1357677 九、發明說明： 【發明所屬之技術領域】 本發明係關於使用於高分子鋰離子二次電池之外裝外殼 之包裝材料及使用該包裝材料所成形之電池外殼。 【先前技術】 近年來隨著個人電腦等之辦公自動化（0A)機器、手提 式電話機等電子機器之小型化、輕量化，當然也對於其驅 動源的電池要求高性能化、小型化、輕量化，使得目前高 分子鋰離子二次電池演變成爲其主流且已實施各種不同的 改良。 用作爲該電池外殼之包裝材料，係一種以由耐熱性樹脂 薄膜所構成之外層、鋁箔、及由熱塑性樹脂薄膜所構成之 內層爲其基本結構者，且必要時在外層與鋁箔芯層間、鋁 箔芯層與內層間設置由樹脂薄膜所構成之中間層。 上述包裝材料之結構，係已記載於如下所述之專利文獻 〇 專利文獻1 :曰本國專利特開昭第60 - 22 1,952號公報 在專利文獻1所揭示之扁平薄型非水電解液鋰電池，係 從外側將扁平的發電元伴以由耐熱性薄膜、鋁箔、及多層 結構的內面黏合層所構成之外被包材料加以外裝所構成之 電池，且該內面黏合層係由在鋁箔側熱熔型黏合性樹脂與 最內面熱熔型黏合性樹脂之間，配置將兩面以使用無機氣 體的非平衡電漿（低溫電漿）加以處理的改良熱熔型黏合 性之聚醋薄膜所形成之三層結構所構成，且該內面黏合層 1357677 係以熱熔型黏合加以積層。其中，配置於內面黏合層之間 的耐熱性樹脂薄膜係使用雙軸向延伸聚對苯二甲酸乙二酯 薄膜。 根據專利文獻1，則其在進行外被包材料與集電體之熱 熔型黏合時，及在進行外被包材料彼此間之熱熔型黏合時 ，即使在熱熔型黏合性樹脂層產生針孔，由於耐熱性樹脂 薄膜的存在，使得集電體與鋁箔之電氣接觸受到阻礙，藉 此即可防止外被包材料與集電體之短路。而且·，外被包材 料與集電體、外被包材料之層彼此具有強烈的黏合力，因 此不會發生有機電解液浸透所引起之剝離。 專利文獻2 :日本國專利特開第2000 - 223,088號公報 在專利文獻2中，其係揭示一種具有優越的耐蝕性、容 易成形且具有優越的形狀穩定性之電池容器用蓋與電池用 容器及包裝體。 專利文獻2之電.池容器用蓋，係由將（a)厚度爲15微 米以上之外裝樹脂薄膜' .(b)厚度爲50 ~ 3 00微米之鋁 層、（c)由聚醯胺系樹脂與EVOH (乙烯-乙烯醇共聚合物 )所構成至少2層結構之耐蝕層、及（d)熱密封層依序積 層之積層體所構成。 專利文獻2之電池容器，係將（a)厚度爲15微米以上 之外裝樹脂薄膜、（b)厚度爲50〜300微米之鋁層、（c )聚醯胺系樹脂與EVOH (乙烯-乙烯醇共聚合物）所構成 至少2層結構之耐蝕層 '及（d)熱密封層依序積層之積層. 體加以成形者。 -6- 1357677 專利文獻2之電池容器用蓋或電池容器，其中該耐独層 係由聚醯胺系樹脂/EVOH/聚醯胺系樹脂之3層結構所構成 者。 專利文獻2之電池容器用蓋或電池容器，其中該耐触層 係由聚醯胺系樹脂/EVOH/聚醯胺系樹脂/聚醯胺系樹脂 /EVOH/聚醯胺系樹脂之6層結構所構成者。 專利文獻2之電池容器用蓋或電池容器，其中該外裝樹 脂薄膜係由聚醯胺系樹脂所構成者。 專利文獻2之包裝體係將上述任一項所記載之電池用容 器’與上述任一項所記載之電池容器用蓋加以環形封合者 〇 專利文獻3:日本國專利特開第2000 - 357,494號公報 專利文獻3之包裝材料係一種由至少最外層/氣密層/最 內層所構成之積層體’且在該氣密層之最內層側表面形成 由0_5 ~ 30微米之環氧系、苯酚系、三聚氰胺系·、聚醯亞 胺系、不飽和聚酯系、聚胺甲酸'醋、醇酸系、不飽和羧酸 接枝聚烯烴系、聚對苯二甲酸乙二酯系 '或聚對苯二甲酸 丁二酯系等之共聚合聚酯系；含離子鍵之聚合物；乙烯-醋 酸乙烯共聚合物；乙烯與丙烯酸及甲基丙烯酸衍生物之共 聚合物；聚醚系或至少含有3 0%以上之該等之改質物中之 一的樹脂所構成之保護膜。 根據專利文獻3之包裝材料，其係用作爲收納高分子電 池等的外殼之片，具有對於水蒸氣及其他氣體之氣密性， 且具有耐刺穿性等之機械強度；而且在高溫下也可使用， 1357677 對於電解液也穩定。 專利文獻4:日本國專利特開第2000 - 357，494號公報 在專利文獻4所揭之_次電池用外裝材料，彳系在由金 屬箔本體、與至少在該金屬箔本體之單面以鉻酸鹽胃理所 形成之轉化鉻酸鹽膜所構成之金屬箔的該轉化銘^鹽膜側 設置由酸改質聚烯烴薄膜所構成之熱封合層》 上述金屬箔本體係在表面施加防腐蝕鋁處理之箱。另 外，在專利文獻4所揭示之二次電池用外裝材料，其酸改 質聚烯烴爲順丁烯二酸酐改質聚烯烴。 根據專利文獻4所揭示之二次電池用外裝材料，則其二 次電池之熱封合部（二次電池之端部）係不容易剝離者 專利文獻5:日本國專利特開第2001 - 93，482號公報 在專利文獻5所揭示之高分子電池用包裝材料，係由最 外層/氣密層/最內層 '或最外層/氣密層/中間層/最內層所 構成之積層體，且該最外層係由具有耐熱性、耐針孔性、 成形性、絕緣性之基材所構成，該氣密層係由具有水蒸氣 氣密性、成形性' 耐酸性之氣密性基材所構成，該中間層 係由具有絕緣性、成形性之中間基材所構成，該最內層係 由具有熱熔型黏合性、耐熱性、耐寒性、電解液適性、絕 緣性之熱氣密性基材所構成。 在專利文獻5所揭示之高分子電池用包裝材料之積層體 之層間，則有黏合劑層夾在其中。 用以構成專利文獻5所揭示高分子電池用包裝材料最外 層之基材，係由延伸聚酯系樹脂、延伸聚醯胺系樹脂中任 1357677 一者所構成。 根據專利文獻5所記載之高分子電池用包裝材料，則其 係作爲收納高分子電池的外殻之包裝材料，具有對於水蒸 氣及其他氣體之氣密性，且具有耐刺穿性等以及機械強度 ，而且在高溫下也可使用，對於電解液也是穩定。 在上述先前之包裝材料中，外層與鋁箔之間及鋁箔與內 層之間，一般採取使用乾積層用黏合劑加以黏合，或經由 黏合性樹脂加以熱積層所黏合之方法。乾積層黏合劑雖然 —般使用胺甲酸酯系黏合劑，但是若將鋁箔與內層使用胺 甲酸酯系黏合劑加以黏合時，則有可能往往因高分子電池 之電解液而造成鋁箔與內層的層間黏合強度之時效性退化 ，甚至於有時會造成因層間剝離，使得電解液洩漏致使電 池失去電池應有之機能，或損傷到收容電池的電子機器等 之問題。 有鑒於此，欲能解決該等問題，例如已在下述專利文獻 中記載如下所述之技術。 專利文獻6:日本國專利特開第2001 - 6,63 1號公報 在專利文獻6所揭示之電池外裝用積層體，係在將鋁箔 與內層依序積層所構成之電池外裝用積層體中，上述鋁箔 之至少該內層側之面係由經施加易黏合處理之處理面所構 成，且該處理面與該內層係藉由黏合劑所積層。 電池外裝用積層體之該經處理面，係將上述鋁箔面加以 脫脂處理後，以由磷酸金屬鹽，或由磷酸非金屬鹽構成之 處理液加以處理。1357677 IX. Description of the Invention: [Technical Field] The present invention relates to a packaging material used for an outer casing of a polymer lithium ion secondary battery and a battery casing formed using the packaging material. [Prior Art] In recent years, with the miniaturization and weight reduction of electronic devices such as office automation (0A) devices and portable telephones such as personal computers, it is of course required for high performance, miniaturization, and weight reduction of batteries for their drive sources. Therefore, the current polymer lithium ion secondary battery has evolved into its mainstream and various improvements have been implemented. The packaging material used as the outer casing of the battery is a basic structure composed of a heat resistant resin film, an aluminum foil, and an inner layer composed of a thermoplastic resin film, and if necessary, between the outer layer and the aluminum foil core layer. An intermediate layer made of a resin film is disposed between the aluminum foil core layer and the inner layer. The structure of the above-mentioned packaging material is described in the following patent document: Patent Document 1: Japanese Patent Laid-Open Publication No. SHO No. 60-22 No. 1,952, the flat thin non-aqueous electrolyte lithium battery disclosed in Patent Document 1, The flat power generating element is provided with a battery composed of a heat-resistant film, an aluminum foil, and an inner surface bonding layer of a multilayer structure, and is surrounded by a wrapping material, and the inner surface bonding layer is made of aluminum foil. An improved hot-melt adhesive polyester film which is treated with a non-equilibrium plasma (low temperature plasma) using inorganic gas between the side hot-melt adhesive resin and the innermost hot-melt adhesive resin The formed three-layer structure is formed, and the inner surface adhesive layer 1357677 is laminated by hot-melt bonding. Among them, the heat resistant resin film disposed between the inner surface adhesive layers is a biaxially oriented polyethylene terephthalate film. According to Patent Document 1, when the outer covering material and the current collector are thermally melt-bonded, and when the outer covering material is thermally melt-bonded, even in the hot-melt adhesive resin layer The pinhole has an electrical contact between the current collector and the aluminum foil due to the presence of the heat resistant