KR20230027970A - Packing material for battery and battery comprising the same - Google Patents

Abstract

The present application relates a laminate comprising a substrate layer, a barrier layer, a first adhesive organic layer, and a heat-fusion resin layer, a battery packaging material further comprising an electrolysis resistant layer between the barrier layer and the first adhesive organic layer, and a battery comprising the same. The battery packaging material of the present application has excellent productivity, formability, processability and chemical resistance.

Description

Battery packaging material and battery including the same {PACKING MATERIAL FOR BATTERY AND BATTERY COMPRISING THE SAME}

This application relates to batteries and capacitors used in mobile electric devices such as smartphones and tablets, hybrid vehicles, electric vehicles, wind power generation, photovoltaic power generation, battery exterior materials (packaging materials), etc. It relates to packaging materials used as

As an electrical storage device, secondary batteries such as nickel cadmium batteries, nickel hydride batteries, lithium ion batteries, lithium ion polymer batteries, or lead acid batteries, and electrochemical capacitors such as electric double layer capacitors are known. These secondary batteries or electrochemical capacitors are used not only for small products such as digital cameras, P-DVDs, MP3Ps, mobile phones, PDAs, portable game devices, power tools, and E-bikes, but also for high-output applications such as electric vehicles and hybrid vehicles. It is also applied and used in power storage devices that store large-sized products, surplus generated power or renewable energy, and backup power storage devices.

Patent Document 1 (WO2015/099144) is a battery packaging material in which a substrate layer (outer layer), a second adhesion organic layer, a metal foil layer, a first adhesion organic layer, and a sealant layer (inner layer) are laminated in this order, and the second adhesion organic layer and a first adhesive organic layer are disclosed together with a battery packaging material formed by thermal curing (heat aging).

Referring to Patent Literature 1, in order to form the first and first adhesive organic layers by thermal curing, it is necessary to perform a heat aging treatment at 40° C. for 5 days or 10 days after applying the adhesive (Patent Literature 1 paragraph 0097). Thus, since the battery packaging material formed by thermal curing must be subjected to heat aging treatment for at least 5 days or more, the problem that the lead time (the time required from material input to product completion) is considerably long, that is, productivity is low. There was a problem of falling behind.

Therefore, there is a need to develop a packaging material capable of shortening the lead time and improving productivity.

International Publication Patent WO2015/099144 (published on July 2, 2015)

One aspect of the present application is to provide a battery packaging material manufactured by a photocuring method with excellent productivity and moldability.

One aspect of the present application is to provide a battery packaging material having excellent adhesive strength, moldability and chemical resistance.

One aspect of the present application is to provide a battery including the battery packaging material and a device including the battery.

The problem of the present application is not limited to those mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the description below.

One embodiment of the present application is a laminate comprising a single or multi-layer substrate layer, a barrier layer, an adhesive organic layer, and a heat-sealable resin layer, further comprising an electrolytic resistant layer between the barrier layer and the adhesive organic layer, for a battery Provide packaging materials.

In one embodiment of the present application, the adhesive organic layer may include a photocurable resin composition.

In one embodiment of the present application, the light may be ultraviolet rays, visible rays, X-rays, or γ-rays, and an irradiation amount of 50 mJ/cm ² to 2500 mJ/cm ² .

In one embodiment of the present application, the electrolytic layer is a (modified) polypropylene resin, a (modified) polyethylene resin, a cycloolefin polymer resin, a polyterpene-based resin, a rosin-based resin, an aliphatic petroleum resin, or an alicyclic petroleum resin. At least one resin selected from the group consisting of copolymerized petroleum resins and hydrogenated petroleum resins; cross-linking agent; And an organic solvent; may be formed of a composition containing.

In one embodiment of the present application, the composition, based on the total weight of the composition, 10 to 50% by weight of the resin; 0 to 20% by weight of a crosslinking agent; and 70 to 95% by weight of an organic solvent; can include

In one embodiment of the present application, the electrolytic resistance layer may have a thickness of 0.1 μm to 3 μm.

In one embodiment of the present application, a corrosion-resistant inorganic layer may be further included on at least one surface of the barrier layer.

In one embodiment of the present application, the packaging material may include an anti-corrosion inorganic layer between the barrier layer and the adhesive organic layer, or may include an anti-corrosion inorganic layer between the barrier layer and the base layer, and the barrier layer An anti-corrosion inorganic layer may be included both between the layer and the adhesive organic layer and between the barrier layer and the base layer.

In one embodiment of the present application, the electrolytic resistant layer may be provided between the anti-corrosion inorganic layer and the adhesive organic layer.

In one embodiment of the present application, a second adhesion organic layer may be further included between the base layer and the barrier layer. In this case, an anti-corrosion inorganic layer may be further included between the second adhesion organic layer and the barrier layer.

In one embodiment of the present application, an outer base layer may be further laminated on the outside of the base layer, and a third adhesive organic layer may be further included between the base layer and the outer base layer.

In one embodiment of the present application, the base layer is polyester, polyethylene, polypropylene, polyethylene terephthalate, polyamide, nylon, low density polyethylene (LDPE), high density polyethylene (HDPE), polybutylene terephthalate, polyethylene or It may be formed of at least one resin selected from the group consisting of phthalate, polyester copolymer and linear low density polyethylene (LLDPE).

In one embodiment of the present application, the barrier layer may include aluminum; copper; nickel; alloys of iron, carbon, chromium and manganese; It may be formed of at least one metal selected from the group consisting of alloys of iron, carbon, chromium, and nickel.

In one embodiment of the present application, the anti-corrosion inorganic layer may be formed of at least one selected from the group consisting of phosphoric acid, phosphate salt, chromic acid, chromium (III) salt, chromium phosphate, and zinc phosphate.

In one embodiment of the present application, the heat-sealable resin layer is polyethylene, polypropylene, unstretched polypropylene, biaxially stretched polypropylene, ionomo, ethyl ethylene acrylate, methyl ethylene acrylate, methyl ethylene methacrylate, ethylene vinyl acetate Copolymer resin, maleic anhydride-modified polypropylene resin, maleic anhydride-modified polyethylene resin, polyester resin, polyethylene-propylene copolymer, polypropylene-butylene-ithelene terpolymer, polyethylene and acrylic acid copolymer, polypropylene and acrylic acid It may be formed of at least one resin selected from the group consisting of copolymers of.

In one embodiment of the present application, when the peeling force is measured by T-shaped peeling of a test piece cut to have a sample width of 15mm and a length of 150mm of the battery packaging material at a peeling rate of 30mm/min, the barrier layer and the thermal fusion The peeling force of the resin layer may be 4 N/15 mm or more.

In one embodiment of the present application, after immersing a test piece cut to have a sample width of 15 mm and a length of 150 mm of the battery packaging material in an electrolyte at 85 ° C. for 14 days or more, the laminate strength retention rate of the barrier layer and the heat-sealable resin layer It may be more than 30%.

One embodiment of the present application provides a battery having the packaging material.

One embodiment of the present application provides a device including the battery.

