201238119 ^H40〇pif 六、發明說明：201238119 ^H40〇pif VI. Invention Description:
【發明所屬之技術領域^ J 本發明是有關於—種電池外殼用積層體及使用上述電 池外殼用積層體的二次電池。 【先前技術】 鎳-鎘電池或鎳-氫電池、鋰離子電池等二次電池廣泛 用於行動電話或筆記型個人電腦、攝影機、電動汽車、、衛 星、社會公共建設（infrastructure)元件等電子設備、或電 子零件。特別是輯子二:欠電池由於能量密度及輸出特性 優異，而大多用於要求小型化及輕量性的行動話或 設備等中。先前，該些小型電池的包裝構件就輕量性、成 形性及成本的觀點而言，可使用铭合金。 另外，近年來，二次電池亦用於電動汽車或混合動力 汽車、太陽電池用蓄電池等大型設備。該些大型設備用電 池中，為了提高輸出容量，而需要增加電解液的量，電池 尺寸亦成為大型。此種大型電池的包裝構件要求小型電池 的包裝構件以上的安全性（牢固性或耐久性等）。 先前，用作電池的包裝構件的鋁合金由於剛性低，因 此為了提高對於電池内部的壓力增加的耐壓性，而需要増 加板厚。另外，銘合金由於耐屈曲性差，因此在將電池單 元彼此繫結及固定時，在使用盒體周邊的凸緣部時，需要 輔助的繫結構件。因此，使用鋁合金作為電池的包裝構件 時’電池的省空間化及低成本化存在極限。而且，鋁合金 由於熱膨脹係數大，因而亦存在藉由充放電時的發熱而對 4 201238119 HXHUUpif 包裝構件施加較大的熱衝擊的問題。 作為解決上述問題的方法，提出有將不鏽鋼板用於電 池的包裝構件（例如參照專利文獻υ。專利文獻【中記載， 在將沃斯田鐵（austenite)系不鏽鋼板進行成形加工而得 的盒體構件的内部收納電池構件（正極或負極、分隔件 (seParat0小電解液等），藉由接縫炫接（seamweidmg) 將盒體構件彼此接合，從而製造電池。 包含專利文獻1中所記載的不鏽鋼板的電池外殼用材 料’由於高強度且熱膨脹係數較小，因此可解決上述問題。 然而，在使用專利文獻1中所記載的電池外殼用材料製造 電池時，由於在將電池構件收納於盒體内的狀態下進 接’因此有S熔接熱而電池構件（特別是編製分隔 ^匕，擔憂。另外，並不限定於專利文獻丨的電池，在1 用W不_板等金屬的盒體的電財，存在 的内壓過度上升而使容器韻的擔s 的過度上升’只要設置安全閥即可，由於二 的結構’因此會導致製造成本升高。 W木用银雜 作為解決上述熔接熱及製造成本的問題的方 有將不_板與熱融著性樹脂_積層體用出 構件（例如參照專利文獻2)。專利文獻2中記載，=包裝 酸鹽(ch_te)處理的不鏽鋼板上積層酸改:鉻 樹脂膜而成_脂被覆残鋼板。在包纽樹2烴系 鋼板的盒體構件的内部收納f池構件（正 ^覆不鏽 件、電解液等），藉域融著使盒體構件彼此接人:分隔 ° 错此製 5 201238119 k電池。專利文獻2的技術巾於並非藉*炫接而是藉 由熱融著將盒體構件接合，因此不會產生因炫接熱所引起 的電池構件的劣化。另外，因熱融著所引起的接合強度與 因溶接所引起的接合強度相比特別小。因此，即便容器内 壓過度上升，盒體構件亦會在熱融著面分離，因此無需安 全閥。 先前技術文獻 專利文獻 專利文獻1 :日本專利特開2004_52100號公報 專利文獻2 :日本專利特開2〇〇7_168184號公報 ^專利文獻2所記載的樹脂被覆不鏽鋼板為了破保熱融 著性树脂膜的也、接性，而形成鉻酸鹽處理層。此鉻酸鹽處 理層是使用包含環境負荷較大的六價鉻的處理液.而形成。 因此，專利文獻2所記載的樹脂被覆不鏽鋼板存在環境負 荷較大的問題。 ' 【發明内容】 本發明的目的是提供一種電池外殼用積層體，其是在 不鏽鋼板上形成熱融著性樹脂層而成，且可熱融著，並且 熱融著性樹脂層的密接性優異，而且環境負荷較小。 本發明者發現’藉由在不鑛鋼板的表面形成包含樹脂 組成物的硬化物的有機無機複合處理層，上述樹脂組成物 具有含有缓基的樹脂、含有噁唑啉基的樹脂及鹼性磷酸化 合物，並於其上形成熱融著性樹脂層，而不使用六價鉻便 可提尚熱融著性樹脂層的密接性，並且加以研究而完成了 6 201238119 41400pif 本發明。 即’本發明的第-發明是有關於以下的電池外殼用積 層體。 ⑴-種電池外殼用積層體，其包含：不鏽鋼板，其 具有第1面及第2面；有機無機複合處理層，其形成於上 述不鏽鋼板的第1 ©，包含樹脂組成物的硬^物，上述 树月曰組成物具有含有綾基的樹脂、含有^㈣基的樹脂及 驗性填酸化合物；以及熱融著性聚烯烴系樹脂層，其形成 於上述有機無機複合處理層的表面，且厚度為i〇 pm〜i㈨ μηι。 、[2]如[1]所述之電池外殼用積層體，其中上述有機無 機複合處理層含有5 mg/m2〜800 mg/m2的上述硬化物的 树月日成分’且以磷換算計含有〇 i mg/m2〜1〇〇 mg/m2的上 述硬化物的填成分。 [3] 如[1]或[2]所述之電池外殼用積層體，其中上述樹 脂組成物中的上述含有噁唑啉基的樹脂相對於上述含有羧 基的樹脂及上述含有噁唑啉基的樹脂的合計量的比例為 2.0質量％〜50·0質量％的範圍内。 … [4] 如[1]至[3]中任一項所述之電池外殼用積層體，其 中上述含有羧基的樹脂的酸值以樹脂固體成分換算計為 300 mgKOH/g 以上。 [5] 如[1]至[4]中任一項所述之電池外殼用積層體，其 中上述樹脂組成物還含有鹼性锆化合物，上述有機無機複 合處理層以結換异計含有〇 5 mg/m2〜60 mg/m2的上述硬 201238119 化物的錯成分。 [6] 如[1]所述之電池外殼用積層體，其中在上述有機 無機複合處理層與上述熱融著性聚婦烴系樹脂層之間，還 具有厚度為10 μιη〜100 μιη的酸改質聚烯烴系樹脂層。 [7] 如[1]所述之電池外殼用積層體，其中上述不鏽鋼 板的板厚為20 μπι〜400 μιη的範圍内。 [8] 如[1]所述之電池外殼用積層體，其還具有形成於 上述不鏽鋼板的第2面的樹脂層。 另外，本發明的第二發明是有關於以下的二次電池。 [9] 一種二次電池，其具有將如[1]所述之電池外殼用 積層體的成形品熱融著而形成的盒體。 [發明的效果] 根據本發明，可不使用六價鉻便可製造熱融著性樹脂 層的密接性優異的電池外殼用積層體。因此，根據本發明， 能以更小之環境負射製造熱融著性樹脂層的密接性傷旦的 電池外殼用積層體。 ' 【實施方式】 1.電池外殼用積層體 本發明的電池外殼用積層體是包含不鏽鋼板、有機無 機複合處理層、及熱融著性聚烯烴系樹脂層的積層體。有 機無機複合處理層形成於不鏽鋼板的表面。熱融^性聚烯 烴系樹脂層直接接合於有機無機複合處理層的表面、或經 由酸改質聚稀烴系樹脂而接合於有機無機複合處理層=表 面。本說明書中，將不鏽鋼板的表面中形成了有機無機複 8 201238119 外 IHOOpif 合處理層及熱融著性輯烴系樹脂層的面稱為「第， ^相反側的面稱為「第2面」。將本發明的電池外殼用積層 體用於二次電池時，第1面成為内面（電解質_面），、第 2面成為外面（外界側的面）。 以下，對各構成要素進行說明。 (1)不鏽鋼板 構成不鏽鋼板的不_的鋼種並不特別限定於沃斯田 鐵系（austenitic series)、鐵氧體系（ferdte㈣⑷、麻田 散鐵系（martensite series)等。鋼種的例子可包括. SUS304、S麵〇、腦16等。糾，残鋼板的表面抛 光（surface finishing)的種類亦無特別限定。表面拋光的 種類的例子包括：BA、2B、2D、No.4、HL等。 不鏽鋼板的板厚可根據作為電池外殼材料的要求重量 或要求強度、要求加工深度等進行適當設定。就使電池外 殼材料的重量輕量化的觀點而言，板厚越薄越佳，但越使 板厚變薄，則強度及加工性會越低，且製造成本會越上升。 就確保作為電池外殼材料的強度的觀點而言，較佳為板厚 為20 μιη以上。另外，即便是進行50 mm左右的深引伸加 工（deep drawing)時，若板厚亦為400 μηι，則較為充分。 若考慮到通常所要求的電池外殼材料的強度及加工深度， 則不錄鋼板的板厚較佳為40 μιη〜150 μιη的範圍内。 (2)有機無機複合處理層 有機無機複合處理層形成於不鑛鋼板的第1面。有機 無機複合處理層承擔如下功能：使不鏽鋼板與熱融著性聚 201238119 2煙系樹脂層（或酸改質聚稀煙系樹脂層）牢固地 :二，的劣化或水解而產生的氣酸所引起的不鑛 人右=無機複合處理層包含具有含有縣賴脂⑷、 i成基的樹脂⑻及驗性磷酸化合物⑹的樹脂 樹=的硬化物。含有絲的樹脂（A)、含有射琳基的 _酸化合物（c)藉由配位鍵及化學鍵而 纟結構而相互鍵合，並且與不_板牢固地結 :或附者。具體而言，驗性磷酸化合物（c)與不義板 結合或附著而形成無機處理層，並且發揮出作為樹 m職有賴基簡脂⑻所具有㈣㈣基的反 的功能。其結果，形成源自含有縣的樹脂⑷、 t有°惡姆基的樹脂⑻及驗性顧化合物⑻的3成 ^的^職度的耐化學藥品性優異的有機無機複合處理 二夕’Μιθ(α)所具有的極性基（竣基或經基等） 會，高有機無機複合處理層與熱融著性聚烯烴系樹脂層 (或酸改質聚烯烴系樹脂層）的密接性。 上述樹脂纽成物較佳為，還含有驗性錯化合物（d)。 藉由在，脂組成物中含有驗性錯化合物，而可藉由金屬交 =而更牛固地進行樹脂間的鍵合。另外，驗性錯化合物⑺） 精由，驗„化合物（c)反應㈣成*溶_酸錯鹽， 而進步提n有機無機複合處理層的關性’目此可提高 j無機複合處理層的造難雜陳、以及有機無機複 a处理層與熱融著性聚烯烴系樹脂層（或酸改質聚烯煙系 201238119 樹脂層）的密接性。 有機無機複合處理層對於水或含有酸成分（氟酸等） 的酸彳生水溶液、有機溶劑等表現出優異的難溶性。有機無 機複合處理層藉由上述（A)〜（C)的3成分、或上述（A) 〜（D)的4成分協同作用，而對液體電解質及固體有機 電解質以及該些電解質劣化而成的電解質具有優異的耐 並可維持有機無機複合處理層與熱融著性聚烯烴系樹 月曰層（或酸改質聚烯烴系樹脂層）的牢固的密接性。 一有機無機複合處理層較佳為在5 mg/m2〜8〇〇 mg/m2 的範圍内含有上述樹餘成物的硬化物的樹脂成分（源自 含有縣的樹脂（A)及含有。惡驾基的樹脂⑻），更佳 mg/m2的範_含有。在樹脂成分 二=、於5 mg/m2時，無法特有機錢複合處理層與 烴i樹脂層(或酸改質聚婦咖脂層)的 牛接性m即便翻旨成分 ==置咖機無二= :外，有機無？複合處理層較佳 mg/m〜1〇〇 mg/m2的範圍内含有 + 換异叶在0.1 物的磷成分（源自鹼性磷酸化合物述樹脂組成物的硬化 mg/m2〜50 mg/m2的範圍内含有。♦、)）更佳為在0.25 量小於0.1 mg/m2時，亦無法維^，分的雜算的含 '故無機複合處理層與 201238119 -r x 100 mg/y時，反而^成分的鱗換算的含量超過 聚烯烴f期旨層合處理層與熱融著性 低、或有機無機系樹脂層)的密接性降 =有機無機複合處理層而編量(二Ί 複合由調整在形成有機無機 中的rf⑴佈的樹成物（有機無機複合處理液） 物（有2的3成分的濃度、或調整樹脂組成 内。(有機·，、、枚腹&處理液）的塗佈量，而調整為上述範圍 另外’在形成有機域複合處理料職佈的樹脂組 (有機錢複合處觀）+的含有射魏的樹脂⑻ 相對於含有祕的樹脂⑷及含有t姆基的樹脂⑻ 的合計量的_ ’關體成分計較佳為Μ f量％〜5〇〇 質置％的範圍内，更佳為5Q質量％〜4⑽質量％的範圍 内。藉由使有機無機複合處理液中的含有羧基的樹脂（A) ^含有鳴唾淋基的樹脂（B)的固體成分質量比率為上述 範圍内’而可使有機無機複合處理層中的羧基與噁唑啉基 的比率成為較佳的範圍。其結果，可提高有機無機複合處 理層中的因叛基及噪唾啉基引起的交聯密度，並提高有機 無機複合處理層的阻隔性。另外，藉由使含有羧基的樹脂 12 201238119 41400pll 二=為適當的範圍，而可良好地維持不鏽鋼板斑 齡者性脂層的密接性。在含有^憾基的樹 月二 +二不输3超出上述範圍時’存在有機無機複合處理 :=:===;_ (麻質聚 C提的錯換算的含量小於Μ二:1::[Technical Field] The present invention relates to a laminate for a battery can and a secondary battery using the laminate for the battery can. [Prior Art] Secondary batteries such as nickel-cadmium batteries or nickel-hydrogen batteries and lithium-ion batteries are widely used in electronic devices such as mobile phones or notebook personal computers, video cameras, electric vehicles, satellites, and social infrastructure components. , or electronic parts. In particular, the second series: the under-battery is excellent in energy density and output characteristics, and is often used in mobile phones or devices that require miniaturization and light weight. Previously, the packaging members of these small batteries were used in terms of lightness, formability, and cost. Further, in recent years, secondary batteries have also been used in large-scale equipment such as electric vehicles, hybrid vehicles, and batteries for solar cells. In these large-sized equipment batteries, in order to increase the output capacity, it is necessary to increase the amount of the electrolyte, and the size of the battery is also large. The packaging member of such a large-sized battery requires safety (firmness, durability, etc.) above the packaging member of the small battery. Previously, aluminum alloy used as a packaging member of a battery has a low rigidity, and therefore it is necessary to increase the thickness of the sheet in order to increase the pressure resistance to the pressure inside the battery. Further, since the alloy has poor buckling resistance, when the battery cells are tied and fixed to each other, an auxiliary structural member is required when the flange portion around the casing is used. Therefore, when aluminum alloy is used as the packaging member of the battery, there is a limit to the space saving and cost reduction of the battery. Further, since the aluminum alloy has a large coefficient of thermal expansion, there is a problem that a large thermal shock is applied to the 4201238119 HXHUUpif packaging member by heat generation during charging and discharging. As a method for solving the above problems, a packaging member using a stainless steel plate for a battery has been proposed (for example, refer to the patent document υ. The patent document discloses a case obtained by forming a stainless steel plate of austenite type. A battery member (a positive electrode or a negative electrode, a separator (separat0 small electrolyte, etc.) is housed inside the body member, and the case members are joined to each other by a seam splicing to manufacture a battery. The film described in Patent Document 1 is included. In the case of the battery case material of the stainless steel plate, the material of the battery case is small, and the coefficient of thermal expansion is small. Therefore, when the battery is manufactured using the battery case material described in Patent Document 1, the battery member is housed in the case. In the case of the inside of the body, there is a case where there is a heat of S and the battery member (especially the separation of the battery is concerned. In addition, it is not limited to the battery of the patent document, and the case of a metal such as W is not used. The electric power, the internal pressure is excessively increased, and the burden of the container rhyme is excessively increased. 