201216546 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種鋰離子電池集電器用鋼落 關於一種鋰離子二次電池負極集電器用銅箱。 疋 【先前技術】 :離子電池’具有能量密度高、可得較高電壓的特徵， 被利用於筆記型電腦、攝影機、數位相機、 荨小型電子機器。而作為汽車或一般家庭 話 '/δ ^ M J1 ϊ 刀散配置型雷 ’、 生機器之電源的利用亦已為實用階段。201216546 VI. Description of the Invention: [Technical Field] The present invention relates to a steel box for a lithium ion battery current collector. A copper box for a lithium ion secondary battery anode current collector.疋 [Prior Art]: The ion battery has the characteristics of high energy density and high voltage, and is used in notebook computers, video cameras, digital cameras, and small electronic devices. As a car or a general family, the use of '/δ ^ M J1 ϊ 散 配置 配置 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、
鐘離子電池之電極體，—般而言，係：圖i所示，I =11、隔板u及負極13捲繞或積層幾十層 ;表：型上，正極係―正極集電器與設二 為材料ί LL1C°。2、L1Nl。2及LlMn2。4等鐘複合氧化物作 負性物質所構成，而負極係由以銅落構成之 物質所構I與设置於其表面之以碳等作為材料之負極活性 (=:成。正極彼此與負極彼此係分別以各片狀端子 接，而其亦可Γ、:正極與！極係與紹或錦製之片狀端子連 進行。，、^接來進行。溶接通常係以超音波熔接來 對作為負極之集電考傕用 歲自[. 使用之”所要求的特性，可舉 與負極活性物質之密合性、與銅 舉 接性、以及防鏽性。 子之超音波熔 事先二 之密合性之一般方法，可舉稱為 化處理之於㈣表面形成凹凸的表面處理。粗化處 201216546 理之方法，已知有噴砂處理'藉由粗面輥所進行之壓延、 機械研磨、電解研磨、化學研磨及電沉積粒子之鍍敷等方 法’該等之中，特別以電沉積粒子之鑛敷最為常用。該技 術係為了下述目的而進行：使用硫酸銅酸性鍍敷浴，於 銅羯表面將銅電沉積為多數之樹枝狀或小球狀，形成微細 之凹凸’ II定準效應課求密合性的改善，或於體積變化大 之活性物質膨脹時，使應力集中於活性物質層的凹部而形 成龜裂，防止因應力集中於集電器界面所導致之剝離（例 如，日本特許第3733067號公報）。 作為提升防鏽性之方法，已知有對銅羯表面進行鉻酸 處理或矽烷偶合處理之方法。矽烷偶合處理，亦可得到提 升密合性之效果。例如，於日本特開2〇〇8 _丨84657號公報， 石己載有·於銅箱之至少一面，形成以選自錄、始、鎢、翻 之中至少一者以上之金屬或該等金屬與類金屬之磷或硼之 間所形成之障壁層’接著，於所形成之障壁層i，實施以 二價絡作為鉻源之鉻酸處理，於所得之三價鉻㈣㈣i 鈀以矽烷偶合處理，藉此提升密合性及防鏽性。此處，矽 烷偶合處理之條件’係記載使矽烷偶合劑之濃度為〇5灿 / L以上、l〇mL// L α下，以液溫3〇〇c浸潰5秒鐘後，立 即由處理液取出使其乾燥。 專利文獻1 .日本特許第3733067號公報 專利文獻2 :日本特開2〇〇8— 184657號公報 【發明内容】 如上’用以提升作為鐘離子電池之集電器使用之銅箱 4 201216546 之密合性及防鏽性的技術開發雖在進行中，但關於該等特 性經均衡提升之銅，於實際現況中錢沒有能滿足者。 因此，本發明之第一課題在力，提供一種密合性及防鑛性 之特性經均衡提升的鋰離子電池集電器用銅羯。再者，本 發明之第二課題在於’提供一種製造此種銅落之方法。再 者，本發明之第三課題在於，提供一種將本發明之銅羯作 為集電器使用之鋰離子電池。 本發明人為了解決上述課題而經反覆研究後，藉由銅 落表面之錢偶合處理，確認活性物質之密合性，並確切 較未實施錢偶合處理之㈣具更良好之㈣性。然而: 關於防錄性’相較於廣泛使用於銅之以嗤系化合物所進行 之表面處王里，確認為較差。因此，進一步反覆研究後，發 現藉由以錢偶合劑與^表面處理劑的混合液進行表面 處理，為解決問題的契機。經詳細探討後，得知藉由以石夕 貌偶合劑與唾系表面處理劑的混合液對銅荡表面進行表面 处里相較於單獨使用各表面處理劑之濃度時，可以較低 濃度均衡得到充分之活性物質密合性及防it性的效果。兮 t果’係於分別單獨重複進行使用錢偶合劑之表面處理 ^使用坐系表面處理劑之表面處理（重覆塗布表面處理劑） 時無法得到者。㈣，發現藉由以#偶合劑與㈣ 處理劑的混合液進杆矣 履進仃表面處理，可提供以往無法得到之密 合性及防鏽性之均衡性優異的銅羯。 丞毛延戶斤 枝 7〜从〜个货明打一態樣’係於銅 泊衣面之至少一部公花； 刀九成有唑化合物及矽烷偶合劑之混合 201216546 層的链離子電池集電3| 本發明之銅饴， 尽發明之鋼箔，於—實施形態中，以XPS之深度方向 分析檢測Si及Ν，且c檢測量大於背景程度（background level)之深度範圍的平均值d〇為丄〇〜5 〇nm。 本發明之銅箔，於另一實施形態中’於該銅箔表面與 該混合層之間’形成有以唑化合物或鉻酸鹽層所構成之中 間層。 本發明之銅箔，於再另一實施形態中’該唑化合物係 苯并三唑系化合物。 本發明之銅箔，於再另一實施形態中，該苯并三唑系 化合物為1，2,3—笨并三唑。 本發明之銅箔，於再另一實施形態中，該矽烷偶合劑 於分子内含有N。 本發明之銅箔，於再另一實施形態中，該於分子内含 有N之矽烷偶合劑，含有咪唑基。 本發明之銅箔，於再另一實施形態中，該含有咪唑基 之錢偶合劑’係藉由3—環氧丙氧基丙基三甲氧基石夕燒與 咪唑的反應而得。 、 本發明之銅箱，於再另一實施形態中，係鋰離子二次 電池負極集電器用。 係將本發明之鋼箔作為集電器 本發明’於另一態樣，係 使用之鋰離子電池。 係鋰離子電池集電器用鋼箔 .對於銅箔表面之至少一部 本發明，於再另一態樣，令 之製造方法’其含有下述步驟： 6 201216546 力’以唑化口物及矽烷偶合劑的混合液實施表面處理，以 形成該唑化合物及該矽烷偶合劑之混合層。 本發明之鐘離子電池集電器用mi之製造方法，於一 實施形態中’該混合液含有嗤化合物ΐχΐ〇_4〜2〇χΐ〜 /L、及我偶合劑丨川]〜3GXHTWL。 藉由本發明之鋼箱，可均衡提升與負極活性物質之接 著性、及防鏽性。因此 奋 、用作為鐘離子電池之集電™。 【實施方式】 ° 1 ·銅箔基材 又 制 定 本發月巾銅、,白可為電解銅落或壓延銅箱之任一者。 「銅羯」亦包含鋼合金羯。銅羯之材料，並無特別限The electrode body of the ion battery, in general, is shown in Figure i, I = 11, the separator u and the negative electrode 13 are wound or laminated dozens of layers; Table: type, positive electrode - positive current collector and device The second is material ί1C°. 2, L1Nl. 2 and LlMn2. 