In one embodiment of the present application, the device may be a mobile phone, a portable computer, a smart phone, a smart pad, a netbook, a light electronic vehicle (LEV), an electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, or a power storage device. there is.

Since the battery packaging material according to one embodiment of the present application is produced by a photocuring method, it has the advantage of significantly reducing lead time, improving productivity, and securing excellent formability.

In addition, the battery packaging material according to one embodiment of the present application includes an electrolysis resistant layer at the interface between an inorganic layer such as a barrier layer or an anti-corrosion inorganic layer and an adhesive organic layer, thereby having excellent resistance to electrolyte and acid even at high temperatures. Therefore, it has the advantage of excellent chemical resistance.

In addition, the battery packaging material according to one embodiment of the present application has an advantage of having excellent adhesive strength and peel resistance.

Effects according to the present application are not limited by the contents exemplified above, and various more effects are included in the present specification.

1 to 4 show a battery packaging material according to one embodiment of the present application.
5 shows a battery packaging material prepared according to Comparative Example 6.

Advantages and features of the present application, and how to achieve them, will become clear with reference to the embodiments described below in detail. However, the present application is not limited to the embodiments disclosed below and may be implemented in various different forms, but only the present embodiments make the disclosure of the present application complete, and common knowledge in the art to which this application belongs. It is provided to fully inform the person who has the scope of the application, and this application is only defined by the scope of the claims. Like reference numbers designate like elements throughout the specification.

Unless otherwise defined, all terms (including technical and scientific terms) used in this specification may be used in a meaning commonly understood by those of ordinary skill in the art to which this application belongs. In addition, terms defined in commonly used dictionaries are not interpreted ideally or excessively unless explicitly specifically defined.

Terminology used herein is for describing the embodiments and is not intended to limit the present application. In this specification, singular forms also include plural forms unless specifically stated otherwise in a phrase. As used herein, "comprises" and/or "comprising" does not exclude the presence or addition of one or more other elements other than the recited elements.

In this specification, the numerical range represented by "-" means "above" and "below". For example, notation with 2 to 15 mm means 2 mm or more and 15 mm or less.

In one embodiment of the present application, a base layer, a second adhesive organic layer, a barrier layer, an anticorrosive inorganic layer, a first adhesive organic layer, and a heat-sealable resin layer are laminated in this order, and between the anticorrosive inorganic layer and the first adhesive organic layer. Provided is a battery packaging material provided with an electrolysis resistant layer.

When the battery packaging material manufactured by the photocuring method does not include the electrolytic resistant layer, the electrolyte solution permeates into the first adhesive organic layer, resulting in poor chemical resistance. In addition, when the electrolytic resistant layer is not provided, if a resin having elongation is used for the first adhesive organic layer, chemical resistance may be further deteriorated. In one embodiment of the present application, by providing an electrolysis resistant layer between the anti-corrosion inorganic layer and the first adhesive organic layer, there is an advantage in maintaining chemical resistance while increasing elongation.

Hereinafter, embodiments of the present application will be described in detail with reference to the accompanying drawings.

1 to 4 show a battery packaging material according to one embodiment of the present application.

internal electrolytic layer

In one embodiment of the present application, the electrolytic resistant layer 50 is made of (modified) polypropylene resin, (modified) polyethylene resin, cycloolefin polymer resin, polyterpene-based resin, rosin-based resin, aliphatic petroleum resin, alicyclic One or two or more resins selected from the group consisting of family-based petroleum resins, copolymerized petroleum resins, and hydrogenated petroleum resins; cross-linking agent; And an organic solvent; may be formed of a composition containing.

As the crosslinking agent, one or two or more of an isocyanate-based resin or an epoxy-based resin may be used.

Examples of the isocyanate-based resin include tolylene diisocyanate, xylylene diisocyanate or a hydrogenated product thereof, hexamethylene diisocyanate ((1,6-diisocyanatohexane), 4,4'-diphenylmethane diisocyanate or Diisocyanates such as hydrogenated products and isophorone diisocyanate; or adducts obtained by reacting these isocyanates with polyhydric alcohols such as trimethylolpropane, biuret obtained by reacting with water, or isocyanurate as a trimer polyisocyanates such as sieves; or block polyisocyanates obtained by blocking these polyisocyanates with alcohols, lactams, oximes, etc., specifically hexamethylene diisocyanate, 4,4'-diphenylmethanedi It is preferred to use isocyanate or isophorone diisocyanate.

Examples of epoxy resins include glycidyl ether type epoxy resins, glycidyl amine type epoxy resins, cycloaliphatic epoxy resins, glycidyl ester type resins, heterocyclic epoxy resins, urethane-modified epoxy resins, and the like. , one or more can be selected and used.

More specifically, the glycidyl ether type epoxy resin includes bisphenol A type epoxy resin, bisphenol F type epoxy resin, brominated bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin , biphenyl type epoxy resin, naphthalene type epoxy resin, fluorene type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, DPP novolak type epoxy resin, trifunctional type epoxy resin, tris hydroxyphenyl There are methane-type epoxy resins, tetraphenylolethane-type epoxy resins, and the like.

More specifically, the glycidyl amine type epoxy resin includes tetraglycidyldiaminodiphenylmethane epoxy resin, triglycidyl isocyanurate epoxy resin, hydantoin type epoxy resin, 1,3-bis(N,N -Diglycidylaminomethyl) cyclohexane epoxy resin, aminophenol type epoxy resin, aniline type epoxy resin, toluidine type epoxy resin and the like.

As the organic solvent, various known organic solvents can be used alone or in combination of two or more. As such an organic solvent, any solvent that has sufficient solubility in the above materials and imparts good film properties can be used without particular limitation. cellosolve solvents such as methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, and ethyl cellosolve acetate; propylene glycol solvents such as propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol dimethyl ether, and propylene glycol monoethyl ether acetate; ester solvents such as butyl acetate, amyl acetate, methyl lactate, ethyl lactate, 3-methoxypropionic acid, and ethyl 3-ethoxypropionate; alcohol solvents such as methanol, ethanol, propanol, benzyl alcohol, cresol, hexanol, and diacetone alcohol; ketone solvents such as cyclohexanone, methyl amyl ketone, methyl cyclohexane, and methyl ethyl ketone; ether solvents such as methylphenyl ether and diethylene glycol dimethyl ether; highly polar solvents such as N,N-dimethylformamide, N-methylpyrrolidone, dimethylacetamide, dimethylsulfoxide, N-methylcaprolactam, methyl triglyme, and methyl diglyme; or a mixed solvent thereof.

In one embodiment of the present application, the electrolytic resistant layer 50 includes 10 to 50 wt%, preferably 20 to 50 wt% of a resin, 0 to 20 wt% of a crosslinking agent, based on the total weight of the composition; More preferably, 0.1 to 20% by weight is included, and 70 to 95% by weight of an organic solvent; can include If the crosslinking agent is 0.1% by weight or more, a crosslinked structure is easily formed, and if it is 20% by weight or less, the pot life of the composition may be improved.

