JP5725070B2 - Battery packaging materials - Google Patents

Description

  The present invention is a film-like battery packaging material that can be produced by curing an adhesive layer provided between a base material layer and a barrier layer in a short time to provide excellent adhesion strength and shortening the lead time. About.

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

  Therefore, in recent years, a film-like laminate in which a base material layer / adhesive layer / barrier layer / sealant layer are sequentially laminated as a battery packaging material that can be easily processed into various shapes and can be reduced in thickness and weight. Has been proposed (see, for example, Patent Document 1). Such a film-shaped battery packaging material is formed so that the battery element can be sealed by causing the sealant layers to face each other and heat-sealing the peripheral portion by heat sealing.

  On the other hand, in conventional film-like battery packaging materials, a base material layer, an adhesive layer, and a barrier layer are usually bonded together by a dry lamination method using a two-component curable adhesive. In order to cure the adhesive layer, it is necessary to perform aging under high temperature conditions for several days to several weeks. Therefore, the conventional film-shaped battery packaging material has a drawback that the lead time is prolonged by the curing process of the adhesive layer, and product defects are caused by being exposed to high temperature conditions and temperature changes for a long time.

  In order to overcome the above-mentioned drawbacks, it is effective to employ an adhesive material capable of quick curing (curing in a short time) of the adhesive layer. Since the quick curing of the adhesive layer has a short curing time, it is important to supply a stable amount of heat. If the amount of heat supplied becomes non-uniform when the adhesive layer is quick cured, variations in the cured state of the adhesive layer occur, and the adhesive strength of the adhesive layer decreases, resulting in product defects. For this reason, the quick cure of the adhesive layer has a drawback that it is difficult to industrially manufacture because it requires precise control of the amount of heat supplied, the distance from the heat source to the adhesive layer, etc., and requires advanced process control.

  Therefore, in film-like battery packaging materials, the adhesive layer provided between the base material layer and the barrier layer can be cured in a short time to provide excellent adhesion strength, and lead time can be shortened. The development of technology that can improve efficiency is eagerly desired.

JP 2001-202927 A

  The present invention provides a film-like battery packaging material capable of curing an adhesive layer provided between a base material layer and a barrier layer in a short time to provide excellent adhesion strength and shortening the lead time. For the purpose.

  The inventors of the present invention have made extensive studies to solve the above-mentioned problems.At least, in a battery packaging material comprising a laminate having a base layer, a first adhesive layer, a barrier layer, and a sealant layer in this order, The first adhesive layer is a cured product of a resin composition containing a thermosetting resin and a curing accelerator, and at least one layer contained in the laminate includes a light-absorbing exothermic substance, It has been found that the first adhesive layer provided between the base material layer and the barrier layer can be cured in a short time to provide excellent adhesion strength, and lead time can be shortened. The present invention has been completed by further studies based on such knowledge.

That is, this invention provides the invention of the aspect hung up below.
Item 1. It consists of a laminate having at least a base material layer, a first adhesive layer, a barrier layer, and a sealant layer in this order,
The first adhesive layer is a cured product of a resin composition containing a thermosetting resin and a curing accelerator, and at least one layer included in the laminate includes a light-absorbing exothermic substance. A battery packaging material.
Item 2. Item 2. The battery packaging material according to Item 1, wherein the first adhesive layer contains a light-absorbing exothermic substance.
Item 3. Item 3. The item 1 or 2, wherein the thermosetting resin is at least one selected from the group consisting of an epoxy resin, an amino resin, an acrylic resin, a urethane resin, a phenol resin, an unsaturated polyester resin, and an alkyd resin. Battery packaging material.
Item 4. Item 1. The hard curing accelerator is at least one selected from the group consisting of an amidine compound, a carbodiimide compound, a ketimine compound, a hydrazine compound, a sulfonium salt, a benzothiazolium salt, and a tertiary amine compound. 4. The battery packaging material according to any one of 3 above.
Item 5. Item 5. The battery packaging material according to any one of Items 1 to 4, wherein the light-absorbing exothermic substance is at least one selected from the group consisting of metal powders, inorganic pigments, carbon, and organic dyes.
Item 6. Item 6. The battery packaging material according to any one of Items 1 to 5, wherein the resin composition used for forming the first adhesive layer further contains an elastomer resin.
Item 7. Item 7. The battery packaging material according to any one of Items 1 to 6, wherein the barrier layer is a metal foil.
Item 8. On the base material layer opposite to the first adhesive layer, from the base material layer side, the third adhesive layer, the insulating layer, and the coating layer are provided in this order.
Any one of Items 1 to 7, wherein at least one layer selected from the group consisting of the coating layer, the insulating layer, the third adhesive layer, the base material layer, the first adhesive layer, and the sealant layer contains a light-absorbing exothermic substance. A packaging material for a battery according to claim 1.
Item 9. Production of battery packaging material including a laminating step of laminating at least a base material layer, a first adhesive layer, a barrier layer, and a sealant layer in this order, and including the following first step and second step in the laminating step Method:
A laminate having at least a base material layer, an uncured first adhesive layer, and a barrier layer in this order, wherein the uncured first adhesive layer contains a thermosetting resin and a curing accelerator. A first step of forming a laminate in which at least one layer included in the laminate includes a light-absorbing and exothermic substance, and the light-absorbing and exothermic material for the laminate obtained in the first step Is heated while irradiating light having a wavelength capable of generating heat to cure the thermosetting resin contained in the uncured first adhesive layer, thereby converting the uncured first adhesive layer into a first adhesive layer. Second step.
Item 10. Item 9. A battery in which a battery element including at least a positive electrode, a negative electrode, and an electrolyte is accommodated in the battery packaging material according to any one of Items 1 to 8.

  In the battery packaging material of the present invention, the first adhesive layer provided between the base material layer and the barrier layer can be cured in a short time without requiring aging under high temperature conditions by including a curing accelerator. As a result, the lead time can be shortened, and further, the occurrence of product defects due to long-term exposure to high temperature conditions can be prevented. Further, in the battery packaging material of the present invention, when the first adhesive layer is cured, a uniform amount of heat can be applied by the light-absorbing exothermic substance contained in at least one layer in the laminate, so that there is no variation in the cured state. It is also possible to form a first adhesive layer that is homogeneous and has excellent adhesion strength.

It is a figure which shows an example of the cross-section of the packaging material for batteries of this invention.

  The battery packaging material of the present invention is composed of a laminate having at least a base material layer, a first adhesive layer, a barrier layer, and a sealant layer in this order, and the first adhesive layer includes a thermosetting resin and curing acceleration. It is a cured product of a resin composition containing an agent, and at least one layer contained in the laminate includes a light-absorbing exothermic substance. Hereinafter, the battery packaging material of the present invention will be described in detail.

1. As shown in FIG. 1, the battery packaging material is a laminate composed of a laminate having at least a base material layer 1, a first adhesive layer 2, a barrier layer 3, and a sealant layer 4 in this order. It has a structure. That is, in the battery packaging material of the present invention, the base material layer 1 is located outside, and the sealant layer 4 is the innermost layer. When assembling the battery, the sealant layers 4 located on the periphery of the battery element are brought into contact with each other and thermally welded to seal the battery element and seal the battery element.

  Further, the battery packaging material of the present invention may be provided with a second adhesive layer 5 between the barrier layer 3 and the sealant layer 4 as necessary for the purpose of enhancing these adhesive properties.

