JP6136432B2 - Battery packaging materials - Google Patents

Description

The present invention relates to a film-shaped battery packaging material in which a slip coating layer that can be cured in a short time and can suppress the release of a slip agent and has an excellent slip effect is provided on the surface of a base material layer.
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.

  Such film-like battery packaging materials are usually used after being molded and processed into a desired shape that can accommodate battery elements by press molding or embossing. Formability, workability and operability in press molding or embossing are used. Is required to be good. As a technique for improving such moldability / workability and operability, the surface of the base material layer of the battery packaging material is provided with a slip effect by providing a coating layer containing a slip agent (slip coating layer). Methods are known (see, for example, Patent Documents 2 and 3). Conventionally, in order to provide a slip coating layer on the surface of a pond packaging material, usually a thermosetting resin layer is formed on the base layer and a slip agent is coated on the thermosetting resin layer. The method to do is adopted. In the process of forming this thermosetting resin layer, it is generally performed using a two-component curable resin, and it is necessary to perform aging under high temperature conditions for several days to several weeks. The problem is that product defects occur due to long-term exposure to high temperature conditions. In the prior art, the slip coating layer is laminated in a state where the slip agent is not chemically bonded to the thermosetting resin layer. Further, there is a drawback that the slip effect is lowered due to the passage of time or exposure to a high temperature atmosphere.

  Therefore, in a film-like battery packaging material in which a slip coating layer is laminated on a base material layer, the coating layer can be formed in a short time, and the slip agent can be prevented from being released, thereby providing an excellent slip effect. Technology development is anxious.

JP 2001-202927 A JP 2007-294382 A JP 2007-257852 A

  The present invention provides a film-like packaging material for a battery, which can be cured in a short time, and can suppress the release of a slip agent, and has a slip coating layer having an excellent slip effect provided on the surface of a base material layer. The purpose is to do.

  As a result of intensive studies to solve the above problems, the present inventors have found that the battery packaging is composed of a laminate having at least a slip coating layer, a base material layer, an adhesive layer, a barrier layer, and a sealant layer in this order. In the material, the slip coating layer is cured in a short time by forming the slip coating layer with a cured product of a resin composition containing a thermosetting resin, a curing accelerator, and a reactive slip agent. It has been found that the slip agent can be prevented from being detached from the slip coating layer and an excellent slip effect can be obtained. 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 slip coating layer, a substrate layer, an adhesive layer, a barrier layer, and a sealant layer in this order,
The battery packaging material, wherein the slip coating layer is a cured product of a resin composition containing a thermosetting resin, a curing accelerator, and a reactive slip agent.
Item 2. Item 2. The battery according to Item 1, wherein the thermosetting resin is at least one selected from the group consisting of epoxy resins, amino resins, acrylic resins, urethane resins, phenol resins, unsaturated polyester resins, and alkyd resins. Packaging material.
Item 3. Item 1 or 2 wherein 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. A packaging material for a battery as described in 1.
Item 4. Item 4. The packaging material for a battery according to any one of Items 1 to 3, wherein the reactive slip agent is a reactive slip agent having 1 to 3 functional groups that react and chemically bond with the thermosetting resin. .
Item 5. Item 5. The battery packaging material according to any one of Items 1 to 4, wherein the barrier layer is a metal foil.
Item 6. A method for producing a battery packaging material comprising a laminate having a slip coating layer, a base material layer, an adhesive layer, a barrier layer, and a sealant layer in this order,
A first step of laminating a base material layer and a barrier layer through an adhesive layer to form a laminate in which the base material layer, the adhesive layer, and the barrier layer are sequentially laminated, and the laminate obtained in the first step A second step of laminating a sealant layer on the barrier layer of
Before the first step, after the first step and before the second step, or after the second step, a thermosetting resin is provided on the surface of the base material layer opposite to the surface on which the adhesive layer is laminated. And a resin composition containing a curing accelerator and a reactive slip agent, and heated and cured to form a slip coating layer, and a method for producing a battery packaging material, .
Item 7. The battery in which the battery element provided with at least the positive electrode, the negative electrode, and the electrolyte is accommodated in the battery packaging material according to any one of Items 1 to 5.