In one embodiment of the present application, the electrolysis resistant layer 50 may have a thickness of 0.1 μm to 3 μm. When the thickness is 0.1 μm or more, adhesive strength and chemical resistance are improved, and when the thickness is 3 μm or less, moldability is improved.

base layer

The single-layer or multi-layer substrate layers 10 and 12 impart heat resistance in the sealing process when manufacturing a battery and play a role in suppressing the occurrence of pinholes that may occur during molding or distribution. In particular, in the case of an exterior material for a large-sized battery, etc., scratch resistance, chemical resistance, insulation, and the like can be imparted.

It is preferable that the said base material layer is a layer which consists of a resin film formed with resin which has insulating property. As the resin film, polyester, polyolefin, polyethylene, polypropylene, polyethylene terephthalate, polyamide, nylon, low density polyethylene (LDPE), high density polyethylene (HDPE), polybutylene terephthalate, polyethylene naphthalate, polyester copolymer And a resin selected from the group consisting of linear low-density polyethylene (LLDPE), or a modified product thereof, or a copolymer thereof, or a modified product of the copolymer. The resin film may be a stretched or unstretched film. The substrate layer may be a single-layer film composed of any of these resin films, or may be a laminated film composed of two or more types of these resin films.

Specific examples of the polyester include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene isophthalate, co-polyester, and the like. Moreover, as co-polyester, the co-polyester etc. which made ethylene terephthalate repeatingly and made a main unit are mentioned. Specifically, copolymer polyester (hereinafter referred to as polyethylene (terephthalate/isophthalate), polyethylene (terephthalate/adipic acid), polyethylene (terephthalate/sodium sulfoisophthalate), polyethylene (terephthalate/sodium isophthalate), polyethylene (terephthalate/phenyldicarboxylate), polyethylene (terephthalate/decanedicarboxylate), etc. These polyesters are 1 You may use them individually, or you may use them in combination of 2 or more types.

Specific examples of the polyamide include aliphatic polyamides such as nylon 6, nylon 66, nylon 610, nylon 12, nylon 46, and a copolymer of nylon 6 and nylon 66; structural units derived from terephthalic acid and/or isophthalic acid; Including nylon 6I, nylon 6T, nylon 6IT, nylon 6I6T (I stands for isophthalic acid, T stands for terephthalic acid), etc. Hexamethylene diamine isophthalic acid terephthalic acid copolymerized polyamide, polyamide MXD6 (polymethaxylene adipamide), etc. Aromatic polyamides including; aliphatic polyamides such as polyamide PACM6 (polybis(4-aminocyclohexyl) methaneazipamido); In addition, polyamide copolymerized with lactam component or isocyanate component such as 4,4'-diphenylmethane diisocyanate, polyester amide copolymer or polyether ester amide, which is a copolymer of copolymerized polyamide and polyester or polyalkylene ether glycol Copolymer; Polyamide, such as these copolymers, is mentioned. These polyamides may be used singly or in combination of two or more.

The substrate layers 10 and 12 preferably include at least one of a stretched polyester film, a stretched polyamide film, and a stretched polyolefin film, and a stretched polyethylene terephthalate film, a stretched polybutylene terephthalate film, and a stretched nylon. It may include at least one of a film and a stretched polypropylene film, and includes at least one of a biaxially stretched polyethylene terephthalate film, a biaxially stretched polybutylene terephthalate film, a biaxially stretched nylon film, and a biaxially stretched polypropylene film. can do.

The base layers 10 and 12 may be a single layer or may be composed of two or more layers. When the substrate layers 10 and 12 are composed of two or more layers, the substrate layers 10 and 12 may be a laminate obtained by laminating resin films with an adhesive or the like, or a resin film laminate obtained by extruding all of the resin to form two or more layers. A chair is also good. Moreover, the resin film layered product made into two or more layers by extruding all the resins may be referred to as an unstretched substrate layer, or may be a uniaxially stretched or biaxially stretched substrate layer.

In the substrate layers 10 and 12, specific examples of the resin film laminate of two or more layers include a laminate of a polyester film 12 and a nylon film 10, and a laminate of two or more layers of nylon films 10 and 12. sieve, a laminate of two or more layers of polyester films 10, 12, etc. Preferably, a laminate of a stretched nylon film 12 and a stretched polyester film 10, a stretched nylon film of two or more layers ( 10, 12) A laminate and a laminate of two or more layers of stretched polyester films (10, 12) are preferred. For example, when the base layer is a two-layer resin film laminate, a polyester resin film 12 and polyester resin film 10 laminate, a polyamide resin film 12 and polyamide resin film 10 laminate. , or a laminate of a polyester resin film 12 and a polyamide resin film 10 is preferable, a laminate of a polyethylene terephthalate film 12 and a polyethylene terephthalate film 10, a nylon film 12 and a nylon film 10 ) A laminate or a polyethylene terephthalate film 12 and a nylon film laminate 10 are more preferred. In addition, since the polyester resin is difficult to change color when, for example, electrolytic solution adheres to the surface, when the base material layer is a resin film laminate of two or more layers, it is preferable that the polyester resin film is located on the outermost layer of the base material layer. do. When the substrate layer has two or more layers, it may be bonded with an adhesive organic layer made of a photocurable resin composition described later.

Additives such as a lubricant, a flame retardant, an antiblocking agent, an antioxidant, a light stabilizer, a tackifier, and an antistatic agent may be present on at least one surface and inside of the substrate layer. One type of additive may be used, or two or more types may be mixed and used.

The thickness of the substrate layer is not particularly limited as long as the thickness of the laminate is 75 μm or less and the function as the substrate is exhibited, but may be, for example, about 3 to 50 μm, specifically about 10 to 35 μm. When the substrate layer is a resin film laminate of two or more layers, the thickness of the resin film constituting each layer may be, specifically, about 2 to 25 μm.

adhesive organic layer

In one embodiment of the present application, the second adhesion organic layer 20 and the first adhesion organic layer 60 may be made of a photocurable resin composition. When the base layer is a multilayer, a third adhesive organic layer 22 may be formed between the two base layers, and this may also be made of a photocurable resin composition.

In one embodiment of the present application, the light may be ultraviolet rays, visible rays, X-rays, or γ-rays, and an irradiation amount of 50 mJ/cm ² to 2500 mJ/cm ² .

The photocurable resin composition may be a composition containing a polymerizable oligomer and a photopolymerization initiator, or may be a composition containing a polymerizable oligomer, a polymerizable monomer and a photopolymerization initiator.

