KR20160078331A - Biaxially oriented nylon film for cold molding - Google Patents

Biaxially oriented nylon film for cold molding Download PDF

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Publication number
KR20160078331A
KR20160078331A KR1020167007953A KR20167007953A KR20160078331A KR 20160078331 A KR20160078331 A KR 20160078331A KR 1020167007953 A KR1020167007953 A KR 1020167007953A KR 20167007953 A KR20167007953 A KR 20167007953A KR 20160078331 A KR20160078331 A KR 20160078331A
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South Korea
Prior art keywords
resin
film
nylon film
layer
battery case
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KR1020167007953A
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Korean (ko)
Inventor
슈이치 나가에
쯔바사 혼다
타케노리 무라카미
준 코우하라
신이치로 이시하라
Original Assignee
코진 필름 앤드 케미칼즈 가부시키가이샤
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Priority to KR1020217040457A priority Critical patent/KR20220000905A/en
Publication of KR20160078331A publication Critical patent/KR20160078331A/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
    • H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
    • H01M50/121—Organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/023—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets using multilayered plates or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
    • B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
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    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
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    • H01M50/129—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material having a layered structure comprising three or more layers with two or more layers of only organic material
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Abstract

리튬이온 이차전지 등의 전지케이스용 포재의 주요기재로서 이용하는 나일론필름에 있어서, 히트씰하여 밀봉하는 공정이나 고온고습도하에서나 인쇄층이 개재된 상태에서 장시간 사용된 경우에도, 배리어층과 기재층간에서의 디라미네이션의 발생을 억제하고, 또한 모든 금형형상이나 성형깊이의 냉간성형가공시에 있어서도 알루미늄박의 파단이나 핀홀 등의 발생이 없고, 안정된 성형성을 갖는 나일론필름을 얻는 것을 과제로 한다. 강도특성을 갖는 연신 또는 미연신의 열처리되지 않은 나일론필름의 표면에 폴리우레탄 수지 또는 아크릴계 공중합체 수지 및 그 가교제를 도공함으로써, 상기 과제를 해결하였다.In a nylon film used as a main base material for a battery case of a lithium ion secondary battery or the like in a process of heat sealing and sealing or in a case of using for a long time under high temperature and high humidity or in a state in which a printing layer is interposed, It is an object of the present invention to obtain a nylon film having a stable moldability without inhibiting the occurrence of delamination and free from the occurrence of breakage or pinholes of the aluminum foil even during cold forming of all mold shapes and forming depths. A polyurethane resin or an acrylic copolymer resin and a crosslinking agent thereof are coated on the surface of a stretched or unstretched nylon film having heat resistance and strength properties and solved the above problems.

Description

냉간성형용 이축연신 나일론필름{BIAXIALLY ORIENTED NYLON FILM FOR COLD MOLDING}BIAXIALLY ORIENTED NYLON FILM FOR COLD MOLDING BACKGROUND OF THE INVENTION 1. Field of the Invention [0001]

본 발명은 냉간성형용 포재, 특히 리튬이온 이차전지 등의 전지케이스용 포재의 주요기재로서 호적하게 이용되는, 냉간성형용 이축연신 나일론필름에 관한 것이다.The present invention relates to a biaxially stretched nylon film for cold forming, which is suitably used as a main substrate for a battery case, such as a cold forming latice, particularly a lithium ion secondary battery.

종래부터, 리튬이온전지, 리튬이온 폴리머전지, 연료전지, 전해형 콘덴서 등, 화학적 에너지를 전기적 에너지로 변환하는 소자를 포함하는 다양한 전지가, 컴퓨터, 휴대전화, PDA, 비디오카메라, 전기자동차, 에너지저장용 축전지, 로봇, 위성 등에 넓은 용도로 이용되고 있다. 이들 전지의 외장체로는, 금속을 프레스 가공하여 원통상 또는 직방체상으로 용기화한 금속제 캔, 혹은, 플라스틱필름, 금속박 등을 라미네이트하여 얻어지는 적층체를 대상(袋狀; 주머니 형상)으로 한 것 등이 이용되고 있었다.
BACKGROUND ART Conventionally, various batteries including a lithium ion battery, a lithium ion polymer battery, a fuel cell, an electrolytic capacitor, and the like that convert chemical energy into electric energy have been widely used in computers, mobile phones, PDAs, video cameras, Storage batteries, robots, and satellites. As the outer body of these batteries, a metal can made of a metal by press working to form a cylindrical or rectangular parallelepiped shape, or a laminate obtained by laminating a plastic film, a metal foil or the like in a pouch shape or the like .

그러나, 전지의 외장체 중, 금속제 캔타입에 있어서는, 용기외벽이 리지드이므로, 기기 본체측을 전지의 형상에 맞추어 설계할 필요가 있어, 형상의 자유도가 없어진다는 문제가 있었다. 또한, 금속제 캔타입은 용기 자체가 두껍기 때문에, 장시간 사용시 등 전지가 발열한 경우에 방열되기 어렵다는 결점도 있었다. 한편, 적층체 타입은, 금속단자의 취출 용이성이나 밀봉 용이성과 같은 이점 외에, 유연성을 가지므로, 전자기기나 전자부품의 적당한 공간에 맞춘 형상으로 할 수 있어, 전자기기나 전자부품 자체의 형상을 어느 정도 자유롭게 설계할 수 있다는 이점이 있다. 나아가, 박막에서 방열성도 우수하므로, 발열에 의한 이상방전이 일어나기 어렵다. 이와 같이, 적층체 타입은 금속제 캔타입에 비해 소형화, 경량화를 도모하기 쉽고, 또한 안전성이 높은 등의 이점으로부터, 전지용 외장체로서 주류가 되고 있다.
However, in the outer can body of the battery, in the metal can type, since the outer wall of the container is rigid, it is necessary to design the body side of the apparatus to match the shape of the battery. Further, since the metal can type is thick, the battery itself has a drawback that it is difficult to dissipate heat when the battery is heated during long-time use. On the other hand, the laminate type has flexibility in addition to the advantages such as ease of taking out the metal terminals and ease of sealing, so that the laminate type can be formed into a shape suitable for an appropriate space of electronic equipment and electronic parts, There is an advantage that it can be freely designed to some extent. Further, since the thin film has excellent heat dissipation properties, it is difficult to cause an abnormal discharge due to heat generation. As described above, the laminate type has become mainstream as an external battery for a battery due to its advantages such as miniaturization and weight reduction as compared with the metal can type and high safety.

적층체 타입의 외장체를 이용한 리튬전지의 형태로는, 주머니 타입(袋タイプ)과 성형 타입이 알려져 있다. 주머니 타입은, 포재를 통상(筒狀)으로 가공하고, 거기에 리튬전지 본체를 양극과 음극의 각각에 접속된 금속단자를 외측으로 돌출시킨 상태로 수납하고, 개구부를 열접착하여 밀봉한 것(예를 들어, 특허문헌 1의 도 2 참조)이다. 성형 타입은, 포재를 용기상으로 성형하고, 이 용기내에 리튬전지 본체를 양극과 음극의 각각에 접속된 금속단자를 외측으로 돌출시킨 상태로 수납하고, 평판상의 포재 내지 용기상으로 성형한 포재로 피복함과 함께, 4주연부를 열접착하여 밀봉한 것(예를 들어, 특허문헌 1의 도 3 참조)이다.
As a form of a lithium battery using an external body of a laminate type, a bag type and a molding type are known. The bag type is a case in which the inlaid material is processed into a cylindrical shape and the lithium battery body is housed in a state where the metal terminals connected to the positive electrode and the negative electrode are protruded outwardly and the openings are thermally adhered to each other For example, see FIG. 2 of Patent Document 1). The forming type is a method in which a porous material is formed into a vessel and the lithium battery body is housed in the container in such a state that the metal terminals connected to the positive electrode and the negative electrode are protruded outwardly, (See, for example, Fig. 3 of Patent Document 1).

그리고, 성형 타입은 주머니 타입에 비해, 전지 본체를 타이트(딱 맞는 상태)하게 수납할 수 있으므로, 체적에너지 밀도를 향상시킬 수 있음과 함께, 리튬전지 본체의 수납의 용이성 등의 이점이 있다. 성형 타입의 성형가공법에는 가열성형법과 냉간(상온)성형법이 있다. 가열성형법은 가열에 의한 강도의 저하, 열수축의 발생과 같은 문제가 일어나기 쉬운 것에 반해, 냉간(상온)성형법은 성형가공시에 이러한 포재 자체의 특성의 변화는 일어나기 어렵고, 나아가 성형장치도 저렴하며, 간편함과 함께 생산성도 높은 점에서, 현재 주류의 성형방법으로 되어 있다.
Since the molding type can store the battery body in a tight state (fit state) as compared with the bag type, the volume energy density can be improved and the lithium cell main body can be easily accommodated. The molding process of the molding type includes a heat molding method and a cold (room temperature) molding method. In the hot molding method, problems such as lowering of strength due to heating and occurrence of heat shrinkage are likely to occur. In the cold (room temperature) molding method, the properties of such a carrier itself are unlikely to change at the time of molding, In terms of convenience and high productivity, it is currently the mainstream molding method.

전지용 외장체에 요구되는 물성·기능으로는, 고도의 방습성, 밀봉성, 내찌름성(耐突刺性), 내핀홀성, 절연성, 내열·내한성, 내전해질성(내전해액성), 내부식성(전해질의 열화나 가수분해에 의해 발생하는 불산에 대한 내성) 등이 필요불가결하며, 특히 방습성은 중요한 요소이다. 적층체 타입, 특히 냉간성형 타입에 있어서, 금속박으로서 일반적으로 이용되는 알루미늄박은, 성형성이 우수한 반면, 성형시에 발생하는 불균일 변형에 의해 핀홀이나 크랙이 발생하기 쉬우므로, 샤프한 형상으로 깊고 안정적으로 성형한다는 성형안정성의 점에 있어서 개선의 여지가 있었다. 또한, 적층체 타입은, 적어도, 기재층, 배리어층, 실란트층으로 구성되어 있으나, 상기 각 층간의 접착강도는 전지의 외장체로서 필요한 성질에 영향을 준다. 예를 들어, 배리어층과 기재층간의 접착강도가 불충분하면, 전지 본체를 수납후 히트씰하여 밀봉하는 공정에 있어서, 혹은 고온의 상태로 장시간 사용될 때에, 기재층의 열수축응력이 층간접착강도보다 커지고, 배리어층과 기재층의 사이에서 디라미네이션(박리)이 발생하는 문제가 있었다. 특히 200℃ 전후의 열이 기재층에 가해지는 히트씰시에, 디라미네이션의 발생빈도가 높았다. 배리어층과 기재층의 사이에서 디라미네이션이 발생한 경우, 전지용 외장체에 요구되는 특성 중, 내찌름성, 내핀홀성 등의 강도특성의 저하를 초래하여, 외부로부터 수증기가 침입하는 원인이 될 수 있다. 내부에 수증기가 침입한 경우, 전지를 형성하는 성분 중 하나인 전해질과 반응하여 불화수소산을 발생하고, 이에 따라 상기 배리어층인 알루미늄박이 부식된다는 문제가 있었다.
Examples of the physical properties and functions required for a battery external body include high moisture resistance, sealing property, puncture resistance, pinhole resistance, insulation property, heat resistance and cold resistance, electrolyte resistance (electrolyte resistance), corrosion resistance And resistance to hydrofluoric acid generated by hydrolysis) are indispensable. Particularly, moisture resistance is an important factor. Aluminum foil, which is generally used as a metal foil in a laminate type, particularly in a cold forming type, is excellent in moldability, but pinholes and cracks are likely to occur due to non-uniform deformation occurring at the time of molding, There was room for improvement in terms of molding stability of molding. The laminate type is composed of at least a base layer, a barrier layer and a sealant layer, but the bonding strength between the layers affects properties required as an external body of the battery. For example, when the adhesive strength between the barrier layer and the substrate layer is insufficient, the heat shrinkage stress of the substrate layer becomes larger than the interlaminar bond strength in the step of sealing the battery body after heat sealing, or when used for a long time at a high temperature , There is a problem that delamination (peeling) occurs between the barrier layer and the substrate layer. Especially, in the heat seal process in which heat of about 200 캜 is applied to the substrate layer, the occurrence frequency of delamination is high. When the delamination occurs between the barrier layer and the base layer, the strength properties such as resistance to bite and pinhole are deteriorated among the properties required for battery external body, and it may cause invasion of water vapor from the outside . When water vapor intrudes into the inside of the battery, it reacts with an electrolyte, which is one of the components forming the battery, to generate hydrofluoric acid, thereby causing corrosion of the aluminum foil as the barrier layer.