  Furthermore, in the battery packaging material of the present invention, an insulating layer 6 may be provided on the outer side of the base material layer 1 as necessary for the purpose of enhancing the insulating properties. Further, when the insulating layer 6 is provided, a third adhesive layer 7 may be provided between the base material layer 1 and the insulating layer 6 as necessary for the purpose of improving the adhesion. Good.

  Moreover, in the battery packaging material of the present invention, a coating layer 8 may be provided as the outermost layer for the purpose of imparting functionality such as chemical resistance and slipping property as necessary. That is, the coating layer 8 is provided on the outer surface of the base material layer 1 or on the outer surface of the insulating layer 6 when the insulating layer 6 is provided, as necessary.

2. Absorbing Exothermic Substance In the battery packaging material of the present invention, at least one layer contains an absorbing exothermic substance. By containing the light-absorbing and exothermic substance in this way, when the resin composition used for forming the first adhesive layer 2 is heated and quick-cured, when light irradiation is performed, the resin composition as a whole is stable. A uniform amount of heat can be supplied, variation in the cured state is suppressed, and the first adhesive layer 2 having excellent adhesion strength can be formed.

  In the battery packaging material of the present invention, the light-absorbing exothermic substance is at least one of the base material layer 1, the first adhesive layer 2, the barrier layer 3, the sealant layer 4, and other layers provided as necessary. As long as it is included. Specifically, if at least one of the second adhesive layer 5, the insulating layer 6, the third adhesive layer 7, and the coating layer 8 is provided, the light-absorbing exothermic material is at least one of these layers. It may be contained in at least one of the base material layer 1, the first adhesive layer 2, the barrier layer 3, and the sealant layer 4.

  The layer containing the light-absorbing exothermic substance is preferably the first adhesive layer from the viewpoint of improving the adhesion strength of the first adhesive layer 2 and further shortening the curing time of the first adhesive layer 2. At least one of the second adhesive layer 5 provided, the insulating layer 6 provided as needed, the third adhesive layer 7 provided as needed, and the coating layer 8 provided as needed; Is preferably at least one of the first adhesive layer, the second adhesive layer 5 provided if necessary, the third adhesive layer 7 provided if necessary, and the coating layer 8 provided if necessary; Includes a first adhesive layer.

  In the present invention, the light absorption exothermic substance is a substance that generates heat by absorbing at least a part of light having a wavelength of about 300 to 2000 nm. The light-absorbing exothermic substance used in the present invention is not particularly limited, and examples thereof include metal powder, inorganic pigment, carbon, and organic dye.

  Examples of the metal powder include metal powders such as aluminum, stainless steel, iron, titanium, tungsten, nickel, and alloys thereof. These metal powders may be used individually by 1 type, and may be used in combination of 2 or more type.

  Specific examples of the inorganic pigment include zinc oxide, titanium oxide, barium sulfate, aluminum borate, potassium titanate, iridium oxide, tin oxide, and composites thereof. These inorganic pigments have a property of generating heat by absorbing far-infrared light, mid-infrared light, and near-infrared light. These inorganic pigments may be used alone or in combination of two or more.

  Specific examples of the carbon include carbon black.

  Specific examples of the organic dyes include methine dyes, cyanine dyes, merocyanine dyes, mercurochrome dyes, xanthene dyes, porphyrin dyes, phthalocyanine dyes (copper phthalocyanine, etc.), azo dyes, and coumarin dyes. . You may use individually by 1 type and may be used in combination of 2 or more type.

  Among these light-absorbing and exothermic substances, carbon, metal powder, more preferably carbon black, titanium powder, aluminum powder, iron powder, tungsten powder, stainless steel powder, nickel powder, and carbon black are more preferable.

  The average particle diameter of the light-absorbing and exothermic substance is not particularly limited, and examples thereof include 1000 nm or less, preferably 10 to 1000 nm. Here, the average particle diameter of the light-absorbing and exothermic substance means an average value when the particle diameters of primary particles of 1000 light-absorbing and exothermic substances are measured using a transmission electron microscope.

In the battery packaging material of the present invention, the content of the light-absorbing and exothermic substance may be appropriately set according to the type of the light-absorbing and exothermic substance, the type and number of layers containing the light-absorbing and exothermic substance, Examples include a range in which the content of the light-absorbing exothermic substance is about 4 to 200 μg per 1 m ² of the battery packaging material of the present invention.

3. Composition of each layer forming base material for battery [base material layer 1]
The material for forming the base material layer 1 is not particularly limited as long as it has insulating properties. Examples of the material for forming the base material layer 1 include polyester, polyamide, epoxy, acrylic, fluororesin, polyurethane, silicon resin, phenol, polyetherimide, polyimide, and a mixture or copolymer thereof.

  Specific examples of the polyester include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene isophthalate, polycarbonate, copolymerized polyester mainly composed of ethylene terephthalate, and repeating units of butylene terephthalate. Copolyester etc. mainly composed of The copolymer polyester mainly composed of ethylene terephthalate is a copolymer polyester that polymerizes with ethylene isophthalate mainly composed of ethylene terephthalate (hereinafter, polyethylene (terephthalate / isophthalate)). Abbreviated), polyethylene (terephthalate / isophthalate), polyethylene (terephthalate / adipate), polyethylene (terephthalate / sodium sulfoisophthalate), polyethylene (terephthalate / sodium isophthalate), polyethylene (terephthalate / phenyl-dicarboxylate) And polyethylene (terephthalate / decanedicarboxylate). In addition, as a copolymer polyester mainly composed of butylene terephthalate as a repeating unit, specifically, a copolymer polyester that polymerizes with butylene isophthalate having butylene terephthalate as a repeating unit (hereinafter referred to as polybutylene (terephthalate / isophthalate)). For example), polybutylene (terephthalate / adipate), polybutylene (terephthalate / sebacate), polybutylene (terephthalate / decanedicarboxylate), polybutylene naphthalate and the like. These polyesters may be used individually by 1 type, and may be used in combination of 2 or more type. Polyester has the advantage of being excellent in electrolytic solution resistance and less likely to cause whitening due to the adhesion of the electrolytic solution, and is suitably used as a material for forming the base material layer 1.

  Specific examples of the polyamides include aliphatic polyamides such as nylon 6, nylon 66, nylon 610, nylon 12, nylon 46, and a copolymer of nylon 6 and nylon 6,6; terephthalic acid and / or Or hexamethylenediamine-isophthalic acid-terephthalic acid copolymerized polyamide, polymer, such as nylon 6I, nylon 6T, nylon 6IT, nylon 6I6T (I represents isophthalic acid, T represents terephthalic acid) containing structural units derived from isophthalic acid Polyamides containing aromatics such as taxylylene adipamide (MXD6); Alicyclic polyamides such as polyaminomethylcyclohexyl adipamide (PACM6); and isocyanate components such as lactam components and 4,4′-diphenylmethane-diisocyanate Copolymerized polyamide, Polyester amide copolymer and polyether ester amide copolymer is a copolymer of polymerized polyamide and polyester and polyalkylene ether glycol; copolymers thereof, and the like. These polyamides may be used individually by 1 type, and may be used in combination of 2 or more type. The stretched polyamide film is excellent in stretchability, can prevent whitening due to resin cracking of the base material layer 1 during molding, and is suitably used as a material for forming the base material layer 1.