resin film, thereby preventing short-circuiting of the outer covering material and the current collector. Further, the outer covering material and the layers of the current collector and the outer covering material have a strong adhesive force with each other, so that peeling due to the penetration of the organic electrolyte does not occur. Patent Document 2: Japanese Laid-Open Patent Publication No. 2000-223,088, which discloses a battery container cover and a battery container which have excellent corrosion resistance, are easy to form, and have excellent shape stability. Package. The lid for the battery container of Patent Document 2 is made of (a) a resin film having a thickness of 15 μm or more, (b) an aluminum layer having a thickness of 50 to 300 μm, and (c) a polyamine. The resin is composed of a corrosion-resistant layer composed of at least two layers of EVOH (ethylene-vinyl alcohol copolymer) and a layered body of (d) a heat seal layer. The battery container of Patent Document 2 is a (a) resin film having a thickness of 15 μm or more, (b) an aluminum layer having a thickness of 50 to 300 μm, (c) a polyamidamide resin, and EVOH (ethylene-ethylene). The alcohol copolymer) comprises at least two layers of the corrosion resistant layer 'and (d) the heat seal layer is sequentially laminated. The body is formed. -6- 1357677 A battery container lid or a battery container of Patent Document 2, wherein the resistant layer is composed of a three-layer structure of a polyamide resin/EVOH/polyamide resin. A battery container lid or a battery container of Patent Document 2, wherein the contact resistant layer is a six-layer structure of a polyamide resin/EVOH/polyamide resin/polyamine resin/EVOH/polyamine resin. The constituents. A battery container lid or a battery container of Patent Document 2, wherein the exterior resin film is made of a polyamide resin. In the packaging system of the patent document 2, the battery container of any one of the above-mentioned ones is sealed with the cover for the battery container of any one of the above-mentioned ones. Patent Document 3: Japanese Patent Laid-Open No. 2000-357,494 The packaging material of the patent document 3 is a laminate body composed of at least the outermost layer/inner inner layer/the innermost layer, and an epoxy system of 0_5 to 30 μm is formed on the innermost side surface of the inner liner. Phenol type, melamine type, polyimide type, unsaturated polyester type, polyamic acid 'vinegar, alkyd type, unsaturated carboxylic acid grafted polyolefin type, polyethylene terephthalate type' or a copolymerized polyester based on polybutylene terephthalate or the like; a polymer containing an ionic bond; an ethylene-vinyl acetate copolymer; a copolymer of ethylene and an acrylic acid and a methacrylic acid derivative; A protective film comprising at least 30% or more of the resins of the modifiers. According to the packaging material of Patent Document 3, it is used as a sheet for housing a polymer battery or the like, and has airtightness against water vapor and other gases, and has mechanical strength such as puncture resistance; Can be used, 1357677 is also stable to the electrolyte. Patent Document 4: Japanese Laid-Open Patent Publication No. 2000-357,494, the entire disclosure of which is incorporated herein by reference to the entire disclosure of the entire disclosure of The conversion of the metal foil composed of the chromate film formed by the chromate stomach is provided with a heat-sealing layer composed of an acid-modified polyolefin film on the side of the salt film. The above-mentioned metal foil system is on the surface. Apply a corrosion-resistant aluminum treatment box. Further, in the exterior material for secondary batteries disclosed in Patent Document 4, the acid-modified polyolefin is a maleic anhydride-modified polyolefin. According to the external material for a secondary battery disclosed in Patent Document 4, the heat sealing portion of the secondary battery (the end portion of the secondary battery) is not easily peeled off. Patent Document 5: Japanese Patent Laid-Open No. 2001-93 The packaging material for a polymer battery disclosed in Patent Document 5 is a laminate composed of an outermost layer/inner/internal layer/inner layer' or an outermost layer/inner/internal layer/intermediate layer/inner layer. And the outermost layer is composed of a substrate having heat resistance, pinhole resistance, moldability, and insulation, and the airtight layer is made of a gas-tight layer having water vapor tightness and formability. The intermediate layer is composed of an intermediate substrate having insulating properties and moldability, and the innermost layer is made of hot air-tight type having hot-melt adhesiveness, heat resistance, cold resistance, electrolyte compatibility, and insulation. Composition of a substrate. In the layer of the laminate of the packaging material for a polymer battery disclosed in Patent Document 5, an adhesive layer is sandwiched therebetween. The base material for constituting the outermost layer of the packaging material for a polymer battery disclosed in Patent Document 5 is composed of one of the extended polyester resin and the extended polyamine resin, 1357677. The packaging material for a polymer