided heat seal-type soft packaging bag to produce a battery container. Next, a lithium secondary battery power generating element having a positive electrode terminal and a negative electrode terminal is filled from the opening of the battery container manufactured as described above, and then the opening is heat-sealed to form a lithium secondary battery. Was manufactured.

Comparative Example 2 (1). A 25 μm-thick biaxially stretched polyethylene terephthalate film (manufactured by Teijin Limited, trade name, NSC, single-sided corona treatment) was used, and this was mounted on a delivery roll of a roll-up type vacuum evaporation apparatus. This was fed out onto a coating drum, and under the following conditions, using aluminum as an evaporation source and supplying oxygen gas, the above-mentioned two by the reactive vacuum evaporation method using an electron beam (EB) heating method. On the surface of the axially stretched polyethylene terephthalate film, a deposited film of aluminum oxide having a thickness of 220 ° was formed. (Evaporation conditions) Evaporation source: Aluminum Degree of vacuum in vacuum chamber: 7.5 × 10 ⁻⁶ mbar Degree of vacuum in evaporation chamber: 2.1 × 10 ⁻⁶ mbar EB output: 25 kW Film transport speed: 480 m / Next, immediately after the biaxially stretched polyethylene terephthalate film on which the 220-nm-thick aluminum oxide vapor-deposited film was formed, a glow discharge plasma generator was used on the aluminum oxide vapor-deposited film surface. Then, using a mixed gas of plasma output of 1500 W, oxygen gas (O ₂ ): argon gas (Ar) = 19: 1, mixed gas pressure of 6 × 10 ⁻⁵ Toor, processing speed of 420 m / mi
A plasma treatment surface was formed by performing an oxygen / argon mixed gas plasma treatment with n to produce a barrier material. (2). Next, a two-component curable polyurethane-based laminating adhesive was coated on one surface of a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm by a gravure roll coating method. 0.0 g / m ² (dry state)
To form a laminating adhesive layer of
The barrier material produced above is superimposed on the adhesive layer surface with its biaxially stretched polyethylene terephthalate film surface facing the other, and both are dry-laminated to produce a first laminate. did. Then, another thickness 1
On one surface of a 2 μm biaxially stretched polyethylene terephthalate film, a two-part curable polyurethane-based laminating adhesive is coated by a gravure roll coating method,
A first laminated body manufactured by forming a laminating adhesive layer having a thickness of 2.0 g / m ² (dry state) and then dry laminating on the laminating adhesive layer surface Were laminated with the plasma-treated surfaces of the aluminum oxide deposited film of the barrier material facing each other facing each other, and both were dry-laminated to produce a second laminate. Next, a two-part curable polyurethane-based laminating adhesive is applied to the surface of the biaxially stretched polyethylene terephthalate film having a thickness of 12 μm constituting the second laminate produced above by a gravure roll coating method. 2.0g / m thickness
( ² ) An adhesive layer for a laminate in a (dry state) was formed, and then an acid-modified polypropylene film having a thickness of 50 μm was dry-laminated on the surface of the adhesive layer for a laminate to form a laminate for a battery according to the present invention. A packaging material was manufactured. (3) Next, a pair of the battery packaging materials manufactured as described above is prepared, and the 50 μm thick acid-modified polypropylene film surfaces of the pair of battery packaging materials are superimposed on each other, and then the three sides are overlapped. A heat seal was applied to the end around the outer periphery to produce a three-sided heat seal-type soft packaging bag to produce a battery container. Next, a lithium secondary battery power generating element having a positive electrode terminal and a negative electrode terminal is filled from the opening of the battery container manufactured as described above, and then the opening is heat-sealed to form a lithium secondary battery. Was manufactured.

Experimental Example The water vapor permeability and oxygen permeability of the battery packaging materials according to the present invention produced in Examples 1 to 9 and the battery packaging materials according to Comparative Examples 1 and 2 were measured. (1). Measurement of Water Vapor Permeability and Oxygen Permeability The water vapor permeability was measured at a temperature of 40 ° C. and a humidity of 90% RH using a measuring instrument (model name, PERMATRAN) manufactured by MOCON, USA. Measured, and the oxygen permeability was measured at a temperature of 23 ° C and a humidity of 90% RH.
Under the conditions described above, the measurement was carried out with a measuring instrument (model name, OXTRAN) manufactured by MOCON, USA. The results of the above measurements are shown in Table 1 below.

[0054] In Table 1 above, the water vapor barrier is [g / m ² / d
ay / 40 ° C / 100% RH], and the oxygen barrier is [cc / m ² / day · 23 ° C / 90% RH].
H].

As is clear from the measurement results shown in Table 1 above, the packaging materials for batteries according to Examples 1 to 9 were excellent in water vapor barrier properties and oxygen barrier properties. Specifically, the packaging materials for batteries according to Examples 1 to 9 have a temperature of 4
Water vapor permeability at 0 ° C. and 100% relative humidity is 2.0 g
/ M ² · day · atm or less and at a temperature of 25
Oxygen permeability at 90 ° C. and 90% relative humidity is 2.0 cc / m
^{It was 2} * day * atm or less. On the other hand, the packaging materials for batteries according to Comparative Examples 1 and 2 were inferior in water vapor barrier properties and oxygen barrier properties.