  In the battery packaging material of the present invention, a slip coating layer containing a reactive slip agent is provided on the resurface opposite to the sealant layer, and the coating layer has an excellent slip effect. , Formability, workability and operability in press molding and embossing are improved. Further, in the battery packaging material of the present invention, since the slip agent contained in the slip coating layer is bonded to the curable resin by a chemical bond, the slip coating layer can be obtained over time or exposure to a high temperature atmosphere. Therefore, it is difficult for the slip agent to lose bleed, and it is possible to suppress the occurrence of powder blowing and set-off during use and to prevent the slip effect of the slip coating layer from being lowered. Furthermore, in the battery packaging material of the present invention, the slip coating layer can be cured in a short time without requiring aging under high temperature conditions by including a curing accelerator, so that the lead time can be shortened. It is also possible to prevent the occurrence of product defects due to long-term exposure to high temperature conditions.

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 comprises a laminate having at least a slip coating layer, a base material layer, an adhesive layer, a barrier layer, and a sealant layer in this order, and the slip coating layer comprises a thermosetting resin and It is a cured product of a resin composition containing a curing accelerator and a reactive slip agent. 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 having at least a slip coating layer 1, a base material layer 2, an adhesive layer 3, a barrier layer 4, and a sealant layer 5 in this order. It has a laminated structure consisting of bodies. That is, in the battery packaging material of the present invention, the slip coating layer 1 is the outermost layer and the sealant layer 5 is the innermost layer. When the battery is assembled, the battery element is hermetically sealed by thermally sealing the sealant layers 5 positioned at the periphery of the battery element to contact each other, thereby sealing the battery element.

  Further, the battery packaging material of the present invention may be provided with an adhesive layer 6 between the barrier layer 4 and the sealant layer 5 as necessary for the purpose of enhancing the adhesiveness.

2. Composition of each layer forming battery packaging material [slip coating layer 1]
In the battery packaging material of the present invention, the slip coating layer 1 is a layer that forms the outermost layer as the surface coating layer of the base material layer 2. The slip coating layer 1 is formed of a cured product of a resin composition containing a thermosetting resin, a curing accelerator, and a reactive slip agent. Thus, by forming the slip coating layer 1 by curing a resin composition having a specific composition, the slip agent is hard to lose bleed, and is cured in a short time without requiring aging under high temperature conditions during production. As a result, the lead time can be shortened.

(Thermosetting resin)
The resin composition used for forming the slip coating layer 1 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. Specific examples of thermosetting resins used to form the slip coating layer 1 include epoxy resins, amino resins (melamine resins, benzoguanamine resins, etc.), acrylic resins, urethane resins, phenol resins, unsaturated polyester resins, An alkyd resin etc. are mentioned.

  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 viewpoints of further shortening the curing time of the slip coating layer 1 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. In addition, the acryloyl group is easy to chemically bond with the reactive slip agent, and the bleed-out of the slip agent can be more effectively suppressed. Therefore, among thermosetting resins, those having an acryloyl group (acrylic urethane resin, etc.) ) Is preferred.

  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 acrylic polyol, polyester polyol, polyester polyurethane polyol, polyether polyol, polyether polyurethane polyol, and the like. Includes allyl 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 slip coating layer 1 contains a curing accelerator. In this way, by coexisting a curing accelerator together with a thermosetting resin, it is possible to cure the slip coating layer 1 in a short time without requiring aging under high temperature conditions during production, thereby shortening the lead time. become. Moreover, it becomes possible to show effectively the slip effect by the reactive slip agent mentioned later by containing a hardening accelerator.