  The base material layer 1 may be formed of a uniaxially or biaxially stretched resin film, or may be formed of an unstretched resin film. Among them, a uniaxially or biaxially stretched resin film, in particular, a biaxially stretched resin film has improved heat resistance by orientation crystallization, and thus is suitably used as the base material layer 1.

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

  The base material layer 1 can also be laminated with resin films of different materials in order to improve pinhole resistance and insulation when used as a battery package. Specific examples include a multilayer structure in which a polyester film and a nylon film are laminated, and a multilayer structure in which a biaxially stretched polyester and a biaxially stretched nylon are laminated. When making the base material layer 1 into a multilayer structure, each resin film may be adhere | attached through an adhesive agent, and may be laminated | stacked directly without an adhesive agent. In the case of bonding without using an adhesive, for example, a method of bonding in a hot melt state such as a co-extrusion method, a sand lamination method, or a thermal laminating method can be mentioned. In the case of bonding via an adhesive, the composition of the adhesive to be used is not particularly limited, but the curing time is shortened to shorten the lead time, and further a uniform cured state is formed. From a viewpoint, Preferably, the resin composition as described in the column of the [1st contact bonding layer 2] mentioned later is mentioned.

  Further, the base material layer 1 may be made to have low friction in order to improve moldability. In the case of reducing the friction of the base material layer 1, the friction coefficient of the surface is not particularly limited, but for example, 1.0 or less can be mentioned. In order to reduce the friction of the base material layer 1, for example, a mat treatment can be mentioned. Examples of the mat treatment include a transfer method by heating or pressurizing with an embossing roll, and a method of mechanically roughening the surface by a dry or wet blast method or a file.

  As for the thickness of the base material layer 1, 10-50 micrometers is mentioned, for example, Preferably 15-30 micrometers is mentioned.

[First adhesive layer 2]
The 1st contact bonding layer 2 is a layer provided in order to adhere these layers between the base material layer 1 and the barrier layer 3, and is a resin composition containing a thermosetting resin and a hardening accelerator. It is formed of a cured product. As described above, the resin composition having a specific composition is used for forming the first adhesive layer 2, and at least one layer in the laminate includes the light-absorbing heat-generating substance so that the light-absorbing heat-generating substance can generate heat. It is possible to form the first adhesive layer having an excellent adhesion strength in a short time by a simple method of heating while irradiating light.

(Thermosetting resin)
The resin composition used for forming the first adhesive layer 2 contains a thermosetting resin. Any thermosetting resin may be used as long as it causes polymerization upon heating to form a polymer network structure and cure. Specifically, as the thermosetting resin used for forming the first adhesive layer 2, epoxy resin, amino resin (melamine resin, benzoguanamine resin, etc.), acrylic resin, urethane resin, phenol resin, unsaturated polyester resin, An alkyd resin etc. are mentioned.

  Moreover, a two-component curable resin can also be used as the thermosetting resin. Examples of the two-component curable resin include a two-component curable urethane resin, a two-component curable urethane-acrylic copolymer resin, a two-component curable acrylic polyol-based resin, and a two-component curable epoxy resin. .

  These thermosetting resins may be used individually by 1 type, and may be used in combination of 2 or more type.

  Among these thermosetting resins, from the viewpoint of further shortening the curing time of the first adhesive layer 2 and further improving the moldability, preferably a urethane resin, an epoxy resin, and more preferably a two-component curable urethane. Resin, two-component curable epoxy resin, particularly preferably two-component curable urethane resin.

  Specific examples of the two-component curable urethane resin include a combination of a polyol compound (main agent) and an isocyanate compound (curing agent). As the two-component curable epoxy resin, specifically, an epoxy resin (main agent) and , Acid anhydrides, amine compounds, or combinations of amino resins (curing agents).

  In the two-component curable urethane resin, the polyol compound used as the main agent is not particularly limited, and examples thereof include polyester polyol, polyester polyurethane polyol, polyether polyol, and polyether polyurethane polyol. These polyol compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

  In the two-component curable urethane resin, the isocyanate compound used as a curing agent is not particularly limited. For example, polyisocyanate, its adduct, its isocyanurate modified, its carbodiimide modified, The allophanate modified body, the bullet modified body, etc. are mentioned. Specific examples of the polyisocyanate include diphenylmethane diisocyanate (MDI), polyphenylmethane diisocyanate (polymeric MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), and bis (4-isocyanatocyclohexyl) methane (H12MDI). , Aromatic diisocyanates such as isophorone diisocyanate (IPDI), 1,5-naphthalene diisocyanate (1,5-NDI), 3,3′-dimethyl-4,4′-diphenylene diisocyanate (TODI), xylene diisocyanate (XDI) Aliphatic diisocyanates such as tramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate DOO; 4,4'-methylenebis (cyclohexyl isocyanate), alicyclic diisocyanates such as isophorone diisocyanate. Specific examples of the adduct include those obtained by adding trimethylolpropane, glycol and the like to the polyisocyanate. These isocyanate compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

(Curing accelerator)
The resin composition used for forming the first adhesive layer 2 contains a curing accelerator. Thus, by making a hardening accelerator coexist with a thermosetting resin, it is possible to cure in a short time without requiring aging under high temperature conditions during production, and to shorten the lead time.

  Here, the “curing accelerator” is a substance that does not form a crosslinked structure by itself, but promotes a crosslinking reaction of a thermosetting resin, and has an action of promoting a crosslinking reaction of a thermosetting resin. Is also a substance that may form a crosslinked structure.

  The type of curing accelerator is appropriately selected according to the thermosetting resin used. For example, an amidine compound, a carbodiimide compound, a ketimine compound, a hydrazine compound, a sulfonium salt, a benzothiazolium salt, a tertiary amine. Compounds and the like.

  The amidine compound is not particularly limited, and examples thereof include imidazole compounds, 1,8-diazabicyclo [5.4.0] undec-7ene (DBU), 1,5-diazabicyclo [4.3.0] none. 5-ene (DBN), a guanidine compound, etc. are mentioned. Specific examples of the imidazole compound include 2-methylimidazole, 2-ethylimidazole, 2-undecylimidazole, 2,4-dimethylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 1,2 -Diethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-benzyl- 2-methylimidazole, 2,4-diamino-6- [2′-methylimidazolyl- (1) ′]-ethyl-S-triazine, 2,4-diamino-6- [2′-ethyl-4′-methyl Imidazolyl- (1) ′]-ethyl-S-triazine, 2,4-diamino- -[2'-undecylimidazolyl] -ethyl-S-triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1) ']-ethyl-S-triazine isocyanurate oxidation adduct, 2- Examples include phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-aryl-4,5-diphenylimidazole and the like. These amidine compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

  The carbodiimide compound is not particularly limited. For example, N, N′-dicyclohexylcarbodiimide, N, N′-diisopropylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide, N- [3- ( Dimethylamino) propyl] -N'-ethylcarbodiimide, N- [3- (dimethylamino) propyl] -N'-ethylcarbodiimide methiodide, N-tert-butyl-N'-ethylcarbodiimide, N-cyclohexyl-N Examples include '-(2-morpholinoethyl) carbodiimide meso-p-toluenesulfonate, N, N'-di-tert-butylcarbodiimide, N, N'-di-p-tolylcarbodiimide, and the like. These carbodiimide compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