The photopolymerization initiator is benzophenone, p-dimethylaminobenzophenone, pchlorobenzophenone, benzophenone methyl ether, methylbenzophenone, 4,4-dichlorobenzophenone, 4,4-bisdiethylaminobenzophenone, benzaldehyde, Anthraquinone, 3-methylacetophenone, 1-(4-isopropyl-phenol)-2-hydroxy-2-methylpropan-1-one, thioxanthone, 4-chlorobenzophenone, 4,4'-dimethoxy Benzophenone, 4,4'-diaminobenzophenone, benzoin propyl ether, benzoin, benzoin methyl ether, benzoin ether, benzoin isobutyl ether, benzoin isopropyl ether, methyl benzoin, benzoin- n-butyl ether, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, 2-aminoanthraquinone, 2,4- Dimethylthioxanthone (2,4-dimethylthioxanthone), 2,4-diisopropylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 2, 2-dimethoxy-2-phenylacetophenone, α,α-dichloro-4-phenoxyacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, 2,2-diethoxyaceto Phenone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-mol Polynopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, bis( 2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, etc. are mentioned. You may use these individually by 1 type or in mixture of 2 or more types.

The photopolymerizable oligomer may be a (meth)acrylate having at least one skeleton selected from the group consisting of polymerizable urethane oligomer, polybutadiene, hydrogenated polybutadiene, polyisoprene, and hydrogenated polyisoprene.

In this specification, the term "(meth)acrylate" is a term indicating either one or both of acrylate and methacrylate. In addition, the term "(meth)acryloyl group" mentioned later is a term which points out either one or both of an acryloyl group and a methacryloyl group. For example, the term "octyl (meth)acrylate" refers to either or both of octyl acrylate and octyl methacrylate.

As the photopolymerizable oligomer, a polymerizable urethane oligomer may be used from the viewpoint of adhesive strength. The polymerizable urethane oligomer is preferably polyfunctional, and the polymerizable groups of the polymerizable urethane oligomer preferably exist at terminals, particularly at both terminals. As a kind of the said polymeric group, a (meth)acryloyl group, a vinyl group, etc. are preferable, for example, and a (meth)acryloyl group is especially preferable. That is, the polymerizable urethane oligomer is preferably a polyfunctional (meth)acrylate oligomer, in other words, preferably a urethane acrylate oligomer containing two or more acryloyl groups or two or more vinyl groups.

The urethane acrylate oligomer is, for example, polyalkylene polyol, polyether polyol, polyester polyol, a polyhydric alcohol such as hydrogenated isoprene having a hydroxy group terminal, hydrogenated butadiene having a hydroxy group terminal, and polyisocyanate It can be obtained by esterifying the polyurethane oligomer obtained by the reaction with (meth)acrylic acid or a (meth)acrylic acid derivative.

As the polyhydric alcohol, for example, polybutadiene glycol, hydrogenated polybutadiene glycol, polyisoprene glycol, hydrogenated polyisoprene glycol, neopentyl glycol, 3-methyl-1,5-pentanediol, ethylene glycol, propylene glycol, 1 Alkylene glycols having 1 to 10 carbon atoms such as 4-butanediol and 1,6-hexanediol, triols such as trimethylolpropane and pentaerythritol, tricyclodecanedimethylol, bis-[hydroxymethyl]-cyclohexane, etc. alcohols having a cyclic skeleton of and polyester polyols obtained by reacting these polyhydric alcohols with polybasic acids (e.g., succinic acid, phthalic acid, hexahydrophthalic anhydride, terephthalic acid, adipic acid, azelaic acid, tetrahydrophthalic anhydride, etc.), polyhydric alcohols and caprolactone. Caprolactone alcohol obtained by the reaction of , polycarbonate polyol (for example, polycarbonate diol obtained by the reaction of 1,6-hexanediol and diphenyl carbonate, etc.) or polyether polyol (for example, polyethylene glycol, poly propylene glycol, polytetramethylene glycol, ethylene oxide-modified bisphenol A, etc.). From the viewpoint of adhesive strength and moisture resistance, polypropylene glycol, polybutadiene glycol, hydrogenated polybutadiene glycol, polyisoprene glycol, and hydrogenated polyisoprene glycol are preferred as the polyhydric alcohol, and from the viewpoint of transparency and flexibility, the weight average molecular weight is 2000 or more polypropylene glycol, hydrogenated polybutadiene glycol, and hydrogenated polyisoprene glycol are particularly preferred. From the viewpoint of discoloration properties such as heat discoloration resistance and compatibility, hydrogenated polybutadiene glycol or polypropylene glycol is preferable. On the other hand, from the viewpoint of compatibility with other components, polypropylene glycol is preferred. Although the upper limit of the weight average molecular weight at this time is not specifically limited, 10000 or less are preferable and 5000 or less are more preferable. Moreover, you may use together 2 or more types of polyhydric alcohol as needed.

Examples of the polyisocyanate include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylene diisocyanate; Aromatic diisocyanate, such as tolylene diisocyanate, xylylene diisocyanate, and diphenyl diisocyanate; and alicyclic diisocyanates such as dicyclohexylmethane diisocyanate and isophorone diisocyanate. Among these, alicyclic diisocyanates are preferably used, and dicyclohexylmethane diisocyanates are particularly preferably used. Since the alicyclic structure is bulky and low in polarity, by using a urethane acrylate-based oligomer containing an alicyclic structure derived from an alicyclic diisocyanate, the obtained adhesive has more excellent blister resistance. In addition, by using dicyclohexylmethane diisocyanate, the chemical structure of the urethane acrylate-based oligomer obtained is similar to that of glycidyl ethers suitable as an ion polymerizable component described later, and the compatibility is good. do. In addition, polyisocyanate is not limited to bifunctional, but a trifunctional or higher functional polyisocyanate can also be used.

Examples of the (meth)acrylic acid derivative include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl acrylate and 4-hydroxybutyl acrylate, 2-isocyanatoethyl acrylate, and 2-isocyanatoethyl metha acrylate, 1,1-bis(acryloxymethyl)ethyl isocyanate, and the like, and it is particularly preferable to use 2-isocyanatoethyl acrylate.

Although it does not specifically limit as said (meth)acrylate monomer, A (meth)acrylate which has one (meth)acryloyl group in a molecule suitably can be used suitably. Here, the (meth)acrylate monomer has at least one skeleton selected from the group consisting of urethane (meth)acrylate, polypropylene, polybutadiene, hydrogenated polybutadiene, polyisoprene, and hydrogenated polyisoprene. Shows (meth)acrylates other than (meth)acrylates.

As the (meth)acrylate monomer having one (meth)acryloyl group in the molecule, specifically, octyl (meth)acrylate, isooctyl (meth)acrylate, isoamyl (meth)acrylate, lauryl ( meth)acrylate, isodecyl (meth)acrylate, stearyl (meth)acrylate, cetyl (meth)acrylate, isomyristyl (meth)acrylate, isostearyl (meth)acrylate, tridecyl (meth)acrylate ) (meth)acrylate having an alkyl group having 5 to 25 carbon atoms such as acrylate, benzyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, acryloylmorpholine, cyclic trimethylolpropane formal acryl rate, phenylglycidyl (meth)acrylate, tricyclodecane (meth)acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, dicy Clopentanyl (meth)acrylate, 1-adamantyl acrylate, 2-methyl-2-adamantyl acrylate, 2-ethyl-2-adamantyl acrylate, 1-adamantyl methacrylate, Polypropylene oxide-modified nonylphenyl (meth)acrylate, ethoxylated o-phenylphenol acrylate, dicyclopentadienoxyethyl (meth)acrylate, etc. (meth)acrylates having a cyclic skeleton, carbon atoms having 2 hydroxyl groups Polyalkylene glycols such as (meth)acrylates having an alkyl group of to 7, ethoxydiethylene glycol (meth)acrylates, polypropylene glycol (meth)acrylates, and polypropylene oxide-modified nonylphenyl (meth)acrylates ( meth)acrylate, ethylene oxide-modified phenoxylated phosphoric acid (meth)acrylate, ethylene oxide-modified butoxylated phosphoric acid (meth)acrylate, ethylene oxide-modified octyloxylated phosphoric acid (meth)acrylate, caprolactone-modified tetrafurfuryl (meth) ) Acrylate etc. are mentioned.