battery described in Patent Document 5 is a packaging material for housing a polymer battery, and has airtightness against water vapor and other gases, and has puncture resistance and the like. It is also strong in strength and can be used at high temperatures and is stable to electrolytes. In the above-mentioned prior packaging materials, a method of bonding between the outer layer and the aluminum foil and between the aluminum foil and the inner layer is carried out by using a dry laminate with a binder or by heat-bonding a layer of an adhesive resin. Although the dry laminate adhesive generally uses an urethane-based adhesive, if the aluminum foil and the inner layer are bonded with an urethane-based adhesive, the aluminum foil may be caused by the electrolyte of the polymer battery. The aging of the interlayer adhesion strength of the inner layer is degraded, and sometimes the interlayer peeling is caused, so that the leakage of the electrolyte causes the battery to lose its function of the battery, or damages the electronic device that houses the battery. In view of the above, in order to solve such problems, for example, the following techniques have been described in the following patent documents. In the battery exterior assembly disclosed in Patent Document 6, the laminate for battery exterior is formed by sequentially laminating an aluminum foil and an inner layer in a battery assembly. In the body, at least the inner layer side surface of the aluminum foil is composed of a treated surface to which an easy adhesion treatment is applied, and the treated surface and the inner layer are laminated by an adhesive. The treated surface of the laminate for battery exterior is subjected to degreasing treatment of the aluminum foil surface, and then treated with a treatment liquid composed of a metal phosphate or a non-metal phosphate.
1357677 1 I 另外’上述電池外裝用積層體之該經處理面，係將上述 鋁箔面加以脫脂處理後，以由磷酸金屬鹽或磷酸非金屬鹽 與水系合成樹脂之混合物所構成之處理液加以處理。 上述水系合成樹脂爲丙烯酸系樹脂、苯酚系樹脂、或胺 甲酸酯系樹脂。 電池外裝用積層體之該經處理面，係在將上述鋁箔面加 . 以脫脂處理後，施加陽極氧化處理。 上述黏合劑層係由混合矽烷偶合劑之層所構成。 φ 該矽烷偶合劑爲具有縮水甘油基之環氧系有機矽烷化合 物。 根據專利文獻6之電池外裝用積層體，其係一種具有優 越的對於水蒸氣或其他氣體之氣密性，特別是對於電解液 具有優越的抵抗性，且鋁箔與內層的層間黏合強度不致於 下降者。 專利文獻7:日本國專利特開第2001 - 176461號公報 在專利文獻7所揭示之高分子電池用包裝材料之製造方 φ 法，該包裝材料係一種由至少基材層、黏合層、化學轉化 處理層 '鋁、化學轉化處理層、黏合層、及最內層所構成 之用以形成壓花型外裝體之積層體，其製造方法係在鋁之 單面施加化學轉化處理，並將基材與該化學轉化處理面面 積層後，在該鋁之未處理面施加化學轉化處理，然後將熱 密封層積層在該處理面上所形成。 在專利文獻7所揭示之高分子電池用包裝材料之製造方 法中，該化學轉化處理爲磷酸鹽處理。 -10- 1357677 * » 另外，該積層係實施乾積層法所獲得。 根據專利文獻7所記載之高分子電池用包裝材料之製造 方法，用作爲壓花型高分子電池用包裝之材料，其可以穩 定的製造方法提供一種具有高分子電池之保護物性，同時 具有優越的成型加工性之材料。 如該等專利文獻6和7所記載，預先在鋁箔表面施加鉻 系化學轉化處理膜後，使用胺甲酸酯系黏合劑加以黏合內 層之方法，也是已眾所皆知者。 【發明內容】 發明所欲解決夕課顆 然而，如專利文獻6和7所記載，只要仍然使用胺甲酸 酯系黏合劑加以黏合時，還是不能達到根本性的解決，因 此期望能開發出一種不容易受到電解液影響之乾積層黏合 劑。 於是已開發出下述專利文獻8所記載之電池外裝用積層 體以取代該胺.甲酸酯系黏合劑。 專利文獻8 :日本國專利特開第2002 - 1 10,109號公報 在專利文獻8所揭示之電池外裝用積層體，係在依外層 、鋁箔、易黏合處理層、黏合層、烯烴系熱黏合性樹脂層 之順序所積層之電池外裝用積層體中，該黏合層係以由環 氧改質聚酯樹脂、與環氧樹脂及多官能性異氰酸酯化合物 所構成之反應固化型黏合劑所形成者。 並且，上述外層係由1至2層以上之厚度爲6 ~ 25微米 之層所構成，且至少其表層爲聚酯薄膜或聚醯胺薄膜。另 -11 - .1357677 » « 外，上述鋁箔係由厚度爲20 ~ 80微米之軟質鋁箔所構成 e 根據專利文獻8所記載之電池外裝用積層體，其係具有 即使受到電解液之影響，也不容易產生鋁箔與內層的層間 黏合強度之時效性下降之密封性。 如該專利文獻8所記載之發明，以環氧改質聚酯樹脂爲 主成份之黏合劑也已爲眾所皆知，但是反正仍在希望開發 出一種不容易受到電解液影響之穩定的黏合劑。 $ 本發明係有鑑於上述問題所達成者，其目的係提供一種 不容易產生電解液所引起鋁箔芯層與內層的時效性退化， 且透水率小，而且具有優越的成形性及穩定性之電池外殻 用包裝材料，及使用該包裝材料所成形之使用期限長且穩 定的電池外設。 解決課願之枝術方法 爲達成上述目的，本發明申請專利範圍第1項之發明， 其係一種至少包含由耐熱性樹脂薄膜所構成之外層、鋁箔 φ 芯層'及由熱塑性樹脂薄膜所構成之內層之電池外殻用包 裝材料，且其特徵爲：該鋁箔芯層與內層係由以聚烯烴多 元醇與多官能性異氰酸酯硬化劑爲必要成份之黏合劑組成 物所黏合。 上述黏合劑組成物相對於聚烯烴多元醇的多官能性異氰 酸酯硬化劑之使用量，相對於聚烯烴多元醇之羥基的異氰 酸基’以莫耳比（NCO/OH)計較佳爲1.0 ~ 10.0之範圍。 另外，較佳爲在上述黏合劑組成物添加熱塑性彈性體、 •12- 1357677 黏合賦予劑等。 此外，本發明之.電池外殼係使用上述電池外殼用包裝材 料，以深拉成型法或撐壓內形法（bulging)成形法所成形 發明之效罢 根據本發明之包裝材料，則在至少包含由耐熱性樹脂薄 膜所構成之外層、鋁箔芯層、及由熱塑性樹脂薄膜所構成 之內層光電池外殻用包裝材料中，由於上述鋁箔芯層與內 層係由以聚烯烴多元醇與多官能性異氰酸酯硬化劑爲必要 成份之黏合劑組成物所黏合，因此可顯現電池之電解液所 引起鋁箔芯層與內層樹脂之層間黏合強度的時效性退化少 ，且透水率小，而且可製成具有優越的成形性之穩定的電 池外殼用包裝材料之效果。 另外，使用該包裝材料所成形本發明之電池外殼，可顯 現能製成使用期限長且穩定者之效果。 【實施方式】 茲就本發明具體說明如下。 本發明之電池外殼用包裝材料，係至少包含由耐熱性樹 脂薄膜所構成之外層、鋁箔芯層、及由熱塑性樹脂薄膜所 構成之內層，且將該鋁箔芯層與內層使用以聚烯烴多元醇 與多官能性異氰酸酯硬化劑爲必要成份之黏合劑組成物加 以黏合。 (包裝材料之結構） 包裝材料雖然係以至少包含由耐熱性樹脂薄膜所構成之 1357677 外層、鋁箔芯層、及由熱塑性樹脂薄膜所構成之內層的基 本結構，但是必要時，也可採用附加第1中間樹脂層和/或 第2中間樹脂層等之結構以提高包裝材料之機械強度或特 性。具體而言，其係包括如下所述之結構： (1) 外層/鋁箔芯層/內層 (2) 外層/第1中間樹脂層/鋁箔芯層/內層 (3) 外層/鋁箔芯層/第2中間樹脂層/內層 (4) 外層/第1中間樹脂層/鋁箔芯層/第2中間樹脂層/內 層。 (外層之耐熱性樹脂薄膜） 使用於外層之樹脂薄膜係具有優越的耐熱性、成形性、 絕緣性者，一般是使用聚醯胺（耐綸）樹脂或聚酯樹脂之 延伸薄膜。該外.層薄膜之厚度爲9 ~ 50微米，若爲小於9 微米時，則在實施包裝材料的成形時，延伸薄膜之伸度將 不足夠，在鋁箔芯層會產生頸縮部，容易導致成形不良。 相對地，若爲超過50微米厚度時，則並非爲有助於格外地 提高成形性之效果，反而將導致體積能量密度下降，同時 會涉及到成本上升而已》厚度特佳爲15〜30微米。 使用於該外層之薄膜，從爲製得更尖銳的形狀之觀點來 考慮，則宜使用薄膜之4方向（0°、45°、90°、135·)之拉 伸強度爲150 N/mm2，較佳爲200 N/mm2者；且拉伸伸度 爲80 %以上，較佳爲100 %以上者。若拉伸強度爲小於 150 N/mm2 '或拉伸伸度爲小於80 %時，則其效果不佳。 另外，在本發明中，拉伸強度及拉伸伸度之値係指根據 -14- 1357677 下述方法所測得者。 拉伸強度及拉伸伸度：在薄膜之拉伸試驗（試料寬度爲 15毫米、標點間距離爲50毫米、拉伸速度爲1〇〇毫米/分 鐘）時，4方向之直至破斷爲止之値》 (鋁箔芯層） 鋁箔芯層係用以提供對於水蒸氣等之氣密性，其材質一 般使用純鋁系或鉛-鐵系合金之〇材（JIS中表示「軟質材 」之代表符號）。關於鋁箔芯層之厚度，欲能確保加工性 Φ 及確保防止氧氣或水份侵入於外殼內的氣密性，則需要10 ~ 100微米。 .若鋁箔芯層之厚度爲小於10微米時，則在成型時會引起 鋁箔破斷，或產生針孔，使得氧氣或.水份侵入之危險性增 加。相對地，若爲超過100微米時，則並非爲有助於格外 地提高成型時的破斷之改善效果或針孔產生之防止效果， 僅會造成包裝材料之總厚度變厚、重量增加、體積能量密 度下降而已，所以不佳。一般而言，係使用30 ~ 50微米 Φ 之厚度者。 另外，欲能提高與樹脂薄膜之黏合性，或提高耐蝕性， 較佳爲預先施加矽烷偶合劑或鈦偶合劑等之底塗處理，鉻 酸處理等之化學轉化處理。 (內層之熱塑性樹脂薄膜） 內層之樹脂薄膜係使用聚丙烯、聚乙烯、順丁烯二酸改 質聚丙烯、乙烯-丙烯酸酯共聚合物、或含離子鍵之聚合物 樹脂等之未延伸薄膜。