  The ketimine compound is not particularly limited as long as it has a ketimine bond (N = C), and examples thereof include a ketimine compound obtained by reacting a ketone with an amine. Specific examples of the ketone include methyl ethyl ketone, methyl isopropyl ketone, methyl tertiary butyl ketone, methyl cyclohexyl ketone, diethyl ketone, ethyl propyl ketone, ethyl butyl ketone, dipropyl ketone, dibutyl ketone, and diisobutyl ketone. Specific examples of the amine include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, m-xylylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, and diaminodiethyldiphenylmethane; ethylenediamine , Propylenediamine, butylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexamethylenediamine, trimethylhexamethylenediamine, 1,2-propanediamine, iminobispropylamine, methyliminobispropylamine, etc. Aliphatic polyamines; N-aminoethylpiperazine, 3-butoxyisopropylamine and the like monoamines and polyesters having an ether bond in the main chain Terpone diamines; cyclophoric amines such as isophorone diamine, 1,3-bisaminomethylcyclohexane, 1-cyclohexylamino-3-aminopropane, 3-aminomethyl-3,3,5-trimethylcyclohexylamine: norbornane skeleton Polyamide amine having an amino group at the molecular end of polyamide; 2,5-dimethyl-2,5-hexamethylenediamine, mensendiamine, 1,4-bis (2-amino-2-methylpropyl) piperazine, etc. Is given as a specific example. These ketimine compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

  The hydrazine compound is not particularly limited, and examples thereof include dipic acid dihydrazide and isophthalic acid dihydrazide. These hydrazine compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

  The sulfonium salt is not particularly limited. For example, 4-acetophenyldimethylsulfonium hexafluoroantimonate, 4-acetophenyldimethylsulfonium hexafluoroarsenate, dimethyl-4- (benzyloxycarbonyloxy) phenylsulfonium hexafluoroantimony , Alkylsulfonium salts such as dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroarsenate; benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, benzyl-4-methoxypheny Benzylsulfonium salts such as methylsulfonium hexafluoroantimonate, benzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroarsenate, 4-methoxybenzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate; dibenzyl-4-hydroxyphenyl Dibenzylsulfonium such as sulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, dibenzyl-4-methoxyphenylsulfonium hexafluoroantimonate, benzyl-4-methoxybenzyl-4-hydroxyphenylsulfonium hexafluorophosphate Salt; p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexa Luoantimonate, p-nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 3,5-dichlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, o-chlorobenzyl-3-chloro-4- Examples thereof include substituted benzylsulfonium salts such as hydroxyphenylmethylsulfonium hexafluoroantimonate. These sulfonium salts may be used individually by 1 type, and may be used in combination of 2 or more type.

  The benzothiazolium salt is not particularly limited. For example, 3-benzylbenzothiazolium hexafluoroantimonate, 3-benzylbenzothiazolium hexafluorophosphate, 3-benzylbenzothiazolium tetrafluoroborate, Such as 3- (p-methoxybenzyl) benzothiazolium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazolium hexafluoroantimonate, 3-benzyl-5-chlorobenzothiazolium hexafluoroantimonate Benzylbenzothiazolium salt. These benzothiazolium salts may be used individually by 1 type, and may be used in combination of 2 or more type.

  The tertiary amine compound is not particularly limited, and examples thereof include trimethylamine, triethylamine, tripropylamine, tributylamine, triethylenediamine, 1,4-diazabicyclo [2.2.2] octane, quinuclidine, and 3-quinuclidinol. And aliphatic tertiary amines; aromatic tertiary amines such as dimethylaniline; and heterocyclic tertiary amines such as isoquinoline, pyridine, collidine, and betapicoline. These tertiary amine compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

  As a suitable example of the said hardening accelerator, what functions as a thermal acid generator is mentioned. A thermal acid generator is a substance that generates an acid by heating and functions as a curing accelerator. Specific examples of the curing accelerator that can function as a thermal acid generator include sulfonium salts and benzothiazolium salts.

  In addition, another suitable example of the curing accelerator is a thermal latent that is activated under a predetermined heating condition (for example, 80 to 160 ° C., preferably 100 to 120 ° C.) to promote the crosslinking reaction of the thermosetting resin. The thing with sex is mentioned. Among the above-mentioned curing accelerators, specific examples of the heat-latent substance include an epoxy adduct obtained by adding an epoxy compound to an amidine compound, a hydrazine compound, a tertiary amine compound, or the like.

  Furthermore, as another preferable example of the curing accelerator, it does not function as a curing agent in a sealed state, that is, in a moisture blocking state, but the sealed state is opened and hydrolyzed under the presence of moisture as a curing agent. Those having a hydrolytic potential that functions. Among the above-mentioned curing accelerators, specific examples of the hydrolytic latent substance include an epoxy adduct obtained by adding an epoxy compound to an amidine compound, a hydrazine compound, a tertiary amine compound, or the like.

  These hardening accelerators may be used individually by 1 type, and may be used in combination of 2 or more type. Among these curing accelerators, an amidine compound and a sulfonium salt are preferable, and an amidine compound is more preferable.

  About content of the hardening accelerator in the resin composition used for formation of the 1st adhesion layer 2, although suitably set according to the kind of thermosetting resin to be used, the kind of hardening accelerator, etc., for example, With respect to 100 parts by mass of the thermosetting resin, the total amount of the curing accelerator is 0.01 to 6 parts by mass, preferably 0.05 to 5 parts by mass, and more preferably 0.1 to 2 parts by mass.

(Absorbing pyrogen)
When the light absorption exothermic substance is contained in the first adhesive layer 2, the first adhesive layer 2 may be formed using a resin composition containing a thermosetting resin, a curing accelerator, and a light absorption exothermic substance.

  When the first adhesive layer 2 contains a light-absorbing and exothermic substance, the content of the light-absorbing and exothermic substance in the resin composition used for forming the first adhesive layer 2 is not particularly limited. For example, the thermosetting resin 100 The light-absorbing exothermic substance is 0.1 to 10 parts by mass, preferably 0.1 to 3 parts by mass, with respect to parts by mass.

(Other additives)
In addition to the components described above, the resin composition used for forming the first adhesive layer 2 may contain other additives such as a solvent and an elastomer resin as necessary. In particular, by adding an elastomer resin to the resin composition, the first adhesive layer 2 is imparted with appropriate flexibility while suppressing shrinkage of the first adhesive layer 2 during curing, and the battery packaging. It becomes possible to provide the material with excellent formability.

  When the resin composition used for forming the first adhesive layer 2 contains an elastomer resin, the type of the elastomer resin is not particularly limited. For example, ethylene and one or two or more carbon atoms of 2 or more are used. Polyolefin elastomers such as ethylene elastomers containing 20 α-olefins (excluding ethylene) as constituent monomers; styrene elastomers; polyester elastomers; urethane elastomers; acrylic elastomers; bisphenol A epoxy elastomers and other epoxies -Based elastomers; polyol-based elastomers such as polyester polyols, polyester polyurethane polyols, polyether polyols, polyether polyurethane polyols; nitrile rubber, fluorine rubber, acrylic rubber, silicone Arm, chloroprene rubber, isoprene rubber, a rubber component such as butadiene rubber. These elastomer resins may be used individually by 1 type, and may be used in combination of 2 or more type.

