WO2018194176A1 - 電池用包装材料、その製造方法、及び電池 - Google Patents

電池用包装材料、その製造方法、及び電池 Download PDF

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Publication number
WO2018194176A1
WO2018194176A1 PCT/JP2018/016367 JP2018016367W WO2018194176A1 WO 2018194176 A1 WO2018194176 A1 WO 2018194176A1 JP 2018016367 W JP2018016367 W JP 2018016367W WO 2018194176 A1 WO2018194176 A1 WO 2018194176A1
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Prior art keywords
layer
resin layer
resin
packaging material
battery
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PCT/JP2018/016367
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English (en)
French (fr)
Japanese (ja)
Inventor
かおる 津森
山下　孝典
山下　力也
Original Assignee
大日本印刷株式会社
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Application filed by 大日本印刷株式会社 filed Critical 大日本印刷株式会社
Priority to CN201880025574.0A priority Critical patent/CN110537266B/zh
Priority to JP2019502828A priority patent/JP6525119B2/ja
Publication of WO2018194176A1 publication Critical patent/WO2018194176A1/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/78—Cases; Housings; Encapsulations; Mountings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
    • H01M50/105—Pouches or flexible bags

Definitions

  • the present invention relates to a packaging material for a battery, a manufacturing method thereof, and a battery.
  • a concave portion is formed by molding, and a battery element such as an electrode or an electrolytic solution is arranged in the space formed by the concave portion, and a heat-fusible resin layer A battery in which the battery element is accommodated in the battery packaging material is obtained by heat-sealing them together.
  • the battery In the process of manufacturing a battery packaging material formed by such a film-like laminate, and the process of manufacturing a battery using the battery packaging material, the battery is transported until the battery is completed.
  • Surface characteristics on the base material layer side may be deteriorated, such as scratches, heat deterioration during heat fusion, and adhesion of the electrolyte when encapsulating the electrolyte. Since the surface on the base material layer side is located outside the battery, it is required to avoid such characteristic deterioration as much as possible.
  • Patent Document 1 discloses a protective film characterized in that the adhesive strength is almost eliminated by heating or ultraviolet irradiation in advance for a laminated film having a three-layer structure in which a protective layer and a heat sealing layer are laminated on a metal foil.
  • a method has been proposed in which a battery is manufactured after affixing, and a protective film having a reduced adhesive strength is peeled off by applying heat or ultraviolet light.
  • Patent Document 1 has a problem that a layer or the like located under the protective film is deteriorated by heating or ultraviolet irradiation. In addition, it is necessary to set the heating temperature and the wavelength of ultraviolet rays, and there is also a problem that the adhesive force of the protective film does not become constant because these set values change.
  • the present invention is an invention made in view of such problems of the prior art. That is, the main object is to provide a battery packaging material that can effectively suppress deterioration of characteristics of the outer surface of the battery packaging material in the process of manufacturing the battery or the battery packaging material. Furthermore, another object of the present invention is to provide a method for producing the battery packaging material, a battery using the battery packaging material, and a method for producing the battery.
  • the present inventors have intensively studied to solve the above problems. As a result, it is composed of a laminate including at least a resin layer, a bonding layer, a base material layer, a barrier layer, and a heat-fusible resin layer in this order, the bonding layer includes a polyester resin,
  • the battery packaging material that can be peeled off from the laminate using an aqueous liquid does not require heating, ultraviolet irradiation, or the like that deteriorates the characteristics of the outer surface of the battery packaging material as in Patent Document 1, and is used for batteries or batteries. It has been found that the characteristic deterioration of the outer surface of the battery packaging material in the process of producing the packaging material can be effectively suppressed.
  • the present invention has been completed by further studies based on these findings.
  • this invention provides the invention of the aspect hung up below.
  • Item 1. At least, it is composed of a laminate comprising a resin layer, a bonding layer, a base material layer, a barrier layer, and a heat-fusible resin layer in this order,
  • the bonding layer includes a polyester resin,
  • the battery packaging material wherein the resin layer is peelable from the laminate using an aqueous liquid.
  • Item 2. In an environment of a temperature of 25 ° C., a relative humidity of 50%, and atmospheric pressure, the peel strength when the resin layer is peeled from the laminate without water adhering to the bonding layer is 2.0 N / 15 mm or more.
  • Item 2 The peel strength when peeling the resin layer from the laminate using the aqueous liquid in an environment of temperature 25 ° C., relative humidity 50%, and atmospheric pressure is 1.0 N / 15 mm or less, Item 2.
  • the battery packaging material according to Item 1 wherein the aqueous liquid is water.
  • Item 3. The battery packaging material according to Item 1 or 2, wherein a lubricant is present on the surface of the laminate on the resin layer side.
  • Item 4. Item 4.
  • Item 5. Item 5.
  • Item 6. The battery packaging material according to any one of Items 1 to 5, wherein a light stabilizer is contained in at least one of the resin layer, the bonding layer, and the base material layer.
  • Item 7. Item 7. The battery packaging material according to Item 6, wherein the light stabilizer is a hindered amine light stabilizer.
  • the manufacturing method of the packaging material for batteries using the said joining layer contains the polyester resin and the said resin layer can peel from the said laminated body using an aqueous liquid.
  • Item 9 A battery in which a battery element including at least a positive electrode, a negative electrode, and an electrolyte is accommodated in a package formed of the battery packaging material according to any one of Items 1 to 7.
  • a laminate comprising a resin layer, a bonding layer, a base material layer, a barrier layer, and a heat-fusible resin layer in this order for a battery packaging material
  • the bonding layer includes a polyester resin
  • the present invention it is possible to provide a battery packaging material that can effectively suppress the deterioration of characteristics of the outer surface of the battery packaging material in the process of manufacturing the battery or the battery packaging material. Moreover, according to this invention, the manufacturing method of the said packaging material for batteries, the battery using the said packaging material for batteries, and the manufacturing method of the said battery can also be provided.
  • the battery packaging material of the present invention is composed of a laminate including at least a resin layer, a bonding layer, a base material layer, a barrier layer, and a heat-fusible resin layer in this order.
  • the resin layer is characterized in that the resin layer can be peeled off from the laminate using an aqueous liquid.
  • the numerical range indicated by “to” means “above” or “below”.
  • the notation of 2 to 15 mm means 2 mm or more and 15 mm or less.
  • the battery packaging material of the present invention comprises at least a resin layer 1a, a bonding layer 1b, a base material layer 2, a barrier layer 3, and a heat as shown in FIGS. It is comprised from the laminated body which has the fusible resin layer 4 in this order.
  • the resin layer 1a is the outermost layer
  • the heat-fusible resin layer 4 is the innermost layer. That is, when the battery is assembled, the battery element is sealed by heat-sealing the heat-fusible resin layers 4 positioned at the periphery of the battery element to seal the battery element.
  • FIG. 1 to 3 show a mode in which a laminate of a resin layer 1a and a bonding layer 1b containing a polyester resin constitutes the protective layer 1.
  • FIG. The bonding layer 1b is provided for bonding (more specifically, sticking) the resin layer 1a to another layer.
  • the bonding layer 1b can be referred to as an adhesive layer.
  • an adhesive layer is formed between the base material layer 2 and the barrier layer 3 as necessary for the purpose of enhancing the adhesion between them. 5 may be provided.
  • the battery packaging material 10 of the present invention is bonded between the barrier layer 3 and the heat-fusible resin layer 4 as necessary for the purpose of improving the adhesion between them.
  • a layer 6 may be provided.
  • illustration is abbreviate
  • the resin layer 1a can be peeled off from the laminate constituting the battery packaging material 10 using an aqueous liquid. This is because the bonding layer 1b has adhesiveness due to the polyester resin.
  • the resin layer 1a can be easily peeled from the laminate constituting the battery packaging material 10 using an aqueous liquid. Further, peeling using an aqueous liquid has little effect on the base material layer 2 and the surface coating layer, and even if the base material layer 2 absorbs moisture, it only needs to be dried. Can be suppressed.
  • the term “adhesiveness” or “adhesiveness” means a property of joining a plurality of objects, and is a concept included in a broad sense of adhesion, and is a sticking property (tackiness).
  • the aqueous liquid is not particularly limited as long as it is a liquid containing water, but specific examples of the aqueous liquid include water, a hydrous polar organic solvent, and the like.
  • the hydrous polar organic solvent include aqueous solutions of polar organic solvents such as alcohol, acetone, ethyl acetate, and dimethyl ether.
  • the aqueous solution of alcohol (hydrous alcohol) include aqueous solutions of lower alcohols such as methanol and ethanol.
  • the mass ratio of water to the polar solvent (water: polar solvent) in the hydrous polar organic solvent is about 100: 1 to 100: 100.
  • the aqueous liquid may be constituted by one type of liquid or may be constituted by two or more types of liquids.
  • the fact that the resin layer 1a can be peeled from the laminate means that the resin layer 1a can be peeled from the layer in contact with the bonding layer 1b.
  • the bonding layer 1b may be peeled off from the surface on the base material layer 2 side together with the resin layer 1a, and the components of the bonding layer 1b may remain on the surface on the base material layer 2 side.
  • the upper limit of the peel strength (A) of the resin layer 1a when water is adhered to the bonding layer 1b in an environment of temperature 25 ° C., relative humidity 50%, and atmospheric pressure (1 atm) is preferably about 1.0 N. / 15 mm or less, more preferably about 0.5 N / 15 mm or less, although there is no particular lower limit, preferably about 0.0 N / 15 mm or more, more preferably about 0.01 N / 15 mm or more, and still more preferably about 0.1 N / 15 mm or more is mentioned.
  • the range of the peel strength (A) is preferably about 0.0 to 1.0 N / 15 mm, about 0.0 to 0.5 N / 15 mm, about 0.01 to 1.0 N / 15 mm, 0.01 ⁇ 0.5 N / 15 mm, 0.1 ⁇ 1.0 N / 15 mm, and 0.1 ⁇ 0.5 N / 15 mm.
  • “releasable from the laminate using an aqueous liquid” means, for example, that the resin layer 1a can be easily peeled from the laminate using an aqueous liquid.
  • Strength (A) satisfies the above value.
  • the lower limit of the peel strength (B) of the resin layer 1a when water is not adhered to the bonding layer 1b in an environment of a temperature of 25 ° C., a relative humidity of 50%, and atmospheric pressure (1 atm) is preferably about 2. 0 N / 15 mm or more, more preferably about 2.2 N / 15 mm or more, and there is no particular upper limit, but preferably about 30.0 N / 15 mm or less.
  • the range of the peel strength (B) is preferably about 2.0 to 30.0 N / 15 mm, more preferably about 2.2 to 30.0 N / 15 mm.
  • the peel strength (B) of the resin layer 1a when water does not adhere to the bonding layer 1b is about 2.0 N / 15 mm or more, and water adheres to the bonding layer 1b.
  • the peel strength (A) of the resin layer 1a in the case of being made is preferably about 1.0 N / 15 mm or less, the peel strength (B) is about 2.2 N / 15 mm or more, and the peel strength More preferably, (A) is about 0.5 N / 15 mm or less.
  • the resin layer 1a has high peel strength before water adheres to the bonding layer 1b, and the battery is used as the outermost layer of the laminate constituting the battery packaging material.
  • the characteristic deterioration of the packaging material is suitably suppressed, and the peel strength of the resin layer 1a is reduced by attaching an aqueous liquid to the bonding layer 1b at a desired timing. More specifically, when water adheres to the bonding layer 1b, moisture penetrates into at least one of the resin layer 1a, the bonding layer 1b, and the base material layer 2, and the adhesive strength of the bonding layer 1b decreases. The peel strength of the resin layer 1a is reduced. Thereby, the resin layer 1a can be suitably peeled from the laminated body.