  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 2000 ° C., preferably 100 to 160 ° 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.

  The content of the curing accelerator in the resin composition used for forming the slip coating layer 1 is appropriately set according to the type of thermosetting resin used, the type of curing accelerator, etc. 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.

(Reactive slip agent)
The resin composition used for forming the slip coating layer 1 contains a reactive slip agent. In the present invention, the use of the reactive slip agent makes it difficult for the slip agent to lose bleed from the slip coating layer, and powder blowing or set-off occurs during use, and the slip effect of the slip coating layer is deteriorated over time. Can be suppressed.

  The reactive slip agent is a compound having a functional group that reacts with the thermosetting resin and chemically binds, and can impart slip properties (slip properties). The type of functional group of the reactive slip agent is appropriately set according to the type of the thermosetting resin. For example, a hydroxyl group, a mercapto group, a hydrolyzable silyl group, an isocyanate group, an epoxy group, and a polymerizable vinyl are used. Group, (meth) acryloyl group and the like.

  In the reactive slip agent, the number of functional groups per molecule is not particularly limited, and examples thereof include 1 to 3, preferably 1 or 2.

  Specific examples of the reactive slip agent include modified silicone having the functional group; modified fluororesin having the functional group; silicone modified resin having the functional group; stearic acid amide, oleic acid amide, erucic acid amide, ethylene Examples thereof include a compound in which the functional group is introduced to a fatty acid amide such as bis-stearic acid amide; a metal soap in which the functional group is introduced; paraffin in which the functional group is introduced. These reactive slip agents may be used individually by 1 type, and may be used in combination of 2 or more type.

  Among these reactive slip agents, the modified silicone having the functional group, the fluororesin having the functional group, and the silicone-modified resin having the functional group are preferable. As the modified silicone, specifically, a modified silicone obtained by block polymerization of a polymer having the functional group, such as a modified silicone obtained by block polymerization of an acrylic resin; a modified silicone obtained by graft polymerization of an acrylate, or the like, Examples thereof include modified silicone obtained by graft polymerization of a monomer having a functional group. Further, as the modified fluororesin, specifically, a modified fluororesin in which a monomer having the functional group is graft-polymerized, such as a fluororesin in which acrylate is graft-polymerized; modified fluorine in which an acrylic resin is block-polymerized Examples of the resin include a fluororesin in which a polymer having the functional group is block polymerized. Further, as the silicone-modified resin, specifically, the silicone having a functional group and the silicone having undergone graft polymerization, such as a silicone-modified acrylic resin in which silicone is graft-polymerized to the acrylic resin having the functional group. Examples include silicone-modified resins. Further, as the modified fluororesin, specifically, a modified fluororesin in which a monomer having the functional group is graft-polymerized, such as a fluororesin in which acrylate is graft-polymerized; modified fluorine in which an acrylic resin is block-polymerized Examples of the resin include a fluororesin in which a polymer having the functional group is block polymerized. Among these, as a particularly preferable reactive slip agent, a modified silicone in which the monomer or polymer having the functional group is polymerized at one terminal of the silicone; the monomer or polymer having the functional group is fluorine. Examples thereof include a modified fluororesin that is polymerized at one end of the resin. As such modified silicone and modified fluororesin, for example, “Modiper (registered trademark) F / FS series” (manufactured by NOF Corporation), “Symac (registered trademark) series” (manufactured by Toagosei Co., Ltd.) and the like are commercially available. These commercial products can also be used.

  The content of the reactive slip agent in the resin composition used for forming the slip coating layer 1 is not particularly limited. For example, the total amount of the reactive slip agent is 100 parts by mass of the thermosetting resin. 1-12 mass parts, Preferably it is 3-10 mass parts, More preferably, 5-8 mass parts is mentioned.