적층체 타입, 특히 냉간성형 타입의 전지용 외장체의 주된 품질적인 과제, 즉 우수한 냉간성형성의 확보와 각 층간에서의 디라미네이션의 억제에 관하여, 지금까지 다양한 제안이 이루어지고 있다. 우수한 냉간성형성을 확보하는 방법으로서, 예를 들어 특허문헌 2에는, 기재층 표면에 지방산아마이드계의 활성부여성분을 코팅하고, 성형시에 금형내로의 슬라이딩을 좋게 하여 성형성을 개선하는 방법이 기재되어 있다. 특허문헌 3, 특허문헌 4, 특허문헌 5, 및 특허문헌 6에는, 나일론필름 등의 기재층의 강도물성에 착안하여, 냉간성형시에 있어서의 알루미늄박의 파단을 억제하기 위해서, 이방성이 적고, 또한 고강도 혹은 고신도 등의 성질을 갖는 기재를 사용하여 알루미늄박을 보강하는 방법이 기재되어 있다. 나아가, 특허문헌 7에는, 기재층의 결정성에 착안한 방법이 제안되어 있다. 한편, 디라미네이션을 억제하는 방법으로서, 특허문헌 8에는 기재층의 열수수축율을, 특허문헌 9에는 기재층의 밀도를 어느 범위로 한정하는 방법이 제안되어 있다.
Various proposals have heretofore been made on the main quality problems of laminate type, particularly cold-formed type battery outer shells, that is, securing of excellent cold formability and suppression of delamination in each layer. As a method for ensuring excellent cold forming property, for example, Patent Document 2 discloses a method of coating a surface of a substrate layer with a fatty acid amide type activity-imparting component and improving the moldability by improving the sliding into the mold at the time of molding . Patent Literatures 3, 4, 5, and 6 disclose a multilayer structure in which the anisotropy is small in order to suppress breakage of the aluminum foil during cold forming, taking into consideration the strength properties of a base layer such as a nylon film, Also disclosed is a method of reinforcing an aluminum foil using a substrate having properties such as high strength or high elongation. Furthermore, Patent Document 7 proposes a method which focuses on the crystallinity of the base layer. On the other hand, as a method for suppressing delamination, Patent Document 8 proposes a method of limiting the heat shrinkage rate of the base layer, and Patent Document 9 proposes a method of limiting the density of the base layer to a certain range.

그러나, 기재층의 표면에 활성부여성분을 코팅하는 방법은, 코팅하는 공정을 마련해야 하고, 또한, 전지의 진공탈기시나 씰가공시에 활성부여성분이 증발하여, 이 증발성분이 가공설비에 부착되므로, 이들을 제거하는 청소작업이 필요하게 된다는 문제가 있었다. 고강도 혹은 고신도의 기재를 사용하여 알루미늄박을 보강하는 방법은, 성형성의 향상은 보이나, 디라미네이션을 억제하는 효과는 없다. 기재층의 열수수축율을 제한하여 디라미네이션을 억제하는 방법은, 특히 디라미네이션 발생빈도가 높은 상황, 예를 들어 200℃ 전후의 열이 기재에 가해지는 히트씰공정이나 고온고습도와 반드시 조건이 합치하는 것은 아니며, 디라미네이션의 방지책으로서 충분하지는 않았다.
However, in the method of coating the surface of the substrate layer with the activity-imparting component, a coating process must be provided, and the activity-imparting component is evaporated during vacuum degassing or sealing of the cell, and this evaporation component is attached to the processing equipment , There is a problem that a cleaning work for removing them is required. The method of reinforcing the aluminum foil by using the base material having high strength or high degree of durability shows improvement in moldability but has no effect of suppressing delamination. The method of suppressing delamination by restricting the rate of heat shrinkage of the substrate layer is particularly effective in a situation where the occurrence frequency of delamination is high, for example, a heat sealing process in which heat is applied to the substrate at about 200 캜, And it is not sufficient as a preventive measure against delamination.

필자들은 상기 과제를 감안하여, 기재층인 나일론필름의 열수축응력, 및 인장강도를 어느 범위로 한정함으로써, 냉간성형 타입의 전지용 외장체의 주된 과제였던, 우수한 냉간성형성의 확보와 각 층간에서의 디라미네이션의 억제를 양립할 수 있는 것을 발견하였다(특허문헌 10). 그러나, 최근에는 리튬이온전지 등의 이차전지는 널리 보급되어 있고, 예를 들어 자동차용 등, 가혹한 조건에서 장시간 사용되는 경우가 있어, 외장재에 보다 향상된 내구성이 요구되고 있다. 종래의 기술에서는 가혹조건, 특히 고온고습도하에서나 ONy필름과 알루미늄박간에 인쇄층을 마련한 경우에 있어서는, 각 층간의 접착력이 약해지는 경우가 있어, 디라미네이션 발생의 리스크가 높아진다.
In view of the above problems, the inventors have found that by limiting the heat shrinking stress and the tensile strength of the nylon film as the substrate layer to a certain range, it is possible to secure the excellent cold forming property, which is the main object of the cold- It is possible to achieve both suppression of lamination (Patent Document 10). However, in recent years, secondary batteries such as lithium ion batteries have become widespread, and they are often used for a long period of time under severe conditions such as automobiles, for example. In the prior art, when a print layer is provided between the ONy film and the aluminum foil under severe conditions, particularly at high temperature and high humidity, the adhesive force between the respective layers is weakened, and the risk of occurrence of delamination is increased.

한편, 라미네이트 강도개선을 목적으로서, 특히 보일, 레토르트(レトルト)시의 접착성이 요구되는 용도로 이접착 나일론필름이 개발되어 있다(특허문헌 11, 12, 13). 그러나, 이것이 전지용 외포재의 기재로서 응용된 예는 없다.On the other hand, this adhered nylon film has been developed for the purpose of improving the laminate strength, in particular, in applications requiring adhesion at the time of boiling and retorting (Patent Documents 11, 12 and 13). However, there is no example in which this is applied as a base material for a battery outer covering material.

일본특허공개 2004-74419호 공보Japanese Patent Application Laid-Open No. 2004-74419 일본특허공개 2002-216714호 공보Japanese Patent Application Laid-Open No. 2002-216714 일본특허공개 2000-123800호 공보Japanese Patent Application Laid-Open No. 2000-123800 일본특허공개 2006-236938호 공보Japanese Patent Application Laid-Open No. 2006-236938 일본특허공개 2008-44209호 공보Japanese Patent Application Laid-Open No. 2008-44209 일본특허공개 2005-22336호 공보Japanese Patent Application Laid-Open No. 2005-22336 일본특허공개 2007-42469호 공보Japanese Patent Application Laid-Open No. 2007-42469 일본특허공개 2006-331897호 공보Japanese Patent Application Laid-Open No. 2006-331897 일본특허공개 2008-288117호 공보Japanese Patent Application Laid-Open No. 2008-288117 일본특허공개 2011-162702호 공보Japanese Patent Application Laid-Open No. 11-162702 일본특허공고 S57-26236호 공보Japanese Patent Publication S57-26236 일본특허공개 H8-258232호 공보Japanese Patent Application Laid-Open No. H8-258232 일본특허공개 H11-20104호 공보Japanese Patent Application Laid-Open No. H11-20104

본 발명은, 적층체의 기재로서 이용했을 때, 냉간성형성이 우수하고, 또한 가혹조건에서의 내구성이 우수한 냉간성형용 나일론필름, 특히 고온고습도조건 하에서나, 본 필름과 알루미늄박간에 인쇄층을 마련한 경우에 있어서도, 디라미네이션이 발생하기 어려운, 냉간성형용 나일론필름을 얻는 것을 과제로 한다.The present invention relates to a nylon film for cold forming which is excellent in cold formability and durability under severe conditions when used as a base material of a laminate, and in particular, under the conditions of high temperature and high humidity, It is an object of the present invention to provide a nylon film for cold forming which is less likely to cause delamination.

본 발명자는 본 과제에 대하여 예의 연구를 거듭한 결과, 어느 특정한 강도특성을 갖는 이축연신필름의 표면이 어느 특정한 수지로 얇게 도공되어 있음으로써, 이것을 기재로서 이용한 전지용 외장재가 우수한 특성을 갖는 것을 발견하였다. 구체적으로는, 냉간성형성이 우수하고, 또한 고온고습도하에서나 인쇄층의 개재와 같은 가혹조건하에서도 각 층간에서의 디라미네이션이 일어나기 어렵다는 특성을 양립할 수 있는 것을 발견하였다.
The inventor of the present invention has conducted intensive researches on this subject and as a result has found that the surface of a biaxially stretched film having a specific strength characteristic is thinly coated with a specific resin so that the battery casing material using the biaxially stretched film as a base material has excellent properties . Specifically, it has been found that it is possible to combine the characteristics that the cold-formability is excellent and the delamination between the respective layers is difficult to occur even under severe conditions such as under high temperature and high humidity or intervening in the print layer.

즉 본 발명은,That is,

[1], 폴리우레탄 수지, 아크릴계 공중합체 수지, 폴리에스테르 수지, 에폭시계 수지, 폴리이미드계 수지로부터 선택되는 적어도 1종의 수지 및 그 가교제가 적어도 편면에 도포된 필름으로서, 170~210℃에 있어서의 열수축응력의 최대값이 MD, TD 모두 5.0MPa 이하이고, 또한 일축인장시험(시료폭 15mm, 척간거리 100mm, 인장속도 200mm/min.)에 있어서의 4방향(0°(MD), 45°, 90°(TD), 135°)의 모든 파단강도가 240MPa 이상인 것을 특징으로 하는 이축연신 나일론필름.At least one resin selected from a polyurethane resin, an acrylic copolymer resin, a polyester resin, an epoxy resin, and a polyimide resin, and a crosslinking agent thereof, (0 DEG (MD), 45 DEG) in the uniaxial tensile test (sample width 15 mm, chuck distance 100 mm, tensile speed 200 mm / min) Deg.], 90 [deg.] (TD), 135 [deg.]) Of 240 MPa or more.

[2], 미연신의, 또는 연신 후의, 열처리되지 않은 나일론필름에, 폴리우레탄 수지, 아크릴계 공중합체 수지, 폴리에스테르 수지, 에폭시계 수지, 폴리이미드계 수지로부터 선택되는 적어도 1종의 수지 및 가교제를 도공 후, 열처리한 것을 특징으로 하는 상기 [1]에 기재된 이축연신 나일론필름.[2] At least one resin selected from a polyurethane resin, an acrylic copolymer resin, a polyester resin, an epoxy resin, and a polyimide resin and a crosslinking agent are added to a non-heat treated nylon film after unstretched or stretched The biaxially stretched nylon film according to the above [1], characterized in that it is heat-treated after coating.

[3], 상기 수지 및 그 가교제가 하기의 A, B로서 고형분중량비 A/B=98~30/2~70으로 이루어진 조성물을 주성분으로 하는 수성 도공제가 도공되어 있고, 그 도공량이 필름연신 후에 있어서 고형분으로 0.005~0.200g/m2인 상기 [1] 또는 [2]에 기재된 이축연신 나일론필름.[3] An aqueous coating material comprising, as a main component, a composition comprising the resin and the crosslinking agent as A and B in terms of solids weight ratio A / B = 98 to 30/2 to 70, The biaxially stretched nylon film according to the above [1] or [2], which has a solid content of 0.005 to 0.200 g / m 2 .

A: 3중 결합의 2개의 인접탄소원자에 모두 수산기 및 메틸기가 치환된 아세틸렌글리콜 및/또는 그 에틸렌옥사이드 부가물인 비이온계 계면활성제를 함유한 수계 폴리우레탄 수지.A: An aqueous polyurethane resin containing a nonionic surfactant which is an acetylene glycol and / or an ethylene oxide adduct thereof substituted with a hydroxyl group and a methyl group at two adjacent carbon atoms of a triple bond.

