WO2014133317A1

WO2014133317A1 - Battery packaging material and method for producing same

Info

Publication number: WO2014133317A1
Application number: PCT/KR2014/001574
Authority: WO
Inventors: 김홍건; 도현성; 진홍기
Original assignee: 한화폴리드리머 주식회사
Priority date: 2013-02-26
Filing date: 2014-02-26
Publication date: 2014-09-04
Also published as: KR101366217B1

Abstract

The present invention relates to a battery packaging material and a method for producing same and, more specifically, to a battery packaging material having improved electric insulation and enhanced stability by applying a barrier resin to a sealant layer and thereby improving barrier properties against an electrolyte and moisture and to a method for producing same.

Description

【Specification】

[Name of invention]

Battery packaging material and manufacturing method thereof [Detailed Invention]

Technical Field

The present invention relates to a polymer battery packaging material including an outer protective layer, a barrier layer, a surface treatment layer and an inner sealant layer formed on at least one surface of the barrier layer, and excellent in acid resistance and moldability, and a method of manufacturing the same.

Background Art

Because lithium ion secondary batteries use a liquid electrolyte, lithium ion secondary batteries use aluminum cans as packaging materials to prevent leakage of electrolyte and reduce the risk of explosion. Therefore, the lithium ion secondary battery is heavy and bulky due to the aluminum can used as a packaging material, and even if such an aluminum can is used, the risk of explosion exists because of the use of a liquid electrolyte in a hidden state. There is a low disadvantage. As a result, research and development by companies to continue to increase the energy density while reducing the safety and volume is constantly being continued.

Recently, a lithium polymer secondary battery has been developed as a battery which improves and supplements the disadvantages of the lithium ion secondary battery. Such polymer batteries are used in notebooks, portable terminal devices (mobile phones, PDAs, etc.), video cameras, electric vehicles, energy storage batteries, robots, satellites, and the like.

Lithium polymer secondary batteries can be made of pouches to reduce the weight of batteries, thereby reducing the production cost when producing batteries, and increasing the shape of the batteries to enhance product competitiveness. Can be. Since the lithium polymer secondary battery uses a laminate pouch as a packaging material, the lithium polymer secondary battery can be thinned. The structure of the lithium polymer secondary battery having such an advantage is a laminate that is a packaging material The aluminum pouch is connected to a metal electrode terminal (anode: A1, cathode: Ni or Cu), and an electrolyte is layered inside. However, when the internal electrolyte is exposed to moisture, acid and heat are generated by hydrolysis, and when exposed to air vapor, acid and heat are generated by hydrolysis, and when exposed to air, the internal electrolyte is strongly acidic in combination with moisture. Toxic gas (Gas) is generated to corrode aluminum inside the packaging material, shortening the life of the battery or short circuiting with the electrode terminal.

In addition, hydrofluoric acid (HF) in the electrolyte has a high permeability and passes through the polypropylene film layer, which is the innermost sealant layer of the pouch, to reach the aluminum thin film layer and dissolve and corrode the aluminum thin film layer surface. When the surface of the aluminum thin film layer is corroded, the adhesion between the aluminum thin film layer and the innermost sealant layer is reduced, and the innermost layer is peeled off, and the internal electrolyte is more exposed to air or moisture, thereby increasing the risk of battery explosion.

A general battery packaging material is composed of an outermost layer made of a polyester resin and / or a polyamide resin, a barrier layer made of aluminum or an alloy thereof, and an innermost layer of a thermoplastic resin. In order to prevent peeling of the inner layer of the packaging material generated by the electrolyte inside the battery, the surface of the aluminum thin film layer is treated with a chemical conversion treatment solution and then laminated with a thermoplastic resin to produce a packaging material.

Due to the occurrence of delamination in the aluminum barrier layer and the sealant layer in the inside of the conventional polymer battery, it causes a big problem in the battery performance. Also, the whitening of the sealant layer occurs during battery molding, which causes problems in appearance and performance. ， If the sealant layer lacks the barrier property, it is vulnerable to insulation resistance and moisture barrier, causing problems in performance and stability.

[Content of invention]

Problem to be solved

The present invention by applying a barrier resin to the sealant layer, by increasing the barrier properties for the electrolyte and moisture, to achieve high insulation resistance performance, stability An object of the present invention is to provide a battery packaging material and a method of manufacturing the same.

In addition, the present invention is to provide a polymer battery packaging material excellent in acid resistance and moldability and a manufacturing method thereof.

[Task solution]

An embodiment of the present invention includes an outer protective layer, a barrier layer containing aluminum or an aluminum alloy, a surface treatment layer and an inner sealant layer formed on at least one surface of the barrier layer, wherein the inner sealant layer has a melting point of 130 ^° C. Heat including a modified adhesive resin layer containing a resin having a melt index (Ml) of 20 or less, a barrier resin layer containing a thermoplastic elastomer, and a thermally bondable resin that can be thermally bonded under a temperature condition and pressure of 170 ^° C or higher. It relates to a battery packaging material containing a sealing resin dance.

In a preferred embodiment of the present invention, the modified adhesive resin layer of the inner sealant layer includes an olefinic copolymer grafted with maleic anhydride or phthalic acid, and may optionally include a thermoplastic elastomer, the barrier water The layer includes a thermoplastic elastomer selected from the group consisting of styrene ethylene copolymers, styrene butylene copolymers, styrene-butylene-styrene copolymers, and styrene ethylene butylene styrene copolymers, wherein the heat-bonding resin of the heat sealing resin layer May be an olefinic homopolymer or copolymer.

In another embodiment, the surface treatment layer having an organic-inorganic composite film exhibits improved electrical insulation, and firmly adheres to the adhesive resin of the aluminum foil and the inner sealant layer to prevent delamination of the sealant layer while providing corrosion protection. It is preferable as the surface treatment layer below.

Another embodiment of the present invention relates to a method for manufacturing the battery packaging material.