  • printing may be performed on the outside of the battery from the viewpoint of battery identification.
  • the battery packaging material of the present invention until printing is performed, the deterioration of the characteristics of the surface of the battery packaging material on the substrate layer 2 side is effectively suppressed, and an aqueous liquid is used when printing is performed.
  • an aqueous liquid is used when printing is performed.
  • the resin layer 1a is peeled off from the laminate using an aqueous liquid, so that the resin layer 1a becomes a pin of the barrier layer 3
  • the resin layer 1a becomes a pin of the barrier layer 3
  • the heat-fusible resin layer 4 is heat-sealed using the battery packaging material of the present invention having the resin layer 1a, the deterioration of the base material layer 2 and the surface coating layer due to high temperature and high pressure is caused by the resin layer. It can suppress effectively by the protection by 1a.
  • the resin layer 1a when using for the battery by which heat dissipation is calculated
  • the method for measuring the peel strength of the resin layer 1a in an environment of a temperature of 25 ° C., a relative humidity of 50%, and an atmospheric pressure (1 atm) is as follows.
  • the battery packaging material is cut into a rectangular shape of 100 mm (MD: Machine Direction) ⁇ 15 mm (TD: Transverse Direction) to obtain a test sample.
  • MD Machine Direction
  • TD Transverse Direction
  • 35% hydrochloric acid is attached to the end portions of the resin layer 1a and the bonding layer 1b of the test sample, and is shown in the schematic diagram of FIG.
  • the resin layer 1a is peeled off about 30 mm in the MD direction.
  • the hydrochloric acid adhering to the test sample is wiped off and dried as it is.
  • water (W) is made to adhere to the part from which the resin layer 1a has been peeled off (the bonding layer 1b between the resin layer 1a and the base layer 2 side surface) using a dropper. At this time, water (W) is adhered to the entire boundary in the TD direction at the boundary between the resin layer 1a and the surface of the base material layer 2 side. The water is used in such an amount that the water adheres sufficiently throughout the TD direction at the boundary portion.
  • the resin layer 1a is removed from the surface of the base material layer 2 side under the measurement conditions of a distance between chucks of 50 mm, a peeling speed of 50 mm / min, and a peeling angle of 180 °.
  • the peel strength when the distance between chucks reaches 57 mm is defined as the peel strength (N / 15 mm) with water attached.
  • the thickness of the laminate constituting the battery packaging material 10 of the present invention is not particularly limited, but the battery packaging material is excellent in moldability while reducing the thickness of the battery packaging material to increase the energy density of the battery. From the viewpoint of, for example, 180 ⁇ m or less, preferably 150 ⁇ m or less, more preferably about 60 to 180 ⁇ m, and still more preferably about 60 to 150 ⁇ m.
  • each layer forming the battery packaging material [resin layer 1a and bonding layer 1b]
  • the resin layer 1a is located in the outermost layer of the battery packaging material, and can be peeled from the laminate constituting the battery packaging material using an aqueous liquid at a desired timing. Is a layer.
  • the resin layer 1a is preferably laminated with a single bonding layer 1b to form a protective layer 1 having a two-layer structure.
  • the bonding layer 1b is adhered to the base material layer 2 (a surface coating layer when a surface coating layer described later is present).
  • the resin layer 1a is located on the outermost layer side.
  • the battery packaging material or the battery is damaged during transportation, the heat deterioration during heat fusion, the adhesion of the electrolyte when encapsulating the electrolyte, etc.
  • the surface characteristics of the packaging material for the base material layer 2 may be deteriorated, and such characteristic deterioration is required to be avoided as much as possible.
  • the battery packaging material of the present invention since the specific resin layer 1a and the bonding layer 1b that can be peeled are provided, in the process of manufacturing the battery or the battery packaging material, the battery packaging as in Patent Document 1 is provided. Heating, ultraviolet irradiation, or the like that deteriorates the characteristics of the outer surface of the material is unnecessary, and the deterioration of the characteristics of the outer surface of the battery packaging material can be effectively suppressed.
  • the bonding layer 1b contains a polyester resin. Moreover, it is preferable that the joining layer 1b is a thermoplastic resin.
  • the fact that the bonding layer 1b is a thermoplastic resin means that, for example, in measuring the displacement of the probe using thermomechanical analysis, a probe is placed on the surface of the bonding layer 1b at the end of the battery packaging material (laminate) and measured. When the probe is heated from 40 ° C. to 250 ° C. under the conditions that the deflection setting of the probe at the start is ⁇ 4 V and the heating rate is 5 ° C./min, the probe position is lower than the initial value. Can be confirmed.
  • the details of the probe displacement measurement using thermomechanical analysis are the same as the method described in the resin layer 1a described later. Moreover, it can confirm that the joining layer 1b contains the polyester resin, for example by infrared spectroscopy.
  • the polyester resin contained in the bonding layer 1b is not particularly limited as long as the bonding layer 1b can be peeled and adhered to a layer adjacent to the bonding layer 1b by contacting the aqueous liquid. Until the bonding layer 1b comes into contact with the aqueous liquid, it adheres firmly to the layer adjacent to the bonding layer 1b, and easily peels off from the layer adjacent to the bonding layer 1b when the bonding layer 1b comes into contact with the aqueous liquid. From the viewpoint of enabling, a polyester elastomer is preferable as a specific example of the polyester resin. Since the polyester elastomer is polyester, the heat resistance is good.
  • the polyester elastomer is polyester, the polarity is high and the wettability of the aqueous liquid is good, and it is easy to peel off using the aqueous liquid. Elastomers have many low molecular weight components and are easy to peel off.
  • the resin layer contains a polyester resin, the polyester elastomer has good adhesion to the polyester base material. Therefore, when the resin layer is peeled off, the bonding layer is peeled off together with the resin layer, and the base material layer 2 side. This is preferable because the components of the bonding layer hardly remain.
  • the polyester elastomer is not particularly limited, but is preferably a saturated polyester elastomer, and more preferably a saturated polyester elastomer containing a polyalkylene ether glycol segment.
  • a saturated polyester-based elastomer containing a polyalkylene ether glycol segment for example, a block copolymer composed of an aromatic polyester as a hard segment and a polyalkylene ether glycol or an aliphatic polyester as a soft segment is preferable.
  • the polyester polyether block copolymer which has polyalkylene ether glycol as a soft segment is more preferable.
  • the polyester polyether block copolymer includes (i) an aliphatic and / or alicyclic diol having 2 to 12 carbon atoms, and (ii) an aromatic dicarboxylic acid or an alkyl ester thereof and / or an aliphatic dicarboxylic acid or
  • the alkyl ester and (iii) polyalkylene ether glycol are used as raw materials, and those obtained by polycondensing oligomers obtained by esterification reaction or transesterification reaction are preferred.
  • the joining layer 1b contains an elastomer, for example by having tack property (viscosity) at normal temperature.
  • aliphatic and / or alicyclic diol having 2 to 12 carbon atoms for example, those generally used as a raw material for polyester, particularly as a raw material for polyester elastomer, can be used.
  • Specific examples include ethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and the like.
  • 1,4-butanediol or ethylene glycol is preferable, and 1,4-butanediol is particularly preferable.
  • These diols may be used alone or in combination of two or more.
  • aromatic dicarboxylic acid those generally used as raw materials for polyester, particularly polyester-based elastomers, can be used. Specific examples include terephthalic acid, isophthalic acid, phthalic acid, and 2,6-naphthalenedicarboxylic acid. Among these, terephthalic acid or 2,6-naphthalenedicarboxylic acid is preferable, and terephthalic acid is particularly preferable. These aromatic dicarboxylic acids may be used alone or in combination of two or more.
  • alkyl ester of aromatic dicarboxylic acid examples include dimethyl ester and diethyl ester of aromatic dicarboxylic acid. Among these, dimethyl terephthalate and 2,6-dimethyl naphthalene dicarboxylate are preferable.
  • aliphatic dicarboxylic acid cyclohexane dicarboxylic acid and the like are preferable, and as the alkyl ester, dimethyl ester and diethyl ester are preferable.
  • a small amount of a trifunctional alcohol, tricarboxylic acid or an ester thereof may be copolymerized, and an aliphatic dicarboxylic acid such as adipic acid or a dialkyl ester thereof may be used as a copolymerization component.
  • polyalkylene ether glycol examples include polyethylene glycol, poly (1,2- and / or 1,3-propylene ether) glycol, poly (tetramethylene ether) glycol compound, poly (hexamethylene ether) glycol compound, etc. Is mentioned. Of these, poly (tetramethylene ether) glycol compounds are preferred.
  • the poly (tetramethylene ether) glycol-based compound includes poly (tetramethylene ether) glycol and its related compounds.
  • the poly (hexamethylene ether) glycol-based compound includes poly (hexamethylene ether) glycol and its related compounds.
  • the preferable lower limit of the number average molecular weight of the polyalkylene ether glycol is about 400 or more, and the preferable upper limit is about 6000 or less.
  • the block property of the copolymer is increased, and by setting the upper limit to about 6000 or less, phase separation in the system hardly occurs and polymer physical properties are easily developed.
  • a more preferred lower limit is about 500 or more, a more preferred upper limit is about 4000 or less, a still more preferred lower limit is about 600 or more, and a still more preferred upper limit is about 3000 or less.
  • a number average molecular weight means what was measured by the gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • the measurement of the number average molecular weight by GPC is a standard polymer (polystyrene) conversion molecular weight.
  • the lower limit of the content of the polyalkylene ether glycol component is preferably about 5% by mass or more, more preferably About 30 mass% or more, More preferably, about 55 mass% or more is mentioned, Preferably an upper limit becomes like this. Preferably about 90 mass% or less, More preferably, about 80 mass% or less is mentioned.
  • the content of the polyalkylene ether glycol component can be calculated using nuclear magnetic resonance spectroscopy (H 1 -NMR measurement) based on the chemical shift of the hydrogen atom and its integrated value.
  • the polyester elastomer is preferably a modified polyester elastomer modified with a modifier.
  • the modification reaction for obtaining the modified polyester elastomer is carried out, for example, by reacting the polyester elastomer with an ⁇ , ⁇ -ethylenically unsaturated carboxylic acid as a modifier.
  • a graft reaction in which an ⁇ , ⁇ -ethylenically unsaturated carboxylic acid or a derivative thereof is added to a polyester elastomer mainly occurs, but a decomposition reaction also occurs.
  • the modified polyester elastomer may have a lower molecular weight and a lower melt viscosity.
  • a transesterification reaction or the like usually occurs as another reaction, and the obtained reaction product is generally a composition containing unreacted raw materials.
  • the content of the modified polyester elastomer in the obtained reaction product is about 10% by mass or more, more preferably about 30% by mass or more, and the content of the modified polyester elastomer is about 100% by mass. Further preferred.
  • Examples of the ⁇ , ⁇ -ethylenically unsaturated carboxylic acid used as the modifier include unsaturated carboxylic acids such as acrylic acid, maleic acid, fumaric acid, tetrahydrofumaric acid, itaconic acid, citraconic acid, crotonic acid, and isocrotonic acid.
  • unsaturated carboxylic acids such as acrylic acid, maleic acid, fumaric acid, tetrahydrofumaric acid, itaconic acid, citraconic acid, crotonic acid, and isocrotonic acid.