'As long as the safety valve is installed, the structure of the second is due to This causes an increase in the production cost. The use of the silver-based silver miscellaneous material as a solution to the above-mentioned problem of the heat of fusion and the production cost is as follows: (for example, see Patent Document 2). In the case of the packaged acid salt (ch_te), the stainless steel sheet is replaced with a chrome resin film to form a residual steel sheet. The inside of the box member of the hydrocarbon-coated steel sheet of the Bunny tree 2 is housed in the f-pool. The member (positively covering the stainless steel, the electrolyte, etc.), the box member is connected to each other by the fusion of the domain: the partition is wrong. 5201238119 k battery. The technical towel of Patent Document 2 is not borrowed* Since the case member is joined by heat fusion, deterioration of the battery member due to heat of stun does not occur. In addition, the joint strength due to heat fusion is extremely small compared to the joint strength due to fusion. Therefore, even if the internal pressure of the container is excessively increased, the case member is separated on the hot-melt surface, and thus the safety valve is not required. PRIOR ART DOCUMENT Patent Document Patent Document 1: Japanese Patent Laid-Open No. 2004-52100 Patent Document 2: Japanese Patent Open 2〇 In the resin-coated stainless steel sheet described in Patent Document 2, a chromate-treated layer is formed in order to break the thermal conductivity of the heat-melting resin film. The chromate treatment layer contains a large environmental load. Therefore, the resin-coated stainless steel sheet described in Patent Document 2 has a problem that the environmental load is large. [ SUMMARY OF THE INVENTION An object of the present invention is to provide a laminate for a battery can. The heat-melting resin layer is formed on a stainless steel plate, and is heat-meltable, and the heat-melting resin layer is excellent in adhesion and environmental load is small. The inventors found that 'by the non-mineral steel plate The surface forms an organic-inorganic composite treatment layer containing a cured product of a resin composition, the resin composition having a resin containing a slow group, a resin containing an oxazoline group, and an alkali phosphate compound, and forming a heat-melting property thereon The resin layer can be used to improve the adhesion of the heat-melting resin layer without using hexavalent chromium, and has been studied to complete the invention of 201232119 41400pif. In other words, the first invention of the present invention relates to the following laminated body for a battery can. (1) A laminated body for a battery case, comprising: a stainless steel plate having a first surface and a second surface; and an organic-inorganic composite treatment layer formed on the first portion of the stainless steel plate, and comprising a resin composition The tree sap composition comprises a thiol-containing resin, a siloxane-containing resin, and an acid-filling compound; and a heat-fusible polyolefin-based resin layer formed on the surface of the organic-inorganic composite treatment layer, and The thickness is i〇pm~i(nine) μηι. [2] The laminate for a battery can according to [1], wherein the organic-inorganic composite treatment layer contains a tree-month component of the cured product of 5 mg/m2 to 800 mg/m2 and is contained in a phosphorus conversion amount. The filling component of the above-mentioned cured product of 〇i mg/m2 to 1〇〇mg/m2. [3] The laminate for a battery case according to [1] or [2] wherein the oxazoline group-containing resin in the resin composition is relative to the carboxyl group-containing resin and the oxazoline group-containing resin The ratio of the total amount of the resins is in the range of 2.0% by mass to 50% by mass. [4] The laminate for a battery can according to any one of the above [1], wherein the acid value of the carboxyl group-containing resin is 300 mgKOH/g or more in terms of resin solid content. [5] The laminate for a battery can according to any one of [1], wherein the resin composition further contains a basic zirconium compound, and the organic-inorganic composite treatment layer contains 〇5 in a changeover ratio. The wrong component of the above hard 201238119 compound of mg/m2 to 60 mg/m2. [6] The laminate for a battery can according to [1], wherein an acid having a thickness of 10 μm to 100 μm is further provided between the organic-inorganic composite treatment layer and the heat-fusible polysulfide resin layer. The polyolefin resin layer is modified. [7] The laminate for a battery can according to [1], wherein the stainless steel plate has a thickness of 20 μm to 400 μm. [8] The laminate for a battery can according to [1], further comprising a resin layer formed on the second surface of the stainless steel plate. Further, the second invention of the present invention relates to the following secondary battery. [9] A secondary battery comprising a case in which a molded article of a battery case laminate according to [1] is thermally fused. [Effects of the Invention] According to the present invention, it is possible to produce a laminate for a battery can which is excellent in adhesion of a heat-fusible resin layer without using hexavalent chromium. Therefore, according to the present invention, it is possible to produce a laminate for a battery case in which the adhesion of the heat-fusible resin layer is intimately damaged in a smaller environment. [Embodiment] 1. The laminated body for a battery can of the present invention is a laminated body comprising a stainless steel plate, an organic inorganic composite treatment layer, and a heat-fusible polyolefin-based resin layer. The organic inorganic composite treatment layer is formed on the surface of the stainless steel plate. The hot-melt polyolefin resin layer is directly bonded to the surface of the organic-inorganic composite treatment layer or bonded to the surface of the organic-inorganic composite treatment layer by an acid-modified polyolefin resin. In the present specification, the surface on which the organic-inorganic composite 8 201238119 outer IHOOpif combined treatment layer and the hot-melt synthetic hydrocarbon-based resin layer are formed on the surface of the stainless steel sheet is referred to as "the first surface, and the opposite side surface is referred to as the "second surface". "." When the laminate for a battery can of the present invention is used for a secondary battery, the first surface is an inner surface (electrolyte_surface), and the second surface is an outer surface (outer side surface). Hereinafter, each component will be described. (1) Stainless steel sheet The steel type of the stainless steel sheet is not particularly limited to an austenitic series, a ferrite system (fer), a martensite series, etc. Examples of steel types may include. SUS304, S-face, brain 16, etc. The type of surface polishing of the residual steel sheet is not particularly limited. Examples of types of surface polishing include BA, 2B, 2D, No. 4, HL, etc. The thickness of the plate can be appropriately set according to the required weight or required strength of the battery casing material, the required processing depth, etc. From the viewpoint of reducing the weight of the battery casing material, the thinner the plate thickness, the better the plate is. When the thickness is reduced, the strength and the workability are lower, and the manufacturing cost is increased. From the viewpoint of the strength of the battery casing material, the thickness is preferably 20 μm or more. In addition, even 50 mm is performed. In the deep drawing of the left and right, if the plate thickness is also 400 μηι, it is sufficient. If the strength and processing depth