【Effects of the Invention】 Providing a battery packaging material according to the present invention, by applying a barrier resin to the sealant layer, there is an advantage to increase the barrier properties against the electrolyte and moisture to improve the electrical insulation and increase the stability.

[Brief Description of Drawings]

1 is an inner sealant composed of three films according to one embodiment of the present invention; Surface treatment layers formed on both sides of the barrier layer; And a laminated structure of a battery packaging material having an outer protective layer composed of a PET layer and a nylon layer.

2 is an inner sealant layer consisting of three films in accordance with one embodiment of the present invention; Surface treatment layers formed on both sides of the barrier layer; And a laminated structure of a battery packaging material having an outer protective layer composed of a 0-nylon layer.

3 is an inner sealant layer consisting of three films in accordance with one embodiment of the present invention; A surface treatment worm formed on one surface of the barrier layer; And a schematic diagram showing an embodiment of a laminated structure of a battery packaging material having an outer protective layer composed of a PET layer and a 0-nylon layer.

4 is an inner sealant layer consisting of three films in accordance with one embodiment of the present invention; A surface treatment layer formed on one surface of the barrier layer; It is a schematic diagram which shows one Embodiment of the laminated structure of the battery packaging material provided with the outer protective layer which consists of a 0-nylon layer.

[Specific contents for implementation of the invention]

Hereinafter, the present invention will be described in more detail.

The battery packaging material according to the embodiment of the present invention includes an outer protective layer 10, a barrier layer 23 including aluminum or an aluminum alloy, surface treatment layers 21a and 21b and an inner sealant layer formed on at least one surface of the barrier layer. (30). The battery packaging material may be a battery pouch packaging material, preferably a lithium polymer secondary battery packaging material. The inner sealant layer 30 It has a structure containing the modified adhesive resin layer 31, the barrier resin layer 33, and the heat sealing resin layer 35. As shown in FIG.

As shown in FIG. 1, a battery packaging material according to an embodiment of the present invention includes an outer protective layer 10 including a PET layer 11 and a 0-nylon layer 13; Barrier layer 23; First and second oxide film layers 21a and 21b formed on both surfaces of the barrier layer; And an inner sealant layer 30 including the modified adhesive resin layer 31, the barrier resin layer 33, and the heat sealing resin layer 35. As shown in FIG. 2, the battery packaging material according to another embodiment of the present invention has a laminated structure similar to that of FIG. 1 except that the outer protective layer has a structure composed of one film layer. As shown in FIG. 3, a battery packaging material according to an embodiment of the present invention includes an outer protective layer 10 including a PET layer 11 and a 0-nylon filler 13; Barrier layer 23; A first oxide film layer formed on one surface of the barrier layer; And an inner sealant layer 30 including a modified adhesive resin layer, a barrier resin layer, and a heat sealing resin layer. And, as shown in Figure 4, the battery packaging material according to another embodiment of the present invention has a laminated structure similar to Figure 3 except that the outer protective layer has a structure consisting of one film layer.

Hereinafter, each component layer of the battery packaging material according to the present invention will be described in detail. Barrier layer and surface treatment

The barrier layer 23 is for preventing gas and water vapor from penetrating into the lithium battery from the outside, and requires pinholes and processability (pouching, embossing) of the barrier layer. In the present invention, the barrier layer is preferably a foil of aluminum or aluminum alloy having a thickness of 20 to 80 in consideration of workability. The aluminum alloy is silicon, boron, germanium, arsenic, antimony, copper, magnesium, manganese, zinc, lithium, iron, krum, barnacle, titanium, bismuth, potassium, tin, lead zirconium, nickel, cobalt and combinations thereof It may include an element selected from the group consisting of. The aluminum or alloy is a high purity series 10, 80 because of excellent workability Alloy based aluminum foil is preferred. Preferably, the surface of the aluminum or aluminum alloy is washed with an acid or an alkali to remove oil from the surface.

According to the present invention, a surface treatment worm may be formed on at least one surface of the barrier layer, that is, both surfaces of the barrier worm or one surface thereof by various surface treatment methods. It is preferable to form a surface treatment layer on one surface. For example, the surface treatment layer may include i) a chemical conversion treatment using metal and phosphoric acid, Π) anodizing to form a porous oxide layer, or iii) an aminated phenolic polymer, a metal or metal compound, and a phosphoric acid compound. It can manufacture using the method of manufacturing the organic-inorganic composite membrane formed from the surface treatment layer composition containing.

In addition, in one embodiment of the present invention, the surface treatment layer may be a porous anodization film formed by anodizing. In addition, the surface treatment layer may include pores having 0.2 i to 10 μιη and pore diameters of Iran to Ι, ΟΟΟηηι.

In the anodizing method, an aluminum oxide or an alloy foil thereof may be anodized to form a porous oxide film. The metal surface is converted into alumina ceramics using an electrochemical method. The oxide film layer is a porous oxide (Α1 ₂ 0 ₃ ) layer, and has an intrinsic function of the barrier layer, and improves electrical insulation, acid resistance, metal adhesion, and abrasion resistance.

The anodizing treatment can be used in various ways such as sulfuric acid method, hydroxyl method, chromic acid method, phosphoric acid method or boric acid method. For example, anodizing is carried out at current densities of 0.5 A / dirf to 50 A / dirf using an electrolyte solution of about 10 ^° C. to 35 ^° C. containing sulfuric acid, citric acid, boric acid, oxane or their mixtures. The reaction can be performed for about 5 seconds to 60 minutes. The surface treatment layer having the organic-inorganic composite film exhibits improved electrical insulation, and firmly adheres to the adhesive resin layer of the aluminum foil and the inner sealant layer, thereby preventing delamination with the sealant layer and providing a corrosion protection function.

Specifically, the amination phenol on the surface of the aluminum or alloy By coating with a surface treatment liquid containing a polymer, a metal or a metal compound, and a phosphoric acid compound to form a surface treatment film, corrosion of the aluminum surface by hydrofluoric acid (HF) can be prevented and adhesion can be improved. The manufacturing method of the organic-inorganic composite membrane is environmentally friendly, there is an advantage that can be bonded to the barrier layer and the inner sealant layer without the intermediate worms.