  • Unsaturated carboxylic acids such as oct-5-ene-2,3-dicarboxylic acid anhydride and bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic acid anhydride Anhydrides are mentioned. Of these, acid anhydrides are preferred because of their high reactivity.
  • the ⁇ , ⁇ -ethylenically unsaturated carboxylic acid can be appropriately selected according to the copolymer containing the polyalkylene ether glycol segment to be modified and the modification conditions, and two or more types may be used in combination. .
  • the ⁇ , ⁇ -ethylenically unsaturated carboxylic acid can also be used after being dissolved in an organic solvent.
  • radical generator examples include t-butyl hydroperoxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-bis (t -Butylperoxy) hexane, 3,5,5-trimethylhexanoyl peroxide, t-butylperoxybenzoate, benzoyl peroxide, dicumyl peroxide, 1,3-bis (t-butylperoxyisopropyl) benzene
  • Organic and inorganic peroxides such as dibutyl peroxide, methyl ethyl ketone peroxide, potassium peroxide, hydrogen peroxide, 2,2′-azobisisobutyronitrile, 2,2′-azobis (isobutylamide) dihalide, 2,2'-azobis [2-methyl-N- (2-hydroxy Ethyl) propionamide], azo compounds such as azodi -t- butan
  • the radical generator can be appropriately selected according to the type of polyester elastomer used in the modification reaction, the type of ⁇ , ⁇ -ethylenically unsaturated carboxylic acid and the modification conditions, and two or more types can be used in combination. Also good. Furthermore, the radical generator can be used by dissolving in an organic solvent.
  • the preferable lower limit of the blending amount of the ⁇ , ⁇ -ethylenically unsaturated carboxylic acid is about 0.01 parts by mass or more and the preferable upper limit is about 30.0 parts by mass or less with respect to 100 parts by mass of the polyester elastomer.
  • the amount is about 0.01 parts by mass or more, the modification reaction can be sufficiently performed, and when the amount is about 30.0 parts by mass or less, it is economically advantageous.
  • a more preferred lower limit is about 0.05 parts by mass or more, a more preferred upper limit is about 5.0 parts by mass or less, a further preferred lower limit is about 0.10 parts by mass or more, and a more preferred upper limit is about 1.0 part by mass or less.
  • the preferable lower limit of the blending amount of the radical generator is about 0.001 part by mass or more with respect to 100 parts by mass of the polyester elastomer, and the preferable upper limit is about 3.00 part by mass or less.
  • the preferable upper limit is about 3.00 part by mass or less.
  • a more preferred lower limit is about 0.005 parts by mass or more
  • a more preferred upper limit is about 0.50 parts by mass or less
  • a still more preferred lower limit is about 0.010 parts by mass or more
  • a more preferred upper limit is about 0.20 parts by mass or less.
  • a particularly preferred upper limit is about 0.10 parts by mass or less.
  • reaction methods such as a melt-kneading reaction method, a solution reaction method, and a suspension-dispersion reaction can be used. Reaction methods are preferred.
  • the above-described components are uniformly mixed at a predetermined blending ratio and then melt kneaded.
  • Henschel mixer, ribbon blender, V-type blender, etc. can be used for mixing each component, and Banbury mixer, kneader, roll, uniaxial or biaxial multi-screw kneading extruder etc. are used for melt-kneading. can do.
  • the preferred lower limit of the kneading temperature when melt kneading is about 100 ° C. or more, and the preferred upper limit is about 300 ° C. or less. By setting it within the above range, thermal deterioration of the resin can be prevented.
  • a more preferred lower limit is about 120 ° C. or more, a more preferred upper limit is about 280 ° C. or less, a still more preferred lower limit is about 150 ° C. or more, and a still more preferred upper limit is about 250 ° C. or less.
  • the preferable lower limit of the modification rate (graft amount) of the modified polyester elastomer is about 0.01% by mass or more, and the preferable upper limit is about 10.0% by mass or less.
  • the content is about 0.01% by mass or more, the affinity with the polyester is increased, and when the content is about 10.0% by mass or less, a decrease in strength due to molecular degradation during modification can be reduced.
  • a more preferred lower limit is about 0.03% by mass or more, a more preferred upper limit is about 7.0% by mass or less, a still more preferred lower limit is about 0.05% by mass or more, and a further more preferred upper limit is about 5.0% by mass or less. is there.
  • the modification rate (graft amount) of the modified polyester elastomer can be determined from the spectrum obtained by H 1 -NMR measurement.
  • the material constituting the resin layer 1a is not particularly limited, and examples thereof include a thermoplastic resin and a thermosetting resin, and preferably a thermoplastic resin. Although it does not restrict
  • the resin layer 1a is preferably made of a biaxially stretched polyester film. The biaxially stretched polyester film has enhanced orientation and is excellent in moldability, tensile strength, and puncture strength.
  • the resin constituting the resin layer 1a may be only one type or two or more types.
  • polyester resin examples include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and copolyester.
  • the polyester resin may be composed of only one type or may be composed of two or more types.
  • the polyester resin may contain, for example, polyethylene terephthalate as a main component (the content is, for example, 90% by mass or more, 95% by mass or more, 99% by mass or more), and polybutylene terephthalate may be included as a subcomponent.
  • the resin constituting the resin layer 1a preferably has a higher melting point than the resin constituting the base material layer 2. Due to the high melting point of the resin constituting the resin layer 1a, the deterioration of the base material layer 2 due to high temperature and high pressure when the heat-fusible resin layer 4 of the battery packaging material is heat-sealed is caused by the resin layer 1a. It can suppress effectively by protection by. As an aspect in which the deterioration suppressing effect of the base material layer 2 by the resin layer 1a is particularly effectively exhibited, there is an aspect in which the resin layer 1a is made of a polyester resin and the base material layer 2 is made of polyamide.
  • the probe in the resin layer 1a, in the probe displacement measurement using thermomechanical analysis, the probe is placed on the surface of the resin layer 1a at the end of the battery packaging material (laminate), and the probe at the start of measurement
  • the probe is heated from 40 ° C. to 220 ° C. under the condition that the deflection is set to -4V and the temperature raising rate is 5 ° C./min
  • the position of the probe is preferably not lower than the initial value. .
  • the probe In measuring the displacement of the probe, first, the probe is placed on the surface of the resin layer 1a at the end of the battery packaging material (laminated body).
  • the edge part at this time is a part where the cross section of the resin layer 1a obtained by cutting in the thickness direction so as to pass through the central part of the battery packaging material is exposed. Cutting can be performed using a commercially available rotary microtome or the like.
  • the amount of displacement is measured for battery packaging materials used in batteries encapsulating electrolytes, etc., the portions where the heat-fusible resin layers of the battery packaging materials are heat-sealed together. , Measure.
  • a cantilever with a heating mechanism for example, an afm plus system manufactured by ANASIS INSTRUMENTS is used, and a cantilever ThermoLever AN2-200 manufactured by ANASYS INSTRUMENTS is used as a probe (spring constant 0.5 to 3 N / m). ) Can be used.
  • the probe tip radius is 30 nm or less, the probe deflection setting is ⁇ 4 V, and the temperature rise rate is 5 ° C./min.
  • the probe position is the initial value (position when the probe temperature is 40 ° C.).
  • the heating temperature is further increased, the resin layer 1a is softened, the probe is pierced into the resin layer 1a, and the position of the probe is lowered.
  • the probe displacement measurement using an atomic force microscope including a nanothermal microscope composed of a cantilever with a heating mechanism the battery packaging material to be measured is in a room temperature (25 ° C.) environment. A probe heated to ° C is placed on the surface of the resin layer 1a, and measurement is started.
  • the set value of the deflection of the probe at the start of measurement is ⁇ 4 V, and the temperature rising rate is 5 ° C./min.
  • the position of the probe installed on the surface of the resin layer 1a is not lowered below the initial value (position when the probe temperature is 40 ° C.). It is more preferable that the position of the probe placed on the surface of the resin layer 1a does not decrease when heated from 200C to 200C.
  • the step of heat-sealing the heat-fusible resin layers of the battery packaging material to seal the battery element is usually performed by heating at about 160 ° C. to 200 ° C.
  • the battery packaging material in which the position of the probe installed on the surface of the resin layer 1a does not decrease can exhibit particularly high heat resistance.
  • the position of the probe placed on the surface of the resin layer 1a is not lowered below the initial value, and further, heated from 160 ° C. to 200 ° C. More preferably, the position of the probe placed on the surface of the resin layer 1a does not decrease.
  • the thickness of the resin layer 1a is not particularly limited, but is preferably about 2 to 50 ⁇ m, more preferably about 2 to 20 ⁇ m, from the viewpoint of suppressing deterioration of surface characteristics on the base material layer 2 side of the battery packaging material. More preferably, it is about 2 to 10 ⁇ m.
  • the thickness of the bonding layer 1b is preferably about 0.2 to 10 ⁇ m, more preferably about 0.2 to 5 ⁇ m, and still more preferably about 0.2 to 3 ⁇ m.
  • the total thickness of the resin layer 1a and the bonding layer 1b is preferably about 2 to 50 ⁇ m, more preferably about 2 to 20 ⁇ m, and further preferably about 2 to 10 ⁇ m.
  • a lubricant may be present on the surface of the resin layer 1a. Since the lubricant is present on the surface of the resin layer 1a, the moldability of the battery packaging material can be improved.
  • the type of the lubricant is not particularly limited, and examples thereof include the same lubricants exemplified in the heat-fusible resin layer described later.
  • Preferable lubricants are erucic acid amide, palmitic acid amide, stearic acid amide, and oleic acid amide, and more preferable lubricant is erucic acid amide.
  • the amount of lubricant present on the surface of the resin layer 1a is preferably about 2 to 20 g / m 2 , more preferably about 3 to 17 g / m 2 , and further preferably about 3 to 8 g / m 2 .
  • the lubricant present on the surface of the resin layer 1a may be exuded from the inside of the resin layer 1a, or may be applied on the surface of the resin layer 1a.
  • the amount of lubricant present on the surface of the resin layer 1a can be confirmed by the following measuring method.
  • a battery packaging material is cut into A4 size (ISO 216) to prepare a sample.
  • the resin layer surface of each sample is washed with acetone, and the collected acetone is volatilized and dried by nitrogen blowing to obtain a solid.
  • 10 ml of chloroform was added to the solid substance to redissolve the solid substance, and a gas chromatograph (GC, for example, GC-2010 manufactured by Shimadzu Corporation, column: UltraALLOY-1 (MS / HT), detector: FID, Quantitative method: Absolute calibration curve method) is used to measure the amount of lubricant on the resin layer surface.
  • GC gas chromatograph
  • Base material layer 2 In the battery packaging material of the present invention, after the resin layer 1a is peeled off, the base material layer 2 becomes a layer located on the outermost layer side. When no other layer (for example, a surface coating layer described later) is provided between the resin layer 1a and the base material layer 2, the base material layer 2 is a layer adjacent to the bonding layer 1b.
  • the material for forming the base material layer 2 is not particularly limited as long as it has insulating properties.
  • the material for forming the base material layer 2 include resin films such as polyester resin, polyamide resin, epoxy resin, acrylic resin, fluorine resin, polyurethane resin, silicon resin, phenol resin, and mixtures and copolymers thereof. Can be mentioned. Among these, Preferably a polyester resin and a polyamide resin are mentioned, More preferably, a biaxially stretched polyester resin and a biaxially stretched polyamide resin are mentioned.
  • the polyester resin include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, copolymerized polyester, and polycarbonate.