4 is composed of a composite oxide as a negative substance, and the negative electrode is composed of a substance composed of a copper drop and a negative electrode active as a material provided on the surface thereof (=: positive. Each of the negative electrodes and the negative electrode are connected to each other by a sheet-like terminal, and the positive electrode and the +-pole are connected to the chip terminal of the Shao or Jin. The welding is usually performed by ultrasonic waves. The characteristics required for the current collection of the negative electrode as the negative electrode are as follows: the adhesion to the negative electrode active material, the adhesion to the copper, and the rust preventive property. The general method of the second adhesiveness may be referred to as (4) surface treatment for forming irregularities on the surface. The method of roughening 201216546 is known as sandblasting 'calendering by a rough roll, Mechanical polishing, electrolytic polishing, chemical polishing, and plating of electrodeposited particles, etc. Among these, mineralization of electrodeposited particles is most commonly used. This technique is carried out for the following purposes: using copper sulfate acid plating Bath, copper on the surface of the copper enamel Deposited into a plurality of dendritic or globular shapes, forming fine concavities and convexities. II. The quasi-effect effect is to improve the adhesion, or to concentrate the stress on the concave portion of the active material layer when the active material with a large volume changes expands. Cracking to prevent peeling due to stress concentration at the interface of the current collector (for example, Japanese Patent No. 3733067). As a method for improving rust resistance, it is known to perform chromic acid treatment or decane coupling treatment on the surface of the copper ruthenium. The method of decane coupling treatment can also obtain the effect of improving the adhesion. For example, in Japanese Laid-Open Patent Publication No. 2 〇〇 8 丨 84457, the stone has been placed on at least one side of the copper box to form a selected one. a barrier layer formed between at least one of the first, tungsten, and overturned metals or between the metal and the metalloid phosphorus or boron. Next, in the barrier layer i formed, a bivalent network is used as the chromium source The chromic acid treatment is carried out by treating the obtained trivalent chromium (tetra) (iv) i palladium with decane coupling, thereby improving the adhesion and rust resistance. Here, the condition of the decane coupling treatment is described as the concentration of the decane coupling agent is 〇5/ L or more, l 〇 mL / / L α, after being immersed for 3 seconds at a liquid temperature of 3 〇〇 c, and then taken out by the treatment liquid and dried. Patent Document 1 Japanese Patent No. 3733067 Patent Document 2: Japanese Unexamined Patent Application Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Regarding the copper whose characteristics are balanced and upgraded, the money is not satisfied in the actual situation. Therefore, the first subject of the present invention is to provide a lithium ion battery set whose balance of adhesion and anti-mineral properties is balanced. Further, the second object of the present invention is to provide a method for producing such a copper drop. Further, a third object of the present invention is to provide a copper crucible of the present invention as a current collector. Lithium Ion Battery. In order to solve the above problems, the inventors of the present invention have conducted a research on the surface of the copper drop surface to confirm the adhesion of the active material, and it is more excellent (4) than the (4) which has not been subjected to the money coupling treatment. However, the anti-recording property was confirmed to be inferior