The aminated phenolic polymer of the surface treatment layer composition may be represented by the following Chemical Formula 1, and includes an alkenylphenol polymer or a Mannich additive product of tannin. Tannins are complex natural products containing polyphenols.

[Formula 1]

In Formula 1, R1 is a substituted or unsubstituted C1-C6 alkylene group, preferably an ethylene group or a propylene group, R2 and R3 may be the same or different from each other, independently hydrogen or a hydroxyl group, for example R2 Is a hydroxy group and R3 is hydrogen, R2 is hydrogen and is a hydroxy group,

Y is hydrogen; Water-soluble functional group Z represented by the formula (2); C1-C18 straight or branched chain alkyl group; C3-C18 alicyclic alkyl group; Or a C6-C18 aryl group,

[Formula 2] ·

m is an integer from 1 to 4, n is an integer from 1 to 1,000,

R7 to R10 may be the same as or different from each other, and independently hydrogen; Unsubstituted C1-C6 alkyl group; Hydroxy, amino, mercapto and phosphate groups A C1-C6 alkyl group substituted with one or more substituents selected from the group consisting of; Or a C6-C18 aryl group.

Z is a water-soluble functional group represented by the formula (2), and is a product obtained by adding Mannich reaction of phenol, specifically, a product obtained by Mannich reaction using the phenol polymer, amines or ammonia, and formaldehyde, preferably form Mannich addition product of aldehyde and N-methylglucamine.

The phenolic polymer has an average of about 0.5 to about 1.5 Z groups per unit of monomer, and may preferably comprise an average of 0.6 to about 1.2 Z groups per unit of monomers.

The aminated polyphenols may be prepared by, for example, polymerizing a phenol compound to prepare a polymer and then introducing water-soluble functional groups (Z) into the phenol polymer using formaldehyde and amines.

Preferred examples of the polyphenol portion of the aminated phenolic polymer may be a homo or copolymer of ethenylphenol, propenylphenol or butenylphenol.

The repeating unit (n) of the polyphenol may be 1 to 1,000, preferably about 10 to 850. The number average molecular weight of the aminated phenolic polymer is preferably 500 to about 1,000,000, more preferably 1,000 to 20, 000.

According to one embodiment of the present invention, the metal or metal compound that can be applied to the organic-inorganic composite film may be at least one metal or metal compound selected from the group consisting of titanium, zirconium, hafnium, nickel, zinc, and alloys thereof. , Preferably at least one metal or metal compound selected from the group consisting of titanium and zirconium, more preferably fluorinated titanic acid (eg ¾TiF ₆ solution) and fluorine zirconic acid (eg H ₂ ZrF ₆ solution) It may be added to the aqueous surface treatment layer composition in one or more forms selected from the group consisting of.

In particular, the at least one metal or metal compound selected from the group consisting of titanium, zirconium, hafnium, nickel, zinc, and alloys thereof As a non-crumb compound different from the chromium compound used to prepare a conventional surface treatment layer, the organic-inorganic composite membrane formed of the surface treatment layer composition including the non-chromium compound, an aminoated phenol polymer, and a phosphoric acid compound uses a creme-based compound. Compared with the organic-inorganic composite membrane prepared by the adhesive, it is excellent in adhesion with the sealant and can minimize corrosion.

In addition, the surface treatment layer having the organic-inorganic composite film formed by using the non-crack-based compound exhibits improved electrical insulation property, and firmly adheres to the adhesive resin layer of the aluminum foil and the inner sealant layer to prevent delamination of the inner sealant layer. At the same time it can provide corrosion protection.

In addition, recently, due to environmental concerns, the tendency to chromium compounds, in particular, hexavalent world avoided in the case of chromate, inde tendency to preferably avoid the use because trivalent size reduction potential of the chromate also hexavalent ^chrome, the Battery packaging material of one embodiment does not use such a chromium compound is environmentally friendly, as described above may exhibit excellent adhesion, corrosion resistance and the like.

The phosphate compound used in the surface treatment layer composition of the present invention may be used as long as it is a phosphate compound capable of releasing phosphate ions in an aqueous solution. Examples thereof include condensed phosphoric acid such as phosphoric acid and polyphosphoric acid, and salts thereof.

More specifically, the solid content of the surface treatment layer obtained after treating aluminum or an alloy thereof with the surface treatment layer composition containing an aminated phenolic polymer, a metal or a metal compound, and a phosphoric acid compound according to the present invention is a surface treatment layer. Per 1 iif, the aminated phenolic polymer is about 1 to 200 rag and the phosphorus compound is about 0.5 to 50 nig in terms of phosphorus, and may be contained in a proportion of 0.5 to 50 mg when the metal compound is in terms of total metal content. have. Preferably, aluminum or _. The solids content of the surface treatment layer after treating the alloy thereof is about 5.0 to 150 mg of the amino ring phenol polymer per 1 itf of the surface treatment layer, and about 1.0 to 40 rag and the metal compound when the phosphorus compound is converted to phosphorus. When converted to the sum of the respective metals it may be contained in a ratio of 1.0 to 40 mg. The surface treatment layer composition to the surface treatment layer After applying the composition to the lum to 200um thickness by dip coating, spray coating, bar coating, or coating, the temperature may be dried from 80 to 250 ^° C., preferably 150 to 250 ^° C. Internal sealant layer

The inner sealant layer 30 includes a modified adhesive resin layer 31, a barrier resin layer 33, and a heat sealing resin layer 35. In order to manufacture the inner sealant layer, a modified adhesive resin layer, a barrier resin layer and a heat sealing resin layer may be bonded to prepare an inner sealant layer, and the adhesion may be performed by an adhesive method using dry lamination, coextrusion, or an adhesive. It may be carried out and is not particularly limited to these methods. For example, the film can be processed by melt-extruding the modified adhesive resin filling, the barrier resin layer, and the heat sealing resin layer. When the modified adhesive resin layer, the barrier resin layer, and the heat sealing resin layer are coextruded to extrude the film, the modified adhesive resin layer can be heated above the melting point of the modified resin layer to be bonded by a thermal lamination method. Alternatively, the barrier resin layer and the heat-sealing resin layer may be coextruded to extrude into a film, and the modified resin layer may be manufactured by melt coating through a T-die process.