B: 수용성 폴리에폭시 화합물.B: Water-soluble polyepoxy compound.

[4], 상기 [3]에 기재된 도공제에 평균입자경이 0.001~1.0μm인 미립자C가 고형분중량비 A/B/C=98~30/2~70/0.1~10이 되도록 포함되어 있는 것을 특징으로 하는 상기 [3]에 기재된 이축연신 나일론필름.[4] It is characterized in that the coating agent described in [3] includes fine particles C having an average particle size of 0.001 to 1.0 μm in a solid content weight ratio A / B / C of 98 to 30/2 to 70 / Is the biaxially stretched nylon film according to the above [3].

[5], 일축인장시험(시료폭 15mm, 척간거리 100mm, 인장속도 200mm/min.)에 있어서의 4방향(0°(MD), 45°, 90°(TD), 135°)의 모든 50% 모듈러스값이 120MPa 이상인 것을 특징으로 하는 상기 [1]~[4] 중 어느 하나에 기재된 이축연신 나일론필름.(MD), 45 °, 90 ° (TD), 135 °) in the uniaxial tensile test (sample width 15 mm, chuck distance 100 mm, tensile speed 200 mm / The biaxially stretched nylon film according to any one of [1] to [4], wherein the% modulus value is 120 MPa or more.

[6], 적어도 기재층, 배리어층, 실란트층에 의해 형성된 냉간성형용 전지케이스 포재로서, 상기 기재층으로서, [1]~[5] 중 어느 하나에 기재된 이축연신 나일론필름의 도공면을 배리어층측에 배치한 것을 특징으로 하는 냉간성형용 전지케이스 포재.[6] A battery case for cold forming comprising at least a base layer, a barrier layer and a sealant layer, wherein the coated side of the biaxially stretched nylon film according to any one of [1] to [5] Layer side of the battery case.

[7], 적어도 기재층, 배리어층, 실란트층에 의해 형성된 냉간성형용 전지케이스 포재로서, 상기 기재층으로서, [1]~[5] 중 어느 하나에 기재된 이축연신 나일론필름의 도공면에 인쇄하고, 그 인쇄면을 배리어층측에 배치한 것을 특징으로 하는 냉간성형용 전지케이스 포재.[7] A cold forging battery case comprising at least a base layer, a barrier layer and a sealant layer, wherein the base layer is printed on the coated surface of the biaxially stretched nylon film according to any one of [1] to [5] And the printed surface thereof is disposed on the side of the barrier layer.

[8], 상기 [6] 또는 [7]에 기재된 냉간성형용 전지케이스 포재를 사용하고, 실란트층이 내면이 되도록 돌출성형, 또는 딥드로잉성형하여 오목부분을 형성한 전지케이스.[8] A battery case comprising the battery case for cold forming as described in [6] or [7] above, wherein the concave portion is formed by protrusion molding or deep drawing molding so that the sealant layer becomes the inner surface.

[9], [8]에 기재된 전지케이스의 오목부분에 전지 본체를 수납하고, 밀봉되어 있는 것을 특징으로 하는 전지,A battery in which a battery body is housed in a concave portion of a battery case described in [9] or [8] and is sealed,

를 제공한다.Lt; / RTI >

본 발명의 이축연신 나일론필름을 냉간성형용 포재, 특히 리튬이온 이차전지 등의 전지케이스용 포재의 주요기재로서 이용함으로써, 히트씰하여 밀봉하는 공정이나 고온고습도하에서나 인쇄층이 개재된 상태로 장시간 사용된 경우에 있어서도, 배리어층과 기재층간에서의 디라미네이션이 일어나기 어렵고, 또한 모든 금형형상이나 성형깊이의 냉간성형가공시에 있어서도 알루미늄박의 파단이나 핀홀 등의 발생이 없어, 안정된 성형성을 확보하는 것이 가능하게 되었다. 또한, 종래기술과 같이, 활성부여성분을 코팅하지 않아도 우수한 성형성을 확보할 수 있으므로 생산성도 우수하다.By using the biaxially stretched nylon film of the present invention as a main substrate for a battery case, such as a cold forming post, especially a lithium ion secondary cell, it is possible to perform a heat sealing and sealing process, or a process for sealing for a long time under high temperature and high humidity, It is difficult to cause delamination between the barrier layer and the substrate layer. In addition, even in the cold forming of all the mold shapes and forming depths, there is no occurrence of breakage of the aluminum foil or pinholes, . In addition, as in the prior art, excellent formability can be ensured without coating the activity-imparting component, and productivity is also excellent.

도 1은 본 발명의 이축연신 나일론필름을 제조하는 인라인수지도공 튜블러연신장치의 공정도이다.BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a process drawing of an inline resin coating tubular stretching apparatus for producing a biaxially stretched nylon film of the present invention.

이하에, 본 발명을 실시하기 위한 최량의 형태에 대하여 설명한다.BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the best mode for carrying out the present invention will be described.

(이축연신 나일론필름의 원료)(Raw material of biaxially stretched nylon film)

본 발명의 이축연신 나일론필름(이하, ONy필름)의 원료는, 폴리아미드계 수지이면 특별히 한정되는 것은 아니다. 예를 들어, 나일론6, 나일론66, 나일론11, 나일론12, 나일론610, 나일론612, 나일론6, 66, 12 공중합체, 기타 폴리아미드계 공중합체, 나일론MXD6, 아라미드, 폴리아미드이미드(PAI), 방향족 폴리이미드, 폴리에테르이미드(PEI), 폴리말레이미드아민(PMIA), 폴리아미노비스말레이미드(PABM) 등을 들 수 있으나, 생산성이나 냉간성형성, 강도물성을 주된 필름물성의 관점에서 나일론6이 가장 바람직하다. 또한, 나일론6 원료에 있어서, 수평균분자량은 10000~30000이 바람직하고, 특히 바람직하게는 22000~24000이다. 수평균분자량이 10000 미만인 경우, 얻어진 ONy필름의 충격강도나 인장강도가 불충분하다. 또한 수평균분자량이 30000보다 큰 경우, 분자쇄의 뒤엉킴이 현저하고, 연신가공에 의해 과도한 변형이 발생하므로, 연신가공시에 파단이나 펑크가 빈번하게 발생하여, 안정적으로 생산할 수 없다.
The raw material of the biaxially stretched nylon film (hereinafter, ONy film) of the present invention is not particularly limited as long as it is a polyamide-based resin. (PAI), nylon 6, nylon 612, nylon 6, 66, 12 copolymers, other polyamide copolymers, nylon MXD6, aramid, polyamideimide Aromatic polyimide, polyetherimide (PEI), polymaleimide amine (PMIA), polyamino bismaleimide (PABM) and the like. However, in view of main film properties, productivity, cold moldability, Is most preferable. In the nylon 6 raw material, the number average molecular weight is preferably 10,000 to 30,000, particularly preferably 22,000 to 24,000. When the number average molecular weight is less than 10,000, impact strength and tensile strength of the obtained ONy film are insufficient. When the number-average molecular weight is larger than 30,000, the molecular chains are remarkably entangled and excessively deformed by stretching, so that breakage or puncture frequently occurs during the stretching process, and production can not be stably performed.

(도공제의 원료)(Raw material of coating agent)

본 발명에 이용하는 도공제는 폴리우레탄 수지, 또는 아크릴계 공중합체 수지를 주성분으로 하고 가교제로 가교되어 있는 것이 필요하다. 바람직한 수지로는 수계 에멀젼, 가교제는 수용성 가교제가 도공의 용이함이나 환경대응의 점에서도 바람직하다. 이하 수지의 예를 나타내나, 폴리우레탄 수지, 또는 아크릴계 수지로 박막도공할 수 있고 또한 적절한 가교제에 의한 가교구조에 의해 특히 물이나 용제에 대한 수지 자체의 응집력이 극단적으로 저하되는 것이 아니면 특별히 제한 없이 사용할 수 있다.
The coating material used in the present invention is required to be a polyurethane resin or an acrylic copolymer resin as a main component and to be crosslinked with a crosslinking agent. A water-based emulsion is preferable as a resin, and a water-soluble crosslinking agent as a crosslinking agent is preferable from the viewpoints of ease of coating and environmental compatibility. The resin can be applied to a thin film with a polyurethane resin or an acrylic resin and the crosslinking structure of a suitable crosslinking agent can not reduce the cohesion of the resin itself to water or solvent extremely, Can be used.

폴리우레탄 수지로는, 특별히 한정되지 않고 접착제로서 사용되는 용제나 수계의 유화형을 사용할 수 있다.The polyurethane resin is not particularly limited and a solvent used as an adhesive or an emulsion type in an aqueous system can be used.

안정성이 양호한 점에서 입자경이 작은 수계의 자기유화형이 특히 바람직하다.The self-emulsifying type of the water-base having a small particle diameter is particularly preferable from the standpoint of stability.

그 입자경은 10~100nm 정도가 좋다. 본 발명에 이용하는 폴리우레탄 수지는 그 유리전이점(Tg)이 40℃~150℃가 바람직하다. Tg가 40℃ 미만인 것은 도공 후 롤상으로 권취할 때 블로킹이 발생하여, 밀착의 흔적이 남아 투명얼룩이 되고, 더욱 심한 경우에는 되돌릴 수 없으며, 무리하게 되돌리면 필름이 파단된다. 또한, 본 발명은 폴리아미드필름에 도공 후 연신하는 인라인도공이므로, 도공 후의 건조온도 및 연신시에 가해지는 온도보다 Tg가 지나치게 높으면, 균일한 도막을 형성하기 어렵다. 이는 연속된 도막을 형성하는 최저성막온도(MFT)가 일반적으로 Tg부근에 있기 때문이며, 150℃ 미만이 바람직하다.
The particle diameter is preferably about 10 to 100 nm. The polyurethane resin used in the present invention preferably has a glass transition point (Tg) of 40 to 150 캜. When Tg is less than 40 占 폚, blocking occurs when winding the film into a roll shape after coating, leaving traces of adhesion remaining untransparent, and can not be reversed if it is more severe. Further, since the present invention is an in-line coating which is applied to a polyamide film and then stretched, it is difficult to form a uniform coating film if the Tg is higher than the drying temperature after coating and the temperature applied at the time of stretching. This is because the minimum film forming temperature (MFT) forming a continuous coating film is generally in the vicinity of Tg, and it is preferably less than 150 ° C.

본 발명에 있어서, 수계 폴리우레탄 수지를 사용하는 경우, 3중 결합의 2개의 인접탄소원자에 모두 수산기 및 메틸기가 치환된 아세틸렌글리콜 및/또는 그 에틸렌옥사이드 부가물인 비이온계 계면활성제가 첨가되는 것이 바람직하다. 이러한 계면활성제로는, 예를 들어 Nissin Chemical Industry Co., Ltd.제의 Surfynol 104, 440 등을 예시할 수 있다. 첨가량은, 수계 폴리우레탄 수지의 고형분에 대하여 0.01~1.0%인 것이 바람직하다. 종래, 도공제 사용시의 발포와 물의 큰 표면장력에 의한 필름 등으로의 균일한 「습윤」의 곤란함을 해결하기 위해서는 일반적으로 2종류의 계면활성제(소포제, 습윤제)를 첨가해야 했다. 또한 대부분의 경우, 소포효과와 습윤효과는 상반되므로, 한쪽을 해결하면, 다른 쪽이 오히려 악화되는 것이었다. 이 계면활성제를 첨가함으로써, 필름에 대한 습윤이 좋아지고, 도공량이 적어도, 균일한 도막이 얻어지므로 비용저감으로 이어지는 것은 물론, 소포효과도 있는 점에서, 도공제 조제시 및 도공시의 발포에 의한 트러블도 해소된다.
In the present invention, when an aqueous polyurethane resin is used, it is preferred that a nonionic surfactant, which is an acetylene glycol and / or an ethylene oxide adduct thereof substituted with a hydroxyl group and a methyl group, is added to two adjacent carbon atoms of a triple bond desirable. As such a surfactant, for example, Surfynol 104, 440 available from Nissin Chemical Industry Co., Ltd. can be exemplified. The addition amount is preferably 0.01 to 1.0% based on the solid content of the aqueous polyurethane resin. Conventionally, two types of surfactants (antifoaming agent, wetting agent) have been added in order to solve the difficulty of uniform "wetting" with a film or the like due to foaming at the time of using a coating agent and large surface tension of water. Also, in most cases, the vesicle effect and the wetting effect are opposite to each other, and when one side is solved, the other side is rather deteriorated. The addition of the surfactant improves the wettability of the film and provides a coating film having a uniform coating amount at least so that it leads not only to cost reduction but also to a defoaming effect, Also,