(Other additives)
In addition to the components described above, the resin composition used for forming the slip coating layer 1 may contain other additives such as a solvent, a matting agent, and an elastomer resin as necessary. In particular, when a matting agent is contained, the slip effect can be more effectively enhanced in the slip coating layer. 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. As a matting agent, specifically, talc, silica, graphite, kaolin, montmorilloid, montmorillonite, synthetic mica, hydrotalcite, silica gel, zeolite, aluminum hydroxide, magnesium hydroxide, zinc oxide, magnesium oxide, oxidation Aluminum, 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. 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 noodles.

(Thickness of the slip coating layer 1)
The thickness of the slip coating layer 1 is, for example, 1 to 5 μm, preferably 2 to 4 μm.

[Base material layer 2]
In the battery packaging material of the present invention, the base material layer 2 is a layer forming the outermost layer. The material for forming the base material layer 2 is not particularly limited as long as it has insulating properties. Examples of the material for forming the base material layer 2 include polyester, polyamide, epoxy, acrylic, fluorine resin, polyurethane, silicon resin, phenol, polyetherimide, polyimide, and mixtures and copolymers 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 that it is excellent in resistance to electrolytic solution and hardly causes whitening or the like due to adhesion of the electrolytic solution, and is suitably used as a material for forming the base material layer 2.

  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 has excellent stretchability, can prevent whitening due to resin cracking of the base material layer 2 during molding, and is suitably used as a material for forming the base material layer 2.

  The base material layer 2 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, particularly a biaxially stretched resin film has improved heat resistance due to orientation crystallization, and thus is preferably used as the base material layer 2.

  Among these, as a resin film which forms the base material layer 2, Preferably nylon and polyester, More preferably, biaxially stretched nylon, biaxially stretched polyester, Most preferably, biaxially stretched polyester is mentioned.

  The base material layer 2 can also be laminated with resin films of different materials in order to improve pinhole resistance and insulation when used as a battery packaging. 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 2 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 addition, in the case of bonding via an adhesive, the composition of the adhesive to be used is not particularly limited, but from the viewpoint of shortening the curing time to shorten the lead time, and further improving the moldability. Preferably, the resin composition for an adhesive layer described in the column of [Adhesive layer 3] described later is used.

  As for the thickness of the base material layer 2, 10-50 micrometers, for example, Preferably 15-30 micrometers is mentioned.

[Adhesive layer 3]
The adhesive layer 3 is a layer provided for adhering these layers between the base material layer 2 and the barrier layer 4.

  The adhesive component used for forming the adhesive layer 3 is not particularly limited as long as the base material layer 2 and the barrier layer 4 can be bonded, and may be a two-component curable adhesive. It may be a liquid curable adhesive. Further, the adhesion mechanism of the adhesive component used for forming the adhesive layer 3 is not particularly limited, and may be any of a chemical reaction type, a solvent volatilization type, a heat melting type, a hot pressure type, and the like. 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; polyolefin resins such as polyolefins, carboxylic acid modified polyolefins, metal modified polyolefins, polyvinyl acetate resins; cellulose adhesives; (meth) acrylic Tree ; Polyimide resin; urea resins, amino resins such as melamine resins; - chloroprene rubbers, nitrile rubbers, styrene rubbers such as butadiene rubber, silicone-based resins.

  In the formation of the adhesive layer 3, from the viewpoint of shortening the lead time by curing in a short time without requiring aging under high temperature conditions during production, and further improving the moldability, preferably thermosetting A resin composition for an adhesive layer containing a resin, a curing accelerator, and an elastomer resin is preferably used. By using a thermosetting resin and a curing accelerator in combination, the lead time can be shortened by curing in a short time without requiring aging under high temperature conditions. Further, by containing an elastomer resin, the adhesive layer 3 is imparted with appropriate flexibility while suppressing the shrinkage of the adhesive layer 3 during curing, and the battery packaging material has excellent moldability. Is possible.

  About the kind of thermosetting resin used for the said resin composition for contact bonding layers, a preferable thing, etc., it is the same as that of the thermosetting resin as described in the column of said [slip property coating layer 1].