該樹脂具有熱密封性，用以提供提 -15 -1357677 1 I In addition, the treated surface of the laminate for the battery exterior is subjected to degreasing treatment of the aluminum foil surface, and then treated with a treatment liquid composed of a mixture of a metal phosphate or a non-metal phosphate and a water-based synthetic resin. deal with. The water-based synthetic resin is an acrylic resin, a phenol resin, or an urethane resin. The treated surface of the laminate for battery exterior is applied to the surface of the aluminum foil. After degreasing treatment, anodizing treatment is applied. The above adhesive layer is composed of a layer of a mixed decane coupling agent. φ The decane coupling agent is an epoxy-based organodecane compound having a glycidyl group. The laminate for battery exterior according to Patent Document 6 is a gas-tight property superior to water vapor or other gas, particularly excellent in electrolyte resistance, and the interlayer adhesive strength between the aluminum foil and the inner layer is not high. For the decline. Patent Document 7: Japanese Laid-Open Patent Publication No. 2001-176461. The manufacturing method of the packaging material for a polymer battery disclosed in Patent Document 7 is a method in which at least a substrate layer, an adhesive layer, and a chemical conversion are used. a layered body formed of an aluminum layer, a chemical conversion treatment layer, an adhesive layer, and an innermost layer for forming an embossed exterior body, which is produced by applying a chemical conversion treatment on one side of aluminum and After the material and the chemical conversion treatment surface area layer, a chemical conversion treatment is applied to the untreated surface of the aluminum, and then a heat seal layer is formed on the treated surface. In the method for producing a packaging material for a polymer battery disclosed in Patent Document 7, the chemical conversion treatment is phosphate treatment. -10- 1357677 * » In addition, the laminate was obtained by the dry layer method. According to the method for producing a packaging material for a polymer battery according to Patent Document 7, a material for packaging a embossed polymer battery can provide a protective property of a polymer battery and a superior method. Molding process material. As described in the above-mentioned Patent Documents 6 and 7, a method of applying a chromium-based chemical conversion treatment film to the surface of an aluminum foil and then bonding the inner layer using an urethane-based adhesive is well known. SUMMARY OF THE INVENTION However, as described in Patent Documents 6 and 7, as long as the urethane-based adhesive is still used for bonding, a fundamental solution cannot be achieved, and therefore it is desired to develop a kind of A dry laminate adhesive that is not susceptible to electrolytes. Then, a laminate for battery exterior described in Patent Document 8 below has been developed in place of the amine-formate-based adhesive. The battery assembly for a battery exterior disclosed in Patent Document 8 is based on an outer layer, an aluminum foil, an easy-adhesion layer, an adhesive layer, and an olefin-based thermal adhesive property, as disclosed in Japanese Laid-Open Patent Publication No. 2002-110. In the battery exterior laminate for laminating the resin layer, the adhesive layer is formed of a reaction-curing adhesive composed of an epoxy-modified polyester resin, an epoxy resin, and a polyfunctional isocyanate compound. . Further, the outer layer is composed of one to two or more layers having a thickness of 6 to 25 μm, and at least the surface layer thereof is a polyester film or a polyamide film. In addition, the above-mentioned aluminum foil is composed of a soft aluminum foil having a thickness of 20 to 80 μm. According to Patent Document 8, a laminate for a battery exterior is provided, even if it is affected by an electrolyte solution. It is also less likely to cause a decrease in the aging resistance of the interlayer adhesive strength between the aluminum foil and the inner layer. As disclosed in Patent Document 8, an adhesive containing an epoxy-modified polyester resin as a main component is also known, but it is still desired to develop a stable adhesive which is not easily affected by the electrolyte. Agent. The present invention has been made in view of the above problems, and an object thereof is to provide a deterioration of time-dependent property of an aluminum foil core layer and an inner layer which are not easily generated by an electrolyte, and which has a small water permeability and excellent formability and stability. A packaging material for a battery case, and a battery peripheral that is formed using the packaging material and has a long service life and is stable. In order to achieve the above object, the invention of claim 1 is an invention comprising at least an outer layer composed of a heat-resistant resin film, an aluminum foil φ core layer, and a thermoplastic resin film. The inner layer of the battery casing packaging material is characterized in that the aluminum foil core layer and the inner layer are bonded by a binder composition containing a polyolefin polyol and a polyfunctional isocyanate hardener as essential components. The amount of the above-mentioned binder composition relative to the polyfunctional isocyanate hardener of the polyolefin polyol is preferably 1.0 to 0 with respect to the isocyanate group of the hydroxyl group