The barrier resin layer may apply a high density resin to the inner sealant layer of the battery packaging material to prevent a risk of energization due to fine cracks and to block water vapor, thereby improving battery stability. The resin applicable to such a barrier resin layer may be a high density thermoplastic elastomer (TPE), which is essentially a thermoplastic polymer while exhibiting rubbery elasticity. The general structure of the thermoplastic elastomer includes a soft phase (soft segment) and a hard phase (hard segment), and the soft phase exhibits rubber elasticity peculiar to the thermoplastic elastomer. In addition, in the case of molding processing, the soft phase is melted and plasticized to exhibit unique molding processability, and when the molding is completed, it is cured and has a function of preventing plastic deformation.

Specific examples of the thermoplastic elastomer include styrene-based, olefin-based, polyester-based, polyamide-based, and urethane-based, preferably styrene-based thermoplastic elastomers, and more preferably SEBS-based elastomers. Styrene-based thermoplastic elastomer, having a polystyrene on the warp, the soft phase comprises polybutadiene, polyisoprene, polyolefin, or polybutylene,

It can be divided into SBS, SIS, and SEBS. The structure of SBS-based elastomer is styrene-butadiene-styrene (-SBS-), and the SIS-based elastomer is styrene-polyisoprene-styrene (―S-PI— S-), and the SEBS-based elastomer is styrene-polyethylene / polybutylene-styrene It has a structure of. Specifically, the thermoplastic elastomer of the barrier resin layer may block the thermoplastic elastomer selected from the group consisting of styrene ethylene copolymer, styrene butylene copolymer, styrene-butylene-styrene copolymer, and styrene ethylene butylene styrene copolymer. 50 wt% or more based on the solids content of the strata. In particular, when the above-described styrene-based copolymer in the thermoplastic elastomer is used as the barrier resin layer, it is preferable to exhibit excellent flexibility and electrical insulation.

Ellefins include those in which the elastomer has polypropylene as the hard phase and contains EPDM as the soft phase, or has polyethylene as the hard phase and NBR as the soft phase. Polyester-based elastomers have PBT as a hard structure as a general structure, and polyether and polyesters such as polytetramethylene ether glycol (PTMEG) and N6, 66, 12 of terephthalic acid as soft phases.

Urethane-based elastomers also have a framework common to the other elastomers, and have polymers polymerized with diisocyanates and short-chain polyols in a hard phase and polymers polymerized with diisocyanates and long-chain polys. The barrier resin layer is polypropylene, ethylene-propylene copolymer, and propylene-1-butene-ethylene in an amount of 5 to 50% by weight, preferably 20 to 40% by weight, based on the total solids content of the barrier resin layer. It may further comprise at least one olefin resin selected from the group consisting of a copolymer. The barrier resin layer may improve the adhesion and flexibility by mixing an olefin polymer having a melting point of 130 ^° C. or more and a melt index (Ml) of 20 or less in the thermoplastic elastomer. Meanwhile, the modified adhesive resin layer may include a resin having a melting point of 130 ^° C. or more and a melt index (Ml) of 20 or less, and preferably the flexibility, adhesiveness, and whitening of the modified adhesive resin layer. In consideration, the modified adhesive resin layer may include an acid-modified polyolefin resin at 50 to 90% by weight, preferably 60 to 80% by weight of the solid content.

The resin usable for the modified adhesive resin layer may be prepared by imparting a functional group capable of adhering to the aluminum or the surface treatment layer thereof included in the barrier layer to the olefin resin, and preferably, graft modification having excellent heat resistance and chemical resistance. It may be a llepin-based copolymer. For example, maleic anhydride or phthalic acid may be a graft-modified olefinic resin. The polyolefin resin includes at least one homopolymer or copolymer selected from the group consisting of ethylene, propylene and butylene. In one specific example, the olefinic resin is compounded by reaction extrusion with an initiator of 0.1% to 5% of maleic anhydride in a content of the olefinic resin, and the hydroxyl group of maleic anhydride is given a hydrogen bond or a covalent bond with the olepin resin to improve adhesion Let's do it. In addition, in order to improve the adhesive strength and flexibility of the modified adhesive resin layer, the modified adhesive resin layer may be modified adhesive of ethylene propylene copolymer or ethylene propylene-diene monomer terpolymer in addition to the acid-modified olefin resin. 5 to 50% by weight, preferably 20 to 40% by weight, based on the solids content of the strata. Examples of diene monomers used in the production of the ethylene-propylene-diene monomer terpolymers include dicyclopentadiene (DCPD), ethyl i dene norbornene (ENB), vinyl norbornene (VNB), and the like. Including but not limited to.

The heat sealing resin layer may include a heat-bonding olefin resin capable of heat bonding at a temperature of 170 ° C or more. The heat sealing resin layer is a surface of the innermost layer of the battery packaging material is a resin capable of thermal bonding under general heat sealing conditions, for example, temperature conditions and pressures, such as 170 ° C or more for heat sealing, low heat sealing resistance, chemical resistance and Characteristics such as cutting surface falling prevention are required. In addition, the heat sealing resin layer may include an olefin resin selected from at least one member selected from the group consisting of polypropylene, ethylene-propylene copolymer, and propylene-1′butene-ethylene copolymer. Outer protective layer

The outer protective layer is used for the purpose of protecting the aluminum thin film used as a barrier layer and protecting the packaging material from pressure or force applied from the outside, and thus considering the weatherability, chemical resistance, and moldability of the packaging material, The polyester-based resin layer, the stretched polyamide-based resin layer or two or more layers in which these are laminated may include a film. The outer protective layer may include one layer or film, or may be used by laminating two or more layers or films of the same or different materials.