본 발명에 이용하는 폴리우레탄의 가교제로는, 에폭시 화합물, 옥사졸린 화합물 등, 범용의 수용성 가교제를 사용할 수 있으나, 안전성의 관점에서 수용성인 것이 특히 바람직하다. 수용성 에폭시 화합물은 물에 대한 용해성이 있고, 2개 이상의 에폭시기를 갖는 화합물이며, 예를 들어 에틸렌글리콜, 디에틸렌글리콜, 트리에틸렌글리콜, 폴리에틸렌글리콜, 프로필렌글리콜, 디프로필렌글리콜, 트리프로필렌글리콜, 폴리프로필렌글리콜, 1,4-부탄디올, 1,6-헥산디올, 네오펜틸글리콜 등의 글리콜류 1몰과 에피클로르하이드린 2몰과의 에테르화에 의해 얻어지는 디에폭시 화합물, 글리세린, 폴리글리세린, 트리메틸올프로판, 펜타에리스리톨, 솔비톨 등의 다가알코올류 1몰과 에피클로르하이드린 2몰 이상의 에테르화에 의해 얻어지는 폴리에폭시 화합물, 프탈산테레프탈산, 옥살산, 아디프산 등의 디카르본산류 1몰과 에피클로르하이드린 2몰의 에스테르화에 의해 얻어지는 디에폭시 화합물 등을 들 수 있으나 이들로 한정되는 것은 아니다. 이들 수용성 가교제는 수계 폴리우레탄 수지와 가교하고, 도막의 내수성, 내용제성을 향상시키며, 더 나아가 폴리아미드필름과의 접착성에도 기여한다.
As the crosslinking agent for the polyurethane used in the present invention, a general water-soluble crosslinking agent such as an epoxy compound or an oxazoline compound can be used, but it is particularly preferable that the crosslinking agent is water-soluble in view of safety. The water-soluble epoxy compound is a compound having solubility in water and having two or more epoxy groups, and examples thereof include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, Diepoxy compounds obtained by etherification of 1 mole of glycols such as glycol, 1,4-butanediol, 1,6-hexanediol and neopentyl glycol and 2 moles of epichlorohydrin, glycerin, polyglycerin, trimethylolpropane , 1 mole of polyhydric alcohols such as pentaerythritol and sorbitol, and 1 mole of dicarboxylic acids such as polyepoxy compounds, phthalic acid terephthalic acid, oxalic acid and adipic acid obtained by etherification of at least two mol of epichlorohydrin and epichlorohydrin And a diepoxy compound obtained by esterification of 2 moles, and the like, but not limited thereto All. These water-soluble crosslinking agents crosslink with an aqueous polyurethane resin to improve the water resistance and solvent resistance of the coating film and further contribute to the adhesion to the polyamide film.

본 발명에 있어서의 도공제에는 미립자를 첨가하여 라미네이트시의 가공적성을 향상할 수 있다. 도공막에 미립자가 존재함으로써, 내블로킹제, 및 권취, 인쇄, 라미네이트, 도공 등의 후가공공정에서의 적절한 활성을 부여하는 활제의 기능이 발현된다. 평균입자경이 0.001~1.0μm인 미립자가 사용되고, 바람직하게는 진구상의 미립자가 이용된다. 진구상 미립자란 그 전자현미경 사진에 있어서 단경/장경이 0.90 이상인 것을 말한다. 미립자가 진구상인 경우 내블로킹성, 활성에 대한 효과가 우수하고, 또한, 투명성의 저하가 적으므로 바람직하다. 또한, 평균입자경이 0.001μm 미만이면 내블로킹성, 활성에 효과가 없다. 평균입자경이 1.0μm를 초과하면 인쇄적성이 저하된다. 특히 사진판인쇄의 경우, 하이라이트 부분에서의 잉크 누락이 발생한다. 미립자는 무기계일 수도 유기계일 수도 있는데, 제조공정 중에 변형되어 효과를 잃지 않는 내열성이 필요하다.
The coating agent in the present invention can be added with fine particles to improve the processability in laminating. The presence of the fine particles in the coating film exhibits the function of a lubricant which gives an appropriate blocking agent and an appropriate activity in a post-processing step such as winding, printing, laminating and coating. Fine particles having an average particle size of 0.001 to 1.0 μm are used, and fine particle-like fine particles are preferably used. The spherical fine particles refer to those having a short diameter / long diameter of 0.90 or more in their electron micrographs. When the fine particles are spherical phases, the effect on blocking resistance and activity is excellent, and the decrease in transparency is small, which is preferable. When the average particle diameter is less than 0.001 탆, the antiblocking property and activity are not effective. If the average particle size exceeds 1.0 占 퐉, the printability is lowered. In particular, in the case of photographic plate printing, ink is missing in the highlight portion. The fine particles may be inorganic or organic, and heat resistance is required, which is modified during the manufacturing process and does not lose its effect.

미립자는 무기, 유기 화합물로 특별히 한정되지 않으나, 바람직한 미립자로서, 예를 들어, Nissan Chemical Industries, Limited제의 콜로이달실리카 ”SNOWTEX” ST-C(평균입경 0.010~0.020μm), ST-XS(평균입경 0.004~0.006μm) 등을 들 수 있다.Examples of the fine particles include colloidal silica " SNOWTEX " ST-C (average particle diameter 0.010 to 0.020 m) and ST-XS (average particle diameter: Particle size: 0.004 to 0.006 占 퐉).

본 발명에 있어서, 계면활성제를 포함한 수계 폴리우레탄 수지(A)와, 수용성 폴리에폭시 화합물(B)의 배합비율 A/B의 중량비는, 고형분으로 98/2~30/70이다.In the present invention, the weight ratio of the mixing ratio A / B of the water-borne polyurethane resin (A) containing the surfactant to the water-soluble polyepoxy compound (B) is 98/2 to 30/70 in terms of solid content.

A/B의 비율이 98/2보다 크면 가교밀도가 감소하고, 내수성, 내용제성, 접착성이 부족하다. 반대로 A/B의 비율이 30/70보다 작아지면 숙성 중의 블로킹이 문제점으로 남는다. 또한, 미립자(C)의 배합량은, 계면활성제를 포함한 수계 폴리우레탄 수지(A) 및 수용성 폴리에폭시 화합물(B)의 합계량(A+B)과의 비율로서 C/(A+B)는 0.1/100~10/100이다. 이 비율이 0.1/100보다 작으면 내블로킹성, 활성에 효과가 불충분하며, 반대로, 10/100보다 크게 해도 효과는 여전히 경제적으로 불리하다.
When the ratio A / B is larger than 98/2, the crosslinking density decreases and the water resistance, solvent resistance and adhesion are insufficient. Conversely, if the ratio of A / B is less than 30/70, blocking during aging remains a problem. The blending amount of the fine particles (C) is a ratio of the total amount (A + B) of the aqueous polyurethane resin (A) containing the surfactant and the water-soluble polyepoxy compound (B) 100 to 10/100. If the ratio is less than 0.1 / 100, the effect on antiblocking property and activity is insufficient. On the other hand, even if it is larger than 10/100, the effect is still economically disadvantageous.

계면활성제를 포함한 수계 폴리우레탄 수지, 수용성 폴리에폭시 화합물 및 미립자를 주성분으로 한 수성 도공제의 도공량은 연신 후 건조중량으로 0.005~0.2000g/m2, 바람직하게는 0.010~0.050g/m2인 것이 바람직하다. 0.005g/m2 미만이면 균일한 도막이 얻어지지 않고 내수성, 접착성이 불충분하다. 반대로 0.200g/m2 이상 도공하면 코트면/비코트면이 블로킹되기 쉬워진다. 또한 성능의 향상도 보이지 않고, 비용상승이 되어 바람직하지 않다.
The coating amount of the water-based polyurethane resin including the surfactant, the water-soluble polyepoxy compound and the water-based coating material containing fine particles as a main component is 0.005 to 0.2000 g / m 2 , preferably 0.010 to 0.050 g / m 2 . If it is less than 0.005 g / m 2, a uniform coating film can not be obtained and water resistance and adhesiveness are insufficient. Conversely, if the coating is applied at 0.200 g / m 2 or more, the coat surface / non-coating surface is likely to be blocked. Further, the performance is not improved, and the cost is increased, which is undesirable.

아크릴계 공중합수지로는, 그 유리전이점이 40℃ 이상인 것이 바람직하다. 유리전이점이 40℃ 미만인 것은 수용성 폴리에폭시 화합물 등의 가교·경화시키기 위하여 도공 후 롤상으로 권취하고, 30~60℃에서 숙성할 때 블로킹이 발생하여, 밀착의 흔적이 남아 투명얼룩이 되고, 더욱 심한 경우에는 되돌리지 않으며, 무리하게 되돌리면 필름이 파단되므로 바람직하지 않다. 본 발명에 이용하는 아크릴계 수지 및/또는 메타크릴산에스테르류 등으로 이루어진 주모노머와, 에폭시기와 가교반응에 기여하는 관능기를 갖는 코모노머가 특히 바람직하고, 그 외에 필요에 따라 추가로 상기의 모노머와 공중합할 수 있는 중성 모노머를 공중합함으로써 얻어진다.
The acrylic copolymer resin preferably has a glass transition point of 40 캜 or higher. When the glass transition point is less than 40 ° C, the coating is rolled up in the form of a roll in order to crosslink and cure the water-soluble polyepoxy compound or the like, and blocking occurs when aging at 30 to 60 ° C, And the film is broken if it is forcibly restored, which is not preferable. Particularly preferred are a main monomer composed of acrylic resin and / or methacrylic acid ester and the like and a comonomer having an epoxy group and a functional group contributing to the crosslinking reaction, which are used in the present invention. In addition, if necessary, And a neutral monomer capable of reacting with the monomer.

상기의 주모노머 중 아크릴산에스테르류로는 예를 들어 아크릴산메틸, 아크릴산에틸, 아크릴산n-프로필, 아크릴산이소프로필, 아크릴산n-부틸, 아크릴산이소부틸, 아크릴산t-부틸, 아크릴산2에틸헥실 등, 또한, 메타크릴산에스테르류로는 메타크릴산메틸, 메타크릴산에틸, 메타크릴산n-프로필, 메타크릴산이소프로필, 메타크릴산n-부틸, 메타크릴산이소부틸, 메타크릴산t-부틸, 메타크릴산2에틸헥실 등을 들 수 있다.Examples of the acrylate esters of the above-mentioned main monomers include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, Examples of the methacrylic acid esters include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, And 2-ethylhexyl methacrylate.

또한, 상기의 코모노머로는 아크릴산, 메타크릴산, 크로톤산, 말레산, 푸마르산, 시트라콘산, 말레산모노에스테르, 푸마르산모노에스테르 등의 α,β-불포화카르본산류, 메타크릴산2하이드록시에틸, 폴리에틸렌글리콜모노메타크릴레이트 등의 하이드록시 화합물, 메타크릴산글리시딜, 알릴글리시딜에테르 등의 에폭시 화합물, 알릴아민, N,N-디메틸아미노에틸아크릴레이트, N,N-디메틸아미노프로필아크릴아미드 등의 아민류, N-메틸아크릴아미드 등의 아미드류, 무수말레산 등의 산무수물 등을 들 수 있으나 이들로 한정되는 것은 아니다. 이들 모노머의 관능기는 폴리에폭시 화합물과의 가교, 플라스틱필름과의 접착성 등에 기여한다.
Examples of the comonomer include α, 棺 -unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, citraconic acid, maleic acid monoester and fumaric acid monoester, Epoxy compounds such as glycidyl methacrylate and allyl glycidyl ether, allylamine, N, N-dimethylaminoethyl acrylate, N, N-dimethyl Amines such as aminopropylacrylamide, amides such as N-methyl acrylamide, and acid anhydrides such as maleic anhydride, but are not limited thereto. The functional groups of these monomers contribute to crosslinking with the polyepoxy compound, adhesion to the plastic film, and the like.