  • polyamide resin examples include nylon 6, nylon 66, a copolymer of nylon 6 and nylon 66, nylon 6,10, polymetaxylylene adipamide (MXD6), and the like.
  • the polyamide resin may be composed of only one type or may be composed of two or more types.
  • the polyamide resin may contain, for example, nylon 6 and polymetaxylylene adipamide (MXD6).
  • the base material layer 2 may be formed from a single resin film, but may be formed from two or more resin films in order to improve pinhole resistance and insulation. Specific examples include a multilayer structure in which a polyester film and a nylon film are laminated, a multilayer structure in which a plurality of nylon films are laminated, a multilayer structure in which a plurality of polyester films are laminated, and the like.
  • the base material layer 2 has a multilayer structure, a laminate of a biaxially stretched nylon film and a biaxially stretched polyester film, a laminate of a plurality of biaxially stretched nylon films, and a laminate of a plurality of biaxially stretched polyester films The body is preferred.
  • the base material layer 2 is formed from two resin films, a configuration in which a polyester resin and a polyester resin are stacked, a configuration in which a polyamide resin and a polyamide resin are stacked, or a configuration in which a polyester resin and a polyamide resin are stacked are used. It is more preferable to use a structure in which polyethylene terephthalate and polyethylene terephthalate are laminated, a structure in which nylon and nylon are laminated, or a structure in which polyethylene terephthalate and nylon are laminated.
  • the thickness of each layer is preferably about 2 to 25 ⁇ m.
  • the two or more resin films may be laminated via an adhesive component such as an adhesive or an adhesive resin, and the type and amount of the adhesive component used. This is the same as in the case of the adhesive layer 5 described later.
  • an adhesive component such as an adhesive or an adhesive resin
  • stacking two or more resin films A well-known method can be employ
  • laminating by the dry laminating method it is preferable to use a urethane-based adhesive as the adhesive layer. At this time, the thickness of the adhesive layer is, for example, about 2 to 5 ⁇ m.
  • the thickness of the base material layer 2 is not particularly limited as long as it exhibits a function as a base material layer, and is, for example, about 3 to 50 ⁇ m, preferably about 10 to 35 ⁇ m.
  • the adhesive layer 5 is a layer provided between the base material layer 2 and the barrier layer 3 as necessary in order to firmly bond the base material layer 2 and the barrier layer 3.
  • the adhesive layer 5 is formed of an adhesive capable of bonding the base material layer 2 and the barrier layer 3 together.
  • the adhesive used for forming the adhesive layer 5 may be a two-component curable adhesive or a one-component curable adhesive.
  • the adhesive mechanism of the adhesive used for forming the adhesive layer 5 is not particularly limited, and may be any of a chemical reaction type, a solvent volatilization type, a heat melting type, and a hot pressure type.
  • adhesive components that can be used to form the adhesive layer 5 include polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene isophthalate, polycarbonate, and copolyester; Polyether adhesives; Polyurethane adhesives; Epoxy resins; Phenol resin resins; Polyamide resins such as nylon 6, nylon 66, nylon 12 and copolymerized polyamides; polyolefins, carboxylic acid modified polyolefins, metal modified polyolefins, etc.
  • polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene isophthalate, polycarbonate, and copolyester
  • Polyether adhesives such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate
  • Polyolefin resins polyvinyl acetate resins; Cellulosic adhesives; (Meth) acrylic resins; Polyimide resins; Urea resins, melamine resins and other amino resins; Chloroprene rubber, Nitriles - arm, styrene rubbers such as butadiene rubber; and silicone resins.
  • These adhesive components may be used individually by 1 type, and may be used in combination of 2 or more type. Among these adhesive components, a polyurethane adhesive is preferable.
  • the thickness of the adhesive layer 5 is not particularly limited as long as it exhibits a function as an adhesive layer, and for example, it is about 1 to 10 ⁇ m, preferably about 2 to 5 ⁇ m.
  • An ultraviolet absorber for a layer outside the barrier layer 3 of the battery packaging material of the present invention (preferably at least one of the resin layer 1a, the bonding layer 1b, the base material layer 2 and the adhesive layer 5), It is preferable to contain at least one component among the light stabilizer and the antioxidant. By including one of these components, delamination between layers is effectively suppressed outside the barrier layer 3.
  • delamination of the layer outside the barrier layer 3 of the battery packaging material mainly means delamination between these layers.
  • GC / MS gas chromatograph mass spectrometer
  • HPLC liquid chromatography
  • the ultraviolet absorber contained in the outer layer (preferably at least one of the resin layer 1a, the bonding layer 1b, the base material layer 2, and the adhesive layer 5) of the battery packaging material of the present invention.
  • the total content of is preferably 10 to 500 ppm, more preferably about 30 to 100 ppm, and particularly preferably about 40 to 80 ppm from the viewpoint of interlayer adhesion stability.
  • the total content of the light stabilizer is preferably 10 to 500 ppm, more preferably about 100 to 200 ppm, and particularly preferably 120 to 180 ppm from the viewpoint of interlayer adhesion stability.
  • the total content of the antioxidant is preferably 10 to 1000 ppm, more preferably about 200 to 800 ppm, and particularly preferably about 420 to 600 ppm from the viewpoint of interlayer adhesion stability.
  • the type of the ultraviolet absorber is not particularly limited, but a benzotriazole-based ultraviolet absorber is preferable.
  • Specific examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone).
  • 2-hydroxybenzophenones such as 2-; 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3, 5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5 -Dicumylphenyl) benzotriazole, 2,2'-methylenebis (4-tertiary o Polyethylene glycol ester of 2- (2-hydroxy-3-tert-butyl-5-carboxyphenyl) benzotriazole, 2- [2-hydroxy-3- (2-acryloyloxy) Ethyl) -5-methylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-butylphenyl]
  • UV absorbers examples include TINUVIN571, TINUVIN460, TINUVIN213, TINUVIN234, TINUVIN329, and TINUVIN326 manufactured by BASF, and among these, TINUVIN326 (2- [5-chloro (2H) -benzotriazole- 2-yl] -4-methyl-6- (tert-butyl) phenol) is effective.
  • UV absorbers may be used alone or in combination of two or more.
  • the type of light stabilizer is not particularly limited, but a hindered amine light stabilizer is preferable.
  • Specific examples of the light stabilizer include, for example, 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2, 6,6-tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1 , 2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (2,2, 6,6-tetramethyl-4-piperidyl) -di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,
  • TINUVIN 765 TINUVIN 770
  • TINUVIN 780 TINUVIN 780
  • TINUVIN 144 TINUVIN 144
  • TINUVIN 622LD TINUVIN 622LD manufactured by BASF
  • TINUVIN 770 bis (2,2,6,6-tetramethyl-4-piperidyl sebacate)
  • One kind of light stabilizer may be used alone, or two or more kinds may be used in combination.
  • the type of the antioxidant is not particularly limited, but preferably a hindered phenol antioxidant is used.
  • the antioxidant include Irganox 1330 (2,4,6-tris (3 ′, 5′-di-tert-butyl-4′-hydroxybenzyl) mesitylene), Irganox 1098 (N, N′-hexamethylenebis) [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propanamide]), Irganox 1010 (tetrakis [3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propion Acid] pentaerythritol).
  • a layer outside the barrier layer 3 of the battery packaging material of the present invention preferably, a resin layer 1a, a bonding layer 1b, a base material
  • the total content of Irganox 1330 contained in at least one of the layer 2 and the adhesive layer 5 is preferably about 10 to 500 ppm, more preferably about 90 to 200 ppm, and particularly preferably about 110 to 170 ppm. .
  • One type of antioxidant may be used alone, or two or more types may be used in combination.
  • the barrier layer 3 is a layer having a function of preventing water vapor, oxygen, light and the like from entering the battery, in addition to improving the strength of the battery packaging material.
  • the barrier layer 3 is preferably a metal layer, that is, a layer formed of metal. Specific examples of the metal constituting the barrier layer 3 include aluminum, stainless steel, and titanium, and preferably aluminum.
  • the barrier layer 3 can be formed by, for example, a metal foil, a metal vapor-deposited film, an inorganic oxide vapor-deposited film, a carbon-containing inorganic oxide vapor-deposited film, a film provided with these vapor-deposited films, etc. Is preferable, and it is more preferable to form with an aluminum alloy foil.
  • the barrier layer is made of, for example, annealed aluminum (JIS H4160: 1994 A8021H-O, JIS H4160: 1994 A8079H-O, JIS H4000: 2014 A8021P-O, JIS H4000: 2014 A8079P-O) and the like are more preferable.
  • the thickness of the barrier layer 3 is not particularly limited as long as it functions as a barrier layer such as water vapor, but is preferably about 100 ⁇ m or less, more preferably about 10 to 100 ⁇ m from the viewpoint of reducing the thickness of the battery packaging material. More preferably, about 10 to 80 ⁇ m is mentioned.
  • the barrier layer 3 is preferably subjected to chemical conversion treatment on at least one side, preferably both sides, in order to stabilize adhesion, prevent dissolution and corrosion, and the like.
  • the chemical conversion treatment refers to a treatment for forming an acid-resistant film on the surface of the barrier layer.
  • chromate treatment using a chromium compound such as chromium nitrate, chromium fluoride, chromium sulfate, chromium acetate, chromium oxalate, chromium biphosphate, chromic acid acetyl acetate, chromium chloride, potassium sulfate chromium; Phosphoric acid treatment using a phosphoric acid compound such as sodium phosphate, potassium phosphate, ammonium phosphate, polyphosphoric acid; an aminated phenol polymer having a repeating unit represented by the following general formulas (1) to (4) is used And chromate treatment.
  • the repeating units represented by the following general formulas (1) to (4) may be contained singly or in any combination of two or more. Also good.
  • X represents a hydrogen atom, a hydroxy group, an alkyl group, a hydroxyalkyl group, an allyl group or a benzyl group.
  • R 1 and R 2 are the same or different and each represents a hydroxy group, an alkyl group, or a hydroxyalkyl group.
  • examples of the alkyl group represented by X, R 1 and R 2 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, Examples thereof include straight-chain or branched alkyl groups having 1 to 4 carbon atoms such as a tert-butyl group.
  • Examples of the hydroxyalkyl group represented by X, R 1 and R 2 include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, 3- Linear or branched chain having 1 to 4 carbon atoms substituted with one hydroxy group such as hydroxypropyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group An alkyl group is mentioned.
  • the alkyl group and hydroxyalkyl group represented by X, R 1 and R 2 may be the same or different.
  • X is preferably a hydrogen atom, a hydroxy group or a hydroxyalkyl group.
  • the number average molecular weight of the aminated phenol polymer having a repeating unit represented by the general formulas (1) to (4) is preferably about 500 to 1,000,000, for example, about 1,000 to 20,000. More preferred.
  • a phosphoric acid is coated with a metal oxide such as aluminum oxide, titanium oxide, cerium oxide, tin oxide, or barium sulfate fine particles dispersed therein.
  • a method of forming an acid-resistant film on the surface of the barrier layer 3 by performing a baking treatment at 150 ° C. or higher can be mentioned.
  • a resin layer obtained by crosslinking a cationic polymer with a crosslinking agent may be further formed on the acid resistant film.
  • examples of the cationic polymer include polyethyleneimine, an ionic polymer complex composed of a polymer having polyethyleneimine and a carboxylic acid, a primary amine graft acrylic resin obtained by graft polymerization of a primary amine on an acrylic main skeleton, and polyallylamine. Or the derivative, aminophenol, etc. are mentioned.
  • these cationic polymers only one type may be used, or two or more types may be used in combination.