  Among these elastomer resins, a urethane elastomer, an epoxy elastomer, and a polyol elastomer are preferable.

  The content of the elastomer resin in the resin composition used for forming the first adhesive layer 2 is not particularly limited. For example, the elastomer resin is 3 to 50 mass in total with respect to 100 mass parts of the thermosetting resin. Parts, preferably 5 to 30 parts by mass, more preferably 10 to 20 parts by mass.

(Thickness of the first adhesive layer 2)
About the thickness of the 1st contact bonding layer 2, 2-50 micrometers, for example, Preferably 3-25 micrometers is mentioned.

[Barrier layer 3]
In the battery packaging material of the present invention, the barrier layer 3 is a layer that functions as a barrier layer for preventing water vapor, oxygen, light, and the like from entering the battery, in addition to improving the strength of the packaging material. Specific examples of the material of the barrier layer 3 include metal foils such as aluminum, stainless steel, and titanium; films obtained by vapor deposition of inorganic compounds such as silicon oxide and alumina. Among these, metal foil is preferable, and aluminum foil is more preferable. In order to prevent wrinkles and pinholes during the production of the battery packaging material, as the barrier layer 3 in the present invention, a soft aluminum foil, for example, annealed aluminum (JIS A8021P-O) or (JIS A8079P-O) foil Etc. are preferably used.

  Although it does not restrict | limit especially about the thickness of the barrier layer 3, For example, when using metal foil, 10-200 micrometers normally, Preferably 20-100 micrometers is mentioned.

  When a metal foil is used as the barrier layer 3, at least one surface, preferably at least the surface on the sealant layer side, and more preferably both surfaces are subjected to chemical conversion treatment in order to stabilize adhesion, prevent dissolution and corrosion, and the like. It is preferable. Here, the chemical conversion treatment is a treatment for forming an acid-resistant film on the surface of the barrier layer 3. Chemical conversion treatment is, for example, chromate chromate treatment using a chromic acid compound such as chromium nitrate, chromium fluoride, chromium sulfate, chromium acetate, chromium oxalate, chromium biphosphate, chromic acetyl acetate, chromium chloride, potassium sulfate chromium, etc. ; Phosphoric acid chromate treatment using phosphoric acid compounds such as sodium phosphate, potassium phosphate, ammonium phosphate, polyphosphoric acid; aminated phenol heavy consisting of repeating units represented by the following general formulas (1) to (4) Examples thereof include chromate treatment using a coalescence.

In general formulas (1) to (4), X represents a hydrogen atom, a hydroxyl 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 represent a hydroxyl group, an alkyl group, or a hydroxyalkyl group. In the general formulas (1) to (4), examples of the alkyl group represented by X, R ₁ and R ₂ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, C1-C4 linear or branched alkyl groups, such as a tert- butyl group, are mentioned. 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- A 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. be able to. In the general formulas (1) to (4), X is preferably any one of a hydrogen atom, a hydroxyl group, and a droxyalkyl group. The number average molecular weight of the aminated phenol polymer composed of the repeating units represented by the general formulas (1) to (4) is, for example, about 500 to about 1,000,000, preferably about 1000 to about 20,000.

  Further, as a chemical conversion treatment method for imparting corrosion resistance to the metal foil, a metal oxide such as aluminum oxide, titanium oxide, cerium oxide, tin oxide or the like, in which fine particles of barium sulfate are dispersed in phosphoric acid, is coated. A method of forming a corrosion-resistant treatment layer on the surface of the metal foil by performing a baking treatment at a temperature of 0 ° C. or higher can be mentioned. A resin layer obtained by crosslinking a cationic polymer with a crosslinking agent may be formed on the corrosion-resistant treatment layer. Here, as the cationic polymer, for example, polyethyleneimine, an ionic polymer complex composed of a polymer having polyethyleneimine and a carboxylic acid, a primary amine-grafted acrylic resin in which a primary amine is grafted on an acrylic main skeleton, polyallylamine, or Examples thereof include aminophenols and derivatives thereof. These cationic polymers may be used individually by 1 type, and may be used in combination of 2 or more type. Examples of the crosslinking agent include compounds having at least one functional group selected from the group consisting of isocyanate groups, glycidyl groups, carboxyl groups, and oxazoline groups, silane coupling agents, and the like. These crosslinking agents may be used alone or in combination of two or more.

  These chemical conversion treatments may be performed alone or in combination of two or more chemical conversion treatments. 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. Among these, chromic acid chromate treatment is preferable, and chromate treatment in which a chromic acid compound, a phosphoric acid compound, and the aminated phenol polymer are combined is more preferable.

The amount of the acid-resistant film to be formed on the surface of the metal foil in the chemical conversion treatment is not particularly limited. For example, if the chromate treatment is performed by combining a chromic acid compound, a phosphoric acid compound, and the aminated phenol polymer, for example. The chromic acid compound is about 0.5 to about 50 mg, preferably about 1.0 to about 40 mg in terms of chromium, and the phosphorus compound is about 0.5 to about 50 mg in terms of phosphorus per 1 m ² of the surface of the metal foil. About 1.0 to about 40 mg, and the aminated phenol polymer is desirably contained in an amount of about 1 to about 200 mg, preferably about 5.0 to 150 mg.

  In the chemical conversion treatment, a solution containing a compound used for forming an acid-resistant film is applied to the surface of the metal foil by a bar coating method, a roll coating method, a gravure coating method, a dipping method or the like, and then the temperature of the metal foil is 70. It is carried out by heating to about 200 ° C. In addition, before the chemical conversion treatment is performed on the barrier layer 3, the metal foil may be 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 in advance. By performing the degreasing treatment in this way, it becomes possible to more efficiently perform the chemical conversion treatment on the surface of the metal foil.

[Sealant layer 4]
In the battery packaging material of the present invention, the sealant layer 4 corresponds to the innermost layer, and is a layer that seals the battery element by heat-sealing the sealant layers when the battery is assembled.

  The resin component used for the sealant layer 4 is not particularly limited as long as it can be thermally welded, and examples thereof include polyolefin, cyclic polyolefin, carboxylic acid-modified polyolefin, and carboxylic acid-modified cyclic polyolefin.

  Specific examples of the polyolefin include polyethylene such as low density polyethylene, medium density polyethylene, high density polyethylene, and linear low density polyethylene; homopolypropylene, polypropylene block copolymer (for example, block copolymer of propylene and ethylene), polypropylene Crystalline polypropylene or amorphous polypropylene such as a random copolymer of propylene and ethylene; an ethylene-butene-propylene terpolymer; and the like. Among these polyolefins, 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, styrene, butadiene, and isoprene. Is mentioned. 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. Among these polyolefins, cyclic alkene is preferable, and norbornene is more preferable.

  The carboxylic acid-modified polyolefin is a polymer obtained by modifying the polyolefin with a carboxylic acid. Examples of the carboxylic acid used for modification include maleic acid, acrylic acid, itaconic acid, crotonic acid, maleic anhydride, itaconic anhydride and the like.

  The carboxylic acid-modified cyclic polyolefin is obtained by copolymerizing a part of the monomer constituting the cyclic polyolefin in place of the α, β-unsaturated carboxylic acid or its anhydride, or α, β with respect to the cyclic polyolefin. -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 that used for modification of the acid-modified cycloolefin copolymer.