[0056]

As is apparent from the above description, the present invention provides:
At least a substrate layer, a barrier layer, and a heat seal
In a battery packaging material comprising a conductive layer, or at least, a base material layer, a barrier layer, an intermediate layer, and a heat-sealing layer, the barrier material constituting the barrier layer may be an inorganic material. A barrier material consisting of two layers, a deposited film of an oxide and a coating film made of a composition comprising a polycondensate obtained by hydrolysis of a silicon compound, is used as a plastic film or the like. The battery packaging material is manufactured by laminating by a method or an extrusion laminating method or the like, and the battery packaging material is used,
The heat-sealing layers are superimposed on each other, and the outer peripheral edges of the three sides are heat-sealed to produce a soft packaging bag, which is used as a battery container. ,
It consists of a soft packaging bag that has excellent properties in various conditions such as oxygen gas barrier properties and electrolytic solution resistance, has no peeling phenomenon between layers, etc., has excellent durability, etc., and has extremely excellent properties that can withstand practical use. A battery using a battery container can be manufactured.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view schematically showing a layer configuration of an example of a battery packaging material according to the present invention.

FIG. 2 is a schematic cross-sectional view schematically showing a layer configuration of an example of a battery packaging material according to the present invention.

FIG. 3 is a schematic perspective view schematically showing the configuration of a battery container made of a soft packaging bag manufactured using the battery packaging material according to the present invention.

FIG. 4 is a schematic perspective view showing the outline of the configuration of a battery manufactured using a battery container formed of a soft packaging bag manufactured using the battery packaging material according to the present invention.

FIG. 5 is a schematic configuration diagram of a roll-up type vacuum deposition apparatus showing an outline of a method for forming an inorganic oxide deposition film by a physical vapor deposition method.

FIG. 6 is a schematic configuration diagram of a low-temperature plasma-enhanced chemical vapor deposition apparatus showing an outline of a method for forming a deposited film of an inorganic oxide by a chemical vapor deposition method.

[Explanation of symbols]

A Battery Packaging Material A ₁ Battery Packaging Material 1 Base Layer 2 Barrier Layer 2a Barrier Layer 3 Heat-Sealable Layer 4 Battery Packaging Material 4a Battery Packaging Material 5 Inorganic Oxide Vapor Deposition Film 5a Inorganic Oxide deposited film 6 Coating film 6a Coating film 7 Barrier layer composed of two layers 7a Barrier layer composed of two layers 8 Intermediate layer 9 Heat seal portion 10 Opening 11 Flexible bag 12 Battery container 13 Battery power generation element 14 Upper heat seal part 15 Battery 16 Positive terminal 17 Negative terminal

Continued on the front page F-term (reference) 4F100 AA17A AA17C AA19A AA20A AK42D AK52B AK52K AR00E AT00D BA03 BA04 BA05 BA07 BA10A BA10D BA10E BA13 CC00B EH66A EH66C EJ38D GB15 JA20A JD10 A10A01A05A AL12 AM16 CJ24 DJ02 DJ03 EJ03 EJ05 EJ11 EJ12 HJ00 HJ02 HJ04

Claims (9)

[Claims] At least a substrate layer, a barrier layer, and a heat-sealing layer, or at least a substrate layer,
In the packaging material for a battery comprising a barrier layer, an intermediate layer, and a heat-sealing layer,
A packaging material for a battery, comprising a barrier layer composed of two layers: a deposited film of an inorganic oxide and a coating film made of a composition comprising a polycondensate obtained by hydrolysis of a silicon compound. 2. A single-layer film comprising one layer of a vapor-deposited inorganic oxide film, a multilayer film comprising two or more layers of a vapor-deposited inorganic oxide film, or a heterogeneous inorganic oxide film 2. The battery packaging material according to claim 1, wherein the composite material is a composite film composed of two or more layers of the vapor-deposited film. 3. The packaging material for a battery according to claim 1, wherein the deposited film of the inorganic oxide has a thickness of 60 to 4000 °. 4. The method according to claim 1, wherein the silicon compound has the general formula R′SiR
₃ (wherein, R ′ is stable to hydrolysis,
R represents a group polymerizable by irradiation with heat and / or ionizing radiation, and R represents an OH group and / or a group susceptible to hydrolysis. The packaging material for batteries according to any one of claims 1 to 3, wherein the packaging material comprises a silicon compound represented by the formula: 5. The above-mentioned claim, wherein R ′ in the general formula R′SiR ₃ comprises a group containing an epoxy atom group or a group containing an atom group having a CC double bond. Item 1
5. The packaging material for a battery according to any one of items 1 to 4. 6. The packaging material for a battery according to claim 1, wherein R ′ in the general formula R′SiR ₃ comprises a group containing a (meth) acrylic atomic group. 7. A composition has the general formula MR _n (In the formula, M represents silicon, aluminum, titanium, zirconium, vanadium, boron, or an element selected from tin, R represents, OH group And / or n represents a group which is susceptible to hydrolysis, and n represents a valence of a metal element). 7. The battery packaging material according to any one of items 1 to 6. 8. The packaging material for a battery according to claim 1, wherein the composition comprises a resin having a hydrogen bond-forming group. 9. The oxygen permeability at a temperature of 25 ° C. and a relative humidity of 90% is 2.0 cc / m ² · day · atm or less, and the water vapor permeability at a temperature of 40 ° C. and a relative humidity of 100% is 2%. The battery packaging material according to any one of claims 1 to 8, wherein the content is not more than 0.0 g / m ² · day · atm.