of the battery casing material are usually required, The plate thickness of the plate is preferably in the range of 40 μm to 150 μm. (2) Organic-inorganic composite treatment layer The organic-inorganic composite treatment layer is formed on the first surface of the non-mineral steel sheet. The organic-inorganic composite treatment layer assumes the following functions: The plate and the hot-melt poly 201238119 2 flue-based resin layer (or the acid-modified poly-smoke-based resin layer) are firmly: second, the deterioration or hydrolysis of the gas produced by the non-mineral right = inorganic composite treatment The layer contains a cured resin having a resin tree (8) containing a preservative (4), an i-based resin, and an inorganic phosphate compound (6). The resin containing the silk (A) and the compound (c) containing a shower group are used by The coordination bond and the chemical bond are bonded to each other and are firmly bonded to the non-plate: or the attached. Specifically, the phosphoric acid compound (c) is bonded or attached to the non-essential plate to form an inorganic treatment layer, and It is a function of the reverse of the (4) (4) group which is based on the resin (4), and the resin (8) derived from the prefecture, the resin (8) having a gamma group, and the compound (8) of the test compound (8) are formed. ^The degree of chemical resistance is excellent Organic-inorganic composite treatment of the polar group (fluorenyl group or thiol group) of Erxi'Μιθ(α), high organic-inorganic composite treatment layer and hot-melt polyolefin resin layer (or acid-modified polyolefin system) Adhesiveness of the resin layer. Preferably, the resin binder further contains an organic compound (d). By including an organic compound in the fat composition, it is possible to Bonding between resins is carried out on the ground. In addition, the test compound (7) is finely tested, and the compound (c) is reacted (4) into *dissolved acid salt, and the properties of the organic-inorganic composite layer are improved. This can improve the adhesion of the inorganic composite treatment layer and the adhesion between the organic-inorganic composite a-treatment layer and the hot-melt polyolefin resin layer (or the acid-modified polyene-based system 201238119 resin layer). The organic-inorganic composite treatment layer exhibits excellent poor solubility in water or an aqueous acid solution containing an acid component (such as hydrofluoric acid), an organic solvent, and the like. The organic-inorganic composite treatment layer is obtained by synergistically acting on the three components of the above (A) to (C) or the four components (A) to (D), thereby degrading the liquid electrolyte, the solid organic electrolyte, and the electrolytes. The electrolyte has excellent resistance and can maintain strong adhesion between the organic-inorganic composite treatment layer and the hot-melt polyolefin tree layer (or the acid-modified polyolefin resin layer). The organic-inorganic composite treatment layer is preferably a resin component containing a cured product of the above-mentioned tree residue in a range of 5 mg/m 2 to 8 〇〇 mg/m 2 (from a resin containing a county (A) and contained. Resin (8)), more preferably mg/m2. When the resin component is 2 = at 5 mg/m2, the bovine joint property of the organic solvent composite treatment layer and the hydrocarbon i resin layer (or the acid modified poly-cream layer) cannot be adjusted. No two = : Outside, organic? The composite treatment layer preferably contains a phosphorus component of 0.1 in the range of mg/m to 1 〇〇mg/m2 (hardening mg/m2 to 50 mg/m2 derived from the alkaline phosphate compound resin composition) The range of ♦,)) is better than 0.25 when the amount is less than 0.1 mg/m2, and it is not possible to maintain the enthalpy of the mixed inorganic layer with 201238119 -rx 100 mg/y. ^The content of the scale of the component exceeds that of the polyolefin f-phase lamination treatment layer and the thermal fusion property is low, or the organic-inorganic resin layer) is reduced in the adhesion = organic-inorganic composite treatment layer and the amount is quantified. In the formation of an organic-inorganic rf(1) cloth (organic-inorganic composite treatment liquid) (the concentration of the three components of two or the composition of the resin is adjusted. (Organic,,, and abdomen & treatment liquid) The amount of cloth is adjusted to the above range. In addition, the resin group (8) containing the resin (8) in the resin group formed by the organic domain composite treatment material is compared with the resin containing the secret (4) and the t-containing group. The total amount of the resin (8) is preferably Μf%%5〇〇 In the range of 5Q% by mass to 4 (10)% by mass, the solid content of the resin containing the carboxyl group in the organic-inorganic composite treatment liquid (A) When the ratio is within the above range, the ratio of the carboxyl group to the oxazoline group in the organic-inorganic composite treatment layer can be made into a preferable range. As a result, the ruthenium-based and noisy porphyrin group in the organic-inorganic composite treatment layer can be improved. The crosslink density is increased, and the barrier property of the organic-inorganic composite treatment layer is improved. Further, by making the carboxyl group-containing resin 12 201238119 41400pll 2 into an appropriate range, the stainless steel plate age-old lipid layer can be favorably maintained. Adhesiveness. In the case of the tree containing the moon, the second and the second are not exceeding the above range, 'there are organic-inorganic composite treatments: =:===; _ (the content of the misc conversion of the hemp poly-C is less than Μ2: 1::
==i性降低、或有機無機複合處理層的 ===的擔憂。另外’有機無機複合處理層中的S 層而得輸機複合處理 時所：:::==:=無機複合處理層 錯化合物⑻_、====中的驗性 合處理液）的塗佈量，而調整為上述範圍内有機無機複 分進=明對樹脂組成物所含的上述⑷〜⑼的各成 [含有羧基的樹脂（A) j 13 201238119 • Λ · w Λ ^ 含有叛基的樹脂（Α)與含有噁唑琳基的樹脂（β) 一 起形成立體網狀結構的硬化物，而提高不鏽鋼板與熱融— 性聚烯烴系樹脂層（或酸改質聚烯烴系樹脂層）的密接性^ 例如，含有羧基的樹脂（Α)是使含有羧基的己烯性 不飽和單體聚合而成的具有多個羧基的聚合物。此種含有 羧基的樹脂（Α)的例子可列舉：使選自由丙烯酸、甲美 丙烯酸、衣康酸、順丁烯二酸及反丁烯二酸所組成的群二 中的1種或2種以上的單體進行自由基聚合而成的聚= 物；使上述1種或2種以上的單體、與丨種或2種以上的 其他乙烯性不飽和單體進行自由基聚合而成的共聚物等。' 其他乙烯性不飽和單體的例子包括：丨）（甲基)丙烯酸 2-羥基乙酯或（曱基）丙烯酸2_羥基丙酯、（曱基）丙烯酸令 羥基丁酯、烯丙醇、曱基烯丙醇、（曱基)丙烯酸2_羥基乙 酯與ε-己内酯的加成物等含有羥基的乙烯性不飽和單體； 2)半醯胺（halfamide)或半硫g旨（halfthioester)等含有 羧基的乙烯性不飽和單體；3)(曱基)丙烯醯胺或N_羥甲基 (甲基)丙烯醯胺、N，N-二曱基（甲基)丙烯醯胺、N，N_二丁基 (甲基)丙烯醯胺、N，N-二辛基（曱基)丙烯醯胺、N_單丁基（甲 基)丙烯醯胺、N-單辛基（曱基)丙烯醯胺等含有醯胺基的乙 烯性不飽和單體；4)(甲基)丙烯酸曱酯或（甲基)丙烯酸乙 酯、（曱基）丙烯酸正丁酯、丙烯酸異丁酯、丙烯酸第三丁 酉曰、（曱基)丙烯酸2-乙基己酯、曱基丙稀酸月桂酯、丙稀 酸苯酯、（曱基)丙烯酸異莰酯、曱基丙烯酸環己酯、（曱基） 丙烯酸正丁基環己酯、（曱基)丙烯酸二環戊二烯酯、（甲基） 201238119 ^AHDopit' ==以:曱第基)丙_單體;”苯乙 稀、乙稀基萘等聚合性芳香族化::基二== ;或丙_等乙婦赌·’” 丁二烯:戈異戊ϊ=: 〜m樹脂（a)的質量平均分子量較佳為_ 、軏圍内。在含有羧基的樹脂（A)的質量平均 刀子里小於10()()時’存在有機無機複合處理層的造膜性不 充分，其結果，存在耐化學藥品性亦不充分的擔憂。、另一 方面’在含有絲的樹脂⑷的質量平均分子量超過 5〇〇〇〇〇時’存仙以喊錢無機複合處理層的樹脂组成 物（有機無機複合處理液）的黏度變高，作業性降低的擔 憂。含有羧基的樹脂（A)的質量平均分子量可使用聚苯 乙烯作為標準，根據凝膠滲透層析法（Gpc)的測定結果 而算出。 含有羧基的樹脂（A)可使用市售品。例如，含有緩 基的樹脂（A)可使用：Aron A30 (聚丙烯酸錄；東亞合 成股份有限公司）、JURYMER AC-10L (聚丙烯酸；日本 純藥股份有限公司）、PIA728 (聚衣康酸；磐田化學工業 股份有限公司）、Aqualic HL580 (聚丙烯酸；曰本觸媒股 份有限公司）。 含有叛基的樹脂（A)較佳為使用··相對於全部單體 15== i is reduced, or the === of the organic-inorganic composite treatment layer. In addition, when the S layer in the organic-inorganic composite treatment layer is subjected to the composite treatment of the conveyor::::==:=Application of the inorganic composite treatment layering compound (8)_, ==== in the test solution) The amount of the organic-inorganic compounding in the above range is adjusted to the above-mentioned (4) to (9) of the resin composition. [The resin containing a carboxyl group (A) j 13 201238119 • Λ · w Λ ^ The resin (Α) forms a cured product of a three-dimensional network structure together with the resin (β) containing an oxazoline group, and the stainless steel plate and the hot-melt polyolefin resin layer (or the acid-modified polyolefin resin layer) are improved. Adhesiveness ^ For example, a resin containing a carboxyl group (Α) is a polymer having a plurality of carboxyl groups obtained by polymerizing a carboxyl group-containing hexene-unsaturated monomer. Examples of the carboxyl group-containing resin (anthracene) include one or two selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, maleic acid, and fumaric acid. a polymer obtained by radical polymerization of the above monomers; copolymerization of one or more of the above monomers, or a mixture of two or more kinds of other ethylenically unsaturated monomers by radical polymerization Things and so on. 