  • examples of the crosslinking agent include a compound having at least one functional group selected from the group consisting of an isocyanate group, a glycidyl group, a carboxyl group, and an oxazoline group, and a silane coupling agent. As these crosslinking agents, only one type may be used, or two or more types may be used in combination.
  • At least the surface on the inner layer side of the aluminum alloy foil is firstly immersed in an alkali soaking method, electrolytic cleaning method, acid cleaning method, electrolytic acid cleaning method.
  • Treatment liquid (aqueous solution) mainly composed of a mixture of metal salts, or treatment liquid (aqueous solution) principally composed of a non-metallic phosphate and a mixture of these non-metallic salts, or acrylic resin Coating a treatment liquid (aqueous solution) consisting of a mixture with a water-based synthetic resin such as phenolic resin or urethane resin by a well-known coating method such as roll coating, gravure printing, or dipping.
  • the acid-resistant coating For example, when treated with a chromium phosphate salt treatment solution, it becomes an acid-resistant film made of chromium phosphate, aluminum phosphate, aluminum oxide, aluminum hydroxide, aluminum fluoride, etc., and treated with a zinc phosphate salt treatment solution. In this case, an acid-resistant film made of zinc phosphate hydrate, aluminum phosphate, aluminum oxide, aluminum hydroxide, aluminum fluoride or the like is obtained.
  • an acid-resistant film for example, at least the surface on the inner layer side of the aluminum alloy foil is first subjected to an alkali dipping method, an electrolytic cleaning method, an acid cleaning method, an electrolytic acid cleaning method, an acid An acid-resistant film can be formed by performing a degreasing process by a known processing method such as an activation method and then performing a known anodizing process on the degreasing surface.
  • acid-resistant films include phosphate-based and chromic acid-based films.
  • phosphate-based and chromic acid-based films examples include zinc phosphate, iron phosphate, manganese phosphate, calcium phosphate, and chromium phosphate.
  • chromic acid system examples include chromium chromate.
  • an acid-resistant film by forming an acid-resistant film such as phosphate, chromate, fluoride, triazine thiol compound, between the aluminum and the base material layer at the time of embossing molding
  • an acid-resistant film such as phosphate, chromate, fluoride, triazine thiol compound
  • hydrogen fluoride generated by the reaction between electrolyte and moisture prevents dissolution and corrosion of the aluminum surface, especially the dissolution and corrosion of aluminum oxide present on the aluminum surface, and adhesion of the aluminum surface This improves the wettability and prevents delamination between the base material layer and aluminum at the time of heat sealing.
  • embossed type it shows the effect of preventing delamination between the base material layer and aluminum at the time of press molding.
  • an aqueous solution composed of three components of a phenol resin, a chromium (III) fluoride compound, and phosphoric acid is applied to the aluminum surface, and the dry baking treatment is good.
  • the acid-resistant film includes a layer having cerium oxide, phosphoric acid or phosphate, an anionic polymer, and a crosslinking agent that crosslinks the anionic polymer, and the phosphoric acid or phosphate is About 1 to 100 parts by mass may be blended with 100 parts by mass of cerium oxide. It is preferable that the acid-resistant film has a multilayer structure further including a layer having a cationic polymer and a crosslinking agent for crosslinking the cationic polymer.
  • the anionic polymer is poly (meth) acrylic acid or a salt thereof, or a copolymer containing (meth) acrylic acid or a salt thereof as a main component.
  • the said crosslinking agent is at least 1 sort (s) chosen from the group which has a functional group in any one of an isocyanate group, a glycidyl group, a carboxyl group, and an oxazoline group, and a silane coupling agent.
  • the phosphoric acid or the phosphate is a condensed phosphoric acid or a condensed phosphate.
  • the chemical conversion treatment only one type of chemical conversion treatment may be performed, or two or more types of chemical conversion processing may be performed in combination. Furthermore, these chemical conversion treatments may be carried out using one kind of compound alone, or may be carried out using a combination of two or more kinds of compounds.
  • a chromate chromate treatment a chemical conversion treatment combining a chromium compound, a phosphoric acid compound, and an aminated phenol polymer are preferable.
  • chromium compounds chromic acid compounds are preferred.
  • the acid resistant film examples include those containing at least one of phosphate, chromate, fluoride, and triazine thiol.
  • An acid resistant film containing a cerium compound is also preferable.
  • cerium compound cerium oxide is preferable.
  • the acid resistant film examples include a phosphate film, a chromate film, a fluoride film, and a triazine thiol compound film.
  • a phosphate film As an acid-resistant film, one of these may be used, or a plurality of combinations may be used.
  • a treatment solution comprising a mixture of a metal phosphate and an aqueous synthetic resin, or a mixture of a non-metal phosphate and an aqueous synthetic resin It may be formed of a treatment liquid consisting of
  • the composition of the acid resistant film can be analyzed using, for example, time-of-flight secondary ion mass spectrometry.
  • time-of-flight secondary ion mass spectrometry for example, a peak derived from at least one of Ce + and Cr + is detected.
  • the surface of the aluminum alloy foil is provided with an acid resistant film containing at least one element selected from the group consisting of phosphorus, chromium and cerium.
  • the acid-resistant film on the surface of the aluminum alloy foil of the battery packaging material contains at least one element selected from the group consisting of phosphorus, chromium and cerium using X-ray photoelectron spectroscopy. can do. Specifically, first, in the battery packaging material, the heat-fusible resin layer, the adhesive layer, and the like laminated on the aluminum alloy foil are physically peeled off. Next, the aluminum alloy foil is put in an electric furnace, and organic components present on the surface of the aluminum alloy foil are removed at about 300 ° C. for about 30 minutes. Then, it confirms that these elements are contained using the X-ray photoelectron spectroscopy of the surface of aluminum alloy foil.
  • the amount of the acid-resistant film to be formed on the surface of the barrier layer 3 in the chemical conversion treatment is not particularly limited.
  • the chromium compound is chromium per 1 m 2 of the surface of the barrier layer 3.
  • About 0.5 to 50 mg in terms of conversion preferably about 1.0 to 40 mg, about 0.5 to 50 mg, preferably about 1.0 to 40 mg in terms of phosphorus, and about 1.0 to 40 mg of aminated phenol polymer. It is desirable that it is contained in a proportion of about 200 mg, preferably about 5.0 to 150 mg.
  • the thickness of the acid-resistant film is not particularly limited, but is preferably about 1 nm to 10 ⁇ m, more preferably 1 to 100 nm, from the viewpoint of the cohesive strength of the film and the adhesive strength with the aluminum alloy foil or the heat-fusible resin layer. About 1 to 50 nm is preferable.
  • the thickness of the acid-resistant film can be measured by observation with a transmission electron microscope or a combination of observation with a transmission electron microscope and energy dispersive X-ray spectroscopy or electron energy loss spectroscopy.
  • a solution containing a compound used for forming an acid-resistant film is applied to the surface of the barrier layer by a bar coating method, a roll coating method, a gravure coating method, a dipping method, etc., and then the temperature of the barrier layer is 70. It is performed by heating to about 200 ° C.
  • the barrier layer may be previously subjected to a degreasing treatment by an alkali dipping method, an electrolytic cleaning method, an acid cleaning method, an electrolytic acid cleaning method, or the like. By performing the degreasing process in this manner, it is possible to more efficiently perform the chemical conversion process on the surface of the barrier layer.
  • the heat-fusible resin layer 4 corresponds to the innermost layer, and is a layer that heat-fuses the heat-fusible resin layers and seals the battery element when the battery is assembled.
  • the resin component used for the heat-fusible resin layer 4 is not particularly limited as long as it can be heat-sealed, and examples thereof include polyolefin, cyclic polyolefin, acid-modified polyolefin, and acid-modified cyclic polyolefin. That is, the heat-fusible resin layer 4 may include a polyolefin skeleton, and preferably includes a polyolefin skeleton. The fact that the heat-fusible resin layer 4 contains a polyolefin skeleton can be analyzed by, for example, infrared spectroscopy, gas chromatography mass spectrometry, etc., and the analysis method is not particularly limited.
  • a peak derived from maleic acid is detected in the vicinity of the wave number of 1760 cm -1 and near the wave number 1780 cm -1.
  • the peak may be small and may not be detected. In that case, it can be analyzed by nuclear magnetic resonance spectroscopy.
  • polystyrene resin examples include polyethylene such as low density polyethylene, medium density polyethylene, high density polyethylene, and linear low density polyethylene; homopolypropylene, block copolymer of polypropylene (for example, block copolymer of propylene and ethylene), polypropylene Polypropylenes such as random copolymers of (for example, random copolymers of propylene and ethylene); ethylene-butene-propylene terpolymers, and the like.
  • polyethylene and polypropylene are preferable.
  • the cyclic polyolefin is a copolymer of an olefin and a cyclic monomer, and examples of the olefin that is a constituent monomer of the cyclic polyolefin include ethylene, propylene, 4-methyl-1-pentene, butadiene, and isoprene. .
  • examples of the cyclic monomer that is a constituent monomer of the cyclic polyolefin include cyclic alkenes such as norbornene; specifically, cyclic dienes such as cyclopentadiene, dicyclopentadiene, cyclohexadiene, and norbornadiene.
  • a cyclic alkene is preferable, and norbornene is more preferable.
  • the acid-modified polyolefin is a polymer obtained by modifying the polyolefin by block polymerization or graft polymerization with an acid component such as carboxylic acid.
  • an acid component such as carboxylic acid.
  • the acid component used for modification include carboxylic acids such as maleic acid, acrylic acid, itaconic acid, crotonic acid, maleic anhydride, and itaconic anhydride, or anhydrides thereof.
  • the acid-modified cyclic polyolefin is obtained by copolymerizing a part of the monomer constituting the cyclic polyolefin in place of the ⁇ , ⁇ -unsaturated carboxylic acid or its anhydride, or by ⁇ , ⁇ - It is a polymer obtained by block polymerization or graft polymerization of an unsaturated carboxylic acid or its anhydride.
  • the cyclic polyolefin to be modified with carboxylic acid is the same as described above.
  • the carboxylic acid used for modification is the same as the acid component used for modification of the polyolefin.
  • polyolefins such as polypropylene and carboxylic acid-modified polyolefins; and more preferred are polypropylene and acid-modified polypropylene.
  • the heat-fusible resin layer 4 may be formed of one kind of resin component alone or may be formed of a blend polymer in which two or more kinds of resin components are combined. Furthermore, the heat-fusible resin layer 4 may be formed of only one layer, but may be formed of two or more layers using the same or different resin components.
  • a lubricant adheres to the surface of the heat-fusible resin layer from the viewpoint of improving the moldability of the battery packaging material.
  • an amide type lubricant is mentioned.
  • Specific examples of the amide-based lubricant include saturated fatty acid amide, unsaturated fatty acid amide, substituted amide, methylolamide, saturated fatty acid bisamide, unsaturated fatty acid bisamide, and the like.
  • Specific examples of the saturated fatty acid amide include lauric acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, hydroxy stearic acid amide and the like.
  • the unsaturated fatty acid amide include oleic acid amide and erucic acid amide.
  • substituted amide include N-oleyl palmitic acid amide, N-stearyl stearic acid amide, N-stearyl oleic acid amide, N-oleyl stearic acid amide, N-stearyl erucic acid amide and the like.
  • methylolamide include methylol stearamide.
  • saturated fatty acid bisamides include methylene bis stearamide, ethylene biscapric amide, ethylene bis lauric acid amide, ethylene bis stearic acid amide, ethylene bishydroxy stearic acid amide, ethylene bisbehenic acid amide, hexamethylene bis stearic acid amide.