또한, 상기의 공중합할 수 있는 중성모노머로는 스티렌, α메틸스티렌 등의 스티렌류, 아크릴로니트릴, 메타크릴로니트릴 등의 아크릴로니트릴류, 아세트산비닐, 프로피온산비닐 등의 지방족 비닐에스테르류, 비닐메틸에테르, 비닐에틸에테르 등의 비닐알킬에테르류, 에틸렌, 프로필렌, 1-부텐 등의 α올레핀, 염화비닐, 염화비닐리덴 등을 들 수 있으나 이에 한정되는 것은 아니다.
Examples of the copolymerizable neutral monomer include styrenes such as styrene and? Methylstyrene, acrylonitriles such as acrylonitrile and methacrylonitrile, aliphatic vinyl esters such as vinyl acetate and vinyl propionate, Vinyl ethers such as methyl ether and vinyl ethyl ether, alpha olefins such as ethylene, propylene and 1-butene, vinyl chloride, vinylidene chloride, and the like.

본 발명에 이용하는 아크릴계 공중합수지 및 에폭시가교제는 수용성이 바람직하다. 유기용제용액에서는 인화폭발의 위험성, 급성, 만성의 중독 및 고가의 유기용제를 사용함으로써 비용상승 등의 문제점이 있어, 본 발명에 있어서는 수계 도공제를 이용하는 것이 바람직하다. 그러나 수용성을 부여하기 위하여 필요최소한의 유기용제를 사용할 수도 있다.
The acrylic copolymer resin and the epoxy crosslinking agent used in the present invention are preferably water-soluble. In the organic solvent solution, there is a risk of flammability, acute toxicity, chronic poisoning, and an increase in cost by using an expensive organic solvent. In the present invention, it is preferable to use a water-based coating agent. However, a minimum amount of organic solvent may be used to impart water solubility.

상기의 공중합체가 수성 분산액인 경우는 수용액에 비해 제막성이 부족하고, 접착성, 내수성, 내용제성에 문제점이 있으므로, 산 혹은 염기의 첨가 등에 의해 수용화하고 나서 이용하는 것이 바람직하다. 이때, 이용하는 수성 분산액은 유화제를 이용하지 않고 유화한 것이 바람직하다. 또한, 소량의 수용성 유기용제를 사용하여 용액중합한 것은 유기용제용액에 산 또는 염기를 첨가함으로써 수용화하여 이용할 수도 있으나, 수용화의 방법은 이들로 한정되는 것은 아니다.
When the above-mentioned copolymer is an aqueous dispersion, it has insufficient film-forming property compared with an aqueous solution and has problems in adhesiveness, water resistance and solvent resistance, so that it is preferable to be used after being made water-soluble by addition of an acid or a base. At this time, the aqueous dispersion to be used is preferably emulsified without using an emulsifier. The solution polymerization using a small amount of the water-soluble organic solvent may be carried out by adding an acid or a base to the organic solvent solution, but the method of the aqueous solution is not limited thereto.

본 발명에 이용하는 아크릴계 공중합수지의 분자량은 5,000 이상 100,000 이하가 바람직하다. 분자량이 5,000 미만이면 내수성, 내용제성, 내찰상성이 부족하고, 분자량이 100,000을 초과하면 수용화가 곤란해지며, 또한 점도도 상승하여 취급이 곤란해진다. 여기서 말하는 분자량이란 GPC(겔퍼미에이션크로마토그래피)에 의한 폴리메타크릴산메틸호모폴리머 환산의 중량평균분자량을 가리킨다.The molecular weight of the acrylic copolymer resin used in the present invention is preferably 5,000 or more and 100,000 or less. If the molecular weight is less than 5,000, the water resistance, solvent resistance and scratch resistance are insufficient. If the molecular weight exceeds 100,000, the water-solubility becomes difficult and the viscosity increases, making handling difficult. The molecular weight as used herein refers to the weight average molecular weight in terms of polymethyl methacrylate homopolymer by GPC (gel permeation chromatography).

본 발명에 이용하는 다른 수지로는 극성을 갖고, 가교제에 의해 가교시킬 수 있는 수계 내지는 용제계의 접착성 수지를 사용할 수 있다. 예를 들어 폴리에스테르 수지, 에폭시계 수지, 폴리이미드계 수지를 들 수 있다.
As another resin used in the present invention, an aqueous resin or a solvent-based adhesive resin having polarity and capable of being crosslinked by a crosslinking agent can be used. For example, a polyester resin, an epoxy resin, and a polyimide resin.

본 발명에 이용하는 가교제로는 도공하는 수지와 반응하여 가교할 수 있는, 다관능기를 갖는 가교제를 사용할 수 있다. 예를 들어 수용성 폴리에폭시 화합물은 물에 대한 용해성이 있고 안전성이 높아 특히 바람직하다. 이는 2개 이상의 에폭시기를 갖는 화합물이면 되고, 예를 들어 에틸렌글리콜, 디에틸렌글리콜, 트리에틸렌글리콜, 폴리에틸렌글리콜, 프로필렌글리콜, 디프로필렌글리콜, 트리프로필렌글리콜, 폴리프로필렌글리콜, 1,4-부탄디올, 1,6-헥산디올, 네오펜틸글리콜 등의 글리콜류 1몰과 에피클로르하이드린 2몰의 에테르화에 의해 얻어지는 디에폭시 화합물, 글리세린, 폴리글리세린, 트리메틸올프로판, 펜타에리스리톨, 솔비톨 등의 다가알코올류 1몰과 에피클로르하이드린 2몰 이상의 에테르화에 의해 얻어지는 폴리에폭시 화합물, 프탈산테레프탈산, 옥살산, 아디프산 등의 디카르본산류 1몰과 에피클로르하이드린 2몰의 에스테르화에 의해 얻어지는 디에폭시 화합물 등을 들 수 있으나 이들로 한정되는 것은 아니다. 이들 폴리에폭시 화합물은 본 발명에 이용하는 아크릴계 공중합수지의 가교성 관능기와 가교하고, 도막의 내수성, 내용제성을 향상시키며, 더 나아가 플라스틱필름과의 접착성에도 기여한다.
As the crosslinking agent used in the present invention, a crosslinking agent having a polyfunctional group capable of reacting with and crosslinking with the coating resin can be used. For example, water-soluble polyepoxy compounds are particularly preferable because they are soluble in water and have high safety. It may be any compound having two or more epoxy groups, and examples thereof include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, , 6-hexanediol, neopentyl glycol, and the like, and a polyhydric alcohol such as glycerin, polyglycerin, trimethylol propane, pentaerythritol, sorbitol, etc., obtained by etherification of 1 mol of epichlorohydrin and 2 mol of epichlorohydrin A polyepoxy compound obtained by etherification of 1 mole of epichlorohydrin and 2 mole of epichlorohydrin, a diepoxy compound obtained by esterification of 1 mole of dicarboxylic acids such as phthalic acid terephthalic acid, oxalic acid and adipic acid, and 2 moles of epichlorohydrin Compounds, and the like, but are not limited thereto. These polyepoxy compounds crosslink with the crosslinkable functional groups of the acrylic copolymer resin used in the present invention to improve the water resistance and solvent resistance of the coating film and further contribute to the adhesion to the plastic film.

(수지도공이축연신 나일론필름의 제조방법)(Manufacturing method of axially stretched nylon film with water guide)

본 발명의 수지도공이축연신 나일론필름(이하 「ONy필름」)은, 폴리아미드수지원료를 다이스로부터 압출하여 원반을 성형 후, 연신하여 열고정되는데, 수지도공은 열처리전 즉 원반 내지는 열처리전의 연신필름에 실시해야 한다. 도공된 수지는 열처리에 의해 필름과 응집력이 비약적으로 높아지고, 강고한 도공층을 형성할 수 있다. 수지도공의 방법은 특별히 한정되지 않고 소정의 박막도공량이 얻어지면 된다. 연신전에 도공하는 편이 후의 연신공정에서 도공층이 얇아지므로, 도공의 용이성의 관점에서 바람직하다. 예를 들어 그라비어도공에서 고형분 1g/m2 도공한 후, MD 및 TD 모두 3.2배의 연신을 실시하면 연신 후의 도공량은 0.1g/m2가 된다. 연신 후로서, 열처리전의 연신나일론필름에 본 발명의 수지를 박막도공해도 된다.
In the shaft-stretched nylon film (hereinafter, referred to as " ONy film ") of the present invention, the polyamide resin raw material is extruded from a die, and the master is extruded after being molded and stretched. The resin coat is stretched before the heat treatment, It should be done on film. The coated resin is remarkably increased in cohesive force with the film by the heat treatment, and a strong coat layer can be formed. The method of resin coating is not particularly limited, and any thin film can be obtained with a sufficient mass. Since the coating layer is thinned in the subsequent drawing step after the coating step before stretching, it is preferable from the viewpoint of easiness of coating. For example, when a solid content of 1 g / m 2 is coated on a gravure coating, and both MD and TD are stretched 3.2 times, the coating amount after stretching becomes 0.1 g / m 2 . After stretching, the resin of the present invention may be applied to the stretched nylon film before the heat treatment.

상기 폴리아미드계 원료 중 어느 하나로부터 구성되는 미연신 원반에 대하여, 연신배율은, MD, 및 TD 각각 2.8~4.0배의 범위인 것이 바람직하고, 특히 바람직하게는 3.0~3.4배의 범위이다. 연신배율이 2.8배 미만인 경우, 얻어진 ONy필름의 충격강도나 인장강도가 불충분하다. 또한 4.0배 이상인 경우, 연신에 의해 적절한 분자쇄의 변형이 발생하므로, 연신가공시에 파단이나 펑크가 빈번하게 발생하여, 안정적으로 생산할 수 없다. 이축연신방식으로는, 예를 들어 튜블러방식이나 텐터방식에 의한 동시이축연신, 혹은 축차(逐次)이축연신을 들 수 있으나, 종횡의 강도밸런스의 점에서, 튜블러법에 의한 동시이축연신이 바람직하다. 이와 같이 이축연신가공을 실시함으로써, 특히 강도물성이 비약적으로 향상되고, 냉간성형성이 우수한 ONy필름을 얻을 수 있다.
The draw ratio of the unstretched master made of any one of the polyamide-based raw materials is preferably 2.8 to 4.0 times, more preferably 3.0 to 3.4 times, in MD and TD, respectively. When the draw ratio is less than 2.8 times, the obtained ONy film has insufficient impact strength and tensile strength. In addition, when it is 4.0 times or more, a suitable molecular chain is deformed by stretching, so that breakage or puncture frequently occurs during stretching, and production can not be stably performed. Examples of the biaxial stretching method include simultaneous axial stretching or sequential biaxial stretching by a tubular method or a tenter method. However, from the viewpoint of longitudinal and longitudinal strength balance, simultaneous axial stretching by the tubular method desirable. By performing the biaxial stretching process in this way, an ONy film having particularly excellent strength properties and excellent cold forming property can be obtained.

일반적으로, 본 발명의 폴리아미드필름은, 인쇄, 금속증착, 타필름과 라미네이트되므로, 도막 표면의 습윤지수는 40~52dyn/cm가 바람직하다. 본원의 수지도공에 의해 습윤지수가 커지므로, 도막형성 후에 코로나 처리 등으로 표면처리하지 않아도 된다.
Generally, since the polyamide film of the present invention is laminated with printing, metal vapor deposition or other films, the wetting index of the coating film surface is preferably 40 to 52 dyn / cm. Since the wetting index is increased by the resin coating of the present invention, the surface treatment may not be performed by corona treatment or the like after the coating film is formed.