  In addition, the types and preferred ones of the curing accelerator used in the adhesive layer resin composition are the same as those of the curing accelerator described in the column of [Slip coating layer 1]. About content of the hardening accelerator in the said resin composition for contact bonding layers, although suitably set according to the kind of thermosetting resin to be used, the kind of hardening accelerator, etc., for example, 100 mass parts of thermosetting resins In contrast, 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.

  Further, the elastomer resin used in the resin composition for the adhesive layer may have a functional group capable of crosslinking with the thermosetting resin, and may crosslink with the thermosetting resin when cured. Moreover, it may not have such a functional group and may not be crosslinked with the thermosetting resin even when cured. The type of elastomer resin is not particularly limited. For example, a polyolefin-based elastomer such as ethylene-based elastomer containing ethylene and one or more α-olefins (excluding ethylene) having 2 to 20 carbon atoms as constituent monomers. Elastomer; Styrenic elastomer; Polyester elastomer; Urethane elastomer; Acrylic elastomer; Epoxy elastomer such as bisphenol A type epoxy elastomer; Polyol elastomer such as polyester polyol, polyester polyurethane polyol, polyether polyol, polyether polyurethane polyol ; Rubber components such as nitrile rubber, fluorine rubber, acrylic rubber, silicone rubber, chloroprene rubber, isoprene rubber, butadiene rubber, etc.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 adhesive layer resin composition is not particularly limited. For example, the elastomer resin is 3 to 50 parts by mass, preferably 5 to 30 parts by mass with respect to 100 parts by mass of the thermosetting resin. A mass part, More preferably, a 10-20 mass part is mentioned.

  Furthermore, the resin composition for an adhesive layer may contain a light-absorbing exothermic substance as necessary. By containing the light-absorbing exothermic substance in this way, when the light irradiation is performed when the adhesive layer resin composition is heated and quickly cured, a stable and uniform amount of heat is applied to the entire adhesive layer resin composition. It is possible to supply, and it is possible to suppress the occurrence of variations in the cured state and to form the adhesive layer 3 in a uniform cured state.

  The light-absorbing 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.

  When the light-absorbing and exothermic substance is contained in the adhesive layer resin composition, the content of the light-absorbing and exothermic substance is, for example, 0.01 to 1 mass in total with respect to 100 parts by mass of the thermosetting resin. Parts, preferably 0.05 to 0.7 parts by mass, more preferably 0.1 to 0.5 parts by mass.

  About the thickness of the contact bonding layer 3, 2-50 micrometers, for example, Preferably 3-25 micrometers is mentioned.

[Barrier layer 4]
In the battery packaging material of the present invention, the barrier layer 4 is a layer that functions as a barrier layer for preventing moisture, 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 4 include metal foils such as aluminum, stainless steel, and titanium; films on which inorganic compounds such as silicon oxide and alumina are deposited. Among these, metal foil is preferable, and aluminum foil is more preferable. In order to prevent wrinkles and pinholes during the production of battery packaging materials, as the barrier layer 4 in the present invention, 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 4, For example, when using metal foil, 10-200 micrometers normally, Preferably 20-100 micrometers is mentioned.

  Further, when a metal foil is used as the barrier layer 4, at least one surface, preferably at least the surface on the sealant layer side, 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 4. 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 4, the metal foil may be subjected to a degreasing treatment in advance 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 treatment in this way, it becomes possible to more efficiently perform the chemical conversion treatment on the surface of the metal foil.

[Adhesive layer 6]
In the battery packaging material of the present invention, the adhesive layer 6 is a layer provided between the barrier layer 4 and the sealant layer 5 as necessary in order to firmly bond the barrier layer 4 and the sealant layer 5.