  • unsaturated fatty acid bisamides include ethylene bisoleic acid amide, ethylene biserucic acid amide, hexamethylene bisoleic acid amide, N, N′-dioleyl adipic acid amide, N, N′-dioleyl sebacic acid amide Etc.
  • fatty acid ester amide include stearoamidoethyl stearate.
  • aromatic bisamide include m-xylylene bis stearic acid amide, m-xylylene bishydroxy stearic acid amide, N, N′-distearyl isophthalic acid amide and the like.
  • One type of lubricant may be used alone, or two or more types may be used in combination.
  • the amount of the lubricant is not particularly limited, but is preferably about 3 mg / m 2 or more, more preferably in an environment of a temperature of 24 ° C. and a relative humidity of 60%. Is about 4 to 15 mg / m 2 , more preferably about 5 to 14 mg / m 2 .
  • a lubricant may be contained in the heat-fusible resin layer 4. Further, the lubricant present on the surface of the heat-fusible resin layer 4 may be one in which a lubricant contained in the resin constituting the heat-fusible resin layer 4 is exuded, or the heat-fusible resin layer. 4 may be obtained by applying a lubricant to the surface.
  • the thickness of the heat-fusible resin layer 4 can be set according to the presence or absence of the adhesive layer 5, the thickness of the adhesive layer 5, and the like, and particularly if the function as the heat-fusible resin layer is exhibited.
  • the upper limit is, for example, about 100 ⁇ m or less, preferably about 85 ⁇ m or less, more preferably 60 ⁇ m or less
  • the lower limit is, for example, about 15 ⁇ m or more, preferably 20 ⁇ m or more. Examples thereof include about 15 to 100 ⁇ m, about 15 to 85 ⁇ m, about 15 to 60 ⁇ m, about 20 to 100 ⁇ m, about 20 to 85 ⁇ m, about 20 to 60 ⁇ m, and about 15 to 40 ⁇ m.
  • the upper limit of the thickness of the heat-fusible resin layer 4 is preferably about 85 ⁇ m or less, more preferably about 60 ⁇ m or less.
  • the lower limit is, for example, about 15 ⁇ m or more, preferably 20 ⁇ m or more, and preferable ranges include about 15 to 85 ⁇ m, about 15 to 60 ⁇ m, about 20 to 85 ⁇ m, and about 20 to 60 ⁇ m.
  • the thickness of the heat-fusible resin layer 4 is preferably about 20 ⁇ m or more, more preferably An example is about 35 to 85 ⁇ m.
  • the adhesive layer 6 is a layer provided between the barrier layer 3 and the heat-fusible resin layer 4 as necessary in order to firmly bond the barrier layer 3 and the heat-fusible resin layer 4.
  • the adhesive layer 6 is formed of a resin capable of bonding the barrier layer 3 and the heat-fusible resin layer 4.
  • the resin used for forming the adhesive layer 6 the same adhesive mechanism and the same types of adhesive components as those exemplified for the adhesive layer 5 can be used.
  • polyolefin resins such as polyolefin, cyclic polyolefin, carboxylic acid-modified polyolefin, carboxylic acid-modified cyclic polyolefin exemplified in the above-mentioned heat-fusible resin layer 4 can also be used. .
  • the polyolefin is preferably a carboxylic acid-modified polyolefin, and particularly preferably a carboxylic acid-modified polypropylene. That is, the adhesive layer 6 may include a polyolefin skeleton, and preferably includes a polyolefin skeleton. The fact that the adhesive layer 6 contains a polyolefin skeleton can be analyzed by, for example, infrared spectroscopy, gas chromatography mass spectrometry, etc., and the analysis method is not particularly limited.
  • a peak derived from maleic acid is detected in the vicinity of the wave number of 1760 cm -1 and near the wave number 1780 cm -1.
  • the peak may be small and may not be detected. In that case, it can be analyzed by nuclear magnetic resonance spectroscopy.
  • the adhesive layer 6 is a cured resin composition containing an acid-modified polyolefin and a curing agent. It may be a thing.
  • Preferred examples of the acid-modified polyolefin include the same carboxylic acid-modified polyolefin and carboxylic acid-modified cyclic polyolefin exemplified in the heat-fusible resin layer 4.
  • the curing agent is not particularly limited as long as it can cure the acid-modified polyolefin.
  • the curing agent include an epoxy curing agent, a polyfunctional isocyanate curing agent, a carbodiimide curing agent, and an oxazoline curing agent.
  • the epoxy curing agent is not particularly limited as long as it is a compound having at least one epoxy group.
  • examples of the epoxy curing agent include epoxy resins such as bisphenol A diglycidyl ether, modified bisphenol A diglycidyl ether, novolac glycidyl ether, glycerin polyglycidyl ether, and polyglycerin polyglycidyl ether.
  • the polyfunctional isocyanate curing agent is not particularly limited as long as it is a compound having two or more isocyanate groups.
  • Specific examples of the polyfunctional isocyanate-based curing agent include isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), those obtained by polymerizing or nurating these, Examples thereof include mixtures and copolymers with other polymers.
  • the carbodiimide curing agent is not particularly limited as long as it is a compound having at least one carbodiimide group (—N ⁇ C ⁇ N—).
  • a polycarbodiimide compound having at least two carbodiimide groups is preferable.
  • the oxazoline-based curing agent is not particularly limited as long as it is a compound having an oxazoline skeleton.
  • Specific examples of the oxazoline-based curing agent include Epocros series manufactured by Nippon Shokubai Co., Ltd.
  • the curing agent may be composed of two or more kinds of compounds.
  • the content of the curing agent in the resin composition forming the adhesive layer 6 is preferably in the range of about 0.1 to 50% by mass, more preferably in the range of about 0.1 to 30% by mass, More preferably, it is in the range of about 0.1 to 10% by mass.
  • the thickness of the adhesive layer 6 is not particularly limited as long as it functions as an adhesive layer.
  • the adhesive exemplified in the adhesive layer 5 is used, it is preferably about 1 to 10 ⁇ m, more preferably 1 to 1 ⁇ m. For example, about 5 ⁇ m.
  • the resin exemplified in the heat-fusible resin layer 4 is used, it is preferably about 2 to 50 ⁇ m, more preferably about 10 to 40 ⁇ m.
  • a cured product of an acid-modified polyolefin and a curing agent it is preferably about 30 ⁇ m or less, more preferably about 0.1 to 20 ⁇ m, and still more preferably about 0.5 to 5 ⁇ m.
  • the adhesive layer 6 is a cured product of a resin composition containing an acid-modified polyolefin and a curing agent, the adhesive layer 6 can be formed by applying the resin composition and curing it by heating or the like.
  • a surface coating layer is provided on the outer side of the base material layer 2 (on the side opposite to the barrier layer 3 of the base material layer 2) as necessary for the purpose of improving the design. It may be provided. When the surface coating layer is provided, the surface coating layer is located between the bonding layer 1 b and the base material layer 2.
  • the surface coating layer can be formed of, for example, polyvinylidene chloride, polyester resin, urethane resin, acrylic resin, epoxy resin, or the like. Of these, the surface coating layer is preferably formed of a two-component curable resin. Examples of the two-component curable resin that forms the surface coating layer include a two-component curable urethane resin, a two-component curable polyester resin, and a two-component curable epoxy resin. Moreover, you may mix
  • Examples of the additive include fine particles having a particle size of about 0.5 nm to 5 ⁇ m.
  • the material of the additive is not particularly limited, and examples thereof include metals, metal oxides, inorganic substances, and organic substances.
  • the shape of the additive is not particularly limited, and examples thereof include a spherical shape, a fiber shape, a plate shape, an indeterminate shape, and a balloon shape.
  • Specific additives include talc, silica, graphite, kaolin, montmorilloid, montmorillonite, synthetic mica, hydrotalcite, silica gel, zeolite, aluminum hydroxide, magnesium hydroxide, zinc oxide, magnesium oxide, aluminum oxide, Neodymium oxide, antimony oxide, titanium oxide, cerium oxide, calcium sulfate, barium sulfate, calcium carbonate, calcium silicate, lithium carbonate, calcium benzoate, calcium oxalate, magnesium stearate, alumina, carbon black, carbon nanotubes, high Melting
  • money, aluminum, copper, nickel etc. are mentioned.
  • additives may be used individually by 1 type, and may be used in combination of 2 or more type.
  • silica, barium sulfate, and titanium oxide are preferably used from the viewpoint of dispersion stability and cost.
  • the surface of the additive may be subjected to various surface treatments such as insulation treatment and high dispersibility treatment.
  • the content of the additive in the surface coating layer is not particularly limited, but is preferably about 0.05 to 1.0% by mass, more preferably about 0.1 to 0.5% by mass.
  • the method for forming the surface coating layer is not particularly limited, and examples thereof include a method of applying a two-component curable resin for forming the surface coating layer to the outer surface of the base material layer 2.
  • the additive may be added to the two-component curable resin, mixed, and then applied.
  • the thickness of the surface coating layer is not particularly limited as long as it exhibits the above function as the surface coating layer, and for example, it is about 0.5 to 10 ⁇ m, preferably about 1 to 5 ⁇ m.
  • the method for producing the battery packaging material of the present invention is not particularly limited as long as a laminate in which layers having a predetermined composition are laminated is obtained. At least the resin layer 1a and the bonding layer 1b, the base material layer 2, the barrier layer 3, and the heat-fusible resin layer 4 are provided in this order, the bonding layer 1b contains a polyester resin, and the resin layer 1a is an aqueous liquid. The method of using what can peel from the base material layer 2 using is mentioned.
  • An example of the method for producing the battery packaging material of the present invention is as follows. First, a laminate in which the resin layer 1 a, the bonding layer 1 b, the base material layer 2, the adhesive layer 5, and the barrier layer 3 are laminated in this order (hereinafter also referred to as “laminate A”) is formed. Specifically, in the formation of the laminate A, first, the resin layer 1a, the bonding layer 1b, and the base material layer 2 are laminated by a method such as coextrusion laminating.
  • a laminated structure of the resin layer 1a and the bonding layer 1b is used, and the resin layer 1a and the base material layer 2 are adhered to each other through the bonding layer 1b, so that the resin layer 1a A laminate of the bonding layer 1b and the base material layer 2 can be formed.
  • a laminate of the resin layer 1a, the bonding layer 1b, and the base material layer 2 and the barrier layer 3 are laminated.
  • an adhesive used for forming the adhesive layer 5 is applied to the base material layer 2 or the barrier layer 3 whose surface is subjected to chemical conversion treatment as necessary, such as a gravure coating method or a roll coating method. After applying and drying by the method, it can be performed by a dry laminating method in which the barrier layer 3 or the base material layer 2 is laminated and the adhesive layer 5 is cured.
  • the heat-fusible resin layer 4 is laminated on the barrier layer 3 of the laminate A.
  • the resin component constituting the heat-fusible resin layer 4 is applied to the barrier layer 3 of the laminate A by a gravure coating method or a roll coating method. It may be applied by such a method.