얻어진 수지도공연신필름을 열롤방식 또는 텐터방식, 혹은 이들을 조합한 열처리설비에 임의의 시간 투입하고, 185~215℃, 특히 바람직하게는 190~210℃에서 열처리를 행함으로써, 본 발명의 ONy필름을 얻을 수 있다. 열처리온도가 215℃보다 높은 경우는, 보잉현상이 지나치게 커져서 폭방향으로의 이방성이 증가하거나, 또는 결정화도가 지나치게 높아져서 강도물성이 저하된다. 한편, 열처리온도가 185℃보다 낮은 경우는, 필름의 열치수안정성이 크게 저하되므로, 라미네이트 가공시에 필름이 축소되기 쉬워지거나, 혹은 냉간성형 후, 히트씰하여 밀폐되는 공정에서 디라미네이션이 발생하기 쉬워지므로, 실용상 문제가 발생한다.
The resulting water-coats-ground new film is put into a heat-roller system or a tenter system or a combination heat treatment system for an arbitrary time period and heat-treated at 185 to 215 ° C, particularly preferably 190 to 210 ° C, Can be obtained. When the heat treatment temperature is higher than 215 캜, the phenomenon of bowing becomes excessively large and the anisotropy in the width direction increases, or the degree of crystallization becomes too high, and the physical properties of the strength are lowered. On the other hand, when the heat treatment temperature is lower than 185 占 폚, the thermal dimensional stability of the film is significantly lowered, so that the film tends to be shrunk during the laminating process, or deglaming occurs in the step of heat sealing and sealing after cold forming So that a practical problem arises.

ONy필름의 두께는, 5~50μm, 보다 바람직하게는 10~30μm인 것이 바람직하다. 두께가 5μm보다 작은 경우는, 라미네이트 포재의 내충격성이 낮아지고, 냉간성형성이 불충분해진다. 한편, 50μm를 초과하면 형상유지의 강도는 향상되지만, 특히 파단방지나 성형성의 향상에 대한 효과는 작고, 체적에너지밀도를 저하시킬 뿐이다.
The thickness of the ONy film is preferably 5 to 50 탆, more preferably 10 to 30 탆. When the thickness is smaller than 5 占 퐉, the impact resistance of the laminate preform is lowered and the cold moldability becomes insufficient. On the other hand, when the thickness exceeds 50 m, the strength of shape retention is improved, but the effect of preventing breakage and improving moldability is small, and only the volume energy density is lowered.

ONy필름의 4방향(0°(MD), 45°, 90°(TD), 135°)에 있어서의 일축인장파단강도, 및 50% 모듈러스값은, 일축인장시험(시료폭 15mm, 표점간거리 50mm, 인장속도 200mm/min)에 의해 얻어진 응력-변형곡선으로부터 구한다. 이 응력-변형곡선에 있어서, 4방향에 있어서의 인장파단강도는, 모두 240MPa 이상인 것이 바람직하고, 더욱 바람직하게는 280MPa 이상이다. 이에 따라, 일반적으로 성형하기 어렵다고 여겨지는 성형깊이가 큰 금형형상의 경우에 있어서도, 냉간성형시에 ONy필름, 및 알루미늄박이 파단되기 어려워져, 안정적으로 우수한 성형성을 확보할 수 있다. 4방향 중, 어느 한방향이라도 인장파단강이 240MPa 미만인 경우, 냉간성형시에 ONy필름이 용이하게 파단하게 되고, 특히 고신도시의 인장강도가 요구되는 성형깊이가 큰 금형형상을 성형하는 경우에, 안정된 성형성이 얻어지지 않는다. 나아가, 응력-변형곡선에 있어서, 4방향에 있어서의 50% 모듈러스값은, 모두 120MPa 이상인 것이 바람직하고, 더욱 바람직하게는 150MPa 이상이다. 이에 따라, 특히 성형깊이가 비교적 작은 금형형상을 성형하는 경우에 있어서, 안정된 성형성을 확보할 수 있다. 4방향 중, 어느 한방향이라도 50% 모듈러스값이 120MPa 이상 미만인 경우, 냉간성형시에 ONy필름이 용이하게 파단하게 되어, 안정된 성형성은 얻을 수 없다.
The uniaxial tensile breaking strength and the 50% modulus value of the ONy film in the four directions (0 ° (MD), 45 °, 90 ° (TD), and 135 °) were measured by a uniaxial tensile test (sample width 15 mm, , Tensile speed: 200 mm / min). In this stress-strain curve, the tensile fracture strength in all four directions is preferably 240 MPa or more, and more preferably 280 MPa or more. Accordingly, even in the case of a metal mold having a large forming depth, which is generally regarded as difficult to be molded, the ONy film and the aluminum foil are hardly broken during cold forming, and stable excellent moldability can be ensured. When the tensile fracture steel is less than 240 MPa in any one of the four directions, the ONy film is easily broken at the time of cold forming, and in the case of molding a mold shape having a large forming depth, Moldability is not obtained. Further, in the stress-strain curve, the 50% modulus value in all four directions is preferably 120 MPa or more, and more preferably 150 MPa or more. Thus, in the case of molding a mold shape having a relatively small molding depth, stable moldability can be ensured. When the 50% modulus value is less than 120 MPa in any one of the four directions, the ONy film easily breaks during cold forming, and stable moldability can not be obtained.

ONy필름의 170~210℃에 있어서의 열수축응력의 최대값은, MD, TD 모두, 5.0MPa 이하가 바람직하고, 성형 후, 히트씰 등의 2차가공시에 있어서도 안정된 품질을 유지할 수 있다. 열수축응력의 최대값이 MD, TD 중 어느 하나라도 5.0MPa보다 커지면, 기재의 열수축응력이 커지고, 특히 200℃ 전후의 열이 기재층에 가해지는 히트씰시나 ONy필름과 알루미늄박간에 인쇄층이 개재되는 경우에, 알루미늄박층과 기재층간에 용이하게 디라미네이션(박리)이 발생하므로 바람직하지 않다.
The maximum value of the heat shrinkage stress of the ONy film at 170 to 210 DEG C is preferably not more than 5.0 MPa in both MD and TD, and it is possible to maintain stable quality even after secondary molding such as heat sealing. When the maximum value of the heat shrinkage stress is larger than 5.0 MPa in either MD or TD, the heat shrinking stress of the substrate becomes large, and in particular, in the case of heat sealing in which heat of about 200 캜 is applied to the base layer, , Delamination (peeling) easily occurs between the aluminum foil layer and the substrate layer, which is not preferable.

(라미네이트 포재의 구성)(Composition of laminate insert)

라미네이트 포재는, 상기한 ONy필름의 적어도 어느 일방의 면에, 1층 혹은 2층 이상 다른 기재를 적층하여 구성되어 있다. 구체적으로, 다른 기재로는, 높은 방습성을 부여하기 위한 순알루미늄박 또는 알루미늄-철계 합금의 연질재로 이루어진 알루미늄박층, 및 밀봉성이나 내약품성을 부여하기 위한 폴리에틸렌, 폴리프로필렌, 말레산변성 폴리프로필렌, 말레산변성 폴리에틸렌, 에틸렌-아크릴레이트 공중합체, 아이오노머수지, 폴리염화비닐 등의 미연신필름으로 이루어진 히트씰층을 들 수 있다. 일반적으로, 알루미늄박층을 포함하는 라미네이트 포재는, 냉간성형시에 알루미늄박층의 파단이나 핀홀이 발생하기 쉬우므로 냉간성형에 적합하지 않다. 그러나 본 발명의 ONy필름을 포함하는 라미네이트 포재는, 우수한 성형성, 내충격성 및 내핀홀성을 가지므로, 냉간에서의 돌출성형이나 딥드로잉성형 등을 할 때에, 알루미늄층의 파단을 억제할 수 있다. 또한, 우수한 접착성을 가지므로, 200℃ 정도의 열이 가해진 경우나 고온고습도하 조건에 있어서도 ONy필름과 알루미늄박간에서의 디라미네이션의 발생을 억제할 수 있다. 또한, 본 발명의 ONy필름은 잉크와의 접착성도 우수한 점에서, 필요에 따라 ONy필름과 알루미늄박층간에 인쇄층을 마련해도 품질상 전혀 지장은 없다.
The laminate carrier is constituted by laminating one or more layers on at least one surface of the ONy film. Specifically, as another substrate, an aluminum thin layer made of a pure aluminum foil or a soft material of an aluminum-iron-based alloy for imparting a high moisture-proofing property, and an aluminum thin layer made of polyethylene, polypropylene, maleic acid- modified polypropylene , A maleic acid-modified polyethylene, an ethylene-acrylate copolymer, an ionomer resin, and a polyvinyl chloride. Generally, a laminate material including an aluminum foil layer is not suitable for cold forming since breakage or pinholes of the aluminum foil layer are liable to occur during cold forming. However, since the laminate carrier including the ONy film of the present invention has excellent moldability, impact resistance and pinhole resistance, it is possible to suppress the fracture of the aluminum layer when the resin is subjected to extrusion molding or deep drawing molding in a cold state. In addition, since it has excellent adhesiveness, it is possible to suppress the occurrence of delamination in the ONy film and the aluminum foil even in the case of applying heat at about 200 DEG C or under the conditions of high temperature and high humidity. Further, since the ONy film of the present invention is excellent in adhesion with ink, even if a printing layer is provided between the ONy film and the aluminum thin layer, there is no problem in quality at all.

ONy필름을 포함하는 라미네이트기재의 총두께는 200μm 이하인 것이 바람직하다. 두께가 200μm를 초과하는 경우, 냉간성형에 의한 코너부의 성형이 곤란해지고, 샤프한 형상의 성형품을 얻지 못하는 경우가 있다.
The total thickness of the laminate base material including the ONy film is preferably 200 mu m or less. When the thickness exceeds 200 탆, it is difficult to form the corner portion by cold forming, and a molded product having a sharp shape may not be obtained.

알루미늄박층의 두께는 20~100μm인 것이 바람직하다. 이에 따라, 성형품의 형상을 양호하게 유지하는 것이 가능해지고, 또한 산소나 수분 등이 포재 내로 침입하는 것을 방지할 수 있다. 알루미늄박층의 두께가 20μm 미만인 경우, 라미네이트 포재의 냉간성형시에 알루미늄박층의 파단이 발생하기 쉽고, 또한, 파단되지 않는 경우에도 핀홀 등이 발생하기 쉬워지므로, 포재 중에 산소나 수분 등에 침입하는 경우가 있다. 한편, 알루미늄박층의 두께가 100μm를 초과하는 경우, 냉간성형시의 파단이나 핀홀발생방지의 효과도 크게 개선되는 것이 아니고, 총두께가 두꺼워지는 것뿐이므로 바람직하지 않다.
The thickness of the aluminum foil layer is preferably 20 to 100 mu m. As a result, it is possible to maintain the shape of the molded article well, and it is possible to prevent oxygen, moisture, and the like from intruding into the filling material. When the thickness of the aluminum foil layer is less than 20 占 퐉, breakage of the aluminum foil layer tends to occur at the time of cold forming of the laminate foil, and pinholes are liable to be generated even when the aluminum foil layer is not broken. Therefore, have. On the other hand, when the thickness of the aluminum foil layer is more than 100 mu m, the effect of preventing breakage or pinhole at the time of cold forming is not greatly improved, and it is not preferable because the total thickness becomes thick.

본 발명의 ONy필름을 포함하는 라미네이트 포재는, 돌출성형, 또는 딥드로잉성형 등의 냉간(상온)성형법에 의해 가공가능한 성능을 갖는 포재이며, 포재 총두께가 얇음에도 불구하고 강도가 크기 때문에, 샤프한 성형이 가능하고, 또한 성형시에 알루미늄박의 파단이나 핀홀의 발생을 방지한 라미네이트 포재이다.
The laminate carrier comprising the ONy film of the present invention is a laminate having performance capable of being processed by a cold (normal temperature) molding method such as extrusion molding or deep drawing molding. Since the laminate is strong in spite of its small total thickness, And is capable of forming and preventing the breakage of the aluminum foil and the occurrence of pinholes at the time of molding.

본 발명의 ONy필름을 포함하는 라미네이트 포재가 사용되는 분야, 및 용도로는, 특히 부식성이 높은 전해액을 사용하고, 또한 수분이나 산소의 침입을 극도로 꺼리는 리튬이차전지용 포재에 가장 적합하나, 그 이외의 경량화, 소형화를 필요로 하는 일차전지, 이차전지 등에 있어서도, 전지케이스로서 경량이고, 샤프한 형상의 성형성이 요구되는 경우에 사용가능하다. 또한 전지용 포재 이외로는, 히트씰성, 내약품성, 성형성 등이 우수하므로, 의약품, 화장품, 사진용 약품 기타 부식성이 강한 유기용제를 포함하는 내용물을 위한 용기용 재료로도 이용가능한 포재이다.
The field and application of the laminate carrier containing the ONy film of the present invention are most suitable for use in a lithium secondary battery in which an electrolytic solution having a high corrosivity is used and extremely intrusion of moisture or oxygen is desired. In the case where a lightweight, sharp shape moldability is required as a battery case even in a primary battery or a secondary battery which requires reduction in weight and size. In addition, other than battery cell materials, since they have excellent heat sealability, chemical resistance and moldability, they are also usable as containers for materials containing medicines, cosmetics, photographic chemicals and other highly corrosive organic solvents.