It is preferable that the said polymerizable monomer contains the monofunctional (meth)acrylate monomer which has an alicyclic ring or a heterocyclic ring from an adhesive viewpoint. As the monofunctional (meth)acrylate monomer (C-2) having an alicyclic or heterocyclic ring, specifically, tetrahydrofurfuryl (meth)acrylate, acryloylmorpholine, dicyclopentenyl (meth)acrylate , cyclic trimethylolpropane formal acrylate, dicyclopentenyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, 1-adamantyl acrylate, 2 -Methyl-2-adamantyl acrylate, 2-ethyl-2-adamantyl acrylate, 1-adamantyl methacrylate, dicyclopentadienoxyethyl (meth)acrylate, etc. are mentioned. Especially, from a compatible viewpoint with other materials, acryloylmorpholine, dicyclopentanyl (meth)acrylate, and isobornyl (meth)acrylate are more preferable.

It is preferable to contain a (meth)acrylate monomer having a hydroxyl group as the (meth)acrylate monomer from the viewpoint of resistance to high temperature and/or high humidity. As a (meth)acrylate monomer which has a hydroxyl group, hydroxybutyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxyethyl (meth)acrylate, etc. are mentioned.

The photocurable resin composition may further include a silane coupling agent, an acid anhydride, a sensitizer, and various additives.

Examples of the silane coupling agent include, but are not particularly limited to, methyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, vinylchlorosilane, and 3-(methacryloyl). yloxy) propyl trimethoxy silane 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclo Hexyl) ethyltrimethoxysilane, N-(2-aminoethyl)3-aminopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, N-(2-aminoethyl)3-aminopropylmethyltri Methoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, N-(2-(vinylbenzylamino)ethyl)3-aminopropyltrimethoxysilane hydrochloride, 3-methacrylic acid Oxypropyl trimethoxysilane, 3-chloropropyl methyldimethoxysilane, 3-chloropropyltrimethoxysilane and the like can be used.

2-(3,4epoxychlorohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p -Styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyl trie Toxysilane, 3-acryloxypropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropyl methyldimethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (amino Ethyl) 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3dimethyl-butylidene)propylamine , N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzene)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3-chloropropyltrimethoxysilane, 3-mercapto At least one of propylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis(triethoxysilylpropyl)tetrasulfide, and 3-isocyanatopropyltriethoxysilane may be used.

Examples of the acid anhydride include, but are not particularly limited to, maleic anhydride, methyl maleic anhydride, itaconic anhydride, hymic acid anhydride, and methylhymic acid anhydride. Especially, as said acid anhydride, it is preferable to use the acid anhydride which has a carbon-carbon double bond, such as maleic anhydride, and the polymerization reaction can be accelerated more by the acid anhydride which has such a double bond.

Although it does not specifically limit as said sensitizer, For example, a tertiary amine etc. are mentioned. Although it is not specifically limited as said tertiary amine, For example, N,N-dimethylethylamine, N,N-dimethylethanolamine, N,N,3,5-tetramethyl aniline is mentioned.

The thickness of the adhesive organic layer 20, 22, 60, that is, the thickness after drying may be 1 μm to 10 μm, specifically 1 μm to 6 μm.

barrier layer

The barrier layer 30 plays a role of imparting gas barrier properties to prevent intrusion of oxygen or moisture to the packaging material of the present application. For the barrier layer 30, a metal foil layer may be used. The barrier layer 30 is not particularly limited, but is, for example, aluminum; copper; nickel; alloys of iron, carbon, chromium and manganese; and metals selected from the group consisting of alloys of iron, carbon, chromium, and nickel. For the barrier layer 30, aluminum can be used from the viewpoint of moisture resistance and workability.

The metal foil of the barrier layer 30 may be degreased, for example, in order to obtain desired electrolyte resistance. Moreover, in order to simplify a manufacturing process, as for the said metal foil, it is preferable that the surface is not etched. As the degreasing treatment, for example, a wet type degreasing treatment or a dry type degreasing treatment can be used, but a dry type degreasing treatment can be used from the viewpoint of simplifying the manufacturing process. As the dry-type degreasing treatment, for example, in the step of annealing the metal foil, a method of performing the degreasing treatment by lengthening the treatment time is exemplified. At the time of the annealing treatment performed to soften the metal foil, sufficient electrolyte resistance is obtained even at the extent of the degreasing treatment performed simultaneously.

As the dry-type degreasing treatment, treatments other than the annealing treatment, such as flame treatment and corona treatment, may be used. Further, as the dry type degreasing treatment, for example, a degreasing treatment in which contaminants are oxidatively decomposed and removed by active oxygen generated when the metal foil is irradiated with ultraviolet rays of a specific wavelength may be used.

As the wet-type degreasing treatment, for example, an acid degreasing treatment, an alkali degreasing treatment, or the like can be used. As an acid used for the acid degreasing treatment, inorganic acids such as sulfuric acid, nitric acid, hydrochloric acid, and hydrofluoric acid can be used, for example. These acids may be used individually by 1 type, and may use 2 or more types together. Moreover, as an alkali used for alkaline degreasing treatment, sodium hydroxide with a high etching effect can be used, for example. Alkaline degreasing treatment may also be performed using a material in which a weakly alkaline material and a surfactant or the like are blended. The wet type degreasing treatment described above can be performed by, for example, an immersion method or a spray method.

The thickness of the barrier layer 30 is preferably 9 μm to 120 μm. If it is 9 μm or more, it is possible to prevent the generation of pinholes during rolling when manufacturing metal foil, and even if stress is applied by molding, it is difficult to break. If it is 120 μm or less, the stress during molding such as expedient molding or drawing can be reduced, formability can be improved, the increase in mass of the packaging material can be reduced, and the decrease in the weight energy density of the battery can be suppressed. Among them, it is particularly preferable that the thickness of the barrier layer 30 is 20 μm to 100 μm.

anti-corrosion inorganic layer

It is preferable to provide anti-corrosion inorganic layers 40 and 42 to which chemical conversion treatment is performed on one or both sides of the barrier layer. The anti-corrosion inorganic layer 40 may be formed between the barrier layer 30 and the first adhesion organic layer 60 . Alternatively, the anti-corrosion inorganic layers 40 and 42 may be formed both between the barrier layer 30 and the first adhesion organic layer 60 and between the barrier layer 30 and the second adhesion organic layer 20 .