'Examples of other ethylenically unsaturated monomers include: hydrazine) 2-hydroxyethyl (meth) acrylate or 2-hydroxypropyl (meth) acrylate, hydroxybutyl acrylate, allyl alcohol, a hydroxyl group-containing ethylenically unsaturated monomer such as mercaptopropanol, an adduct of 2-hydroxyethyl (meth)acrylate and ε-caprolactone; 2) halfamide or hemisulfur (halfthioester) and other carboxyl group-containing ethylenically unsaturated monomers; 3) (mercapto) acrylamide or N-hydroxymethyl (meth) acrylamide, N, N-dimercapto (meth) propylene oxime Amine, N,N-dibutyl(meth)acrylamide, N,N-dioctyl(decyl)propenylamine, N-monobutyl(meth)acrylamide, N-monooctyl (fluorenyl) acrylamide-containing ethylenically unsaturated monomer such as decylamine; 4) decyl (meth) acrylate or ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl acrylate Ester, tributyl acrylate, 2-ethylhexyl (decyl) acrylate, lauryl thioglycolate, phenyl acrylate, isodecyl acrylate, cyclohexyl methacrylate, (曱基) n-Butylcyclohexyl acrylate, dicyclopentadienyl (mercapto) acrylate, (methyl) 201238119 ^AHDopit' ==: 曱diyl) propyl _ monomer; styrene, ethylene Polymerizable aromatization such as naphthalene: base 2 ==; or propylene _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Inside. When the mass average knives of the carboxyl group-containing resin (A) are less than 10 () (), the film-forming property of the organic-inorganic composite treatment layer is insufficient, and as a result, chemical resistance is insufficient. On the other hand, when the mass average molecular weight of the resin containing the silk (4) exceeds 5 ', the viscosity of the resin composition (organic-inorganic composite treatment liquid) of the inorganic composite treatment layer is increased. Concerns about reduced sexuality. The mass average molecular weight of the carboxyl group-containing resin (A) can be calculated from the measurement results of gel permeation chromatography (Gpc) using polystyrene as a standard. A commercially available product can be used as the carboxyl group-containing resin (A). For example, a resin (A) containing a slow group can be used: Aron A30 (polyacrylic acid recording; East Asia Synthetic Co., Ltd.), JURYMER AC-10L (polyacrylic acid; Nippon Pure Chemical Co., Ltd.), PIA728 (polyitaconic acid; Putian Chemical Industry Co., Ltd.), Aqualic HL580 (polyacrylic acid; 曰本触媒股份有限公司). Resin-containing resin (A) is preferably used in relation to all monomers 15
201238119 -r x -rW»|-^I 而使用50莫耳％以上的（曱基)丙稀酸或（曱基)丙烯酸衍生 物或該些的組合而成的樹脂’更佳為所構成的全部單體包 含(甲基)丙烯酸或（甲基)丙烯酸衍生物等丙烯酸系單體。 至於含有緩基的樹脂（A)的酸值，就維持與後述的 含有噁唑啉基的樹脂、鹼性磷酸化合物及鹼性锆化合物的 反應性的觀點而言，較佳為以樹脂固體成分換算計為3〇〇 mgKOH/g以上。在含有缓基的樹脂（a)的酸值小於3〇〇 mgKOH/g時’存在含有羧基的樹脂（a)的反應性降低、 密接性及耐蝕性降低的擔憂。含有羧基的樹脂（A)的酸 值的上限以樹脂固體成分換算計為779 mgKOH/g。 就使包含含有羧基的樹脂（A)、含有噁唑琳基的樹脂 (B)及鹼性磷酸化合物（c)(以及作為任意成分的鹼性 锆化合物（D))的樹脂組成物（有機無機複合處理液）的 經時穩^性提高峨㈣言，較料含有祕的樹脂⑷ 的羧基藉由鹼性中和劑進行中和。作為鹼性中和劑，較佳 為使用揮發性胺錢等，其不㈣存於有機錢複合處理 層中’並且阻礙含有縣的細旨（A)與含㈣嗤琳基的 樹月j (B)、鹼性磷酸化合物（c)或鹼性鍅化合物（d) 的交聯反應的可能性小。揮發性胺的例子包括：單乙醇胺、 $乙醇胺、二甲基乙醇胺、三甲基胺、三乙基胺、嗎福 寻。 [含有噁唑琳基的樹脂（Β)] 3、有⑦姆基的樹脂⑻與含有縣的樹脂（八）一 /成立體·結構的硬化物，並提高不鏽鋼板與熱融著 201238119 ^i^oopif 性聚稀煙系樹脂層（或酸改質聚烯烴系樹脂層）的密接性。 含有噁唑啉基的樹脂（B)只要是主鏈為丙烯酸系骨 架、且具有多個噁唑啉基的樹脂，則並無特別限定。 含有噁唑琳基的樹脂（B )中的噁唑°林基的數量可藉 由D惡0坐琳價（weight per oxazoline equivalent) ( g solid/eq.) 來定義。「噁唑啉價」是指每1莫耳噁唑啉基的聚合物的質 量。若聚合物中的噁唑啉基的數量較多，則噁唑啉價變小。 另一方面’若聚合物中的噁唑琳基的數量較少，則噁唑琳 價變大。 含有噁唑啉基的樹脂（B)的噁唑啉價較佳為40 g solid/eq.〜1000 g s〇lid/eq·的範圍内，更佳為 12〇 g s〇lid/eq 〜240 g solid/eq.的範圍内。在噁唑啉價小於4〇 g s〇lid/eq 時’存在含有噁唑啉基的樹脂（B)的黏度變高，形成有 機無機複合處理層時的作業性降低的擔憂。另一方面，在 噁唑啉價超過1000 g solid/eq.時，存在與含有羧基的樹脂 (A)的反應不充分，其結果耐化學藥品性亦不充分的擔 憂。 含有噁唑啉基的樹脂（B)的質量平均分子量較佳為 麵^麵的範圍内。在含有喔。坐琳基的樹脂⑻的 質，^均分子量小於麵時’存在有機無機複合處理層的 造膜性不充分’其縣耐化學藥品性亦不充分的擔憂。另 -方面，在含有射縣的樹脂（B)的質量平均分 超時’存在用以形成有機無機複合處理層的樹脂 組成物（有機無機複合處理液）的轉㈣，健性降低 201238119 —Γ 上一Γ 的擔憂。含有噁唑啉基的樹脂（Β)的質量平均分子量可 使用聚苯乙烯作為標準，根據凝膠滲透層析法（GPC)的 測定結果而算出。 含有噁唑啉基的樹脂（B)可使用市售品。例如含有 嗔唾琳基的樹脂（B)可使用：Epocros WS_300、Epocros WS-500、Epocfos WS_700 (均為日本觸媒股份有限公司）、 NK Linker FX (新中村化學工業股份有限公司）。 [驗性構酸化合物（C)] 鹼性磷酸化合物（C)與不鏽鋼板牢固地結合或附著 而形成無機處理層。另外，鹼性磷酸化合物（c)亦發揮 出作為樹脂（A)所具有的羧基與樹脂（B)所具有的噁唑 啉基的反應觸媒的功能，是用以形成源自含有羧基的樹脂 (A)、含有°惡唾琳基的樹脂（b)及驗性峨酸化合物（匸） 的3成分的高交聯密度的耐化學藥品性優異的有機無機複 合處理層的必需成分。 麟酸化合物（C)必須為驗性。若在包含含有叛基的 樹脂（A)及含有噁唑啉基的樹脂（B)的樹脂組成物（有 機無機處理液）中添加酸性麟酸化合物，則會導致樹脂成 分凝膠化，因此欠佳。 驗性璘酸化合物（C)可廣泛使用公知的鹼性碌酸化 合物。在鹼性水溶液中表現溶解性的鹼性磷酸化合物（C) 的例子包括.二聚構酸鈉、六偏磷酸鈉、焦碟酸钾、焦填 酸鈉、磷酸二氫鉀、磷酸三銨、磷酸氫二銨'磷酸三^、 磷酸氫二鈉等。該些鹼性磷酸化合物可單獨使用，亦可組 201238119 ϋΗυυριι 合2種以上而使用。 [驗性錯化合物（D)] 、驗化合物（D)藉由將樹脂間進行金屬交聯，而 進—步提回有機無機複合處理層的造膜性、阻隔性及對熱 @著性聚烯;^系樹脂層（或酸改質聚稀烴系樹脂層）的密 接性。另外’在形成有機無機複合處理層時所塗佈的樹脂 組成物（有機無機處理液）中添加鹼性锆化合物時，由於 在。彼此、π由氧進行鍵合而高分子量化，因此會進一步提高 ^機無機複合處理層的阻隔性。而且，驗⑽化合物⑼ 藉由人驗1±㈤酸化合物（c )反應而形成不溶性鱗酸錄鹽， 而會進一步提高有機無機複合處理層的阻隔性。 ^化5物（D)與鹼性麟酸化合物（c)同樣必須為鹼 ^ °右在包含含有叛基的樹脂（A)及含有嚼唾琳基的樹 B)的奶日組成物（有機無機處理液）巾添加酸性結 化&物’則料致樹脂成分凝膠化，因此欠佳。 ，知亿&物（D)可廣泛使用公知的鹼性鍅化合物。 合物（D)的例子包括：碳酸麟、碳酸錯鐘、 碳酸結鉀、氫氧化料。該些驗⑽化合物可 早獨使用，亦可組合2種以上而使用。 化人你w丨 。坐琳基的樹脂⑻及驗性碟酸 :::二r上===還可添加驗性 成有機無機複合皮膜時以達到上述含=:=形 19 ,3 201238119 水性溶劑通常為水，但為了調整有機無機複合處__ 性亦可添加醇。作為可添加於水性溶劑中的醇，可 用公知的醇。可添加的醇的例子包括：曱醇戈乙铲F'显 醇、正丁醇等碳數i〜碳數4的醇。該些醇力:旦j 於水為2G質量％以下即可，較佳為丨f量％〜= f。另外’有機無機複合處理液的pH值較佳為7二上° = 中性〜鹼性。在pH值小於7時，會導 ' 膠化’而無法獲得所需要的品質。處理 適用驗、驗土金屬的氧化物或氫氧化物，驗=即= 的鹽中表現鹼性的化合物或氨、胺類等， ’女 揮發性胺或氨等，其阻礙含有絲的樹脂用 唑啉基的樹脂（B)、鹼性磷酸化合物 /、3惡 ，⑼的交聯反應的可能性較，卜揮發性)胺^^化合 :乙醇胺、乙基乙醇胺、二甲基乙醇胺、,匕括. 基胺、嗎福啉等。 一T基胺、三乙 7要將包含含有絲的樹脂⑷、 2例如 ⑻、鹼性恤合物(c)及 ；樹脂 1=職板的表面，進行加熱 ，的表面較佳為進行清潔化。將時，不讀 ^例子潔化方 /合劑凊洗、電暈放電卢 士〜先洗潔劑清洗、 軍敌電處料。献b方法可組合2種以上。 20 201238119 "ΗΗΟορ,ι 塗佈有機無機複合處理液的方法並無特別限定，可廣 /乏使用公知的方法。塗佈方法的例子包括：浸潰法、噴霧 去、輥塗法、棒塗法、淋塗處理法等。就嚴格管理塗佈量 的觀點而言，特佳為輥塗法及棒塗法。 +加熱乾燥是為了使有機無機複合處理液中的水性溶劑 、-及促進上述（Α)〜（D)的各成分的反應，使有機 ‘田、、複5處理層不容化而進行。加熱乾燥的方法可廣泛使 Z:藉由電烘箱的加熱、或藉由紅外供箱的加熱等公知的 12〇V 8〇^3〇〇°^^^ ^ 益機二二？靶圍内。加熱時間根據加熱溫度、或有機 …、枞稷合處理液的塗佈量進行適當調整即可。 萬 (3)熱融著性聚烯烴系樹脂層 =上所述’熱崎性聚_系樹脂層直接接合於 鋼板的第1面的有機無機複合 由: 於有機無機複合處理層上I由形成 的後述酉夂改貝聚烯烴系樹脂而接 。於有機無機複合處理層。熱 钱 將電池内部與外部氣糸娜層承擔 在使用太私明成密封系統的功能。即， 性聚烯烴系樹脂層與另一齡辨二使積層體的熱融著 層或金電極進行轨融著:二融著性料烴系樹月旨 因此不僅二次電池本身劣料又到水解而生成氟酸， 的擔憂。因此’熱融著性聚烯 21 201238119 鏽鋼板對電解液的耐腐蝕性的功能。 構成熱融著性聚埽烴系樹脂層的熱融著性聚稀煙系樹 脂的種類並無特別限定，可自公知的熱融著性聚稀烴系樹 月曰中適當選擇。熱融著性聚烯烴系樹脂 度^乙烯备中密度聚乙稀、高密度聚乙浠、線狀低密度聚 ^稀、乙細-烯煙共聚物、乙稀-丙稀酸共聚物、乙烯-甲 土丙烯酸共聚物、乙秦丙烯酸酉旨共聚物、乙烯·曱基丙稀 酸醋共聚物、乙烯·乙酸乙_共聚物、離子聚合物、聚丙 烯、乙烯_轉共聚物等。該些中，特佳為聚丙稀。 熱融者性聚烯烴系樹脂層的厚度較佳為 〜1〇〇 :’更佳為2G μιη的範圍内。在厚度小 無法以充分的強度進行熱融著。另外，即便 i太1()()μη1’亦未發現熱融著的強度的提高，而於 降低的擔憂。 子度超過⑽卿日夺’存在加工性 声的=複合處理層上配置熱融著性聚烯烴系樹脂 層無特別限定’可自公知的方法中適當選擇。例 複合處理層场賴料性料烴系樹脂 積層法）’亦可在有機無機複合處理層上塗佈執融著性 組成物(塗佈法)。積層糊; # :，nation)法、砂層a (sandi—a—)法 著性聚稀煙系樹脂膜可使用市售品，亦可 ir進行製作。另外，熱融著性聚稀煙系樹 膜了為未延伸樹脂膜，亦可為經單轴或雙轴延伸的樹脂 22 201238119 ^i^oopif 膜。另一方面，塗佈法的例子包括：將樹脂組成物熔融而 藉由棒塗機或輥塗機等進行塗佈的方法、在經熔融的樹脂 組成物中浸潰形成了有機無機複合處理層的不鏽鋼板的^ 法、將樹脂組成物溶解於溶劑中藉由棒塗機或輥塗機、 塗機等進行塗佈的方法等。 (4)酸改質聚烯烴系樹脂層 本發明的積層體在形成於不鏽鋼板的第丨面的有機無 機複合處理層與熱融著性聚烯烴系樹脂層之間可具有酸改 $聚烯烴系樹脂層。酸改質聚烯烴系樹脂層會使有機無機 複s處理層與聚烯烴系樹脂層的密接性進一步提高。 盈構成酸改質聚烯烴系樹脂層的聚烯烴系樹脂的種類並 限定，可自公知的料烴純脂巾適#選擇。酸改 ^聚樹脂的例子包括：藉由不飽和鲮酸進行接枝改 的^烴樹脂、乙烯或丙烯與丙烯酸或曱基丙烯酸的共聚 盃屬父聯烯烴樹脂等。該些中，就耐熱性的觀點而言， 、佳為藉由不飽和羧酸進行接枝改質的烯烴樹脂。 酸改質聚烯烴系樹脂層的厚度較佳為1〇 μπι〜1〇〇 μιη 圍内，更佳為15 μη1〜50 μιη的範圍内。在厚度小於 ^«1時，存在無法充分確保對於有機無機複合處理層的 對^的擔憂。料，即便使厚度超過⑽_，亦未發現 利。、有機無機複合處理層的密接性的提高，而於成本上不 憂。另外，在厚度超過1〇〇 μιη時，存在加工性降低的擔 配置酸改質聚烯烴系樹脂層的方法並無特別限定，可 23 201238.1迅 自=的方法中適當選擇。例如：可在 1熱融著性聚烯煙系樹脂層之間積層酸改質 有機無機複合處理層上塗佈酸改質輯烴^二且^ ==機⑽…外，酸改質_ = H方^脂膜，亦可為經單軸或雙軸延伸的樹脂 塗法將=== ί成了有機無機複合處理層的不鏞鋼板的方 淤塗機蓉^且f物溶解於溶劑中而藉由棒塗機或輕塗機、 方疋塗機荨進行塗佈的方法等。 (5)外層樹脂層 明的積層體可在不鏽鋼板的第2面侧具有樹脂層 私用^稱為:外層樹脂層」）。外層樹脂層可提高電池外 a ;〃、所要求的加卫性、設計性、耐刺性、絕緣性等。 所I外層柯脂層的樹脂的麵並無特別限定，可根據 自八I、特性（加工性、設計性、耐刺性、絕緣性等）而 樹脂中適當選擇。另外，外層樹脂層的厚度亦無 irt ’可根據所要求的特性進行適當設定。而且，外 曰树月曰層可為單層，亦可為2層以上的多層。 盘為-H上所述I發明的積層體由於在不鏽鋼板的表面 居一*者性聚烯㈣樹脂層之間具有有機減複合處理 θ因此熱w虫著性聚婦楚系樹腊層的密接性優異，上述有 24 201238119 ^ΙΗΌΟρΠ 機無機複合處理層包含具有含有叛基的樹脂、含有嚷 基的樹脂及驗性概化合物的樹脂組成物的硬化物。 2.二次電池 本發明的積層體可較佳地料二次電池的外 I:狀:次電池二形狀並不特別限定於長方體的角筒狀 ΐ 二 的種類亦不特別限定於鋰離子電 池、齡合物電池、錄氫電池、鎳鎖電池等。 甩 ㈣積層體作為二次電池的外殼材料(-=)時，祕級本發明的積層體彼此 : 可使經成形加工的積層體彼此貼合，4二: 體進行成形加工。將本發明的接β Α力J僅將一積層 特別限定，可自壓製加^或拔曰-成形加工的方法並無 方法中適當選擇。卿 使本發明的積層體的第1面的方法較佳為， 面）彼此合在1，藉由熱融行層被覆的 明的積層體成形加工而得的盒體中電收:’只要在將本發 黏接即可。 内容部，藉由熱融著進行 以下，參照實例對本發明進 並不限定於該些實例。 