The thickness of the outer protective layer is preferably 5 to 50, more preferably about 15 to 30. Too thin a thickness reduces the likelihood of pinholes in the layer itself and the protection against external forces.

Examples of the polyester-based resins include polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), polybutylene naphthalate, polycarbonates and copolymers or modified products thereof. The biaxially stretched polyamide-based resin is a single layer or a composite layer comprising at least one resin selected from the group consisting of nylon 6, nylon 6.6, a copolymer of nylon 6 and nylon 6.6, and nylon 6.10. Can be configured. Specifically, the outer protective layer may be a polyester-based resin and a stretched polyamide-based resin may be used alone or bonded to each other, for example, stretched polyethylene terephthalate / stretched nylon. Also, when using polyethylene terephthalate / stretched nylon, it is possible to use dry lamination with urethane adhesive. The outer protective layer may be bonded to the barrier layer or the surface treatment insect by a method such as dry lamination. The adhesive can use a polyurethane adhesive or an isocyanate curing agent having good adhesion, and is adhered by an adhesive layer using a dry lamination method. The outer protective layer may consist of one layer, but may also include two or more layers laminated by a dry lamination method using a urethane-based adhesive or an isocyanate-based curing agent. Manufacturing method of battery packaging material

Yet another embodiment of the present invention includes an outer protective layer, a barrier layer containing aluminum or an aluminum alloy, a surface treatment layer and an inner sealant layer formed on at least one surface of the barrier layer, and the inner sealant layer has a melting point of 1301. Heat-sealing comprising a modified adhesive resin layer comprising a resin having a melt index (Ml) of 20 or less, a barrier resin layer containing a thermoplastic elastomer, and a heat-bondable resin that can be thermally bonded under a temperature condition and pressure of 170 ^° C or higher. The manufacturing method of the battery packaging material containing a resin layer.

In the battery packaging material, the surface treatment layer is a surface treatment layer composition containing a metal or a metal compound, an aminated phenolic polymer having Formula 1, and a phosphoric acid compound, and is coated on at least one surface of the barrier layer and dried to form an organic-inorganic composite film. Can be prepared. The metal or metal compound, an aminoated phenol polymer, a phosphoric acid compound, and the like may be applied without limitation to the above-described bar in the battery packaging material of the embodiment.

. In order to manufacture the surface treatment layer, a surface coating layer composition may be applied by appropriately selecting known coating methods such as a bar coating method, a coating method, a gravure coating method, a comma, a slot die, a micro gravure method, and an immersion method. have. Specifically, using a gravure coater to coat the thickness of 쨋 to um to 50um it is appropriate to coat in the range of 80 ^° C to 250 ^° C.

The inner sealant layer may be prepared by bonding a heat-sealing resin layer and a modified adhesive resin layer on both sides of the thermoplastic elastomer resin layer, and the adhesion may be performed by dry lamination, coextrusion, or an adhesive method using an adhesive. Specifically, the film can be extruded by three layers of coextrusion using T-die. The method of forming each layer of the outer protective layer, barrier layer, or outer protective layer, barrier layer, intermediate layer, inner sealant layer, or laminating method between the layers of the laminate of the present invention specifically includes a T-die method, an inflation method, The film can be laminated by a method such as dry lamination, extrusion lamination, coextrusion lamination, or thermal lamination, and a secondary film can be formed by a technique such as coating, vapor deposition, ultraviolet curing, or electron beam curing, if necessary. The inner sealant layer includes a modified adhesive resin layer, a barrier resin layer, and a heat sealing layer. The lamination method of each resin layer is performed by melt extruding three resin layers to process a film by an unstretched casting method, or The method of melt-extruding a sealing resin layer and a barrier resin layer, and processing a film by an unstretched casting method is mentioned.

When the modified adhesive resin layer, the barrier resin layer and the heat sealing layer are coextruded to produce a film, adhesion by thermal lamination is possible. It is a method of laminating by bonding to the one surface of the aluminum or aluminum alloy foil surface-treated to the modified adhesive resin layer surface of the coextruded film. In this thermal lamination method, the temperature must be heated above the melting point of the modified adhesive resin. On the other hand, the outer protective worm may include two or more layers laminated by a dry lamination method using a urethane-based adhesive or an isocyanate-based curing agent. The outer protective layer may be laminated by a dry lamination method using a barrier layer or a surface treatment layer formed on at least one surface of the barrier layer and a urethane adhesive or an isocyanate curing agent.

The present invention will be described in more detail with reference to the following examples, but the protection scope of the present invention is not limited to the following examples. <Example 1>

A soft aluminum foil of alloy 80 having a thickness of 40 micrometers was immersed in an acid degreasing solution for 30 seconds, washed with water and washed again with deionized water, and dried. The degreasing aluminum foil was reacted for about 2 minutes at a current density of about ΙΑ / dm ² using an electrolyte solution of about 20 ^° C. in which an amount of sulfuric acid was added at an concentration of 0.4% of oxalic acid as an additive to a concentration of 15% of sulfuric acid. An aluminum oxide-forming soft aluminum foil having a film of aluminum oxide (A1 ₂ 0 ₃ ) having a thickness of was prepared.

On one surface of the surface treatment layer, a urethane-based polyurethane-based dry lamination adhesive is applied, PET (about 12 kPa) / 0- nylon (about 15 μπι) was adhered to prepare an outer protective layer with an adhesive layer on the surface treatment layer.

For the production of the inner sealant layer, a barrier resin layer of modified adhesive resin, styrene ethylene butylene styrene copolymer containing 69.9 weight of maleic anhydride grafted polypropylene (trade name Admer) and 30.1 weight% of ethylene propylene rubber And a heat sealing resin layer of propylene-1-butene-ethylene polymer were prepared as a three-layer coextrusion film. On the other side of the surface treatment worm, a urethane-based polyurethane-based dry lamination adhesive is applied, and the prepared three-pack coextrusion film is attached, to prepare an inner sealant layer with an adhesive layer on the surface treatment layer of the present invention. A battery packaging material was prepared.