  • the adhesive layer 6 is provided between the barrier layer 3 and the heat-fusible resin layer 4, for example, (1) the adhesive layer 6 and the heat-fusible resin layer on the barrier layer 3 of the laminate A (2) Separately, a laminate in which the adhesive layer 6 and the heat-fusible resin layer 4 are laminated is formed, and this is formed as a barrier layer of the laminate A (3) A method of extruding or solution-coating an adhesive for forming the adhesive layer 6 on the barrier layer 3 of the laminate A, and drying and baking at a high temperature. And a method of laminating the heat-fusible resin layer 4 previously formed into a sheet (film) on the adhesive layer 6 by a thermal laminating method, and (4) the barrier layer 3 of the laminate A and a sheet in advance. Between the heat-fusible resin layer 4 formed into a film While pouring an adhesive layer 6 which is, and a method of bonding a laminate A and the heat-welding resin layer 4 through the adhesive layer 6 (sandwich lamination method).
  • the order in which the resin layer 1a and the bonding layer 1b are stacked is not particularly limited.
  • the bonding layer 1b and the resin are formed on the surface of the base material layer 2 side.
  • the layer 1a may be laminated.
  • a surface coating layer can be formed by apply
  • the order of the step of laminating the barrier layer 3 on the surface of the base material layer 2 and the step of laminating the surface coating layer on the surface of the base material layer 2 are not particularly limited.
  • the barrier layer 3 may be formed on the surface of the base material layer 2 opposite to the surface coating layer.
  • resin layer 1a / bonding layer 1b / surface coating layer provided as needed / base material layer 2 / adhesive layer 5 provided as needed / one or both surfaces as needed A laminate composed of the barrier layer 3 subjected to the chemical conversion treatment / the adhesive layer 6 provided as necessary / the heat-fusible resin layer 4 is formed.
  • a heat treatment such as a hot roll contact type, a hot air type, a near infrared type or a far infrared type.
  • An example of such heat treatment conditions is 150 to 250 ° C. for 1 to 5 minutes.
  • each layer constituting the laminate improves or stabilizes film forming properties, lamination processing, suitability for final processing of secondary products (pouching, embossing), and the like as necessary. Therefore, surface activation treatment such as corona treatment, blast treatment, oxidation treatment, ozone treatment may be performed. For example, by performing corona treatment on at least one surface of the base material layer, it is possible to improve or stabilize the film forming property, lamination processing, final product secondary processing suitability, and the like.
  • the above-mentioned battery packaging material provided with the resin layer 1a and the joining layer 1b is prepared, and the resin layer 1a is performed by performing the peeling process which peels the resin layer 1a from a laminated body using an aqueous liquid.
  • the battery packaging material from which la is peeled can be produced.
  • What is necessary is just to make aqueous liquid adhere to the joining layer 1b as mentioned above.
  • a printing step of performing printing with ink on the surface of the laminate constituting the battery packaging material on the substrate layer 2 side after the peeling step, a printing step of performing printing with ink on the surface of the laminate constituting the battery packaging material on the substrate layer 2 side. Furthermore, you may provide. Thereby, the packaging material for batteries by which the surface by the side of the base material layer 2 was printed can be manufactured suitably. That is, the battery packaging material of the present invention can be suitably used for applications in which the resin layer 1a is peeled off using an aqueous liquid, and the surface on the base material layer 2 side is printed with ink.
  • the step of peeling the resin layer 1a from the battery packaging material and the printing step may be performed in the battery manufacturing process using the battery packaging material.
  • the battery packaging material of the present invention including the resin layer 1a and the bonding layer 1b is subjected to molding by a mold and then subjected to the peeling step and the printing step, thereby improving the moldability improvement effect by the resin layer 1a and the bonding layer 1b. It can enjoy suitably.
  • printing may be performed on the outside of the battery from the viewpoint of battery identification.
  • the battery packaging material of the present invention until printing is performed, the deterioration of the characteristics of the surface of the battery packaging material on the substrate layer 2 side is effectively suppressed, and an aqueous liquid is used when printing is performed.
  • the surface of the battery packaging material that becomes the printing surface can be easily exposed, and the surface of the base material layer 2 or the surface coating layer can be exposed to ink. It can also be suitably applied to applications where printing is performed.
  • the battery packaging material of the present invention including the resin layer 1a and the bonding layer 1b is subjected to molding using a mold, and then the resin layer 1a is separated from the laminate using an aqueous liquid, whereby the resin layer 1a becomes a barrier.
  • the effect of suppressing the pinhole of the layer 3 and the effect of suppressing the surface of the base material layer 2 and the surface coating layer from being damaged by the mold can be suitably enjoyed.
  • the heat-fusible resin layer 4 is heat-sealed using the battery packaging material of the present invention including the resin layer 1a and the bonding layer 1b, the base material layer 2 and the surface coating layer are deteriorated due to high temperature and high pressure. Can be effectively suppressed by the protection by the resin layer 1a. Note that the timing and purpose of peeling the resin layer 1a are not limited to these.
  • the printing method using ink is not particularly limited, and for example, pad printing and ink jet printing are suitable.
  • Pad printing is a printing method as follows. First, ink is poured into a concave portion of a flat plate in which a pattern to be printed is etched. Next, the silicon pad is pressed from above the concave portion to transfer the ink to the silicon pad. Next, the ink transferred to the surface of the silicon pad is transferred to the printing object to form a print on the printing object.
  • the ink since the ink is transferred to the object to be printed using an elastic silicon pad or the like, it is easy to print on the surface of the battery packaging material after molding, and the battery element is made of the battery packaging material. After sealing, the battery can be printed.
  • ink jet printing has similar advantages.
  • the battery packaging material of the present invention is used in a package for sealing and housing battery elements such as a positive electrode, a negative electrode, and an electrolyte. That is, a battery element including at least a positive electrode, a negative electrode, and an electrolyte can be accommodated in a package formed of the battery packaging material of the present invention to obtain a battery.
  • a battery element including at least a positive electrode, a negative electrode, and an electrolyte is formed using the battery packaging material of the present invention, with the metal terminals connected to each of the positive electrode and the negative electrode protruding outward.
  • a flange portion region where the heat-fusible resin layers are in contact with each other
  • heat-sealing the heat-fusible resin layers of the flange portion to seal the battery
  • the battery packaging material of the present invention is used so that the heat-fusible resin portion is on the inner side (surface in contact with the battery element).
  • the heat-fusible resin layer 4 When the heat-fusible resin layer 4 is heat-sealed using the battery packaging material of the present invention including the resin layer 1a and the bonding layer 1b, deterioration of the base material layer 2 and the surface coating layer due to high temperature and high pressure It can suppress effectively by the protection by the resin layer 1a.
  • the resin layer 1a In the battery packaging material of the present invention, the resin layer 1a can be peeled after the heat-fusible resin layer 4 is heat-sealed.
  • the package formed by the battery packaging material of the present invention can be formed by bending one battery packaging material and heat-sealing the edges of the opposing heat-fusible resin layers, It can also be formed by stacking two battery packaging materials so that the heat-fusible resin layers face each other and heat-sealing the edges.
  • the battery packaging material of the present invention may be used for only one of them, or the battery packaging material of the present invention may be used for both.
  • the resin layer 1a may be peeled first from one of the battery packaging materials according to the desired timing at which the surface of the base material layer 2 is desired to be protected, or the resin layer may be removed from both battery packaging materials at the same timing. 1a may be peeled off.
  • the battery of the present invention may be one in which the resin layer 1a is peeled off.
  • a battery includes, for example, a step of containing a battery element including at least a positive electrode, a negative electrode, and an electrolyte in a package formed of the battery packaging material of the present invention, and an aqueous liquid. It can manufacture by the method provided with the peeling process which peels the layer 1a from a package. About the specific example of the method of peeling the resin layer 1a from a laminated body, it is the same as that of the above-mentioned method.
  • the method for producing a battery of the present invention further includes a printing step of performing printing with ink on the surface on the base material layer 2 side of the package constituting the battery packaging material after the peeling step. Also good.
  • the battery by which the printing was performed on the outer side of a battery can be manufactured suitably.
  • the battery manufacturing process by providing a printing process immediately after the peeling process, the outer surface (the resin layer 1a is peeled off) by the resin layer 1a until immediately before the printing process when manufacturing the battery and the battery packaging material. After that, it is possible to suitably perform printing on the battery in which the deterioration of the characteristics of the base material layer 2 and the surface coating layer (which is the outer surface of the battery) is effectively suppressed.
  • the resin layer 1a can be peeled off, but may be used as it is as a battery from which the resin layer 1a is not peeled off.
  • the resin layer 1a When the resin layer 1a is peeled from the battery including the resin layer 1a and the bonding layer 1b, the resin layer 1a can be peeled at a desired timing. Since the heat dissipation is improved by removing the resin layer 1a from the battery, when the improvement of the heat dissipation of the battery is required, the resin layer 1a is preferably used as a battery having an improved heat dissipation by peeling off the resin layer 1a. Can do. Moreover, since the thickness of the battery can be reduced by peeling the resin layer 1a from the battery, when it is required to make the battery thinner, the battery having a reduced thickness by peeling the resin layer 1a. It can be preferably used. The timing and purpose of peeling the resin layer 1a from the battery are not limited to these. As for the method of peeling the resin layer 1a from the battery, an aqueous liquid may be attached to the bonding layer 1b as described above.
  • the battery packaging material of the present invention may be used for either a primary battery or a secondary battery, but is preferably a secondary battery.
  • the type of secondary battery to which the battery packaging material of the present invention is applied is not particularly limited.
  • a lithium ion battery, a lithium ion polymer battery, a lead storage battery, a nickel-hydrogen storage battery, a nickel-cadmium storage battery, a nickel- Examples include iron storage batteries, nickel / zinc storage batteries, silver oxide / zinc storage batteries, metal-air batteries, multivalent cation batteries, capacitors, capacitors, and the like.
  • lithium ion batteries and lithium ion polymer batteries are suitable applications for the battery packaging material of the present invention.
  • Example 1 A polyethylene terephthalate film and a nylon film were laminated by coextrusion to prepare a biaxially stretched laminated film.
  • the laminated film is a laminate in which a resin layer / bonding layer / base material layer is sequentially laminated, and is biaxially stretched after co-extrusion of resin layer / bonding layer / base material layer.
  • the laminated film contains an ultraviolet absorber (TINUVIN 326), a light stabilizer (TINUVIN 770), and an antioxidant (Irganox 1330, Irganox 1098, Irganox 1010).
  • an aluminum alloy foil (thickness 40 ⁇ m) as a barrier layer was laminated on the surface of the base material layer by a dry laminating method. Specifically, a two-component urethane adhesive (a polyol compound and an aromatic isocyanate compound) is applied to one surface of an aluminum alloy foil having an acid-resistant film formed on the surface, and the adhesive is applied to the surface of the aluminum alloy foil. A layer (thickness 3 ⁇ m) was formed.
  • the resin layer / bonding layer / base material layer / adhesive layer / barrier layer are laminated in order by performing an aging treatment.
  • a laminate was prepared.
  • the aluminum foil used as the barrier layer is provided with an acid resistant film containing cerium oxide and phosphate.
  • an adhesive composed of a non-crystalline polyolefin resin having a carboxyl group and a polyfunctional isocyanate compound (with a thickness of 2 ⁇ m after curing) is formed on the barrier layer of the obtained laminate (the surface of the acid-resistant film).
  • the adhesive layer / heat-sealable resin is applied onto the barrier layer by coating and drying the barrier layer side of the resulting laminate and an unstretched polypropylene film (thickness 80 ⁇ m) through a hot roll and bonding them. The layers were laminated.
  • biaxially stretched polyethylene terephthalate film (5 ⁇ m) / bonding layer (1 ⁇ m) / biaxially stretched nylon film (20 ⁇ m) / adhesive layer (3 ⁇ m) / barrier layer (40 ⁇ m) ) / Adhesive layer (2 ⁇ m) / unstretched polypropylene film (80 ⁇ m) were laminated in this order to obtain a battery packaging material.