仃砰細地說明，但本發明 實例 供試不鏽鋼板是準備板厚201238119 -rx -rW»|-^I, using 50 mol% or more of (mercapto)acrylic acid or (mercapto)acrylic acid derivative or a combination of these resins is more preferably composed of all The monomer contains an acrylic monomer such as (meth)acrylic acid or a (meth)acrylic acid derivative. The acid value of the resin (A) containing a slow group is preferably a resin solid content from the viewpoint of maintaining reactivity with an oxazoline group-containing resin, an alkali phosphate compound, and a basic zirconium compound to be described later. The conversion is 3 〇〇 mgKOH/g or more. When the acid value of the resin (a) containing a slow group is less than 3 〇〇 mgKOH/g, there is a concern that the reactivity of the resin (a) having a carboxyl group is lowered, and the adhesion and corrosion resistance are lowered. The upper limit of the acid value of the carboxyl group-containing resin (A) is 779 mgKOH/g in terms of resin solid content. A resin composition (organic-inorganic) comprising a carboxyl group-containing resin (A), an oxazoline-containing resin (B), and an alkali phosphate compound (c) (and a basic zirconium compound (D) as an optional component) The time-dependent stability of the composite treatment liquid is increased (4), and the carboxyl group of the resin (4) containing the secret is neutralized by an alkaline neutralizing agent. As the alkaline neutralizing agent, it is preferred to use a volatile amine or the like, which is not (IV) stored in the organic money composite treatment layer' and hinders the inclusion of the county's fine purpose (A) and the (four) 嗤琳基's tree month j ( B) The crosslinking reaction of the basic phosphoric acid compound (c) or the basic hydrazine compound (d) is less likely. Examples of volatile amines include: monoethanolamine, ethanolamine, dimethylethanolamine, trimethylamine, triethylamine, and phloem. [Resin (Β) containing oxazolyl] 3. Resin (8) with 7 m base and hardened material containing resin (8)/established body structure of the county, and improved stainless steel plate and heat fusion 201238119 ^i The adhesion of the ^oopif poly-smoke resin layer (or the acid-modified polyolefin resin layer). The oxazoline group-containing resin (B) is not particularly limited as long as it is a resin having a main chain of an acrylic skeleton and a plurality of oxazoline groups. The number of oxazolidine groups in the oxazoline-containing resin (B) can be defined by the weight per oxazoline equivalent (g solid/eq.). "oxazoline valence" means the mass of the polymer per 1 mole of oxazolinyl group. If the amount of the oxazoline group in the polymer is large, the oxazoline valence becomes small. On the other hand, if the number of oxazoline groups in the polymer is small, the oxazoline valence becomes large. The oxazoline group-containing resin (B) preferably has a oxazoline valence of 40 g solid/eq. to 1000 gs 〇lid/eq·, more preferably 12 〇gs〇lid/eq to 240 g solid. Within the scope of /eq. When the oxazoline valence is less than 4 〇 g s〇lid/eq, the viscosity of the oxazoline group-containing resin (B) is high, and the workability in forming the organic inorganic composite treatment layer may be lowered. On the other hand, when the oxazoline valence exceeds 1000 g of the solid/eq., the reaction with the carboxyl group-containing resin (A) is insufficient, and as a result, the chemical resistance is insufficient. The mass average molecular weight of the oxazoline group-containing resin (B) is preferably in the range of the surface. Contains 喔. When the resin of the resin (8) is less than the surface, the film-forming property of the organic-inorganic composite treatment layer is insufficient, and the chemical resistance of the county is insufficient. On the other hand, in the case of the resin (B) containing the shots, the mass average timeout 'has the reversal of the resin composition (organic-inorganic composite treatment liquid) for forming the organic-inorganic composite treatment layer, and the health is lowered. 201238119 - Γ The last worry. The mass average molecular weight of the oxazoline group-containing resin (Β) can be calculated from the measurement results of gel permeation chromatography (GPC) using polystyrene as a standard. A commercially available product can be used for the oxazoline group-containing resin (B). For example, resin (B) containing hydrazine resin can be used: Epocros WS_300, Epocros WS-500, Epocfos WS_700 (both Nippon Catalyst Co., Ltd.), and NK Linker FX (Naka Nakamura Chemical Co., Ltd.). [Analytic acid compound (C)] The basic phosphoric acid compound (C) is firmly bonded or adhered to a stainless steel plate to form an inorganic treatment layer. In addition, the basic phosphoric acid compound (c) also functions as a reaction catalyst of a carboxyl group of the resin (A) and an oxazoline group of the resin (B), and is used to form a resin derived from a carboxyl group. (A) An essential component of the organic-inorganic composite treatment layer which is excellent in chemical resistance of the high-crosslinking density of the three components of the resin (b) and the phthalic acid compound (匸). The linonic acid compound (C) must be an inspective. When an acidic linonic acid compound is added to a resin composition (organic inorganic treatment liquid) containing a resin (A) containing a thiol group and a resin (B) containing an oxazoline group, the resin component is gelated, and thus owes good. A well-known basic acid compound can be widely used as the phthalic acid compound (C). Examples of the basic phosphoric acid compound (C) which exhibits solubility in an aqueous alkaline solution include sodium dimerate, sodium hexametaphosphate, potassium pyrosilicate, sodium pyroantimonate, potassium dihydrogen phosphate, and triammonium phosphate. Diammonium hydrogen phosphate 'sodium phosphate, disodium hydrogen phosphate, and the like. These basic phosphoric acid compounds may be used singly or in combination of two or more of 201238119 ϋΗυυριι. [Inspective Compound (D)], Test Compound (D), by metal-crosslinking between resins, further advances the film-forming property, barrier property, and heat-convergence of the organic-inorganic composite treatment layer. The adhesion of the olefinic resin layer (or the acid-modified poly-saturated resin-based resin layer). Further, when a basic zirconium compound is added to the resin composition (organic inorganic treatment liquid) applied when the organic-inorganic composite treatment layer is formed, it is. Since π is bonded to each other by oxygen and is highly polymerized, the barrier property of the inorganic composite treatment layer is further improved. Further, the compound (9) is tested (10) to form an insoluble sulphuric acid salt by a reaction of the human test 1±(penta) acid compound (c), and the barrier property of the organic-inorganic composite treatment layer is further improved. The chemical substance 5 (D) and the basic linonic acid compound (c) must also be an alkali compound in the form of a milk-containing composition containing a repressive resin (A) and a chelate-containing tree B). Inorganic treatment liquid) The addition of acidic acidification & the material causes the resin component to gel, which is not preferable. A well-known basic hydrazine compound can be widely used for the genus & (D). Examples of the compound (D) include: carbonate, carbonic acid, potassium carbonate, and hydroxide. These compounds of the test (10) may be used alone or in combination of two or more. Make people w丨. Sitting on the Lin-based resin (8) and the test disc acid::: two r on === can also be added to the organic-inorganic composite film to achieve the above === shape 19,3 201238119 The aqueous solvent is usually water, but In order to adjust the organic-inorganic composite, the alcohol may also be added. As the alcohol which can be added to the aqueous solvent, a known alcohol can be used. Examples of the alcohol which can be added include an alcohol having a carbon number i to a carbon number of 4, such as decyl alcohol, F', and n-butanol. The alcoholic force may be 2 g% by mass or less, preferably 丨f%%==f. Further, the pH of the organic-inorganic composite treatment liquid is preferably from 7 to 2 ° = neutral to alkaline. When the pH is less than 7, it will lead to 'gelling' and the desired quality will not be obtained. Treatment of oxides or hydroxides of applicable test and soil metals, test = alkaline compounds such as ammonia, amines, etc., 'female volatile amines or ammonia, etc., which hinder the resin containing silk The oxazoline-based resin (B), the basic phosphoric acid compound/, the three oxins, and the (9) cross-linking reaction are more likely to be combined with the volatility of the amine: ethanolamine, ethylethanolamine, dimethylethanolamine, hydrazine Including. Amine, morphine and the like. A T-based amine or triethyl 7 is to be subjected to heating, and the surface of the resin containing the silk (4), 2, for example, (8), the basic conjugate (c), and the resin 1 = the plate is preferably cleaned. . When not, do not read ^ example cleansing side / mixture wash, corona discharge Lu ~ first detergent cleaning, military and enemy electric materials. Two methods can be combined in the b method. 