Corrosion of the surface of the metal foil by the contents (such as electrolyte solution of the battery) can be sufficiently prevented by such chemical conversion treatment being performed. For example, chemical conversion treatment is performed on metal foil by performing the following treatment.

The anti-corrosion inorganic layers 40 and 42 serve to sufficiently prevent corrosion of the surface of the metal foil by the electrolyte of the battery. The anti-corrosion inorganic layers 40 and 42 may be formed by including one or two or more selected from the group consisting of, for example, phosphoric acid, phosphoric acid salts, chromic acid, chromium (III) salts, chromium phosphate, and zinc phosphate. can Specifically, for the anti-corrosion inorganic layer, an aqueous solution of at least one compound selected from the group consisting of chromic acid and chromium (III) salts may be used. Alternatively, an aqueous solution of a mixture containing phosphoric acid, chromic acid, and at least one compound selected from the group consisting of metal salts of fluorides and nonmetal salts of fluorides can be used. or phosphoric acid, at least one resin selected from the group consisting of acrylic resins, chitosan derivative resins and phenolic resins, and at least one compound selected from the group consisting of chromic acid and chromium (III) salts. An aqueous solution of the mixture may be used. or phosphoric acid, at least one resin selected from the group consisting of acrylic resins, chitosan derivative resins and phenolic resins, and at least one compound selected from the group consisting of chromic acid and chromium (III) salts; An aqueous solution of a mixture containing at least one compound selected from the group consisting of metal salts of fluorides and non-metal salts of fluorides can be used. One of the aqueous solutions may be used, and an organic solvent such as alcohol may be further included.

The corrosion-resistant inorganic layers 40 and 42 preferably have a chromium adhesion amount of 0.1 mg/m ² to 50 mg/m ² , particularly preferably 2 mg/m ² to 20 mg/m ² .

heat fusion resin layer

The heat-sealable resin layer 70 can play a role of imparting excellent chemical resistance even to a highly corrosive electrolyte used in a lithium ion secondary battery or the like.

The heat-sealable resin layer 70 is polyethylene, polypropylene, unstretched polypropylene (CPP: Cast 　 Polypropylene), biaxially oriented polypropylene (OPP: Oriented 　 Polypropylene), ionomo, ethyl ethylene acrylate (EEA), methyl ethylene acrylate (EAA), ethylene methyl methacrylate (EMMA), ethylene vinyl acetate copolymer resin (EVA), maleic anhydride-modified polypropylene, maleic anhydride-modified polyethylene, and formed of one or two or more resins selected from the group consisting of it could be

The thickness of the heat-sealable resin layer 70 may be 15 μm to 100 μm. By setting it to 15 μm or more, sufficient thermal bonding strength can be secured, and by setting it to 100 μm or less, there is an advantage that thinning and lightening can be achieved. More specifically, the thickness of the heat-sealable resin layer 70 may be 50 μm to 100 μm, and a non-stretched resin may be used. The heat-sealable resin layer 70 may be a single layer or a multi-layer.

Battery packaging material

In one embodiment of the present application, when the peeling force is measured by T-shaped peeling of a test piece cut to have a sample width of 15mm and a length of 150mm of the battery packaging material 1 at a peeling speed of 30mm/min, the barrier layer The peel force between (30) and the heat-sealable resin layer 70 may be 4 N/15 mm or more, 6 N/15 mm or more, 7 N/15 mm or more, or 8 N/15 mm or more.

In one embodiment of the present application, a test piece cut to have a sample width of 15 mm and a length of 150 mm of the battery packaging material 1 is immersed in an electrolyte for 14 days or more in an 85 ° C atmosphere, and then thermally fused with the barrier layer 30. The laminate strength retention rate of the resin layer 70 may be 30% or more, 40% or more, 50% or more, 60% or more, or 70% or more.

The packaging material 1 according to one embodiment of the present application can be suitably used as a packaging material for batteries, capacitors, capacitors, and the like. In addition, it can also be used for either a primary battery or a secondary battery. The type of secondary battery to be applied is not particularly limited, and examples thereof include lithium ion batteries, lithium ion polymer batteries, all-solid-state batteries, lead storage batteries, nickel hydride storage batteries, nickel cadmium storage batteries, nickel iron storage batteries, and nickel/metal storage batteries. Zinc storage batteries, silver oxide/zinc storage batteries, metal-air batteries, polycationic batteries, capacitors, capacitors, and the like are exemplified. Among these secondary batteries, lithium ion batteries and lithium ion polymer batteries are highly suitable application targets.

In addition, since the packaging material 1 has good flexibility, it has an advantage of good workability. Therefore, it can be applied to both small batteries and large batteries.

One embodiment of the present application provides a battery having the packaging material.

One embodiment of the present application provides a device including the battery.

The device may be a mobile phone, a portable computer, a smart phone, a smart pad, a netbook, a light electronic vehicle (LEV), an electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, or a power storage device.

Hereinafter, Examples, Comparative Examples, and Experimental Examples of the present application will be described.

< Example 1>

A chemical solution consisting of a chromium (III) salt compound, water and alcohol was applied to both sides of an aluminum foil (aluminum foil of A8079 specified in JIS H4160) with a thickness of 40 μm, and then dried at 200 ° C. to form a film. The chromium coating amount of this film was 10 mg/m ² per side.

In addition, it is a resin obtained by graft polymerization of maleic anhydride to a copolymer of propylene and ethylene on the heat-sealable resin attachment surface of the aluminum foil, and has an acid value of 10 mgKOH / g. Maleic anhydride-modified polypropylene resin (GMP3020E, Sungwon Material ) 15 parts by mass of an organic solvent (mixed solvent of methylcyclohexane: methylethylketone = 8: 2 (mass ratio)) 85 parts by mass of a solution, 1 part by mass of hexamethylene diisocyanate (Aldrich) was mixed as a crosslinking agent, After coating with the obtained composition, it was dried at 100° C. for 1 minute to form an electrolytic resistant layer having a thickness of 1 μm.

As a base layer, a polyethylene terephthalate (PET) film (thickness 12 μm) and a nylon film (thickness 15 μm) were prepared, and 55 parts by mass of a urethane acrylate resin having two acryloyl groups on the PET film, hydroxyethyl acrylate A photocurable resin composition (second bonding organic layer) containing 15 parts by weight, 30 parts by weight of isobornyl acrylate, and 2 parts by weight of benzophenone was applied and bonded at 4 μm, and then bonded to the nylon film by UV curing at 1 J. Then, the chromium surface of the aluminum foil treated with the chromium and electrolysis-resistant layer was coated with an ultraviolet curing adhesive used for bonding PET and nylon to a thickness of 4 μm, and then bonded to the PET and nylon layers by 1 J of ultraviolet curing.