  Among these resin components, preferably a crystalline or amorphous polyolefin, a cyclic polyolefin, and a blend polymer thereof; more preferably polyethylene, polypropylene, a copolymer of ethylene and norbornene, and two or more of these The blend polymer of these is mentioned.

  The sealant 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 sealant layer may be formed of only one layer, but may be formed of two or more layers using the same or different resin components.

  Further, the thickness of the sealant layer 4 is not particularly limited, but may be 2 to 2000 μm, preferably 5 to 1000 μm, and more preferably 10 to 500 μm.

  In order to directly laminate the sealant layer 4 on the barrier layer 3, the resin component constituting the sealant layer 4 may be applied on the barrier layer 3 by a method such as a gravure coating method or a roll coating method. When the second adhesive layer 5 is provided between the barrier layer 3 and the sealant layer 4, for example, (1) the second adhesive layer 5 and the sealant layer 4 are laminated on the barrier layer 3 by coextrusion. (2) A method of separately forming a laminate in which the second adhesive layer 5 and the sealant layer 4 are laminated, and laminating this on the barrier layer 3 by a thermal lamination method, (3) An adhesive for forming the second adhesive layer 5 is laminated on the barrier layer 3 by an extrusion method, a solution-coated high temperature drying or baking method, and the like. A method of laminating the film of the sealant layer 4 by the thermal lamination method, (4) while pouring the melted second adhesive layer 5 between the barrier layer 3 and the sealant layer 4 previously formed into a sheet shape, 2 through adhesive layer 5 It is bonded method laminate A and the sealant layer 4 Te (sand lamination method) and the like.

[Second adhesive layer 5]
In the battery packaging material of the present invention, the second adhesive layer 5 is a layer provided between the barrier layer 3 and the sealant layer 4 as necessary in order to firmly bond the barrier layer 3 and the sealant layer 4.

  The second adhesive layer 5 is formed of a resin composition capable of bonding the barrier layer 3 and the sealant layer 4. The composition of the resin composition used for forming the second adhesive layer 5 is not particularly limited, but from the viewpoint of shortening the curing time and shortening the lead time, and further improving the moldability, etc. Preferably, the resin composition containing a thermosetting resin, More preferably, the resin composition containing a thermosetting resin and a hardening accelerator is mentioned. The types and contents of the thermosetting resin and the curing accelerator contained in the resin composition are the same as those of the resin composition used for forming the first adhesive layer 2.

  When the second adhesive layer 5 contains a light-absorbing and exothermic substance, the light-absorbing and exothermic substance may be contained in the resin composition used for forming the second adhesive layer 5. The content of the light-absorbing and exothermic substance in the resin composition used for forming the second adhesive layer 5 is the same as that for the resin composition used for forming the first adhesive layer 2.

  About the thickness of the 2nd contact bonding layer 5, 1-40 micrometers is mentioned, for example, Preferably 2-30 micrometers is mentioned.

  The second adhesive layer 5 can be laminated by a coating method such as a gravure coating method or a roll coating method.

[Insulating layer 6]
In the battery packaging material of the present invention, the insulating layer 6 is a layer provided as needed on the outer side of the base material layer 1 (on the side opposite to the first adhesive layer) in order to enhance insulation.

  The insulating material used for forming the insulating layer 6 is not particularly limited as long as it has insulating properties and flexibility enough to follow when bent. For example, fluororesin, polyester resin, epoxy resin, melamine resin, phenol Examples thereof include organic insulating materials such as resins, polyurethane resins, silicone resins, polyethylene resins, polyvinyl chloride, acrylic resins and cardo resins; inorganic insulating materials such as silicon oxide and silicon nitride. These insulating materials may be used individually by 1 type, and may be used in combination of 2 or more type.

  When the insulating layer 6 contains a light-absorbing and exothermic substance, the light-absorbing and exothermic substance may be mixed with the insulating material used for forming the insulating layer 6. The content of the light-absorbing and exothermic substance in the insulating layer 6 is not particularly limited. For example, the light-absorbing and exothermic substance is 0.1 to 10 parts by mass, preferably 0. 10 parts by mass per 100 parts by mass of the insulating material contained in the insulating layer 6. 1-3 mass parts is mentioned.

  About the thickness of the insulating layer 6, 0.1-10 micrometers is mentioned, for example, Preferably 0.5-4 micrometers is mentioned.

  In order to directly laminate the insulating layer 6, the insulating layer 6 may be laminated outside the base material layer 1 by a method such as a gravure coating method or a roll coating method. Further, when the third adhesive layer 7 is provided between the base material layer 1 and the insulating layer 6, it is formed outside the base material layer 1 by a coextrusion lamination method, a thermal lamination method, a thermal lamination method, a sand lamination method, or the like. The third adhesive layer 7 and the insulating layer 6 may be laminated.

[Third adhesive layer 7]
In the battery packaging material of the present invention, the third adhesive layer 7 is a layer provided between the base layer 1 and the insulating layer 6 as necessary to enhance the adhesion between the base layer 1 and the insulating layer 6. is there.

  The third adhesive layer 7 is formed of a resin composition capable of bonding the base material layer 1 and the insulating layer 6. The composition of the resin composition used for forming the third adhesive layer 7 is the same as that of the resin composition used for forming the second adhesive layer 5.

  When the third adhesive layer 7 contains a light-absorbing and exothermic substance, the resin composition used for forming the third adhesive layer 7 may contain the light-absorbing and exothermic substance. The content of the light-absorbing and exothermic substance in the resin composition used for forming the third adhesive layer 7 is the same as that for the resin composition used for forming the first adhesive layer 2.

  The thickness of the third adhesive layer 7 is the same as that of the second adhesive layer 5.

  The third adhesive layer 7 can be laminated by a coating method such as a gravure coating method or a roll coating method.

[Coating layer 8]
In the battery packaging material of the present invention, the coating layer 8 is provided on the outer side of the base material layer 1 (on the side opposite to the first adhesive layer) for the purpose of imparting functionality such as chemical resistance, slip resistance, and scratch resistance. Or when providing the insulating layer 6, it is a layer provided as needed outside the insulating layer 6 (the side opposite to the base material layer 1).

  The coating layer 8 is formed of a cured product of a resin composition containing a curable resin. Examples of the resin composition used for forming the coating layer 8 include a resin composition containing a thermosetting resin, and more preferably a resin composition containing a thermosetting resin and a curing accelerator. It is done. The types and contents of the thermosetting resin and the curing accelerator contained in the resin composition are the same as those of the resin composition used for forming the first adhesive layer 2.

  The coating layer 8 may contain additives such as slip agents and matting agents depending on the functionality to be imparted.

  The slip agent is not particularly limited. For example, fatty acid amide, metal soap, hydrophilic silicone, silicone grafted acrylic, silicone grafted epoxy, silicone grafted polyether, silicone grafted polyester, block silicone Examples thereof include acrylic copolymers, polyglycerol-modified silicone, and paraffin. These slip agents may be used individually by 1 type, and may be used in combination of 2 or more type.