of the polyolefin polyol in terms of molar ratio (NCO/OH). The scope of 10.0. Further, it is preferred to add a thermoplastic elastomer, a 12 to 1357677 adhesion imparting agent, or the like to the above-mentioned binder composition. In addition, the battery casing of the present invention is formed by using the above-mentioned packaging material for a battery casing, and is formed by a deep drawing method or a bulging forming method, and the packaging material according to the present invention includes at least The heat-resistant resin film is composed of an outer layer, an aluminum foil core layer, and a packaging material for an inner layer photovoltaic cell casing composed of a thermoplastic resin film, since the aluminum foil core layer and the inner layer are made of polyolefin polyol and polyfunctionality. The isocyanate hardener is bonded to the binder composition of the essential component, so that the time-dependent degradation of the interlayer adhesive strength between the aluminum foil core layer and the inner layer resin caused by the electrolyte of the battery is less, and the water permeability is small, and it can be made to have The superior formability of the stable packaging material for the battery casing. Further, the battery casing of the present invention formed by using the packaging material can exhibit the effect of being long-lasting and stable. [Embodiment] The present invention will be specifically described below. The packaging material for a battery case of the present invention comprises at least an outer layer composed of a heat resistant resin film, an aluminum foil core layer, and an inner layer composed of a thermoplastic resin film, and the aluminum foil core layer and the inner layer are made of polyolefin. The polyol and the polyfunctional isocyanate hardener are bonded to the binder composition of the essential component. (Structure of Packaging Material) The packaging material is a basic structure including at least an outer layer of 1357677 composed of a heat-resistant resin film, an aluminum foil core layer, and an inner layer composed of a thermoplastic resin film, but may be added if necessary. The structure of the first intermediate resin layer and/or the second intermediate resin layer or the like is to improve the mechanical strength or characteristics of the packaging material. Specifically, it includes the following structures: (1) outer layer/aluminum foil core layer/inner layer (2) outer layer/first intermediate resin layer/aluminum foil core layer/inner layer (3) outer layer/aluminum foil core layer/ Second intermediate resin layer/inner layer (4) Outer layer/first intermediate resin layer/aluminum foil core layer/second intermediate resin layer/inner layer. (Outer heat-resistant resin film) When the resin film used for the outer layer has excellent heat resistance, moldability, and insulation, a stretch film of a polyamide (polyester) resin or a polyester resin is generally used. The thickness of the outer layer film is 9 to 50 micrometers. If it is less than 9 micrometers, the elongation of the extension film will not be sufficient when the packaging material is formed, and a neck portion may be generated in the aluminum foil core layer, which may easily cause Poor formation. On the other hand, if it is more than 50 μm thick, it is not advantageous for the purpose of particularly improving the formability, but it will cause a decrease in the volumetric energy density, and at the same time, it involves a cost increase of 15 to 30 μm. The film used for the outer layer is preferably from the viewpoint of producing a sharper shape, and the tensile strength of the film in the four directions (0°, 45°, 90°, 135·) is 150 N/mm 2 . It is preferably 200 N/mm2; and the tensile elongation is 80% or more, preferably 100% or more. If the tensile strength is less than 150 N/mm2' or the tensile elongation is less than 80%, the effect is not good. Further, in the present invention, the tensile strength and the tensile elongation are measured according to the following method of -14-1357677. Tensile strength and tensile elongation: In the tensile test of the film (sample width 15 mm, distance between punctuation 50 mm, tensile speed 1 mm/min), 4 directions until breaking値 (Aluminum foil core layer) The aluminum foil core layer is used to provide airtightness to water vapor, etc. The material is generally made of pure aluminum or lead-iron alloy (the symbol of "soft material" in JIS) ). With regard to the thickness of the aluminum foil core layer, it is necessary to ensure the workability Φ and to ensure the airtightness of preventing oxygen or water from intruding into the outer casing, and it is required to be 10 to 100 μm. If the thickness of the aluminum foil core layer is less than 10 μm, the aluminum foil may be broken or pinholes may be formed during molding, so that the risk of oxygen or water intrusion increases. On the other hand, when it exceeds 100 micrometers, it does not contribute to the improvement of the breaking improvement at the time of shaping|molding, and the prevention effect of pinhole generation, and only the total thickness of the packaging material becomes thick, weight, and volume. The energy density has dropped, so it is not good. Generally, a thickness of 30 to 50 μm Φ is used. Further, in order to improve the adhesion to the resin film or to improve the corrosion resistance, it is preferred to apply a primer treatment such as a decane coupling agent or a titanium coupling agent, or a chemical conversion treatment such as chromic acid treatment. (The inner layer of the thermoplastic resin film) The inner layer of the resin film is made of polypropylene, polyethylene, maleic acid modified polypropylene, ethylene-acrylate copolymer, or ionomer-containing polymer resin. Extend the film. The resin is heat-sealed to provide -15