20 201238119 "ΗΗΟορ,ι The method of applying the organic-inorganic composite treatment liquid is not particularly limited, and a known method can be widely used. Examples of the coating method include a dipping method, a spray removing method, a roll coating method, a bar coating method, a shower coating method, and the like. From the viewpoint of strictly managing the coating amount, a roll coating method and a bar coating method are particularly preferable. + Heating and drying is carried out in order to prevent the reaction of the organic solvent in the organic-inorganic composite treatment liquid and the respective components of the above (Α) to (D), and to prevent the organic "field" and the complex 5 treatment layer from being incapable. The method of heating and drying can be widely used. Z: Well-known 12〇V 8〇^3〇〇°^^^ ^ by machine heating or heating by infrared box. Inside the target. The heating time may be appropriately adjusted depending on the heating temperature or the coating amount of the organic solvent or the kneading treatment liquid. 10,000 (3) hot-melt polyolefin resin layer = the above-mentioned organic-inorganic composite in which the 'hot-smelting poly-based resin layer is directly bonded to the first surface of the steel sheet is formed by: on the organic-inorganic composite treatment layer I The latter is tamper-evident with a polyolefin resin. In the organic-inorganic composite treatment layer. Hot money Takes the inside and outside of the battery into the function of the sealing system. In other words, the polyolefin-based resin layer is fused with the hot-melt layer or the gold electrode of the laminate in another age: the second-melting hydrocarbon-based tree is not only inferior to the secondary battery itself. There is concern about hydrolysis to form hydrofluoric acid. Therefore, the function of the hot-melt polyene 21 201238119 rust steel plate to the corrosion resistance of the electrolyte. The type of the heat-fusible poly-smoke-based resin constituting the heat-melting polyalkylene-based resin layer is not particularly limited, and can be appropriately selected from known hot-melt polycondensate trees. Heat-melting polyolefin resin, ethylene medium density polyethylene, high-density polyethylene, linear low-density, ethylene-olefin copolymer, ethylene-acrylic acid copolymer, ethylene - a tert-acrylic copolymer, a vinyl methacrylate copolymer, an ethylene-mercapto acrylate copolymer, an ethylene-acetic acid copolymer, an ionic polymer, a polypropylene, an ethylene-trans copolymer, and the like. Among these, it is particularly preferred to be polypropylene. The thickness of the hot-melt polyolefin resin layer is preferably in the range of 〜1〇〇 :' more preferably 2G μηη. In the case of small thickness, it is not possible to perform thermal fusion with sufficient strength. Further, even if i too 1 () () μ η 1 ', no improvement in the strength of the heat fusion was observed, and there was a concern of lowering. The number of sub-mass exceeds (10), and there is a processability sound. The heat-fusible polyolefin-based resin layer is not particularly limited in the composite treatment layer, and can be appropriately selected from known methods. For example, a composite treatment layer field-based hydrocarbon resin may be applied to the organic-inorganic composite treatment layer (coating method). Laminating paste; #:,nation) method, sand layer a (sandi-a-) method The polythene resin film can be used as a commercial product or ir. Further, the heat-melting poly-smoke system film is an unstretched resin film, and may be a uniaxially or biaxially stretched resin 22 201238119 ^i^oopif film. On the other hand, examples of the coating method include a method of melting a resin composition and coating by a bar coater or a roll coater, and impregnation in a molten resin composition to form an organic-inorganic composite treatment layer. A method of coating a stainless steel plate, a method of dissolving a resin composition in a solvent, a coating by a bar coater, a roll coater, a coater, or the like. (4) Acid-modified polyolefin-based resin layer The laminate of the present invention may have an acid-modified polyolefin between the organic-inorganic composite treatment layer formed on the second surface of the stainless steel sheet and the heat-fusible polyolefin-based resin layer. A resin layer. The acid-modified polyolefin resin layer further improves the adhesion between the organic-inorganic composite s-treated layer and the polyolefin-based resin layer. The type of the polyolefin-based resin constituting the acid-modified polyolefin-based resin layer is limited, and can be selected from known hydrocarbons. Examples of the acid-modified poly-resin include a hydrocarbon resin grafted with an unsaturated citric acid, a copolymer of ethylene or propylene with acrylic acid or methacrylic acid, and a parent-linked olefin resin. Among these, from the viewpoint of heat resistance, an olefin resin which is graft-modified by an unsaturated carboxylic acid is preferred. The thickness of the acid-modified polyolefin resin layer is preferably in the range of 1 μm to 1 μm, more preferably 15 μη to 50 μm. When the thickness is less than ^«1, there is a fear that the adhesion to the organic-inorganic composite treatment layer cannot be sufficiently ensured. Even if the thickness exceeds (10) _, no benefit is found. The adhesion of the organic-inorganic composite treatment layer is improved, and the cost is not worried. In addition, when the thickness exceeds 1 μm, the method of supporting the acid-modified polyolefin-based resin layer having a decrease in workability is not particularly limited, and may be appropriately selected from the methods of 2012 2012-1. For example, the acid-modified organic-inorganic composite treatment layer may be coated on the acid-modified organic-inorganic composite treatment layer between the heat-melting polyalkylene-based resin layer, and the acid-modified hydrocarbon is added. H-party grease film, which can also be a uniaxial or biaxially stretched resin coating method, === ί becomes an organic-inorganic composite treatment layer of a non-stained steel plate, and the f material is dissolved in a solvent. The coating method is carried out by a bar coater or a light coater or a square coater. (5) Outer resin layer The laminate of the outer layer may have a resin layer on the second surface side of the stainless steel sheet. The outer resin layer can improve the outside of the battery, the required susceptibility, design, stab resistance, insulation and the like. The surface of the resin of the outer layer of the ketone layer is not particularly limited, and may be appropriately selected from the resin according to the characteristics (processability, designability, puncture resistance, insulation, etc.). Further, the thickness of the outer layer resin layer is also not set to irt', and can be appropriately set according to the required characteristics. Further, the outer eucalyptus layer may be a single layer or a multilayer of two or more layers. The laminate of the invention of the type I-H has an organic subtractive treatment θ between the resin layers of the surface of the stainless steel sheet, so that the heat is worm-like. The above-mentioned 24 201238119 ΙΗΌΟ Π 机 inorganic composite treatment layer contains a cured product of a resin composition having a resin containing a thiol group, a resin containing a thiol group, and an organic compound. 