  • Table 1 shows the layer structure of the battery packaging material.
  • a polyethylene terephthalate film (thickness 12 ⁇ m) as a resin layer and a stretched nylon film (thickness 15 ⁇ m) as a base material layer are a two-component urethane adhesive ( A material bonded with a polyol compound and an aromatic isocyanate compound (thickness: 3 ⁇ m) was prepared.
  • an aluminum alloy foil (thickness 40 ⁇ m) as a barrier layer was laminated on the surface of the base material layer by a dry laminating method, and resin layer / bonding layer / base material layer / adhesion A laminate in which the agent layer / barrier layer was sequentially laminated was produced.
  • the acid-resistant film formed on the surface of the aluminum alloy foil is roll-coated with a treatment liquid composed of a phenol resin, a chromium fluoride compound, and phosphoric acid so that the coating amount of chromium is 10 mg / m 2 (dry mass). It is formed by applying and baking on both surfaces of an aluminum alloy foil by the method.
  • an acid-modified polypropylene (thickness: 40 ⁇ m) as an adhesive layer and a polypropylene (thickness: 40 ⁇ m) as a heat-fusible resin layer are laminated by coextrusion laminating method to obtain a resin layer / bonding layer / base material layer.
  • the specific laminated structure is shown in Table 1.
  • an aluminum alloy foil (thickness 40 ⁇ m) as a barrier layer was laminated on the surface of the base material layer by a dry laminating method, and resin layer / bonding layer / base material layer / adhesion A laminate in which the agent layer / barrier layer was sequentially laminated was produced.
  • the acid-resistant film formed on the surface of the aluminum alloy foil is the same as in Comparative Example 1.
  • an adhesive composed of a non-crystalline polyolefin resin having a carboxyl group and a polyfunctional isocyanate compound (thickness after curing is 3 ⁇ m) on the barrier layer (surface of the acid-resistant film) of the obtained laminate.
  • the barrier layer side of the obtained laminate and an unstretched random polypropylene film are passed between hot rolls and bonded to each other, whereby a resin layer / bonding layer / base material layer /
  • a battery packaging material in which an adhesive layer / barrier layer / adhesive layer / heat-fusible resin layer was laminated in order was obtained.
  • the specific laminated structure is shown in Table 1.
  • the base material layer side of the body was bonded to obtain a battery packaging material in which a resin layer / bonding layer / base material layer / adhesive layer / barrier layer / adhesive layer / heat-sealable resin layer were sequentially laminated.
  • the specific laminated structure is shown in Table 1.
  • Comparative Example 4 In Comparative Example 3, the base layer / adhesive layer / barrier layer / adhesive layer / heat-sealable resin was the same as Comparative Example 3 except that the resin layer and the bonding layer were not laminated on the base layer. A battery packaging material in which layers were sequentially laminated was obtained. The specific laminated structure is shown in Table 1.
  • ⁇ Measurement of content of ultraviolet absorber, light stabilizer and antioxidant> About the battery packaging material of Example 1, in the same manner as in the above-described ⁇ Analysis of UV absorber, light stabilizer and antioxidant>, from the laminate of the resin layer, the bonding layer, and the base material layer, an additive component was extracted, and a sample dissolved in the measurement solvent was prepared. About the obtained sample, content of a ultraviolet absorber, a light stabilizer, and antioxidant was measured with the following gas chromatographs (GC) and liquid chromatographs (HPLC).
  • GC gas chromatographs
  • HPLC liquid chromatographs
  • the resin layer was peeled about 30 mm in the MD direction.
  • the hydrochloric acid adhering to the test sample was wiped off and dried as it was.
  • distilled water (W) was adhered to the portion where the resin layer was peeled off (bonding layer 1b between the resin layer and the base layer side surface) using a dropper.
  • distilled water (W) was adhered to the entire boundary in the TD direction at the boundary between the resin layer and the substrate layer side surface.
  • the resin layer 1a was peeled from the surface of the base material layer using a tensile tester (Autograph manufactured by Shimadzu Corporation) under the measurement conditions of a distance between chucks of 50 mm, a peeling speed of 50 mm / min, and a peeling angle of 180 °.
  • the peel strength when the distance between chucks reached 57 mm was defined as the peel strength (N / 15 mm) with distilled water attached.
  • the results are shown in Table 1.
  • the minimum of the detection limit value of the tensile tester used for the measurement of peel strength is 0.3 N / 15 mm.
  • Each battery packaging material obtained above was cut into 150 mm (TD) ⁇ 100 mm (MD) strips, which were used as test samples.
  • the MD of the battery packaging material corresponds to the rolling direction of the aluminum alloy foil
  • the TD of the battery packaging material corresponds to the TD of the aluminum alloy foil.
  • the rolling direction of the aluminum alloy foil can be confirmed by the rolling marks of the aluminum alloy foil.
  • the mold is a rectangular male mold of 30 mm (MD) ⁇ 50 mm (TD) (the surface is defined in Table 2 of Comparative Surface Roughness Standard Pieces for Reference JIS B 0659-1: 2002 Annex 1)
  • the maximum height roughness (nominal value of Rz is 1.6 ⁇ m)
  • the female mold with a clearance of 0.5 mm from this male mold (the surface is JIS B 0659-1: 2002 Annex 1 (reference) comparison)
  • a straight mold having a maximum height roughness (Rz nominal value of 3.2 ⁇ m) defined in Table 2 of the surface roughness standard piece for use was used.
  • the test sample was placed on the female mold so that the heat-fusible resin layer side was positioned on the male mold side.
  • test samples were pressed with a surface pressure of 0.1 MPa so as to have a molding depth of 5.0 mm, and cold-molded (drawn one-step molding).
  • the test samples of Example 1 and Comparative Examples 1 to 3 are molded with the resin layer and the bonding layer laminated. About the sample after cold forming, it was confirmed visually whether the wrinkle was formed in the forming part. The results are shown in Table 1.
  • the printability was evaluated according to the following criteria. The printability measurement was performed in an environment of 24 ° C. and a relative humidity of 50%. The results are shown in Table 1. A: Print missing is 2.5% or less B Print missing is more than 2.5% and 5% or less C: Print missing is more than 2.5%
  • distilled water (W) was adhered to the portion where the resin layer was peeled off (bonding layer 1b between the resin layer and the base layer side surface) using a dropper. At this time, distilled water (W) was adhered to the entire boundary in the TD direction at the boundary between the resin layer and the substrate layer side surface.
  • Table 1 shows whether the resin layer could be peeled from the base material layer by pinching the resin layer with a finger.
  • PET is a polyethylene terephthalate layer
  • Ny is a nylon layer
  • AD is a bonding layer
  • DL is an adhesive layer formed by a dry lamination method
  • ALM is an aluminum alloy foil
  • PPa is an acid-modified polypropylene layer
  • CPP means an unstretched polypropylene layer
  • PP means a polypropylene layer.
  • the numerical value described after each layer of the laminated structure means a thickness ( ⁇ m), for example, “PET (12)” means “a polyethylene terephthalate layer having a thickness of 12 ⁇ m”.
  • peeling strength is 0.3 N / 15 mm or less means that peeling strength was below a detection limit value.
  • the peel strength when peeling the resin layer from the laminate using an aqueous liquid is 1.0 N / 15 mm or less, the resin layer can be suitably peeled, and 0.5 N / 15 mm or less. If it exists, it can be said that a resin layer can be peeled off more suitably.
  • Comparative Examples 1 and 2 using urethane resin as the bonding layer had high peel strength in a state where water was not attached and peel strength in a state where water was attached. Therefore, it was difficult to peel off the resin layer even when water was attached. In addition, there was no wrinkle after molding even when molded in a state where the resin layer and the bonding layer were laminated, and no deterioration was observed even after heat sealing. The resin layer could not be peeled even when water was attached to the end face. This is considered to be because the peel strength of the urethane resin is further increased by the heat of heat fusion, and is more difficult to peel.
  • Comparative Example 3 using a silicone resin as the bonding layer had low peel strength in the state where water was not attached and peel strength in the state where water was attached. For this reason, the resin layer can be easily peeled off even when water is not attached, and there is a flaw when the protective layer is laminated, and the appearance is poor.

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Sealing Battery Cases Or Jackets (AREA)
  • Laminated Bodies (AREA)
PCT/JP2018/016367 2017-04-20 2018-04-20 電池用包装材料、その製造方法、及び電池 WO2018194176A1 (ja)

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JP2020119710A (ja) * 2019-01-22 2020-08-06 大日本印刷株式会社 蓄電デバイス、蓄電デバイス用外装部材、蓄電デバイス集合体、電動自動車及び蓄電デバイスの製造方法
JP2020140775A (ja) * 2019-02-26 2020-09-03 Dic株式会社 電池用包装フィルムおよび電池
JPWO2020138060A1 (ja) * 2018-12-28 2021-11-11 大日本印刷株式会社 蓄電デバイス用外装材、その製造方法、及び蓄電デバイス
US11384337B2 (en) 2018-04-27 2022-07-12 Iovance Biotherapeutics, Inc. Closed process for expansion and gene editing of tumor infiltrating lymphocytes and uses of same in immunotherapy
US12024718B2 (en) 2022-07-01 2024-07-02 Iovance Biotherapeutics, Inc. Closed process for expansion and gene editing of tumor infiltrating lymphocytes and uses of same in immunotherapy

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US11384337B2 (en) 2018-04-27 2022-07-12 Iovance Biotherapeutics, Inc. Closed process for expansion and gene editing of tumor infiltrating lymphocytes and uses of same in immunotherapy
US11866688B2 (en) 2018-04-27 2024-01-09 Iovance Biotherapeutics, Inc. Closed process for expansion and gene editing of tumor infiltrating lymphocytes and uses of same in immunotherapy
JPWO2020138060A1 (ja) * 2018-12-28 2021-11-11 大日本印刷株式会社 蓄電デバイス用外装材、その製造方法、及び蓄電デバイス
JP7435471B2 (ja) 2018-12-28 2024-02-21 大日本印刷株式会社 蓄電デバイス用外装材、その製造方法、及び蓄電デバイス
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JP2020119710A (ja) * 2019-01-22 2020-08-06 大日本印刷株式会社 蓄電デバイス、蓄電デバイス用外装部材、蓄電デバイス集合体、電動自動車及び蓄電デバイスの製造方法
JP7225826B2 (ja) 2019-01-22 2023-02-21 大日本印刷株式会社 蓄電デバイス、蓄電デバイス用外装部材、蓄電デバイス集合体、電動自動車及び蓄電デバイスの製造方法
JP7225825B2 (ja) 2019-01-22 2023-02-21 大日本印刷株式会社 蓄電デバイス、蓄電デバイス用外装部材、蓄電デバイス集合体、電動自動車及び蓄電デバイスの製造方法
JP2020140775A (ja) * 2019-02-26 2020-09-03 Dic株式会社 電池用包装フィルムおよび電池
JP7243287B2 (ja) 2019-02-26 2023-03-22 Dic株式会社 電池用包装フィルムおよび電池
US12024718B2 (en) 2022-07-01 2024-07-02 Iovance Biotherapeutics, Inc. Closed process for expansion and gene editing of tumor infiltrating lymphocytes and uses of same in immunotherapy
US12031157B2 (en) 2022-07-01 2024-07-09 Iovance Biotherapeutics, Inc. Closed process for expansion and gene editing of tumor infiltrating lymphocytes and uses of same in immunotherapy

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