Then, KR-70T (ARDEKA), a solventless UV-curable adhesive, is applied to the primer side of aluminum at a thickness of 4 μm, and an unstretched polypropylene film with a thickness of 80 μm is laminated on the adhesive side. ) to obtain a battery packaging material of FIG. 2.

< Example 2>

An electrolytic resistant layer was formed in the same manner as in Example 1, except that 15 parts by mass of GMP5070E (Sungwon Material) was used as the resin in the electrolytic resistant layer of Example 1. The rest was prepared in the same manner as in Example 1 to obtain a battery packaging material of Example 2.

< Example 3>

An electrolytic resistant layer was formed in the same manner as in Example 1, except that 15 parts by weight of a cycloolefin copolymer (ET356302, Topas) was used as the resin in the electrolytic resistant layer of Example 1. The rest was prepared in the same manner as in Example 1 to obtain a battery packaging material of Example 3.

< Example 4>

An electrolytic resistant layer was formed in the same manner as in Example 1, except that 15 parts by weight of a rosin-based resin (Poly-Pale, Eastman) was used in the electrolytic resistant layer of Example 1. The rest was prepared in the same manner as in Example 1 to obtain a battery packaging material of Example 4.

< Example 5>

An electrolytic resistant layer was formed in the same manner as in Example 1, except that 1 part by weight of hydrogenated bisphenol A epoxy resin (ST3000, Kukdo Chemical) was used as the crosslinking agent in the electrolytic resistant layer of Example 1. The rest was prepared in the same manner as in Example 1 to obtain a battery packaging material of Example 5.

< Example 6>

The electrolytic layer of Example 1 was formed in the same manner as in Example 1, except that 1 part by weight of Neopentyl glycol diglycidyl ether (III) was used as the crosslinking agent. The rest was prepared in the same manner as in Example 1 to obtain a battery packaging material of Example 6.

< Example 7>

An electrolytic layer was formed in the same manner as in Example 1, except that 1 part by weight of hexamethylene diisocyanate (Aldrich) and 0.5 part by weight of hydrogenated bisphenol A epoxy resin (ST3000, Kukdo Chemical) were used as crosslinking agents in the electrolytic layer of Example 1. did The rest was prepared in the same manner as in Example 1 to obtain a battery packaging material of Example 7.

< Example 8>

An electrolytic layer was formed in the same manner as in Example 1, except that 1 part by weight of hexamethylene diisocyanate (Aldrich) and 5 parts by weight of hydrogenated bisphenol A epoxy resin (ST3000, Kukdo Chemical) were used as crosslinking agents in the electrolytic layer of Example 1. did The rest was prepared in the same manner as in Example 1 to obtain a battery packaging material of Example 8.

< Example 9>

In the electrolytic resistant layer of Example 1, the electrolytic resistant layer was prepared in the same manner as in Example 1 except that 1 part by weight of hydrogenated bisphenol A epoxy resin (ST3000, Kukdo Chemical) was used as a crosslinking agent and the electrolytic resistant layer was formed to a thickness of 0.5 μm. formed. The rest was prepared in the same manner as in Example 1 to obtain a battery packaging material of Example 9.

< Example 10>

An electrolytic resistant layer was formed in the same manner as in Example 1, except that 1 part by weight of hydrogenated bisphenol A epoxy resin (ST3000, Kukdo Chemical) was used as the crosslinking agent in the electrolytic resistant layer of Example 1 and the electrolytic resistant layer was formed to a thickness of 2 μm. did The rest was prepared in the same manner as in Example 1 to obtain a battery packaging material of Example 10.

< Example 11>

Except for using KR-15P (ADEKA) instead of UV-curable adhesive KR-70T (ARDEKA) in Example 1, the rest was prepared in the same manner as in Example 1 to obtain a battery packaging material of Example 11.

< Example 12>

A battery packaging material of Example 12 was obtained in the same manner as in Example 1, except that AUB-1332 and Toyochem were used instead of the UV curable adhesive KR-70T (ARDEKA).

< Example 13>

A battery packaging material of Example 13 was prepared in the same manner as in Example 2, except that the crosslinking agent was not used in Example 2.

< comparative example 1>

An electrolytic resistant layer was formed in the same manner as in Example 1, except that polystyrene (Kristalex F85, Eastman) was used as the resin. The rest was prepared in the same manner as in Example 1 to obtain a battery packaging material of Comparative Example 1.

< comparative example 2>

An electrolytic resistant layer was formed in the same manner as in Example 1, except that cellulose acetate butyrate (CAB-531-1, Eastman) was used as the resin. The rest was prepared in the same manner as in Example 1 to obtain a battery packaging material of Comparative Example 2.

< comparative example 3>

A battery packaging material of Comparative Example 3 was obtained in the same manner as in Example 1, except that the thickness of the electrolytic layer was 5 μm.

< comparative example 4>

A battery packaging material of Comparative Example 4 was obtained in the same manner as in Example 1, except that the thickness of the electrolytic layer was 0.05 μm.

< comparative example 5>

A battery packaging material of Comparative Example 5 was prepared in the same manner as in Example 1 except that the UV adhesive was not used in Example 1.

< comparative example 6>

A battery packaging material of Comparative Example 6 was prepared in the same manner as in Example 1, except that the electrolytic resistant layer was not formed in Example 1.

Preparation examples of Examples 1 to 13 and Comparative Examples 1 to 6 are shown in Table 1 below.

division Example comparative example One 2 3 4 5 6 7 8 9 10 11 12 13 One 2 3 4 5 6 internal electrolytic layer polyolefin A 15 15 15 15 15 15 15 15 15 15 15 15 15 B 15 15 C 15 D 15 E 15 F 15 solvent G 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 cross-linking agent I One One One One One One One One One One Ⅱ One 0.5 5 One One One One III One thickness
(um) One One One One One One One One 0.5 2 One One One One One 5 0.05 One glue uv
glue X X X X X X X X X X X X X X X X Y Z

A: GMP3020E, Sungwon Material (maleic anhydride modified polypropylene resin)

B: GMP5070E, Sungwon material (maleic anhydride modified polypropylene resin_A and ratio difference)

C: ET356302, Topas (cycloolefin copolymer)

D : Poly-Pale, rosin coefficient paper, Eastman

E: Kristalex F85, Polystyrene, Eastman

F: CAB-531-1, Cellulose Acetate Butyrate, Eastman

G: methylcyclohexane: methyl ethyl ketone = 8: 2 (mass ratio) mixed solvent

I: 1,6-diisocyanatohexane

II: ST3000, hydrogenated bisphenol A epoxy resin, Kukdo Chemical hydrogenated liquid bis phenol A epoxy resin

III: LD203 Neopentyl glycol diglycidyl ether, Kukdo Chemical

X : KR-70T, ADEKA

Y: KR-15P, ADEKA

Z: AUB-1332, Toyochem

< Experimental example 1> Adhesion strength

Specimens were prepared by peeling between the aluminum and non-stretched polypropylene of the battery packaging material prepared in Examples and Comparative Examples, and cutting to a width of 15 mm and a length of 150 mm. Subsequently, the T-Peel peel force of the sample was measured at a peel speed of 30 mm/min using an autograph (AG-1S, manufactured by SHIMADZU), and is shown in Table 2 below.