1357677 高對於高腐蝕性的鋰二次電池電解液等之耐化學藥品性。 該等薄膜需要9 ~ 50微米之厚度。若爲小於9微米時，則 熱密封強度不足夠，且有對於電解液等之耐蝕性會降低之 危險性。相對地，即使使用超過50微米厚度之薄膜，並非 即能格外地提高熱密封性、耐化學藥品性，反而僅會造成 體積能量密度下降而已。一般是使用20〜40微米之厚度 者。另外，內層係可使用單層之樹脂薄膜，數層之樹脂薄 膜（2層之共擠壓、3層之共擠壓等）。 (中間樹脂層） 作爲第1中間樹脂層，係使用聚醯胺樹脂、聚酯樹脂、 聚乙烯樹脂等以提高包裝材料之機械強度爲目的。另外， 作爲第2中間樹脂層，則使用與第1中間樹脂層相同之樹 脂或聚丙烯等之熱黏合性擠出樹脂，以主要提高耐電解液 性爲目的。第2中間樹脂層係可使用單層之樹脂薄膜或數 層之共擠壓樹脂薄膜。 (黏合劑組成物） 使用於本發明之黏合劑組成物，係以聚烯烴多元醇與多 官能性異氰酸酯硬化劑爲必要成份者》作爲主劑所使用之 聚烯烴多元醇係具有與低分子量聚烯烴相同之碳氫化合物 骨架，且具有數羥基者，包括：聚丁二烯二醇、氫化聚丁 二烯二醇等。聚烯烴多元醇之較佳的數量平均分子量爲 1，000 ~ 10,000，更佳爲1，〇〇〇 ~ 5,000。較佳的聚烯烴多元 醇係每分子之羥基數爲1.5 ~ 3個。 另外，用作爲硬化劑之多官能性異氰酸酯，係包括：甲 -16- 1357677 苯二異氰酸酯、二苯基二異氰酸酯、六亞甲基二異氰酸酯 、異佛酮二異氰酸酯等，或將該等加以異三聚氰酸酯（ isocyanurate)改質、縮二脲改質、以三羥甲基丙烷等之多 元醇加以加成物改質者。多官能性異氰酸酯之較佳的官能 數爲2或3。 對於主劑之聚烯烴多元醇的多官能性異氰酸酯硬化劑之 添加比率，係相對於聚烯烴多元醇之羥基的異氰酸基，以 莫耳比（NCO/OH )計爲1.0 ~ 1〇.〇之範圍。若莫耳比（ · NCO/OH)爲小於1_〇時，則有黏合耐久性會下降之問題； 若莫耳比（NC0/0H)爲超過1〇·〇時，則有黏合強度會下 降之問題，特別是以1.2 ~ 8.0之範圍爲佳。 另外，對於上述黏合劑組成物，以提高積層強度爲目的+ ，較佳爲添加熱塑性彈性體。在此所謂「熱塑性彈性體」 ，係指即使未施加加硫處理，其成形品在常溫下也具有橡 膠彈性之樹脂，即屬於熱塑性樹脂且具有橡膠彈性者，茲 就化學結構上而言，一般爲具有ΑΒΑ型之嵌段、或（Α-Β φ )η型之多嵌段結構之共聚合物。 熱塑性彈性體之具體實例包括：苯乙烯系彈性體、及烯 烴系彈性體（例如乙烯-丙烯共聚合物、乙烯-丙烯三聚物 )等。 熱塑性彈性體之添加量，亦即聚烯烴多元醇與熱塑性彈 性體之比率較佳爲80/2〇 ~ 2/98之範圍，特佳爲60/40 ~ 10/90之範圍。 另外，進一步以提高積層強度爲目的，較佳爲添加聚萜 -17- 1357677 系樹脂 '松香系樹脂、脂肪族系石油樹脂、脂環族系石油 樹脂 '共聚合系石油樹脂、及加氫石油樹脂等之黏合賦予 劑。 黏合賦予劑之添加量，相對於100重量份之聚烯烴多元 醇與熱塑性彈性體之總量，較佳爲5 ~ 100重量份，特隹 爲20 ~ 100重量份之比率。 上述黏合劑組成物之塗佈量爲1 ~ 40 g/m2，特佳爲3 ~ 30 g/m2。 鋁箔芯層與內層之樹脂薄膜，雖然係使用該黏合劑組成 物加以黏合，但是鋁箔芯層與外層之樹脂薄膜，則由於其 並無須考慮及對於電解液之抵抗性，所以不必勉強使用上 述黏合劑組成物，可使用習知的胺甲酸酯系黏合劑即可。 再者，若使第2中間樹脂層夾在鋁箔芯層與內層之間時 ，則可將第2中間樹脂層視爲內層結構材料之一部份，而 以鋁箔芯層與第2中間樹脂層作爲使用上述黏合劑組成物 加以黏合之對象。 【實施例】 茲以實施例更具體說明本發明，但是本發明並不受限於 該等。 眚施例1 ~ 3及比較例1 ~ 3 (電池外殻用包裝材料） 使用如下所述之耐熱性樹脂延伸薄膜、鋁-鐵系合金之鋁 箔（ns中AA規格8079，0材及熱塑性樹脂未延伸 薄膜，且作爲外面用黏合劑而使用胺甲酸酯系乾積層黏合 -18- 1357677 劑〔東洋Moton公司製：AD502/CAT10〕，作爲內面用黏 合劑而使用如下表1所示以聚烯烴多元醇與多官能性異氰 酸酯硬化劑爲主要成份之彈性體系黏合劑組成物。 另外，使用如下所述之代表符號： ON:延伸聚醯胺薄膜 乾積層黏合劑：外面用黏合劑（胺甲酸酯系黏合劑） A1:鋁箔· 彈性體系聚合物黏合劑：內面用黏合劑（含有聚烯烴多元 醇與多官能性異氰酸酯硬化劑之黏合劑組成物） CPP:未延伸聚丙烯薄膜 改質ΡΡ·ΡΡ:改質聚丙烯·聚丙烯共擠壓熱黏合性樹脂 (包裝材料之結構） 外層：延伸聚醯胺薄膜（厚度爲25微米） 乾積層黏合劑：胺甲酸酯系黏合劑（塗佈量爲3 g/m2 ) 鋁箔芯層·· JIS中AA規格8079 - 0材（厚度爲40微米） 彈性體系聚合物黏合劑（塗佈量爲4 g/m2 ) 內層：未延伸聚丙烯薄膜（厚度爲30微米） 換言之，由ON/乾積層黏合劑/A1/彈性體系聚合物黏合劑 /CPP所構成者。 然而，在實施例1至3之包裝材料中，其內面用黏合劑 則使用如下表1所示之彈性體系聚合物黏合劑。1357677 High chemical resistance to highly corrosive lithium secondary battery electrolytes. These films require a thickness of 9 to 50 microns. If it is less than 9 μm, the heat seal strength is insufficient, and the corrosion resistance to the electrolyte or the like may be lowered. In contrast, even if a film having a thickness of more than 50 μm is used, the heat sealability and chemical resistance are not particularly improved, but only the volume energy density is lowered. Generally, thicknesses of 20 to 40 microns are used. Further, as the inner layer, a single layer of a resin film, a plurality of layers of a resin film (coextrusion of two layers, coextrusion of three layers, or the like) may be used. (Intermediate Resin Layer) As the first intermediate resin layer, a polyamide resin, a polyester resin, a polyethylene resin or the like is used to improve the mechanical strength of the packaging material. In addition, as the second intermediate resin layer, the same resin as the first intermediate resin layer or a heat-adhesive extruded resin such as polypropylene is used to mainly improve the electrolyte resistance. As the second intermediate resin layer, a single layer of a resin film or a plurality of layers of a coextruded resin film can be used. (Binder composition) The polyolefin polyol used in the binder composition of the present invention, which is a polyolefin polyol and a polyfunctional isocyanate hardener as an essential component, has a low molecular weight poly The hydrocarbon skeleton having the same olefin and having a plurality of hydroxyl groups includes polybutadiene diol, hydrogenated polybutadiene diol and the like. The preferred number average molecular weight of the polyolefin polyol is from 1,000 to 10,000, more preferably from 1, 〇〇〇 to 5,000. The preferred polyolefin polyol has a hydroxyl number of from 1.5 to 3 per molecule. Further, the polyfunctional isocyanate used as a curing agent includes, for example, methyl-16-1357677 phenylene diisocyanate, diphenyl diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, or the like. The isocyanurate is modified, the biuret is modified, and the addition product is modified with a polyol such as trimethylolpropane. The preferred functional number of the polyfunctional isocyanate is 2 or 3. The ratio of addition of the polyfunctional isocyanate hardener to the polyolefin polyol of the main component is 1.0 to 1 相对 based on the molar ratio of the hydroxyl group of the polyolefin polyol to the isocyanate group of the polyolefin polyol (NCO/OH). The