  Examples of the matting agent include fine particles having a particle size of about 0.5 nm to 5 μm. The material of the matting agent is not particularly limited, and examples thereof include metals, metal oxides, inorganic substances, and organic substances. The shape of the matting agent 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 examples of the matting agent include talc, silica, graphite, kaolin, montmorilloid, montmorillonite, synthetic mica, hydrotalcite, silica gel, zeolite, aluminum hydroxide, magnesium hydroxide, zinc oxide, magnesium oxide, and aluminum oxide. , Neodymium oxide, antimony oxide, titanium oxide, cerium oxide, calcium sulfate, barium sulfate, calcium carbonate, calcium silicate, lithium carbonate, calcium benzoate, calcium oxalate, magnesium stearate, alumina, carbon black, carbon nanotubes, High melting point nylon, crosslinked acrylic, crosslinked styrene, crosslinked polyethylene, benzoguanamine, gold, aluminum, copper, nickel and the like can be mentioned. These matting agents may be used individually by 1 type, and may be used in combination of 2 or more type. Among these matting agents, silica, barium sulfate, and titanium oxide are preferable from the viewpoint of dispersion stability and cost. The matting agent may be subjected to various surface treatments such as insulation treatment and high dispersibility treatment on the surface.

  In addition, when the coating layer 8 is provided with chemical resistance, a chemical resistant coating agent may be used.

  When the coating layer 8 contains a light-absorbing and exothermic substance, the light-absorbing and exothermic substance may be contained in the resin composition used for forming the coating layer 8. The content of the light-absorbing and exothermic substance in the resin composition used for forming the coating layer 8 is the same as that for the resin composition used for forming the first adhesive layer 2.

  The thickness of the coating layer 8 is, for example, 1 to 10 μm, preferably 2 to 5 μm.

  The coating layer 8 can be laminated by a coating method such as a gravure coating method or a roll coating method.

4). Production method of battery packaging material The production method of the battery packaging material of the present invention is not particularly limited as long as a laminate in which layers of a predetermined composition are laminated is obtained. For example, at least the base material layer 1, It includes a laminating step in which the first adhesive layer 2, the barrier layer 3, and the sealant layer 4 are laminated in this order, and the laminating step includes the following first step and second step.
1st process : It is a laminated body which has the base material layer 1, uncured 1st contact bonding layer 2 ', and the barrier layer 3 in this order, Comprising: Said uncured 1st contact bonding layer 2' and thermosetting resin The resin composition containing a curing accelerator, and at least one layer included in the laminate forms a laminate containing a light-absorbing exothermic substance.
Second step : Heat applied to the uncured first adhesive layer 2 ′ by heating the layered product obtained in the first step while irradiating light having a wavelength that can generate heat. The uncured first adhesive layer 2 ′ is converted into the first adhesive layer 2 by curing the curable resin.
Hereafter, the manufacturing method of the packaging material for batteries of this invention is demonstrated for every process.

[First step]
In the first step, the laminate has a base layer 1, an uncured first adhesive layer 2 ′, and a barrier layer 3 in this order, and the uncured first adhesive layer 2 ′ includes a thermosetting resin, A resin composition containing a curing accelerator and at least one layer contained in the laminate forms a laminate (hereinafter also referred to as “laminate A”) containing a light-absorbing exothermic substance. To do. Here, the uncured first adhesive layer 2 ′ is a layer in which the first adhesive layer 2 is not cured, and is formed of a resin composition containing a curable resin and a curing accelerator.

  In the first step, the formation of the laminate A is specifically a resin composition used for forming the first adhesive layer 2 on the base layer 1 or the barrier layer 3 whose surface is subjected to chemical conversion treatment as necessary. The product can be applied by a dry lamination method in which the barrier layer 3 or the substrate layer 1 is laminated after being applied and dried by a coating method such as a gravure coating method or a roll coating method.

  In the case where any one of the base material layer 1, the uncured first adhesive layer 2 ′, and the barrier layer 3 contains a light-absorbing exothermic substance, the laminate A having at least these three layers is processed in the second step. In addition to these three layers, a laminate A in which the sealant layer 4 and other layers laminated as necessary may be used for the second step.

  In addition, when none of the base layer 1, the uncured first adhesive layer 2 ′, and the barrier layer 3 contains a light-absorbing and exothermic substance, a layer containing a light-absorbing and exothermic substance is further added to these layers. What is necessary is just to use the laminated body A laminated | stacked for a 2nd process.

[Second step]
In the second step, the laminate obtained in the first step is heated while being irradiated with light having a wavelength capable of generating heat by the light-absorbing exothermic substance, and is included in the uncured first adhesive layer 2 ′. The uncured first adhesive layer 2 ′ is converted into the first adhesive layer 2 by curing the thermosetting resin.

The light irradiation conditions for curing the uncured first adhesive layer 2 ′ are such that the light-absorbing and exothermic substance contained in the laminate obtained in the first step can generate heat so that the curing reaction of the thermosetting resin can proceed. Thus, the wavelength and output density of the light may be set, and are set as appropriate based on the type of the light-absorbing exothermic substance to be used, heat generation, and the like. Specifically, as the light irradiation conditions, as the output density of the light absorbing heat generating substance is capable fever wavelength light, usually 1 to 10 W · m ^-2, preferably more preferably 3~9W · m ^-2 5~8W · m- ² .

  In addition, the wavelength of the light irradiated when the uncured first adhesive layer 2 ′ is cured may be in a range where the light absorbing and exothermic substance contained in the laminate obtained in the first step can absorb and generate heat. For example, if the light-absorbing and exothermic substance is carbon, it may be irradiated with light having a wavelength including mid-infrared light or near-infrared light. If the light-absorbing and exothermic substance is a metal powder, an inorganic pigment, or an organic dye, If so, light having a wavelength including far-infrared light, mid-infrared light, or near-infrared light may be irradiated. The light irradiation when the uncured first adhesive layer 2 ′ is cured preferably includes irradiation with a halogen lamp.

  The light irradiation is performed by setting a light source so that light is exposed to the light-absorbing exothermic substance. For example, if the light-absorbing exothermic substance is contained in a layer outside the barrier layer, the light irradiation is performed by installing a light source on the base material layer 1 side and irradiating light from the base material layer 1 side. Done. If the light-absorbing exothermic substance is contained in a layer outside the barrier layer, light irradiation is performed by installing a light source on the sealant layer 4 side and irradiating light from the sealant layer 4 side. .

  Moreover, about the heating conditions at the time of hardening uncured 1st contact bonding layer 2 ', it is 150-200 degreeC, for example, Preferably it is 160-190 degreeC, for 0.1 to 60 second, Preferably it is 1 to 30 second. It is done.

  In the present invention, aging under high temperature conditions is not required for curing the uncured first adhesive layer 2 ′, and the first adhesive layer 2 having excellent adhesion strength can be formed only under the above conditions. Compared to, lead time can be greatly shortened.

  When the sealant layer 4 is not laminated on the laminate A subjected to the second step, the sealant layer 4 is laminated on the barrier layer 3 of the laminate obtained after the second step. A battery packaging material is obtained. Moreover, you may laminate | stack the layer laminated | stacked as needed on the laminated body obtained at the 2nd process after the 2nd process as needed.

  Moreover, in the production of the battery packaging material of the present invention, each layer constituting the laminate improves film forming property, lamination processing, suitability for final product secondary processing (pouching, embossing), etc., as necessary. Alternatively, in order to stabilize, surface activation treatment such as corona treatment, blast treatment, oxidation treatment, and ozone treatment may be performed.

4). Application of Battery Packaging Material The battery packaging material of the present invention is used as a packaging material for sealing and housing battery elements such as a positive electrode, a negative electrode, and an electrolyte.