  The adhesive layer 6 is formed of an adhesive that can adhere the barrier layer 4 and the sealant layer 5. The composition of the adhesive used for forming the adhesive layer 6 is not particularly limited, but from the viewpoint of shortening the curing time by shortening the lead time, and further improving the moldability, preferably, The resin composition for adhesive layers described in the column of [Adhesive layer 3] is mentioned.

  About the thickness of the contact bonding layer 6, 1-40 micrometers is mentioned, for example, Preferably 2-30 micrometers is mentioned.

[Sealant layer 5]
In the battery packaging material of the present invention, the sealant layer 5 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 5 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 5 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 5 is not particularly limited, but may be 2 to 2000 μm, preferably 5 to 1000 μm, and more preferably 10 to 500 μm.

3. Method for Producing Battery Packaging Material 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. For example, the following method is exemplified. :
The base material layer 2 and the barrier layer 4 are laminated via the adhesive layer 3, and the base material layer 2, the adhesive layer 3, and the barrier layer 4 are sequentially laminated (hereinafter referred to as “laminate A”). And a second step of laminating a sealant layer 5 on the barrier layer 4 of the laminate A obtained in the first step. Before the first step, the first step The resin composition used for forming the slip coating layer 1 on the surface opposite to the surface on which the adhesive layer 3 is laminated in the base material layer 2 between the first step and the second step or after the second step. Is applied and heated to cure.

  Specifically, the formation of the laminate A in the first step is performed by extruding an adhesive used for forming the adhesive layer 3 on the base material 1 or on the barrier layer 4 whose surface is subjected to chemical conversion treatment as necessary. After applying and drying by a coating method such as a coating method, a gravure coating method, or a roll coating method, the barrier layer 4 or the substrate 1 can be laminated to dry the adhesion layer 3.

  For example, if the resin composition for an adhesive layer is used as the adhesive layer 3, the curing condition is, for example, 150 to 200 ° C, preferably 160 to 190 ° C, preferably 0.1 to 60 seconds. For 1 to 30 seconds. By using the resin composition for an adhesive layer, the adhesive layer 3 can be sufficiently cured only by the curing conditions without requiring aging at a high temperature condition for curing the adhesive layer 3, so that the lead time can be reduced. It can be shortened.

Furthermore, if the resin composition for an adhesive layer further containing a light-absorbing and exothermic substance is used as the adhesive layer 3, the resin composition for the adhesive layer is cured at the time of curing by irradiating light upon curing by the heating. A stable and uniform amount of heat can be supplied to the entire product, and variations in the cured state can be suppressed, and the adhesive layer 3 in a uniform cured state can be formed. The light irradiation may be performed by irradiating light having a wavelength capable of generating heat by the light-absorbing and exothermic substance contained in the resin composition for the adhesive layer, and the light irradiation condition is based on the type and heat-generating property of the light-absorbing and exothermic substance used. Is set as appropriate. As an example of a light irradiation condition, as the output density of the light absorption pyrogens possible exothermic wavelength, usually 1 to 10 W · m ^-2, preferably 3~9W · m ^-2 more preferably 5~8W · m ^{- 2} is mentioned. In addition, light irradiation is performed by installing a light source in the base material layer 2 side, and irradiating light from the base material layer 2 side.

  In the second step, the sealant layer 5 is laminated on the barrier layer 4 of the laminate A. When the sealant layer 5 is directly laminated on the barrier layer 4, the resin component constituting the sealant layer 5 may be applied on the barrier layer 4 of the laminate A by a method such as a gravure coating method or a roll coating method. . When the adhesive layer 6 is provided between the barrier layer 4 and the sealant layer 5, for example, (1) the adhesive layer 6 and the sealant layer 5 are laminated on the barrier layer 4 of the laminate A by coextrusion. (2) Separately forming a laminate in which the adhesive layer 6 and the sealant layer 5 are laminated, and laminating the laminate on the barrier layer 4 of the laminate A by the thermal lamination method, ( 3) An adhesive for forming the adhesive layer 6 is laminated on the barrier layer 4 of the laminate A by an extrusion method or a solution-coated high temperature drying and baking method. (4) A melted adhesive layer 6 is placed between the barrier layer 4 of the laminate A and the sealant layer 5 previously formed into a sheet shape. While pouring Sealable layer 6 adhering the laminate A and the sealant layer 5 via method (sand lamination method) and the like.