2. Secondary Battery The laminate of the present invention can preferably be made of the outer surface of the secondary battery. The shape of the secondary battery is not particularly limited to the rectangular tubular shape. The type of the secondary battery is also not particularly limited to the lithium ion battery. , age composite battery, hydrogen recording battery, nickel lock battery, etc. (4) When the laminated body is used as the outer casing material (-=) of the secondary battery, the laminated bodies of the present invention are secretly bonded to each other: the laminated bodies which are formed by molding can be bonded to each other, and the forming process can be carried out. The bonding force J of the present invention is particularly limited to a laminate layer, and can be appropriately selected from the methods of press-fitting or drawing-forming processing. In the method of forming the first surface of the laminated body of the present invention, it is preferable that the surface of the first surface of the laminated body of the present invention is combined with each other, and the bright laminated body covered by the hot-melt layer is formed into a box body: Adhere the hair to it. The content portion is subjected to heat fusion. Hereinafter, the present invention is not limited to the examples with reference to examples. Illustrated in detail, but the example of the present invention is to test the thickness of the stainless steel plate
材）。將各不鏽鋼板進行鹼脫腊‘ 7；的麵04 (BA 值12、液溫6(TC、浸 25 2〇1238ll9 ---- 潰時間1分錄、，么 處理 j俊’使用棒塗機在各不鏽鋼板的表面塗佈 液），1有，無機複合處理液、有機處理液或無機處理 表面形、160 C的烘箱中乾燥45秒，從而在各不鏽鋼板的 機理層（有機錢複合處理層、有祕理層或無 的樹ί例1〜實例3中’塗佈作為處理液的包含含有緩基 物（曰（Α)、含有噁唑啉基的樹脂（Β)及鹼性磷酸化合 C)的有機無機複合處理液。實例4〜實例11中，塗 的=處理液的包含含有羧基的樹脂（Α)、含㈣嗤淋基 沾二知（Β)、鹼性磷酸化合物及鹼性锆化合物（d) 的有機無機複合處理液（參照表1)。 另一方面’比較例i中，塗佈作為處理液的包含含有 土的樹脂（A)及含有。惡唾啉基的樹脂⑻的有機處理 比較例2巾’塗佈作域理液的包含含有叛基的樹脂 、A) $有°惡唾琳基的樹脂（B)及驗性錯化合物（d) 的有機無機複合處理液。比較例3中，塗佈作為處理液的 包含鹼性磷酸化合物（C)及鹼性锆化合物（D)的無機處 理液（參照表1)。 含有羧基的樹脂（A)按以下順序製備。首先，在具 有加熱裝置及攪拌裝置的4 口容器中加入離子交換水7乃 質量份，一邊進行攪拌及氮氣回流一邊將離子交換水加熱 至8〇t。接著，一邊進行加熱、攪拌及氮氣回流，一邊使 用滴液漏斗歷時3小時滴加丙烯酸120質量份、丙稀酸乙 醋20質量份及甲基丙稀酸2-羥基乙酯6〇質量份的混合單 體液、過硫酸銨1.6質量份、離子交換水23 4質量份二混 26 201238119 "ti'i-uupu' 二液。^加結束後，亦繼續加熱、攪拌及氮氣回流2小時。 j後i停止加熱及氮氣回流，一邊攪拌一邊將内容液冷卻 至30X：。接著，添加25質量％氨水113質量份及離子交 換^ 887質量份。攪拌2〇分鐘後，使用200篩孔（mesh) 的筛進行過濾’而獲得無色透明的含有羧基的樹脂（A) 的水溶液。所得的含有羧基的樹脂（A)的水溶液的不揮 發成分為10質量％。另外，含有羧基的樹脂（A)的酸值 以固體成分換算計為467 mgKOH/g。含有羧基的樹脂（A) 的質量平均分子量為58〇〇〇。 含有°惡唾琳基的樹脂（B)是使用Epocros WS-300( B1 ) (噁唑啉價：120gs〇lid/eq.、質量平均分子量：12〇〇〇〇 ; 日本觸媒股份有限公司）。鹼性磷酸化合物是使用磷 酉文一氫鈉。驗性結化合物（D)是使用碳酸錯鈉 H值為 8.5。 表1表示將各處理液（有機無機複合處理液、有機處 理液或無機處理液）塗佈於不鏽鋼板的表面時的每i m2 的塗佈層的各成分的含量。關於鹼性磷酸化合物（C)及 鹼性錯化合物（D)的含量，是使用螢光X射線解析裝置 (AXIS-NOVA ;島津製作所股份有限公司），測定塗佈了 各處理液的不鏽鋼板的每i m2的塗佈層的磷量、鍅量。另material). Each stainless steel plate is subjected to alkali dewaxing '7' face 04 (BA value 12, liquid temperature 6 (TC, dip 25 2〇1238ll9 ---- break time 1 entry, what process j Jun' use bar coater The coating liquid on the surface of each stainless steel plate, 1 has an inorganic composite treatment liquid, an organic treatment liquid or an inorganic treatment surface shape, and is dried in a 160 C oven for 45 seconds, thereby forming a mechanism layer in each stainless steel plate (organic money composite treatment) Layer, having a secret layer or no tree ί1 to 3, 'coating as a treatment liquid containing a slow-base material (曰(Α), an oxazoline group-containing resin (Β) and an alkaline phosphate compound The organic-inorganic composite treatment liquid of C). In the examples 4 to 11, the coating solution containing the carboxyl group-containing resin (Α), containing (4) 嗤 基 沾 沾 、 、, alkaline phosphate compound and alkaline The organic-inorganic composite treatment liquid of the zirconium compound (d) (see Table 1). On the other hand, in Comparative Example i, a resin containing a soil (A) and a resin containing an oxasulfinyl group (8) as a treatment liquid were applied. Organic treatment comparison example 2 towel 'coating domain liquid containing resin containing rebel, A) The organic-inorganic composite treatment liquid of the base resin (B) and the test compound (d). In Comparative Example 3, the inorganic acid containing the basic phosphoric acid compound (C) and the basic zirconium compound (D) as a treatment liquid is applied. The treatment liquid (see Table 1). The carboxyl group-containing resin (A) was prepared in the following order. First, 7 parts by mass of ion-exchanged water was added to a four-port container equipped with a heating device and a stirring device, and while stirring and nitrogen reflux were performed. The ion-exchanged water was heated to 8 Torr, and then 120 parts by mass of acrylic acid, 20 parts by mass of acetonitrile acetate, and methyl acrylate were added dropwise using a dropping funnel over 3 hours while heating, stirring, and refluxing with nitrogen. 2-hydroxyethyl ester 6 parts by mass of mixed monomer liquid, 1.6 parts by mass of ammonium persulfate, 23 parts by mass of ion-exchanged water, 2 mixed 26 201238119 "ti'i-uupu' two liquids. Heating, stirring, and nitrogen reflux were continued for 2 hours. After i was stopped, the heating and nitrogen reflux were stopped, and the content liquid was cooled to 30X while stirring. Then, 113 parts by mass of 25 mass% aqueous ammonia and ion exchanged 887 parts by mass were added. Minutes An aqueous solution of a colorless transparent carboxyl group-containing resin (A) was obtained by filtration using a sieve of 200 mesh. The non-volatile content of the aqueous solution of the obtained carboxyl group-containing resin (A) was 10% by mass. The acid value of the carboxyl group-containing resin (A) is 467 mgKOH/g in terms of solid content, and the carboxyl group-containing resin (A) has a mass average molecular weight of 58 Å. The resin (B) containing the oxalate group is Epocros WS-300 (B1) (oxazoline valence: 120 gs 〇lid/eq., mass average molecular weight: 12 Å; Nippon Shokubai Co., Ltd.) was used. The alkaline phosphate compound is sodium phosphamate. The test compound (D) was a sodium carbonate equivalent H value of 8.5. Table 1 shows the content of each component of the coating layer per i m 2 when each treatment liquid (organic-inorganic composite treatment liquid, organic treatment liquid or inorganic treatment liquid) was applied to the surface of a stainless steel plate. The content of the basic phosphoric acid compound (C) and the basic compound (D) was measured using a fluorescent X-ray analyzer (AXIS-NOVA; Shimadzu Corporation) to measure the stainless steel plate to which each treatment liquid was applied. The amount of phosphorus and the amount of ruthenium per 1 m 2 of the coating layer. another