24.6 g of resin M (polyvinyl phenol) having an average molecular weight of 5,000 was dissolved in 54.5 g of 1-propoxy-2-propane and heated to dissolve the resin to prepare a 1-propoxy-2-propanol resin solution. The 1-propoxy-2-propane was added to the resin solution and 40.4 g of N-methylglucamine was then heated to a temperature of 60 to 65 ° C. 16.6 g of a 37% aqueous formaldehyde solution prepared by dissolving formaldehyde in water was added to the heated mixture, and the temperature of the solution was then raised to 90 ° C. The reaction mixture was distilled with deionized water to a solids content of about 10% by weight, the mixture containing N-methylglucamine Mannich addition product of polyvinylphenol.

To the mixture, 3% by weight of ¾PO ₄ solution, ₆ % by weight of H ₂ ZrF ₆ solution, and 6% by weight of H ₂ TiF ₆ solution were added to prepare a surface treatment solution for the barrier layer. 1 liter of water was added to the surface treatment solution to prepare a water-soluble surface treatment solution. The soft aluminum foil 40um was immersed in an acid degreasing solution for 30 seconds, washed with water and then washed again with deionized water and dried. The surface treatment solution was coated on both sides of the stripped aluminum foil with a bar coater, and heated and dried at 150 ° C. to form a surface treatment layer on both sides of the aluminum foil. A urethane-based polyurethane-based dry lamination adhesive was applied to one surface of the surface treatment layer, a 25 um biaxially stretched nylon film was attached, and an outer protective layer was prepared on the surface treatment layer with an adhesive layer interposed therebetween. For the production of the internal sealant, a modified adhesive resin layer containing 30.1% of polypropylene (trade name Admer) and ethylene propylene rubber grafted with maleic anhydride, a barrier resin layer of styrene ethylene butylene styrene copolymer, and The heat sealing resin layer of the propylene-1-butene ethylene copolymer was produced as a three-layer coextrusion film. On the other side of the surface treatment layer, by applying a urethane-based polyurethane-based dry lamination adhesive, and attaching the manufactured three-layer coextrusion film, to prepare an inner sealant layer via an adhesive layer on the surface treatment layer to the present invention A battery packaging material was prepared.

Except for the inner sealant layer, the aluminum foil and its surface treatment and outer protector were prepared in substantially the same manner as in Example 2.

Specifically, in order to manufacture the inner sealant layer, a modified adhesive resin layer in which 20% by weight of ethylene propylene rubber is added to 80% by weight of polypropylene (trade name Admer) grafted with maleic anhydride, styrene ethylene butylenestyrene notarization A barrier resin layer containing a copolymer of copolymer and polypropylene, and a heat sealing resin layer of propylene-1-butene-ethylene polymer were prepared as a three-layer coextrusion film. On the other side of the surface treatment layer, by applying a urethane-based polyurethane-based dry lamination adhesive, and attaching the manufactured three-layer co-extrusion film, to prepare an inner sealant layer via an adhesive layer on the surface treatment layer, The packaging material was prepared.

<Example 4

24.6 g of resin M (polyvinyl phenol) having an average molecular weight of 5,000 was dissolved in 54. 1-propoxy 폭 2-propanol, and heated to dissolve the resin to prepare a 1-propoxy ᅳ 2-propanol resin solution. After adding 40.4 g of N-methylglucamine to the 1 ᅳ propoxy—2 ᅳ propanol resin solution at a temperature of 60 to 65 ^° C. Heated. 16.6 g of a 37% aqueous formaldehyde aqueous solution prepared by dissolving formaldehyde in water was added to the heated mixture, and then the temperature of the solution was raised to 90 ^° C. to react. The reaction mixture was diluted with deionized water to a solids content of about 10 weight ¾, the mixture containing N-methylglucamine Mannich addition product of polyvinylphenol.

To the mixture was added 3% by weight of ¾PO ₄ solution, ₆ % by weight of H ₂ ZrF ₆ solution, and 6% by weight of H ₂ TiF ₆ solution to prepare a surface treatment solution of the barrier worms. 1 liter of water was added to the surface treatment solution to prepare a water-soluble surface treatment solution.

40um of 8021A Hoy soft aluminum foil was immersed in an acid degreasing solution for 30 seconds, washed with water and washed again with deionized water and dried. The surface treatment solution was coated on both sides of the degreasing aluminum foil with a bar coater, and heated and dried ^at 150 ^° C. to form a surface treatment layer on both sides of the aluminum foil.

A urethane-based dry lamination adhesive was applied to one surface of the surface treatment worm, and a 25 um biaxially stretched nylon film was attached to prepare an outer protective layer having an adhesive layer on the surface treatment layer. For the production of the inner sealant layer, a modified adhesive resin layer containing only polypropylene (trade name Admer) grafted with maleic anhydride, a barrier resin layer of styrene ethylene butylene styrene copolymer, and propylene-1'butene The heat sealing resin layer of the ethylene copolymer was produced as a three-layer coextrusion film. On the other side of the surface treatment layer, by applying a urethane-based polyurethane-based dry lamination adhesive, and attaching the prepared three-layer coextrusion film, to produce an internal sealant filling the adhesive layer all over the surface treatment layer A battery packaging material was prepared. Example 5

Specifically, in order to manufacture the inner sealant layer, a modified adhesive resin layer, styrene ethylene butylene styrene copolymer, in which 30.1% of ethylene propylene rubber is added to polypropylene (product name Admer) to which maleic anhydride is grafted, A barrier resin layer containing a copolymer of polar propylene, and a heat seal ¾ resin layer of a propylene-1 ᅳ butene-ethylene polymer _. Prepared as a three layer coextrusion film. On the other side of the surface treatment layer, by applying a urethane-based polyurethane-based dry lamination adhesive, and attaching the manufactured three-layer co-extrusion film, to produce an inner sealant layer through the adhesive layer on the surface treatment charge, for the battery The packaging material was prepared.