  Before the first step, after the first step and before the second step, or after the second step, the slip coating layer 1 is formed on the surface of the base material layer 2 opposite to the surface on which the adhesive layer 3 is laminated. The resin composition used for forming is applied by a coating method such as a gravure coating method or a roll coating method, and is cured by heating. Examples of the heating conditions for curing the slip coating layer 1 include 150 to 200 ° C., preferably 160 to 190 ° C., and 0.1 to 60 seconds, preferably 1 to 30 seconds. In the present invention, the curing of the slip coating layer 1 does not require aging under a high temperature condition, and the slip coating layer 1 can be sufficiently cured only by the curing condition. Lead time can be shortened.

  As described above, it is composed of the slip coating layer 1 / base material layer 2 / adhesive layer 3 / barrier layer 4 whose surface is subjected to chemical conversion treatment as required / adhesive layer 6 / sealant layer 5 provided as necessary. A laminate is formed.

  In the battery packaging material of the present invention, each layer constituting the laminate improves or stabilizes film forming properties, lamination processing, suitability for final processing (pouching, embossing), etc., as necessary. Therefore, surface activation treatment such as corona treatment, blast treatment, oxidation treatment, 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 1-32 and Comparative Example 1-18
[Manufacture of battery packaging materials]
On the base material layer 2 made of a biaxially stretched nylon film (thickness 25 μm), a barrier layer 4 made of an aluminum foil (thickness 40 μm) subjected to chemical conversion treatment on both surfaces was laminated by a dry lamination method. Specifically, a two-component urethane adhesive (a polyol compound and an aromatic isocyanate compound) was applied to one surface of the aluminum foil, and an adhesive layer 2 (thickness 4 μm) was formed on the barrier layer 4. Next, after bonding the adhesive layer 3 and the base material layer 2 on the barrier layer 4 under pressure and heating, an aging treatment is carried out at 40 ° C. for 24 hours, whereby base material layer 2 / adhesive layer 3 / barrier layer 4 A laminate was prepared. In addition, the chemical conversion treatment of the aluminum foil used as the barrier layer 4 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, by applying the resin composition shown in Tables 1 to 4 to the surface of the base material layer 1 (surface opposite to the adhesive layer 2), and curing the resin composition under the following curing conditions, The slip coating layer 1 was formed on the surface of the base material layer 2.
Curing condition A : 7 days at 45 ° C
Curing condition B : at 170 ° C. for 60 seconds

  Thereafter, on the barrier layer 4 of the laminate, the 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 5 was laminated on the substrate. Thus, a battery packaging material comprising a laminate in which a slip coating layer 1 / base material layer 2 / adhesive layer 3 / barrier layer 4 / sealant layer 5 (carboxylic acid-modified polypropylene layer / homopolypropylene layer) are laminated in this order. Got.

[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 defective white powder]
About each battery packaging material obtained above, after manufacturing, after storage for 1 week at room temperature and normal humidity, visually confirm the slip coating layer, and 50 slips of battery packaging material The ratio (number of white powder defects:%) of the number of white powder (powder blown) that had bleeded out was calculated.