◎: Strength of 8 N/15 mm or more

○: Strength 6 N/15 mm or more and less than 8 N/15 mm

△: Strength 4 N/15 mm or more and less than 6 N/15 mm

X: strength less than 4 N/15 mm

< Experimental example 2> Electrolytic resistance evaluation

A sample was prepared by cutting the battery packaging material of each of the above Examples and Comparative Examples to have a width of 15 mm and a length of 150 mm, and the electrolyte (dimethyl carbonate: ethyl carbonate = 1: 2 + Li salt) at 85 ° C. Immersed in the atmosphere. Then, for these battery case packaging materials, after being immersed for 2 weeks, the lamination strength between the aluminum foil core layer and the unstretched film layer was measured. The evaluation criteria for electrolyte resistance were determined as follows, and the results obtained are shown in Table 2 below.

Electrolytic solution resistance evaluation criteria

◎: No change in laminate strength

○: Laminate strength retention rate of 60% or more

△: Laminate strength retention rate of 30% or more

X: laminate strength delaminate

< Experimental example 3> Formability evaluation method

With respect to the above examples and comparative examples, each battery packaging material was made into a blank shape of 110 mm × 110 mm, and bulging single-stage molding was performed with a straight mold with a free molding height. Comparison of moldability by molding height of each packaging material did. The punch shape of the mold used was 50 mm on the long side, 50 mm on the short side, corner R = 1 to 2 mm, punch shoulder R = 1 mm, and die shoulder R = 1 mm. The molding height evaluation criteria were determined as follows, and the results obtained are shown in Table 2 below.

◎: 7 mm or more

○: 6 or more and less than 7 mm

△: 5 or more and less than 6 mm

X: less than 5 mm

The physical properties of the battery packaging materials prepared in Examples 1 to 13 and Comparative Examples 1 to 6 were measured by the method of the Experimental Example, and the results are shown in Table 2 below.

division Example comparative example One 2 3 4 5 6 7 8 9 10 11 12 13 One 2 3 4 5 6 adhesive strength O O O O O ◎ O O O ◎ O ◎ O X X O X X O electrolytic resistance ◎ O O O O O ◎ O O O ◎ O O X X O O X X formability O ◎ O O O ◎ O O ◎ O O O O O O X X X O

Those skilled in the art to which this application pertains will understand that this application can be implemented in other specific forms without changing its technical spirit or essential features. Therefore, the embodiments described above should be understood as illustrative in all respects and not limiting. The scope of the present application is indicated by the following claims rather than the detailed description above, and all changes or modifications derived from the meaning and scope of the claims and equivalent concepts thereof should be construed as being included in the scope of the present application.

10: base layer 12: outer base layer
20: second adhesion organic layer 22: third adhesion organic layer
30: barrier layer 40, 42: corrosion-resistant inorganic layer
50: electrolytic resistant layer 60: first adhesive organic layer
70: heat-sealing resin layer

Claims (17)

A laminate comprising a single or multi-layer base layer, a barrier layer, an adhesive organic layer, and a heat-sealable resin layer,
A battery packaging material further comprising an electrolysis resistant layer between the barrier layer and the adhesive organic layer.
The method of claim 1,
The adhesive organic layer,
A battery packaging material comprising a photocurable resin composition.
The method of claim 2,
the light,
ultraviolet rays, visible rays, X-rays, or γ rays;
Irradiation is 50 mJ/cm ² to 2500 mJ/cm ² Packaging material for batteries, characterized in that.
The method of claim 1,
The electrolytic layer,
In the group consisting of (modified) polypropylene resin, (modified) polyethylene resin, cycloolefin polymer resin, polyterpene-based resin, rosin-based resin, aliphatic petroleum resin, alicyclic petroleum resin, copolymerized petroleum resin and hydrogenated petroleum resin At least one or more selected resins;
cross-linking agent; and
A packaging material for a battery, characterized in that it is formed of a composition containing an organic solvent.
The method of claim 1,
The composition is
Based on the total weight of the composition,
10 to 50% by weight of resin;
0 to 10% by weight of a crosslinking agent; and
70 to 95% by weight of an organic solvent; Battery packaging material comprising a.
The method of claim 1,
The thickness of the electrolysis resistant layer,
Battery packaging material, characterized in that 0.1 μm to 3 μm.
The method of claim 1,
Battery packaging material further comprising a corrosion-resistant inorganic layer on at least one surface of the barrier layer.
The method of claim 7,
The electrolytic layer,
Battery packaging material, characterized in that provided between the corrosion-resistant inorganic layer and the adhesive organic layer.
The method of claim 7,
The corrosion-resistant inorganic layer,
A battery packaging material comprising at least one selected from the group consisting of phosphoric acid, phosphoric acid salts, chromic acid, chromium (III) salts, chromium phosphate, and zinc phosphate.
The method of claim 1,
A battery packaging material further comprising a second adhesion organic layer between the substrate layer and the barrier layer.
The method of claim 1,
The base layer,
At least one selected from the group consisting of polyester, polyethylene, polypropylene, polyethylene terephthalate, polyamide, nylon, low-density polyethylene, high-density polyethylene, polybutylene terephthalate, polyethylene naphthalate, polyester copolymers, and linear low-density polyethylene. A packaging material for a battery, characterized in that it is formed of more than one kind of resin.
The method of claim 1,
The barrier layer,
aluminum; copper; nickel; alloys of iron, carbon, chromium and manganese; and at least one metal selected from the group consisting of alloys of iron, carbon, chromium, and nickel.
The method of claim 1,
The heat-sealable resin layer,
Polyethylene, polypropylene, unstretched polypropylene, biaxially oriented polypropylene, ionomo, ethyl ethylene acrylate, methyl ethylene acrylate, methyl ethylene methacrylate, ethylene vinyl acetate copolymer resin, maleic anhydride-modified polypropylene, maleic anhydride-modified polyethylene Characterized in that it is formed of at least one resin selected from the group consisting of polyester, polyethylene-propylene copolymer, polypropylene-butylene-itelin terpolymer, polyethylene and acrylic acid copolymer, and polypropylene and acrylic acid copolymer. Battery packaging material to be.
The method of claim 1,
When the peeling force was measured by T-shaped peeling of a test piece cut to have a sample width of 15mm and a length of 150mm of the battery packaging material at a peeling rate of 30mm/min, the peeling force of the barrier layer and the heat-sealable resin layer was 4N/min. Battery packaging material, characterized in that 15min or more.
The method of claim 1,
The sample width of the battery packaging material is 15 mm and the test piece cut to a length of 150 mm is immersed in an electrolyte for 14 days or more in an 85 ° C atmosphere, and then the laminate strength retention rate of the barrier layer and the heat-sealable resin layer is 30% or more Characterized in that Battery packaging material.
A battery comprising the packaging material of any one of claims 1 to 15.
A device comprising the battery of claim 16 .

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