scope of 〇. If the molar ratio ( · NCO / OH) is less than 1 〇, there is a problem that the adhesive durability is lowered; if the molar ratio (NC0/0H) is more than 1 〇·〇, the adhesive strength is lowered. The problem is especially in the range of 1.2 ~ 8.0. Further, for the above-mentioned binder composition, for the purpose of improving the buildup strength, it is preferred to add a thermoplastic elastomer. The term "thermoplastic elastomer" as used herein refers to a resin which has a rubber elasticity at room temperature even if a vulcanization treatment is not applied, that is, a thermoplastic resin and has rubber elasticity, and it is generally chemically It is a copolymer having a ΑΒΑ-type block or a multi-block structure of (Α-Β φ )η type. Specific examples of the thermoplastic elastomer include a styrene-based elastomer, and an olefin-based elastomer (e.g., an ethylene-propylene copolymer, an ethylene-propylene trimer), and the like. The amount of the thermoplastic elastomer added, that is, the ratio of the polyolefin polyol to the thermoplastic elastomer is preferably in the range of 80/2 Å to 2/98, particularly preferably in the range of 60/40 to 10/90. Further, in order to further increase the strength of the laminate, it is preferred to add a polyfluorene-17-1357677-based resin, a rosin-based resin, an aliphatic petroleum resin, an alicyclic petroleum resin, a copolymerized petroleum resin, and a hydrogenated petroleum. A binder-imparting agent such as a resin. The amount of the adhesion-imparting agent to be added is preferably from 5 to 100 parts by weight, particularly preferably from 20 to 100 parts by weight, per 100 parts by weight of the total of the polyolefin polyol and the thermoplastic elastomer. The coating composition of the above binder is 1 to 40 g/m2, particularly preferably 3 to 30 g/m2. The resin film of the aluminum foil core layer and the inner layer is bonded by using the binder composition, but the resin film of the aluminum foil core layer and the outer layer does not have to be considered and resistant to the electrolyte, so it is not necessary to use the above. As the binder composition, a conventional urethane-based binder can be used. Further, when the second intermediate resin layer is sandwiched between the aluminum foil core layer and the inner layer, the second intermediate resin layer can be regarded as a part of the inner layer structural material, and the aluminum foil core layer and the second intermediate layer The resin layer is used as a target for bonding using the above binder composition. [Examples] The present invention will be more specifically illustrated by the examples, but the invention is not limited thereto. Examples 1 to 3 and Comparative Examples 1 to 3 (Packaging materials for battery cases) The heat-resistant resin stretch film and the aluminum-iron alloy aluminum foil as described below (AA size 8079, 0 material and thermoplastic resin in ns) The unstretched film was used as an adhesive for the outside, and a urethane-based dry laminate was used to bond -18-1357677 (made by Toyo Moton Co., Ltd.: AD502/CAT10), and the inner surface adhesive was used as shown in Table 1 below. Polyolefin polyol and polyfunctional isocyanate hardener are the main components of the elastic system binder composition. In addition, the following symbol is used: ON: extended polyamine film dry laminate adhesive: external binder (amine Formate binders) A1: Aluminum foil · Elastomeric polymer binder: Inner surface adhesive (adhesive composition containing polyolefin polyol and polyfunctional isocyanate hardener) CPP: Unstretched polypropylene film ΡΡ·ΡΡ: modified polypropylene·polypropylene co-extruded thermal adhesive resin (structure of packaging material) outer layer: extended polyamine film (thickness 25 μm) dry laminate adhesive: urethane system Adhesive (coating amount is 3 g/m2) Aluminum foil core layer · JIS AA size 8079 - 0 material (thickness 40 microns) Elastomeric polymer binder (coating amount 4 g/m2) Inner layer: Unstretched polypropylene film (thickness 30 μm) In other words, it is composed of ON/dry laminate adhesive/A1/elastic polymer adhesive/CPP. However, in the packaging materials of Examples 1 to 3, For the surface adhesive, the elastic system polymer binder shown in Table 1 below was used.
彈性體系聚合物黏合劑係以聚烯烴多元醇（數量平均分 子量爲2,〇〇〇，及羥値：50 mg KOH/g )，與多官能性異氰 酸酯（日本聚胺甲酸酯工業公司製，商品名Koron ate HX -19- 1357677 )爲必要成份，溶劑則使用甲苯/ MEK (甲基乙基酮）： 80/20 。 另外，在實施例1和3中，則添加熱塑性彈性體（ Cleitone公司製，商品名Cleitone G - 1657 )，在實施例2 和3中’則添加黏合賦予劑（荒川化學工業公司製， Arcone P - 90 ) 〇 另外’作爲比較例，在比較例1中，則使用雖然爲屬於 彈性體系聚合物黏合劑，但是並未添加多官能性異氰酸酯 硬化劑者’在比較例2中，則在內面側使用共擠壓熱黏合 性樹脂：改質PP(厚度爲3微米）·ΡΡ(厚度爲12微米 )而加以熱壓接者，在比較例3中，則內外面皆使用胺甲 酸酯系黏合劑加以黏合者。 如下表1所示，一倂展示相對於聚烯烴多元醇的ΟΗ之 多官能性異氰酸酯之NCO莫耳比（NCO/OH)。 表1 黏合劑組成（龍份） 實施例1 實施例2 實施例3 比較例1 聚烯烴多元醇 10 20 1 20 熱塑性彈性體 15 - 20 - 黏合賦予劑 - 5 4 5 甲苯/MEK (80/20) 75 . 75 75 75 多官能性異氰酸酯硬化劑 5 10 0.2 - 寞耳比（NCO/OH) 2.85 2.85 1.14 0 (耐電解液性評估方法） 將上述實施例1〜3及比較例1 ~ 3之各電池外殻用包裝 材料，在85 °C大氣中浸漬於電解液（碳酸二甲酯：碳酸乙 -20- 1357677 酯 =1 : 2 +鋰鹽）。然後，茲就該等電池外殼用包裝材 料，在剛浸漬後、經浸漬5天後、經浸漬10天後、及經浸 漬2週後，測定鋁箔芯層與未延伸薄膜層之間的積層強度。 但是，將耐電解液性評估基準設定爲如下所示： 耐電解液性之評估： ◎: 積層強度無變化； Ο · 積層強度保持率爲60 %以上； Δ ： 積層強度保持率爲30 %以上； X: 積層強度剝層。 (成形性之評估方法） 茲就上述實施例1 ~ 3及比較例1 ~ 3,將各電池外殼用 包裝材料製成110毫米X180毫米之坯料片形狀，以成形高 度自由之直線式模具實施撐壓內形法單段成形加工，然後 以各包裝材料之成形高度來比較其成形性。 