Comparative Example 1

Except for the inner sealant layer, the aluminum foil and its surface treatment and outer protective layer were manufactured in the battery packaging material in substantially the same manner as in Example 2.

Specifically, for the production of the inner sealant layer, a modified adhesive water obtained by adding 30.1% of ethylene propylene rubber to polypropylene (trade name Adraer) in which the barrier resin layer of Example 2 does not exist and maleic anhydride is grafted. The ground layer and the heat sealing resin layer of the propylene ᅳ 1-butene-ethylene polymer were produced as a two-layer coextrusion film. Of the surface treatment layer. On the other side, a urethane-based polyurethane-based dry lamination adhesive was applied, and the prepared two-layer coextrusion film was attached to each other to prepare an inner sealant layer with an adhesive layer on the surface treatment layer, thereby manufacturing a battery packaging material.

Except for the inner sealant layer, the aluminum foil and its surface treatment and outer protective layer were manufactured in the same manner as in Example 2 for the battery packaging material.

Specifically, for the production of the inner sealant layer, the modified adhesive resin layer and the heat sealing resin layer was prepared in the same manner as in Example 2, but compared to the styrene ethylene butylene styrene copolymer of the barrier resin layer according to Example 2 In Example 2, an ethylene-propylene block copolymer (Hyosung J351F resin), Comparative Example 3, a homopolypropylene resin (Honam Petrochemical SFI—151 resin), and Comparative Example 4, an ethylene-propylene random polypropylene (Honam Petrochemical L670M) Resin was used. Comparative Example 5

Except for the inner sealant, aluminum foil and its surface treatment and outer protective layer were manufactured in the same manner as in Example 2 for the battery packaging material.

Specifically, in order to manufacture the inner sealant layer, the modified adhesive resin layer and the barrier resin layer were prepared in the same manner as in Example 2, but instead of the propylene ᅳ 1 ᅳ butene-ethylene copolymer of the heat sealing resin layer according to Example 2 The three-layer coextrusion film was produced using the ethylene propylene random polypropylene (Honam Petrochemical L670M) resin film.

On the other side of the surface treatment layer of Example 2, a urethane-based polyurethane-based dry lamination adhesive was applied, and the prepared three-layer coextrusion film was adhered to prepare an inner sealant layer with an adhesive layer on the surface treatment layer. The battery packaging material of the present invention was prepared.

Experimental Example

The electrolytic solution, moldability, insulation resistance, low silver sealing strength, and initial adhesive strength of the battery packaging materials obtained in Examples 1 to 5 and Comparative Examples 1 to 6 were measured and shown below.

(1) How to evaluate the amount of electrolyte

In a solution mixed with ethylene carbonate / diethyl carbonate / dimethyl carbonate-1/1/1 (volume ratio), lithium hexafluorophosphate was dissolved to prepare an electrolyte solution with a solution of 1 mol / liter of lithium hexafluorophosphate salt. An electrolyte solution was impregnated with a pouch film having a width of 1.5 瞧 X 100 醒, preserved in a constant temperature and humidity chamber at 60 ^° C. for 168 hours, and then opened and evaluated for peeling of the aluminum layer and the sealant layer.

Excellent peel strength by evaluation criteria: ©

Can be peeled off but not peeled off: O

Exfoliated aluminum with CPP: X

TABLE 1

(2) Evaluation of moldability

Each sample was visually evaluated for delamination of the sealant layer by molding the sheath film to a depth of 6.0 mm 3 in a 40 mm X 50 mm molded male and female mold.

TABLE 2

(3) Evaluation method of insulation resistance

In a solution mixed with ethylene carbonate / diethyl carbonate / dimethyl carbonate = 1/1/1 (volume ratio), lithium hexafluorophosphate was dissolved to prepare an electrolyte solution with 1 mol / liter of lithium hexafluorophosphate salt solution. After inserting 10g of the electrolyte solution into the molded part by the evaluation method of moldability, install aluminum tab on one side of the exterior film and heat seal at 190 ^° C for 3 seconds, and on the second side at 190 ^° C for 3 seconds The heat conduction test was evaluated by connecting the positive electrode terminal to the tab and the end of the aluminum enclosure by heat sealing.

TABLE 3

(4) Evaluation method of low silver sealing strength

I evaluated the strength after molding for 3 seconds at 0.3 Mpa pressure using a cell pouch molding machine after manufacturing each sample to 15mm size as a method of evaluation of the sealing strength at 17CTC.

TABLE 4

(5) Initial adhesive force evaluation method

After fabrication of 15 瞧 size of each sample, AL and CPP were evaluated for initial adhesive force under the condition of Gt gap 30mm and Speed 300 謹 / mi n using UTM.

As a result of evaluating the initial adhesive strength of the battery packaging material according to Examples 1 to 3 and Example 5, the adhesion between the inner sealant layer and the surface treatment layer was very good and eventually broke, and the modified adhesive resin layer Example 4 was 9 kgf. as Good results have been obtained. Therefore, it was found that when the rubber component was added to the modified adhesive resin layer of the inner sealant layer, better initial adhesion results were obtained.

[Explanation of code]

10 outer protective layer

11 PET outer protective layer

13 nylon outer protective layer

20 Barrier layer formed with surface treatment layer

21a, 21b: surface treatment layer

23 barrier insects

30 Internal Sealant Layer

31 modified adhesive resin layer

33 barrier resin layer

35 heat sealing resin layer

Claims

[Patent Claims]

【Claim 1】 _.