外，關於樹脂成分的（A) + (B)合計量，是使用螢光X 射線解析裝置，測定塗佈了各處理液的不鏽鋼板中每i m2 的塗佈層的碳量，將換算係數設為2倍而由碳量進行換算 而求出。 、 27 201238119 [表1] 樹脂（A) (mg/m2) 樹脂（B) (mg/m2) 樹脂成分 (B)/((A) + ⑻〕 (質量％) (Α)~4Γ(Β) 合計量 (mg/m2) 化合物（C) 磷換算量 (mg/m2) 化合物（D) 锆換算量 (mg/m2) 實例1 4.75 0,25 5.0 5 10 *' 一 實例2 30 10 25.0 40 30 實例3 100 20 16.7 120 40 實例4 100 20 16.7 120 40 20 ~ 實例5 100 20 16.7 120 5 10 實例6 200 200 50.0 400 50 30 實例7 500 150 23.1 650 30 30 實例8 100 300 75.0 400 50 30 實例9 600 300 33.3 900 50 30 實例10 100 20 16.7 120 120 20 實例11 200 200 50.0 400 50 70 比較例1 30 10 25.0 40 比較例2 100 20 16.7 120 • 20 比較例3 姑士日&广Δ' 表古紐J •从姐日& ** - 80 40 樹脂（B):含有噁唑啉基的樹脂 化合物（C):鹼性磷酸化合物 化合物（D):鹼性锆化合物 實例1、實例3中，藉由熱層壓法在形成了有機無機 複合處理層的不鏽鋼板的表面上積層膜厚30 μιη的無延伸 聚丙烯膜（PYLENFILMCT、P1128 ;東洋紡績股份有限 公司），而製作積層體（參照表2)。具體而言，將形成了 有機無機複合處理層的不鑛鋼板以基材溫度為的方 式在烘箱中加熱後，藉由加壓輥在其表面暫時層積無延伸 聚丙烯膜，將暫時層壓的鋼板在160。(：的烘箱中加熱60秒 而製作積層體。 另外，實例2、實例4〜實例11及比較例丨〜比較例3 中’在形成了處理層（有機無機複合處理液、有機處理液 28 201238119 ^ΐΊ-υυρι^ 或無機處理液）的不_鋼板的表面，重疊2片 =膜與上述無延伸聚丙賴，藉由上述熱層壓法進行产 積(參縣2)。酸改f聚丙烯膜是使用^ 只出钱以30 μηι的厚度擠出酸改質聚丙烯（M P553A，三菱化學股份有限公司）而製備。 [表2]In addition, the total amount of (A) + (B) of the resin component is measured by using a fluorescent X-ray analyzer, and the amount of carbon per 1 m 2 of the coating layer in the stainless steel sheet to which each treatment liquid is applied is measured. It is calculated by converting the amount of carbon by two times. , 27 201238119 [Table 1] Resin (A) (mg/m2) Resin (B) (mg/m2) Resin component (B)/((A) + (8)] (% by mass) (Α)~4Γ(Β) Total amount (mg/m2) Compound (C) Phosphorus equivalent amount (mg/m2) Compound (D) Zirconium equivalent amount (mg/m2) Example 1 4.75 0,25 5.0 5 10 *' One example 2 30 10 25.0 40 30 Example 3 100 20 16.7 120 40 Example 4 100 20 16.7 120 40 20 ~ Example 5 100 20 16.7 120 5 10 Example 6 200 200 50.0 400 50 30 Example 7 500 150 23.1 650 30 30 Example 8 100 300 75.0 400 50 30 Example 9 600 300 33.3 900 50 30 Example 10 100 20 16.7 120 120 20 Example 11 200 200 50.0 400 50 70 Comparative Example 1 30 10 25.0 40 Comparative Example 2 100 20 16.7 120 • 20 Comparative Example 3 士士日&广Δ' table Gunu J • From Sister Day & ** - 80 40 Resin (B): Resin compound containing oxazoline group (C): Basic phosphoric acid compound (D): Basic zirconium compound Example 1, Example 3 A non-stretched polypropylene film having a film thickness of 30 μm was laminated on the surface of a stainless steel plate on which an organic-inorganic composite treatment layer was formed by a thermal lamination method (PYLENFILMCT, P1128; Toyobo Co., Ltd.) Co., Ltd.), and to make a laminate (refer to Table 2). Specifically, the non-mineral steel sheet in which the organic-inorganic composite treatment layer is formed is heated in an oven in the manner of a substrate temperature, and is pressed by a pressure roller. The surface was temporarily laminated without a stretched polypropylene film, and the temporarily laminated steel sheet was heated in an oven of 160° for 60 seconds to prepare a laminate. Further, Example 2, Example 4 to Example 11 and Comparative Example 丨 to Comparative Example 3 In the surface of the non-steel plate on which the treatment layer (organic-inorganic composite treatment liquid, organic treatment liquid 28 201238119 ^ΐΊ-υυρι^ or inorganic treatment liquid) is formed, two sheets are overlapped = the film and the above-mentioned non-extended polyprecipitate The above thermal lamination method is used for the production (Shenxian 2). The acid-modified polypropylene film is prepared by extruding acid-modified polypropylene (M P553A, Mitsubishi Chemical Corporation) with a thickness of 30 μηι. . [Table 2]
-----___ "^ -fe,| 1 - ---- __ 酸改質聚丙烯膜 — _ 孓Γ例1 __ 無 右 W~~~--~ ___ ff 例 3 _ 例4 無 古 有 —i----— ίΓ 例 5 Ή 有 _ if 例 6 "ΤΓΤΤ^ζ------ 有 -Λ-- 1Γ例7 有 ~~1~--- __51 例 8 有 Ή '~~-- — If 例 9 有 有 --»~~~ - if 例 10 有 f?例 11 有 -Ί~— —. 比較例1 比較例2 _ 比較例3 -ί_ 有 七 右 i-- 有 ~ϊ --- — J 自所得的各積層體（實例1〜實例11、比較例 比 較例3 )切出試驗片（15 mmxlOO mm)，依據jis K6854 3 以拉伸速度300 mm/分鐘進行密接性試驗。將i延伸嗲丙 烯膜（實例1、實例3)或酸改質聚⑽膜（實例2、$ 4〜實例U及比較例卜比較例3)對有機無理^ =接強度為測15麵以上的情形評價為 = N/15 mm以上且小於15 N/15 mm的情形 」 小於10 N/15 mm的情形評價為「X」。°貝’’’、〇」’網 29 201238119t 另外，自所得的各積層體（實例丨〜實例n、比較例 1〜比較例3)切出新的試驗片（35inmx35mm)，並進行 耐電解液試驗。首先，在可密閉的特氟綸（註冊商標）製 容器内中，將各試驗片在85°C的電解液中浸潰7日、 曰、21日或28日後，將各試驗片藉由乙醇進行清洗並乾 燥。電解液疋在碳酸乙二酯與碳酸二乙酯的混合液（1 : j ) 中以1莫耳/升的方式添加六氟化磷酸鋰（LiPF6)而製備。 接著，將透明膠帶貼附於各試驗片的膜上後，將透明膠帶 剝離，而評價膜密接狀態。將透明膠帶剝離試驗後膜亦未 制離的情形sf價為「◎」，將透明膠帶剝離試驗前膜未剝離 但5式驗後剝離的情形評價「〇」’將僅在電解液中浸潰時膜 剝離的情形評價為「X」。 、 一將密接性試驗及耐電解液試驗的結果示於表3。「_」 表示放棄繼續試驗。 、 」 [表3]-----___ "^ -fe,| 1 - ---- __ Acid modified polypropylene film - _ Example 1 __ No right W~~~-~~ ___ ff Example 3 _ Example 4 Ancient - i----- ίΓ Example 5 Ή _ if Example 6 "ΤΓΤΤ^ζ------ 有-Λ-- 1 Example 7 There are ~~1~--- __51 Example 8 '~~-- — If Example 9 has ---~~~ - if Example 10 has f? Example 11 has -Ί~—. Comparative Example 1 Comparative Example 2 _ Comparative Example 3 - ί_ There are seven right i- - There are ~ϊ --- — J From the obtained laminates (Examples 1 to 11 and Comparative Example 3), test pieces (15 mm x 100 mm) were cut out at a tensile speed of 300 mm/min according to jis K6854 3 The adhesion test was performed. I extended the propylene film (Example 1, Example 3) or the acid modified poly (10) film (Example 2, $4~Example U, and Comparative Example Comparative Example 3) to the organic irrational ^ = joint strength of 15 or more The case was evaluated as = N/15 mm or more and less than 15 N/15 mm. The case of less than 10 N/15 mm was evaluated as "X". ° ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' test. First, each test piece was immersed in an electrolyte solution at 85 ° C for 7 days, 曰, 21 days, or 28 days in a container made of a sealable Teflon (registered trademark), and each test piece was made of ethanol. Wash and dry. The electrolyte solution was prepared by adding lithium hexafluorophosphate (LiPF6) to a mixed liquid (1:j) of ethylene carbonate and diethyl carbonate at 1 mol/liter. Next, after attaching the scotch tape to the film of each test piece, the scotch tape was peeled off, and the film adhesion state was evaluated. When the film was not peeled off after the scotch tape peeling test, the sf price was "◎", and the film was not peeled off before the scotch tape peeling test, but the peeling of the film after the test was evaluated. "〇" will be immersed only in the electrolyte. The case where the film was peeled off was evaluated as "X". The results of the adhesion test and the electrolyte resistance test are shown in Table 3. "_" means to abandon the test. , " [table 3]
膜的黏接強度 實例1 0 實例2 實例3 ◎ 實例4 0 ◎ 實例5 ◎ __實例6 ___ ◎ 實’如丨! 7 ◎ 實例8 〇 實例9 實例10 〇 實例11 比較例1 〇 比較例2 〇 ◎ 比較例3 ◎ 30 201238119 實例1〜實例11的積層體由於緻密地形成包含具有含 有羧基的樹脂（A)、含有噁唑啉基的樹脂（B)及鹼性磷 酸化合物（C)的樹脂組成物的硬化物的有機無機^合處 理層’因此對於膜密接性及耐電解液性可獲得良好的評 價。特別是包含酸改質聚丙烯膜的實例2、實例4〜實例 11的積層體中，對於膜密接性及耐電解液性可獲得更加良 好的評價。另外，有機無機複合處理層亦含有鹼性鍅化合 物⑼的實例4〜實例u _層體中，有機無機複合處 理層的造膜性、阻隔性、膜密接性進一步提高，因此對於 耐電解液性可獲得良好的評價。 、 相對於此，比較例丨〜比較例3的積層體中，由於未 幵/成包3具有含有叛基的樹脂（A)、含有。惡峻琳基的樹脂 (B)及鹼性磷酸化合物（c)的樹脂組成物的硬化物的有 機無機複合處理層’因此對於膜密接性及耐電解液性無法 獲得良好的評價。 本申睛案主張基於2011年2月8日申請的曰本專利特 願2011-025081的優先權。此申請案說明書及圖式所記載 的内容全部引用至本案說明書中。 [產業上之可利用性] 本發明的積層體由於熱融著性聚烯烴系樹脂層的密接 性及耐電解液性優異’因此可較佳地用作電池外殼用材料。 【圖式簡單說明】 益。 【主要元件符號說明】 無0 31Film Bonding Strength Example 1 0 Example 2 Example 3 ◎ Example 4 0 ◎ Example 5 ◎ __ Example 6 ___ ◎ Real '如丨! 7 ◎ Example 8 〇 Example 9 Example 10 〇 Example 11 Comparative Example 1 〇 Comparative Example 2 〇◎ Comparative Example 3 ◎ 30 201238119 The laminate of Example 1 to Example 11 is formed by densely forming a resin containing a resin (A) having a carboxyl group, a resin (B) containing an oxazoline group, and an alkali phosphate compound (C). The organic-inorganic treatment layer of the cured product of the composition 'is therefore excellent in evaluation of film adhesion and electrolyte resistance. In particular, in the laminate of Example 2 and Example 4 to Example 11 containing an acid-modified polypropylene film, a more favorable evaluation was obtained for film adhesion and electrolyte resistance. Further, in the example 4 to the example u _ layer body in which the organic-inorganic composite treatment layer also contains the basic ruthenium compound (9), the film-forming property, barrier property, and film adhesion of the organic-inorganic composite treatment layer are further improved, and thus the electrolyte resistance is improved. A good evaluation can be obtained. On the other hand, in the laminate of the comparative example to the comparative example 3, the untwisted/package 3 has a resin (A) containing a rebel group and is contained. The organic inorganic composite layer of the cured product of the resin composition of the sulphur-based resin (B) and the basic phosphate compound (c) was not able to be satisfactorily evaluated for the film adhesion and the electrolyte solution resistance. The purpose of this application is based on the priority of the patent application 2011-025081 filed on February 8, 2011. The contents described in the specification and drawings of this application are all incorporated in the specification. [Industrial Applicability] The laminate of the present invention is excellent in adhesion to the heat-fusible polyolefin-based resin layer and electrolytic solution resistance. Therefore, it can be preferably used as a material for a battery can. [Simple description of the schema] Benefits. [Main component symbol description] None 0 31