실시예Example

이하에 실시예 및 비교예를 이용하여, 본 발명을 구체적으로 설명한다.Hereinafter, the present invention will be described in detail with reference to examples and comparative examples.

실시예 1Example 1

(도공제의 제조법)(Preparation method of coating agent)

도공제A: Takeda Pharmaceutical Company Limited.제의 자기유화형 폴리우레탄 수지 ”TAKELAC” W-6010에 Nagase Kasei Kogyo K.K.제의 수용성 폴리에폭시 화합물 “DENACOL” EX-521(폴리글리세롤폴리글리시딜에테르), Nissin Chemical Industry Co., Ltd.제의 “SUFYNOL 440”, 및 Nissan Chemical Industries, Limited제의 콜로이달실리카 ”SNOWTEX” ST-C(평균입경 10~20nm)를 70/30/0.05/5의 배합비로 첨가하고, 물로 희석하였다.Coating agent A: A water-soluble polyepoxy compound "DENACOL" EX-521 (polyglycerol polyglycidyl ether), manufactured by Nagase Kasei Kogyo KK, was added to a self-emulsifying polyurethane resin "TAKELAC" W-6010 manufactured by Takeda Pharmaceutical Company Limited "SUFYNOL 440" manufactured by Nissin Chemical Industry Co., Ltd. and colloidal silica "SNOWTEX" ST-C (average particle diameter of 10 to 20 nm) manufactured by Nissan Chemical Industries, Limited were mixed at a compounding ratio of 70/30 / And diluted with water.

(이축연신 나일론필름의 제조)(Production of biaxially stretched nylon film)

나일론6 펠릿(상대점도 3.48)을 압출기 중, 255℃에서 용융혼련한 후, 용융물을 다이스로부터 원통상의 필름으로서 압출하고, 계속해서 물로 급랭하여 원반필름을 제작하였다. 이어서, 도 1에 나타낸 바와 같이, 원반의 양면에 미리 코로나 처리하여 습윤지수를 높인 후, 오프셋그라비어코트에 의해 도공제A를 고형분으로 0.3g/m2 양면도공하여 건조하였다. 이 원반필름을 한쌍의 저속닙롤(1)간에 삽입통과한 후, 중간에 공기를 압입하면서 히터(2), 및 히터(3)로 가열함과 함께, 연신종료점에 에어링(4)으로부터 에어를 분사함으로써, 튜블러법에 의한 MD, 및 TD동시이축 연신필름(5)을 얻었다. 연신배율은, MD가 3.0배, TD가 3.2배였다. 이어서, 이 연신필름(5)을 열롤식, 및 텐터식 열처리설비에 각각 투입하고, 210℃에서 열처리를 실시하여 양단을 트리밍 후 2매로 벌림으로써 편면에 수지도공된 ONy필름을 얻었다. 또한, ONy필름의 두께는 25μm, 수지도공량은 0.03g/m2였다.
Nylon 6 pellets (relative viscosity of 3.48) were melted and kneaded in an extruder at 255 DEG C, and then the melt was extruded from the dies as a cylindrical film and subsequently quenched with water to prepare an original film. Next, as shown in Fig. 1, both sides of the master were corona-treated in advance to increase the wetting index, and then coated with 0.3 g / m 2 of both sides of the coating agent A in an offset gravure coat. After the original film is inserted between the pair of low speed nip rolls 1, air is heated by the heater 2 and the heater 3 while pressurizing air in the middle, and air is jetted from the air ring 4 to the drawing end point Thereby obtaining the MD and TD simultaneous stretched film 5 by the tubular method. The draw ratio was 3.0 times for MD and 3.2 times for TD. Subsequently, the stretched film 5 was put in a heat roll type and a tenter type heat treatment equipment, respectively, and subjected to heat treatment at 210 占 폚. Both ends were trimmed and then spread in two pieces to obtain ONy films coated with resin on one side. The thickness of the film ONy was 25μm, can map gongryang was 0.03g / m 2.

(ONy필름의 일축인장파단강도, 50% 모듈러스값 평가방법)(Uniaxial tensile breaking strength of ONy film, 50% modulus value evaluation method)

ONy필름의 일축인장파단강도, 50% 모듈러스값의 평가방법은, Orientec Co., Ltd.제 -Tensilon(RTC-1210-A)을 사용하고, 시료폭 15mm, 척간 100mm, 인장속도 200mm/min로 실시하였다. ONy필름(18)은, 23℃×50%의 환경하에서 2시간 조습 후, 0℃(MD)방향/45°방향/90°(TD)방향/135°방향의 4방향에 대하여 각각 측정을 행하였다. 얻어진 응력-변형곡선에 기초하여, 각 방향에서의 파단강도, 및 50% 모듈러스값을 구하였다.
The uniaxial tensile fracture strength and the 50% modulus value of the ONy film were evaluated by a method using Orientec Co., Ltd.-Tensilon (RTC-1210-A) Respectively. The ONy film 18 is subjected to the measurement for four directions in the direction of 0 占 폚 (MD) / 45 占 direction / 90 占 (TD) / 135 占 after 2 hours of humidity conditioning in an environment of 23 占 폚 占 50% Respectively. Based on the obtained stress-strain curves, the breaking strength in each direction and the 50% modulus value were determined.

(ONy필름의 열수축응력 평가방법) (Method for evaluating heat shrinkage stress of ONy film)

ONy필름의 열수축응력은, SII NanoTechnology Inc.제-EXSTAR-TMA/SS6100을 사용하고, 시료폭 3mm, 척간 15mm, 30~245℃(승온속도: 10℃/min.)의 온도프로그램으로 측정하였다. ONy필름은, 23℃×50%의 환경하에서 2시간 조습 후, 170~210℃에서 보여지는 최대열수축응력값을 MD, 및 TD 각각에 대하여 측정하였다.
The thermal shrinkage stress of the ONy film was measured by a temperature program of SII NanoTechnology Inc.-EXSTAR-TMA / SS6100 at a sample width of 3 mm, a chuck interval of 15 mm, and a temperature of 30 to 245 ° C (temperature raising rate: 10 ° C / min.). The ONy film was measured for MD and TD for the maximum heat shrinkage stress values shown at 170 to 210 DEG C after 2 hours of humidification in an environment of 23 DEG C x 50%.

(냉간성형성, 디라미네이션의 발생상황 평가방법)(Cold formability, a method for evaluating occurrence situation of delamination)

ONy필름을 포함한 라미네이트 포재의 냉간성형성을 평가하였다. 구체적으로는, 우선 얻어진 ONy필름을 기재층으로 하고, 수지도공면을 알루미늄측으로 하여 알루미늄박(AA8079-O재, 두께 32μm), 및 미연신 폴리프로필렌필름〔PYLEN 필름 CT-P1128(상품명), Toyobo Co., Ltd.제, 두께 30μm〕을 각각 드라이라미네이트(드라이도포량 4.0g/m2)함으로써 라미네이트 포재를 얻었다. 또한, 드라이라미네이트용 접착제로는, Toyo-Morton, Ltd. TM-K55/Toyo-Morton, Ltd. CAT-10(배합비 100/8)을 이용하였다. 또한, 드라이라미네이트 후의 라미네이트 포재는, 60℃에서 72시간 에칭을 행하였다. 이와 같이 하여 얻어진 라미네이트 포재는, 23℃×50%의 환경하에서 2시간 조습 후, 압축용 금형(38mm×38mm)을 이용하여, 미연신 폴리프로필렌필름측으로부터 최대하중 10MPa로 냉간(상온)에서 성형하고, 핀홀이나 크랙 등의 결함이 발생하지 않는 최고성형깊이를 0.5mm 피치로 평가하였다. 상기 방법으로 냉간성형한 라미네이트 포재에 대하여, 오목부분 근방의 잉여부분을 200℃×0.2MPa×2sec.의 조건으로 히트씰하고, 씰 후의 나일론/알루미늄박간에서의 디라미네이션의 발생의 유무를 육안으로 확인하였다. 또한 시료를 고온고습하 조건 50℃×90%RH로 1주간 방치하고, 다시 디라미네이션이 발생하는지 여부를 육안으로 확인하였다.
The cold formability of the laminate materials including ONy films was evaluated. Specifically, an aluminum foil (AA8079-O material, thickness 32 μm) and an unstretched polypropylene film (PYLEN film CT-P1128 (trade name), Toyobo (trade name) Co., Ltd., thickness 30 占 퐉) were each subjected to dry lamination (dry coating amount 4.0 g / m 2 ) to obtain a laminate carrier. As the adhesive for dry lamination, Toyo-Morton, Ltd. TM-K55 / Toyo-Morton, Ltd. CAT-10 (mixing ratio 100/8) was used. The laminate material after the dry lamination was etched at 60 DEG C for 72 hours. The laminated sheet thus obtained was subjected to humidity conditioning in an environment of 23 ° C × 50% for 2 hours, molding (38 mm × 38 mm) from the unstretched polypropylene film side at a maximum load of 10 MPa in a cold , And the maximum molding depth at which defects such as pinholes and cracks did not occur was evaluated at a pitch of 0.5 mm. With respect to the cold-formed laminate blank according to the above method, the excess portion in the vicinity of the concave portion was heat-sealed under the condition of 200 DEG C x 0.2 MPa x 2 sec., And the presence or absence of delamination in the nylon / Respectively. The sample was allowed to stand under high-temperature and high-humidity conditions of 50 ° C × 90% RH for 1 week, and visually confirmed whether or not delamination occurred again.

실시예 2Example 2

실시예 1에 있어서, 연신필름을 열롤, 및 텐터식 열처리설비에 넣고, 195℃에서 열처리한 것 이외는 실시예 1과 동일하게 행하였다.
The procedure of Example 1 was repeated except that the stretched film was placed in hot roll and tenter type heat treatment equipment and heat-treated at 195 ° C.

실시예 3Example 3

도공제B: CHIRIKA. Co., Ltd.제의 수용성 메타크릴산메틸 공중합체 ”Rikabond” SA-R615A(Tg 67℃)에 Nagase Kasei Kogyo K.K.제의 수용성 폴리에폭시 화합물 “DENACOL” EX-521(폴리글리세롤폴리글리시딜에테르) 및 Nippon Shokubai Co., Ltd.제의 진구실리카미립자 “Seahostar” KE-P30(평균입자경 0.3μm)을 75/25/0.5의 배합비로 첨가하고, 물로 희석하였다.Pottery B: CHIRIKA. A water-soluble polyepoxy compound "DENACOL" EX-521 (manufactured by Nagase Kasei Kogyo KK) was added to a water-soluble methyl methacrylate copolymer "Rikabond" SA-R615A Ltd.) and "Seahostar" KE-P30 (average particle diameter 0.3 μm) manufactured by Nippon Shokubai Co., Ltd. were added at a blending ratio of 75/25 / 0.5 and diluted with water.

실시예 1에 있어서, 도공제를 B로 한 것 이외는 실시예 1과 동일하게 행하였다.
The procedure of Example 1 was repeated except that the coating material was changed to B as the coating material.

실시예 4Example 4

실시예 1에 있어서, ONy와 알루미늄박간에 인쇄층을 마련한 것 이외는 실시예 1과 동일하게 행하였다.
Example 1 was carried out in the same manner as in Example 1 except that a printing layer was provided between ONy and an aluminum foil.

실시예 5Example 5

실시예 1에 있어서, 연신필름을 열롤, 및 텐터식 열처리설비에 넣고, 195℃에서 열처리하고, 또한 ONy와 알루미늄박간에 인쇄층을 마련한 것 이외는 실시예 1과 동일하게 행하였다.
Example 1 was carried out in the same manner as in Example 1 except that the stretched film was placed in a hot roll and a tenter type heat treatment facility and heat-treated at 195 ° C and a printed layer was provided between ONy and an aluminum foil.