Outer protective layer; A barrier layer containing aluminum or an aluminum alloy; A surface treatment layer formed on at least one surface of the barrier layer; And an internal sealant worm,

The inner sealant layer may be thermally bonded to a modified adhesive resin layer comprising a resin having a melting point of 130 ^° C. or more and a melt index (Ml) of 20 or less, a barrier resin layer including a thermoplastic elastomer, and a temperature of 170 ^° C. or more. A battery packaging material comprising a heat sealing resin layer containing a thermal bonding resin olefin resin dispersion.

[Claim 2]

The battery packaging material according to claim 1, wherein the modified adhesive resin layer comprises an olefin polymer grafted with maleic anhydride or phthalic acid.

[Claim 3].

The method of claim 2, wherein the modified adhesive resin layer further comprises an ethylene propylene copolymer or an ethylene-propylene-diene monomer terpolymer in an amount of 5 to 50% by weight ^< ¾ based on the solids content of the modified adhesive resin layer. Battery packaging material.

[Claim 4]

The thermoplastic elastomer of claim 1, wherein the thermoplastic elastomer of the barrier resin layer is selected from the group consisting of styrene ethylene copolymer, styrene butylene copolymer, styrene-butylene-styrene copolymer, and styrene ethylene butylene styrene copolymer. Battery packaging material comprising an elastic body of 50% by weight or more based on the solid content of the barrier resin layer.

[Claim 5]

. 5. The barrier resin layer of claim 4, wherein the barrier resin layer comprises at least one olefin resin selected from the group consisting of polypropylene, ethylene-propylene copolymer, and propylene-1-butene-ethylene copolymer. Battery packaging material further comprises from 5% by weight to 50% by weight based on solids content.

[Claim 6] The battery packaging material according to claim 1, wherein the heat sealing resin layer comprises at least one olefin resin selected from the group consisting of polypropylene, ethylene-propylene copolymer, and propylene-1-butene-ethylene copolymer.

[Claim 7]

The battery packaging material according to claim 1, wherein the surface treatment worm is a porous anodized film formed by anodizing.

[Claim 8]

8. The battery packaging material according to claim 7, wherein the surface treatment layer is an aluminum oxide film layer containing pores having a pore size of 0.2 mPa to 10 and a pore size of Inm to 1,000 mPa.

[Claim 9]

The battery packaging material according to claim 1, wherein the surface treatment layer comprises an organic-inorganic composite membrane formed of a surface treatment layer composition comprising a metal or a metal compound, an aminated phenolic polymer having Formula 1 below, and a phosphoric acid compound:

In Chemical Formula 1,

R1 is a substituted or unsubstituted C1-C6 alkylene group,

R2 and R3 may be the same or different from each other and are independently hydrogen or a hydroxyl group,

[Formula 2]

ni is an integer from 1 to 4, n is an integer from 1 to 1,000,

R7 to R10 may be the same or different from each other and independently hydrogen; Unsubstituted C1 'C6 alkyl group; A C1-C6 alkyl group substituted with a hydroxy group, an amino group, a mercapto group or a phosphate group; or a C6-C18 aryl group.

[Claim 10]

The battery packaging material according to claim 9, wherein the metal or metal compound is at least one metal or metal compound selected from the group consisting of titanium, zirconium, hafnium, nickel, zinc, and alloys thereof.

[Claim 11]

Claim 9 wherein said metal or metal compound is peultu climb titanate and at least one member selected from the group consisting of fluorine ^zirconate, cell packing material, the

[Claim 12]

The solid content of the additive surface treatment layer is 1 to 200 mg of the aminated phenolic polymer per surface treatment layer lii, the phosphorus compound is 0.5 to 50 mg in terms of phosphorus, and the metal compound is the total metal content. Battery packaging material of 0.5 to 50mg in terms of.

[Claim 13]

The battery packaging material according to claim 1, wherein the outer protective layer comprises a stretched polyester resin, a stretched polyamide resin, or a mixture thereof.

[Claim 14]

An outer protective layer, a barrier layer containing aluminum or an aluminum alloy, a surface treatment layer formed on at least one surface of the barrier worm, and an inner sealant worm,

The inner sealant layer is a modified adhesive resin layer comprising a resin having a melting point of 130 ^° C. or more and a melt index (Ml) of 20 or less, and a thermoplastic elastomer. A method of manufacturing a battery packaging material comprising a heat-sealing resin layer comprising a barrier resin layer and a heat-bonding resin capable of thermally bonding under a temperature condition and pressure of 170 ^° C. or higher.

[Claim 15]

15. The method of claim 14, wherein the surface treatment layer is a surface treatment layer composition comprising a metal or metal compound, an aminated phenolic polymer having the following formula (1), and a phosphoric acid compound is applied to at least one side of the barrier worm, dried to form an organic-inorganic composite film Forming method for manufacturing a battery packaging material:

[Formula 1]

In Chemical Formula 1,

R1 is a substituted or unsubstituted C1-C6 alkylene group,

R2 and R3 may be the same or different from each other and independently hydrogen or hydroxyl group,

[Formula 2]

m is an integer from 1 to 4, ri is an integer from 1 to 1,000,

R7 to R10 may be the same or different from each other and independently hydrogen; Unsubstituted C1-C6 alkyl group; A C1-C6 alkyl group substituted with a hydroxyl group, an amino group, a mercapto group or a phosphate group; Or C6—C18 aryl group.

[Claim 16] The method of claim 14, wherein the inner sealant layer is melt-extruded from the modified adhesive resin layer, the barrier resin layer, and the heat-adhesive resin layer to process the film by a draw-free casting method, or the heat sealing resin layer and the barrier resin layer. A method for producing a battery packaging material, which is melt-extruded and processed into a film by an unstretched casting method to bond the adhesive resin layer to an extrusion coating method.

[Claim 17]

The method of claim 14, wherein the outer protective layer is laminated by a dry lamination method using a barrier layer or a surface treatment layer formed on at least one surface of the barrier layer and a urethane adhesive or an isocyanate curing agent.

[Claim 18]

15. The method of claim 14, wherein the outer protective layer comprises at least two layers laminated by a dry lamination method using a urethane adhesive or an isocyanate curing agent.