  Specifically, 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 battery using a battery packaging material is formed by covering the periphery of the element so that a flange portion (a region where the sealant layers are in contact with each other) can be formed, and heat-sealing and sealing the sealant layers of the flange portion. Provided. In addition, when accommodating a battery element using the battery packaging material of the present invention, the battery packaging material of the present invention is used such that the sealant portion is on the inner side (surface in contact with the battery element).

  The battery packaging material of the present invention may be used for either a primary battery or a secondary battery, but is preferably a secondary battery. The type of secondary battery to which the battery packaging material of the present invention is applied is not particularly limited. For example, a lithium ion battery, a lithium ion polymer battery, a lead battery, a nickel / hydrogen battery, a nickel / cadmium battery , Nickel / iron livestock batteries, nickel / zinc livestock batteries, silver oxide / zinc livestock batteries, metal-air batteries, polyvalent cation batteries, capacitors, capacitors and the like. Among these secondary batteries, lithium ion batteries and lithium ion polymer batteries are suitable applications for the battery packaging material of the present invention.

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

Example 1-35 and Comparative Example 1-15
[Manufacture of battery packaging materials]
On the base material layer 1 made of a biaxially stretched nylon film (thickness 25 μm), a barrier layer 3 made of an aluminum foil (thickness 40 μm) subjected to chemical conversion treatment on both surfaces was laminated by a dry lamination method. Specifically, the resin compositions shown in Tables 1 to 4 were applied to one surface of the aluminum foil to form an uncured first adhesive layer 2 ′ (thickness 4 μm) on the barrier layer 3. Next, after the first adhesive layer 2 and the base material layer 1 on the barrier layer 3 are pressure-heated and bonded, the thermosetting resin in the uncured first adhesive layer 2 ′ is cured under the following curing conditions. A laminate of base material layer 1 / first adhesive layer 2 / barrier layer 3 was prepared.
Curing condition A : 7 days at 60 ° C. without reaching light
Curing condition B : 1 second at an ultimate temperature of 190 ° C. while irradiating light with an irradiation output of 7.2 W · cm ^{−2 using a} halogen lamp as a light source from the base material layer 1 side
Curing condition C : 1 second at an ultimate temperature of 140 ° C. while irradiating light from the base material layer 1 side with a halogen lamp as a light source at an irradiation output of 4.0 W · cm ⁻²

In addition, the chemical conversion treatment of the aluminum foil used as the barrier layer 3 is performed by rolling 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 weight). The coating was applied to both surfaces of the aluminum foil and baked for 20 seconds under the condition that the film temperature was 180 ° C. or higher.

  Next, on the barrier layer 3 of the laminate, a carboxylic acid-modified polypropylene (arranged on the barrier layer side, thickness 23 μm) and homopolypropylene (innermost layer, thickness 23 μm) are coextruded to form the barrier layer 3 A two-layer sealant layer was laminated thereon. Thus, a battery packaging material comprising a laminate in which the base material layer 1 / first adhesive layer 2 / barrier layer 3 / sealant layer 4 (carboxylic acid-modified polypropylene layer / homopolypropylene layer) was laminated in order was obtained.

[Evaluation of wrinkle occurrence]
For each battery packaging material obtained above, visually check for the occurrence of wrinkles, and the ratio of the number of wrinkles generated per 50 battery packaging materials (thermal wrinkle defect rate:%) Calculated.

[Evaluation of adhesion strength]
Each battery packaging material obtained above is cut and cut to a width of 15 mm, and the maximum force required to peel the base layer 1 and the barrier layer 3 at a peeling rate of 50 mm / min is measured. By doing so, the adhesion strength (peeling strength) between the base material layer 1 and the barrier layer 3 was measured. When the adhesion strength was 6.0 N / 15 mm or more, it was judged as “good”, and when it was 6.0 N / 15 mm, it was judged as “poor”.

[Evaluation results]
The obtained results are shown in Tables 5-8. From this result, the first adhesive layer that bonds the base material layer and the barrier layer is cured under light irradiation conditions using a resin composition containing a thermosetting resin, a curing accelerator, and a light-absorbing exothermic substance. In this case, since a uniform cured state can be formed in a short time, generation of wrinkles due to heat can be suppressed, and high adhesion strength is recognized between the base material layer and the barrier layer (Example 1). ~ 35). On the other hand, when the first adhesive layer was formed only from the thermosetting resin, high adhesion between the base material layer and the barrier layer was observed, but it took a long time to cure, and wrinkles due to heat. Was observed (Comparative Example 1). In addition, when the first adhesive layer is cured under light irradiation conditions using a resin composition containing a thermosetting resin and a light-absorbing exothermic substance, the high adhesion strength between the base material layer and the barrier layer is poor. Thus, satisfactory adhesion strength could not be obtained with quick cure (Comparative Examples 2 to 15).
In the above Examples and Comparative Examples, it can be confirmed that the same results can be obtained even if the main component, curing agent, and curing accelerator of the used thermosetting resin are replaced with other compounds having the same action. ing.

DESCRIPTION OF SYMBOLS 1 Base material layer 2 1st contact bonding layer 3 Barrier layer 4 Sealant layer

Claims (8)

Production of battery packaging material including a laminating step of laminating at least a base material layer, a first adhesive layer, a barrier layer, and a sealant layer in this order, and including the following first step and second step in the laminating step Method:
  A laminate having at least a base material layer, an uncured first adhesive layer, and a barrier layer in this order, wherein the uncured first adhesive layer contains a thermosetting resin and a curing accelerator. A first step of forming a laminate in which at least one layer included in the laminate includes a light-absorbing and exothermic substance; and
  The laminated body obtained in the first step is heated while irradiating light having a wavelength capable of generating heat by the light-absorbing exothermic substance, and the thermosetting resin contained in the uncured first adhesive layer is cured. A second step of converting the uncured first adhesive layer into a first adhesive layer. The method for manufacturing a battery packaging material according to claim 1, wherein the first adhesive layer contains a light-absorbing exothermic substance. The said thermosetting resin is at least 1 sort (s) selected from the group which consists of an epoxy resin, an amino resin, an acrylic resin, a urethane resin, a phenol resin, an unsaturated polyester resin, and an alkyd resin. Manufacturing method for battery packaging materials. The curing accelerator is at least one selected from the group consisting of an amidine compound, a carbodiimide compound, a ketimine compound, a hydrazine compound, a sulfonium salt, a benzothiazolium salt, and a tertiary amine compound. 4. A method for producing a battery packaging material according to any one of 3 above. The method for producing a battery packaging material according to any one of claims 1 to 4, wherein the light-absorbing exothermic substance is at least one selected from the group consisting of a metal powder, an inorganic pigment, carbon, and an organic dye. The manufacturing method of the packaging material for batteries in any one of Claims 1-5 in which the resin composition used for formation of the said 1st contact bonding layer contains elastomer resin further. The manufacturing method of the packaging material for batteries in any one of Claims 1-6 whose said barrier layer is metal foil. A step of laminating a third adhesive layer, an insulating layer, and a coating layer in this order on the base layer opposite to the first adhesive layer from the base layer side;
The at least one layer selected from the group consisting of the coating layer, the insulating layer, the third adhesive layer, the base material layer, the first adhesive layer, and the sealant layer contains a light-absorbing exothermic substance. The manufacturing method of the packaging material for batteries in any one.