비교예 1Comparative Example 1

실시예 1에 있어서, 원반에 코로나 처리 및 수지도공을 하지 않은 것 이외는 실시예 1과 동일하게 행하였다.
The procedure of Example 1 was repeated except that the corona treatment and the resin coating were not performed on the master.

비교예 2Comparative Example 2

실시예 1에 있어서, 연신필름을 열롤, 및 텐터식 열처리설비에 넣고, 220℃에서 열처리한 것 이외는 실시예 1과 동일하게 행하였다.
The procedure of Example 1 was repeated except that the stretched film was placed in a hot roll and tenter type heat treatment equipment and heat-treated at 220 ° C.

비교예 3Comparative Example 3

실시예 1에 있어서, 연신필름을 열롤, 및 텐터식 열처리설비에 넣고, 150℃에서 열처리한 것 이외는 실시예 1과 동일하게 행하였다.
The procedure of Example 1 was repeated except that the stretched film was placed in a hot roll and a tenter type heat treatment facility and heat-treated at 150 ° C.

비교예 4Comparative Example 4

실시예 1에 있어서, ONy필름으로서 Toyobo Co., Ltd.제 이축연신 나일론필름(Harden필름 NAP4142, 두께 25μm)을 사용한 것 이외는 실시예 1과 동일하게 행하였다.
Example 1 was carried out in the same manner as in Example 1 except that a biaxially stretched nylon film (Harden film NAP4142, thickness: 25 m) made by Toyobo Co., Ltd. was used as the ONy film.

비교예 5Comparative Example 5

실시예 1에 있어서, 원반에 코로나 처리 및 수지도공을 하지 않고, 또한 ONy와 알루미늄박간에 인쇄층을 마련한 것 이외는 실시예 1과 동일하게 행하였다.
Example 1 was carried out in the same manner as in Example 1, except that a disc was not subjected to corona treatment or resin coating, and a printed layer was provided between ONy and an aluminum foil.

표 1에 나타낸 바와 같이, 폴리우레탄 수지 내지는 아크릴계 수지를 편면에 도공된 ONy필름에서 170~210℃에 있어서의 열수축응력의 최대값을 MD, TD 모두 5.0MPa 이하로, 또한 일축인장시험에 있어서의 4방향 전부의 파단강도를 240MPa 이상, 50% 모듈러스값을 120MPa 이상으로 조정한 실시예 1, 실시예 2 및 실시예 3에 있어서는, 우수한 성형성의 확보와 디라미네이션의 억제를 양립할 수 있었다. 또한, 파단강도가 280MPa 이상, 50% 모듈러스값이 150MPa 이상인 실시예 2에 있어서는, 디라미네이션의 발생을 억제한 채로, 성형성을 더욱 향상시킬 수 있었다. 나아가 ONy필름과 알루미늄박간의 인쇄층의 유무에 관계없이, 모두 고온고습도하 조건에서 디라미네이션하는 일이 없었다. 한편, 수지도공을 하지 않은 비교예 1, 및 비교예 5는, 성형성은 양호했으나, 성형시 및/또는 고온고습도 조건에서 디라미네이션이 발생하였다. 수지도공된 비교예 2, 4는 성형시의 디라미네이션도 고온고습도하에서의 디라미네이션도 없었으나, 실시예 1~3과 비교했을 때 성형성이 부족했다. 또한 수지도공된 비교예 3은 성형성은 우수했으나, 170~210℃에 있어서의 열수축응력의 최대값이 MD, TD 모두, 혹은 MD, TD 모두 5.0MPa를 초과하고 있으며, 어떤 조건에 있어서도 디라미네이션의 발생이 보였다. 또한 4방향 중 어느 하나의 파단강도가 240MPa 이하, 50% 모듈러스값이 120MPa 이하인 경우는 성형성의 저하가 보였다. 따라서, 비교예 1~비교예 5는 모두 우수한 성형성의 확보와 디라미네이션의 억제를 양립할 수 없었다.
As shown in Table 1, the maximum value of the heat shrinkage stress at 170 to 210 DEG C in the ONy film coated on one side of the polyurethane resin or the acrylic resin was 5.0 MPa or less in both of MD and TD, In Example 1, Example 2 and Example 3 in which the breaking strength of all the four directions was adjusted to 240 MPa or more and the 50% modulus value was adjusted to 120 MPa or more, it was possible to secure both excellent moldability and suppression of delamination. Further, in Example 2 in which the breaking strength was 280 MPa or more and the 50% modulus value was 150 MPa or more, the moldability was further improved while suppressing the occurrence of delamination. Furthermore, regardless of the presence or absence of a print layer between the ONy film and the aluminum foil, neither delamination was performed under conditions of high temperature and high humidity. On the other hand, in Comparative Example 1 and Comparative Example 5 in which resin coating was not performed, moldability was good, but delamination occurred at the time of molding and / or under high temperature and high humidity conditions. In Comparative Examples 2 and 4 coated with resin, there was neither delamination at the time of molding nor delamination at high temperature and high humidity, but the moldability was insufficient as compared with Examples 1 to 3. In Comparative Example 3 coated with resin, the moldability was excellent, but the maximum value of the thermal shrinkage stress at 170 to 210 ° C exceeded 5.0 MPa in both of MD and TD, or both MD and TD. The occurrence was seen. When the breaking strength of any one of the four directions was 240 MPa or less and the 50% modulus value was 120 MPa or less, the moldability was decreased. Therefore, in Comparative Examples 1 to 5, both of securing excellent moldability and inhibiting delamination could not be achieved at the same time.

Figure pct00001

Figure pct00001

산업상의 이용가능성Industrial availability

본 발명은 냉간성형용 포재, 특히 리튬이온 이차전지 등의 전지케이스용 포재의 주요기재로서 호적하게 이용된다.
INDUSTRIAL APPLICABILITY The present invention is suitably used as a main substrate for a battery case, such as a cold forming post, especially a lithium ion secondary battery.

부호의 설명Explanation of symbols

1 도공장치1 coating device

2 튜블러연신장치의 닙롤2 Nipple of tubular stretching device

3 튜블러연신장치의 예열히터3 Preheating heater of tubular stretching device

4 튜블러연신장치의 주열히터4 Heater heater of tubular stretching device

5 튜블러연신장치의 냉각에어링5 Cooling air ring of tubular stretcher

6 튜블러연신시의 필름6 Film for tubular stretching

Claims (9)

폴리우레탄 수지, 아크릴계 공중합체 수지, 폴리에스테르 수지, 에폭시계 수지, 폴리이미드계 수지로부터 선택되는 적어도 1종의 수지 및 그 가교제가 적어도 편면에 도포된 필름으로서, 170~210℃에 있어서의 열수축응력의 최대값이 MD, TD 모두 5.0MPa 이하이고, 또한 일축인장시험(시료폭 15mm, 척간거리 100mm, 인장속도 200mm/min.)에 있어서의 4방향(0°(MD), 45°, 90°(TD), 135°)의 모든 파단강도가 240MPa 이상인 것을 특징으로 하는 이축연신 나일론필름.At least one resin selected from a polyurethane resin, an acrylic copolymer resin, a polyester resin, an epoxy resin and a polyimide resin, and a crosslinking agent thereof are applied on at least one side of the film, and the heat shrinkage stress (MD, 45, 90 °) in the uniaxial tensile test (sample width 15 mm, chuck distance 100 mm, tensile speed 200 mm / min) (TD), 135 DEG) of not less than 240 MPa. 제1항에 있어서,
미연신의, 또는 연신 후의, 열처리되지 않은 나일론필름에, 폴리우레탄 수지, 아크릴계 공중합체 수지, 폴리에스테르 수지, 에폭시계 수지, 폴리이미드계 수지로부터 선택되는 적어도 1종의 수지 및 가교제를 도공 후, 열처리한 것을 특징으로 하는 이축연신 나일론필름.The method according to claim 1,
At least one resin selected from a polyurethane resin, an acrylic copolymer resin, a polyester resin, an epoxy resin, and a polyimide resin, and a crosslinking agent are coated on a non-heat-treated nylon film that has not been subjected to heat treatment, And a biaxially stretched nylon film. 제1항 또는 제2항에 있어서,
상기 수지 및 그 가교제가 하기의 A, B로서 고형분중량비 A/B=98~30/2~70으로 이루어진 조성물을 주성분으로 하는 수성 도공제가 도공되어 있고, 그 도공량이 필름연신 후에 있어서 고형분으로 0.005~0.200g/m2인 이축연신 나일론필름.
A: 3중 결합의 2개의 인접탄소원자에 모두 수산기 및 메틸기가 치환된 아세틸렌글리콜 및/또는 그 에틸렌옥사이드 부가물인 비이온계 계면활성제를 함유한 수계 폴리우레탄 수지.
B: 수용성 폴리에폭시 화합물.3. The method according to claim 1 or 2,
Wherein the resin and the cross-linking agent thereof are A, B as solid components weight ratio A / B = 98 to 30/2 to 70, and the coating amount thereof is in the range of 0.005 - 0.200 g / m 2 biaxially stretched nylon film.
A: An aqueous polyurethane resin containing a nonionic surfactant which is an acetylene glycol and / or an ethylene oxide adduct thereof substituted with a hydroxyl group and a methyl group at two adjacent carbon atoms of a triple bond.
B: Water-soluble polyepoxy compound. 제3항에 있어서,
제3항에 기재된 도공제에 평균입자경이 0.001~1.0μm인 미립자C가 고형분중량비 A/B/C=98~30/2~70/0.1~10이 되도록 포함되어 있는 것을 특징으로 하는 이축연신 나일론필름.The method of claim 3,
The coating material according to claim 3, wherein the fine particles C having an average particle size of 0.001 to 1.0 占 퐉 are contained so that the solid content ratio A / B / C is 98 to 30/2 to 70 / 0.1 to 10. film. 제1항 내지 제4항 중 어느 한 항에 있어서,
일축인장시험(시료폭 15mm, 척간거리 100mm, 인장속도 200mm/min.)에 있어서의 4방향(0°(MD), 45°, 90°(TD), 135°)의 모든 50% 모듈러스값이 120MPa 이상인 것을 특징으로 하는 이축연신 나일론필름.5. The method according to any one of claims 1 to 4,
All the 50% modulus values in the four directions (0 ° (MD), 45 °, 90 ° (TD), 135 °) in the uniaxial tensile test (sample width 15 mm, chuck distance 100 mm, tensile speed 200 mm / A biaxially stretched nylon film having a tensile strength of 120 MPa or more. 적어도 기재층, 배리어층, 실란트층에 의해 형성된 냉간성형용 전지케이스 포재로서, 상기 기재층으로서, 제1항 내지 제5항 중 어느 한 항에 기재된 이축연신 나일론필름의 도공면을 배리어층측에 배치한 것을 특징으로 하는 냉간성형용 전지케이스 포재.The battery case for cold forming, which is formed by at least a base layer, a barrier layer and a sealant layer, wherein the coating layer of the biaxially stretched nylon film according to any one of claims 1 to 5 is placed on the barrier layer side Wherein the battery case is provided with a battery case. 적어도 기재층, 배리어층, 실란트층에 의해 형성된 냉간성형용 전지케이스 포재로서, 상기 기재층으로서, 제1항 내지 제5항 중 어느 한 항에 기재된 이축연신 나일론필름의 도공면에 인쇄하고, 그 인쇄면을 배리어층측에 배치한 것을 특징으로 하는 냉간성형용 전지케이스 포재.A battery case for cold forming, which is formed by at least a base layer, a barrier layer and a sealant layer, is printed on the coated side of the biaxially stretched nylon film described in any one of claims 1 to 5 as the base layer, And the printed surface is disposed on the side of the barrier layer. 제6항 또는 제7항에 기재된 냉간성형용 전지케이스 포재를 사용하고, 실란트층이 내면이 되도록 돌출성형, 또는 딥드로잉성형하여 오목부분을 형성한 전지케이스.A battery case in which a concave portion is formed by using the cold forging battery case according to claim 6 or 7 and forming a sealant layer on the inner surface by protrusion molding or deep drawing molding. 제8항에 기재된 전지케이스의 오목부분에 전지 본체를 수납하고, 밀봉되어 있는 것을 특징으로 하는 전지.A battery characterized in that a battery body is housed in a concave portion of the battery case according to claim 8 and is sealed.
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