所使用模具之凸模形狀：長邊爲60毫米，短邊爲45毫 米 隅 角半徑=1 ~ 2毫 米， 凸模台肩半徑=1 毫米，凹模 台 肩 半 徑=1毫米。 將所丨 濩得 之結果一倂展示於 表2。 另 外 ，成形高度 評估基 準如下所示： ◎ ; 5毫米以上 f 〇 ; 3毫米以上 、小於 5毫 米； △ ; 2毫米以上 、小於 3毫 米； X ： 小於2毫米 〇 1357677 表2 解液性 成形性 剛浸漬後 5曰後 10日後 2週後 實施例1 ◎ ◎ ◎ 〇 ◎ 實施例2 ◎ ◎ ◎ 〇 ◎ 實施例3 ◎ ◎ ◎ ◎ ◎ 比較例1 △ Δ X X △ 比較例2 ◎ ◎ ◎ 〇 Δ 比較例3 △ X X X ◎ 由該表2之結果即可知，根據本發明之實施例1〜3，其 係具有優越的拉伸成形之成形性，能抑制針孔或龜裂等之 發生，同時能實現尖銳且成形高度較深的形狀，而且積層 強度長期不會降低，具有優越的耐電解液性，另外使用本 發明之包裝材料所成形之電池外殼係具有優越的體積能量 密度，同時爲長期穩定者。 與此相對，若根據比較例1，則其係成形高度不充分， 且成形性差，同時積層強度之下降大，且耐電解液性較差 。另外，在比較例2，則由於其係使用共擠壓熱黏合性樹 脂所熱黏合，因此具有優越的耐電解液性，但是成形性卻 非常差。在比較例3,則由於其係內外面皆使用先前之胺 甲酸酯系黏合劑來黏合，因此積層強度之下降大，且耐電 解液性較差。 -22-The elastomeric polymer binder is a polyolefin polyol (a number average molecular weight of 2, hydrazine, and oxindole: 50 mg KOH / g), and a polyfunctional isocyanate (manufactured by Japan Polyurethane Industry Co., Ltd.). The trade name Koron ate HX -19- 1357677 is the essential component, and the solvent is toluene / MEK (methyl ethyl ketone): 80/20. Further, in Examples 1 and 3, a thermoplastic elastomer (trade name: Cleitone G-1657, manufactured by Cleitone Co., Ltd.) was added, and in Examples 2 and 3, a binder-imparting agent (Arcone P, manufactured by Arakawa Chemical Industries, Ltd.) was added. - 90) 〇 In addition, as a comparative example, in Comparative Example 1, a polymer binder which is an elastomer system was used, but a polyfunctional isocyanate hardener was not added. In Comparative Example 2, it was inside. The co-extrusion heat-adhesive resin was used on the side: the modified PP (thickness: 3 μm)·ΡΡ (thickness: 12 μm) was used for thermocompression bonding. In Comparative Example 3, the urethane system was used both inside and outside. Adhesives are glued. As shown in Table 1 below, the NCO molar ratio (NCO/OH) of the polyfunctional isocyanate relative to the cerium of the polyolefin polyol is shown. Table 1 Adhesive Composition (Long) Example 1 Example 2 Example 3 Comparative Example 1 Polyolefin polyol 10 20 1 20 Thermoplastic elastomer 15 - 20 - Adhesive imparting agent - 5 4 5 Toluene / MEK (80/20 75 . 75 75 75 Polyfunctional isocyanate hardener 5 10 0.2 - 寞 Ear ratio (NCO/OH) 2.85 2.85 1.14 0 (Method for evaluating electrolyte resistance) The above Examples 1 to 3 and Comparative Examples 1 to 3 Each battery case was immersed in an electrolyte at a temperature of 85 ° C (dimethyl carbonate: ethyl carbonate-20-1357677 ester = 1: 2 + lithium salt). Then, the laminate strength between the aluminum foil core layer and the unstretched film layer was measured for the battery casing packaging materials immediately after immersion, after immersion for 5 days, after immersion for 10 days, and after immersion for 2 weeks. . However, the evaluation criteria of the electrolyte resistance were set as follows: Evaluation of electrolyte resistance: ◎: No change in laminate strength; Ο · Stacking strength retention rate was 60% or more; Δ: Stacking strength retention rate was 30% or more ; X: Laminated strength peeling. (Evaluation method of formability) With respect to the above-mentioned Examples 1 to 3 and Comparative Examples 1 to 3, each battery case packaging material was formed into a green sheet shape of 110 mm × 180 mm, and a linear mold having a high degree of freedom was formed. The in-line forming method is performed in a single-stage forming process, and then the formability is compared by the forming height of each packaging material. The shape of the punch used for the mold is 60 mm for the long side, 45 mm for the short side, =1 2 mm for the corner, the shoulder radius of the punch = 1 mm, and the shoulder radius of the die is 1 mm. The results obtained by 丨 濩 are shown in Table 2. In addition, the forming height evaluation criteria are as follows: ◎; 5 mm or more f 〇; 3 mm or more and less than 5 mm; △; 2 mm or more and less than 3 mm; X: less than 2 mm 〇 1357677 Table 2 De-liquid formability Immediately after 5 weeks after immersion, after 2 weeks, 2 weeks later, Example 1 ◎ ◎ ◎ ◎ ◎ Example 2 ◎ ◎ ◎ ◎ Example 3 ◎ ◎ ◎ ◎ Comparative Example 1 Δ Δ XX △ Comparative Example 2 ◎ ◎ ◎ 〇 〇 Δ Comparative Example 3 Δ XXX ◎ As is apparent from the results of Table 2, according to Examples 1 to 3 of the present invention, it has excellent moldability for stretch forming, and can suppress occurrence of pinholes, cracks, and the like, and at the same time, A sharp and deep forming shape is achieved, and the laminate strength is not lowered for a long period of time, and has excellent electrolyte resistance. In addition, the battery casing formed by using the packaging material of the present invention has superior volume energy density and is stable for a long period of time. By. On the other hand, according to Comparative Example 1, the molding height was insufficient, and the formability was poor, and the decrease in the laminate strength was large, and the electrolytic solution resistance was inferior. Further, in Comparative Example 2, since it was thermally bonded by using a co-extruded heat-adhesive resin, it had excellent electrolyte resistance, but the formability was very poor. In Comparative Example 3, since the inner and outer layers were bonded using the previous urethane-based adhesive, the decrease in the build-up strength was large and the electrolyte resistance was poor. -twenty two-