[Dynamic friction coefficient (time change)]
Each battery packaging material obtained above is stored in a roll in a constant temperature and humidity chamber (40 ° C., 90% RH) for 3 months, and after 1 day, 3 weeks, and 3 months after storage, The dynamic friction coefficient of the slip coating layer of the packaging material was measured. The measurement was performed with a Haydon-type measuring instrument [manufactured by Toshin Chemical Co., Ltd .: Haydon 14 (trade name)] under the conditions of a load of 100 g and a friction speed of 100 mm / min, and the dynamic friction coefficient was evaluated according to the following criteria.
<Judgment criteria for dynamic friction coefficient>
○: Dynamic friction coefficient is less than 0.15.
(Triangle | delta): A dynamic friction coefficient is 0.15 or more and less than 0.3.
X: A dynamic friction coefficient is 0.3 or more.

[Dynamic friction coefficient (temperature change)]
Each battery packaging material obtained above was allowed to stand in a temperature atmosphere of 25 ° C., 40 ° C., and 55 ° C. for 24 hours, and then the dynamic friction coefficient of the slip coating layer of the battery packaging material was measured in each temperature atmosphere. did. Measurement is performed with a Haydon-type measuring instrument [Toshin Chemical Co., Ltd .: Haydon 14 (trade name)] under the conditions of a load of 100 g and a friction speed of 100 mm / min, and the same determination as in the case of the above-mentioned [dynamic friction coefficient (time change)]. The dynamic friction coefficient was evaluated based on the standard.

[Evaluation results]
The results obtained are shown in Tables 5 and 6. From this result, by using a resin composition containing a thermosetting resin, a curing accelerator, and a reactive slip agent for the formation of the slip coating layer, it can be cured in a short time and wrinkles due to heat. Further, it was confirmed that the dynamic friction coefficient does not increase even with the passage of time or exposure to a high temperature atmosphere, and the reduction of the slip effect can be suppressed (Examples 1 to 14). In contrast, when a non-reactive slip agent (fatty acid amide) is used instead of a reactive slip agent in the formation of a slip coating layer, the white powder defect rate is high and bleed out of the slip agent is observed. Further, when the slip agent was stored for 3 months or under a temperature condition of 55 ° C., the coefficient of dynamic friction increased and the slip effect of the slip coating layer was reduced (Comparative Examples 1 to 7). In addition, even when a reactive slip agent is used in the formation of the slip coating layer, when a curing accelerator is not included, the dynamic friction coefficient is large and a sufficient slip effect cannot be provided. (Comparative Examples 8 to 13)
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 Slip coating layer 2 Base material layer 3 Adhesive layer 4 Barrier layer 5 Sealant layer

Claims (7)

It consists of a laminate having at least a surface coating layer , a substrate layer, an adhesive layer, a barrier layer, and a sealant layer in this order,
The resin composition comprising the surface coating layer containing a thermosetting resin, a curing accelerator, and a compound that has a functional group that reacts with the thermosetting resin to chemically bond and can impart slip properties. A battery packaging material characterized by being a cured product.   The battery according to claim 1, 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. 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. 2. Battery packaging material according to 2. The compound having a functional group that reacts with the thermosetting resin and chemically binds and can impart slip properties has 1 to 3 functional groups that react with the thermosetting resin and chemically bond. The battery packaging material according to any one of claims 1 to 3, which is a compound having the same .   The battery packaging material according to any one of claims 1 to 4, wherein the barrier layer is a metal foil. A method for producing a battery packaging material comprising a laminate having a surface coating layer , a substrate layer, an adhesive layer, a barrier layer, and a sealant layer in this order,
A first step of laminating a base material layer and a barrier layer through an adhesive layer to form a laminate in which the base material layer, the adhesive layer, and the barrier layer are sequentially laminated, and the laminate obtained in the first step A second step of laminating a sealant layer on the barrier layer of
Before the first step, after the first step and before the second step, or after the second step, a thermosetting resin is provided on the surface of the base material layer opposite to the surface on which the adhesive layer is laminated. And a resin composition containing a curing accelerator and a compound that has a functional group that reacts with the thermosetting resin to chemically bond and can impart slip properties, and is cured by heating. The manufacturing method of the packaging material for batteries characterized by forming a surface coating layer by this. 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 claim 1.