to that of the surface of the lanthanide compound widely used in copper. Therefore, after further research, it was found that the surface treatment by the mixture of the money coupling agent and the surface treatment agent was an opportunity to solve the problem. After a detailed discussion, it was found that the concentration of the surface of the copper-plated surface can be balanced by a lower concentration when the surface of the copper-plated surface is compared with the surface treatment agent alone. The effect of sufficient active material adhesion and anti-it property is obtained.兮 果 ’ 于 于 ’ ’ ’ ’ ’ ’ ’ ’ 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 (4) It has been found that by using the mixture of the # coupling agent and the (iv) treating agent, it is possible to provide a copper ruthenium which is excellent in the balance of adhesion and rust resistance which has not been obtained in the past.丞毛延户(1)~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ Electric 3| The copper crucible of the present invention, in the embodiment, the Si and the crucible are analyzed in the depth direction of the XPS, and the c detection amount is greater than the average value of the depth range of the background level. 〇 is 丄〇~5 〇nm. In another embodiment, the copper foil of the present invention has an intermediate layer formed of an azole compound or a chromate layer between the surface of the copper foil and the mixed layer. In still another embodiment of the copper foil of the present invention, the azole compound is a benzotriazole compound. In still another embodiment of the copper foil of the present invention, the benzotriazole-based compound is 1,2,3-pis-triazole. In still another embodiment of the copper foil of the present invention, the decane coupling agent contains N in the molecule. In still another embodiment of the copper foil of the present invention, the decane coupling agent containing N in the molecule contains an imidazole group. In still another embodiment of the copper foil of the present invention, the imidazole-based money coupling agent is obtained by a reaction of 3-glycidoxypropyltrimethoxy sulphur and imidazole. Further, in another embodiment, the copper box of the present invention is used for a lithium ion secondary battery negative electrode current collector. The steel foil of the present invention is used as a current collector. In another aspect, a lithium ion battery is used. A steel foil for a lithium ion battery current collector. For at least one part of the surface of the copper foil, in another aspect, the manufacturing method has the following steps: 6 201216546 Force's oxazole and decane The mixture of coupling agents is subjected to a surface treatment to form a mixed layer of the azole compound and the decane coupling agent. In the embodiment of the present invention, in the embodiment, the mixed liquid contains ruthenium compound ΐχΐ〇4~2〇χΐ~/L, and my coupling agent 丨川]~3GXHTWL. According to the steel box of the present invention, the adhesion to the negative electrode active material and the rust preventive property can be balanced. Therefore, it is used as the collector TM of the clock ion battery. [Embodiment] ° 1 · Copper foil substrate is also prepared. This mooncloth copper, white can be either electrolytic copper or rolled copper box. "Copper" also includes steel alloy crucibles. There is no special limit to the material of the matte
可視用途或要求牯，降、奋# , J 乂晋欠特性適當地加以選擇。例如 當為壓延銅羯時，可兴办丨丄一 ^ 及^ a +例如向純度之銅（無氧銅或精銅 4)、及添加有 Ni、Si、Sn 、Zn、Ag、Fe、Zr、p 笼击 之至少1種元素的銅合金。 中 銅箔的厚度並無特別限制， 選擇。一般為丨〜】〇n ，特性適s地加以 。 # m，但當作為鋰二次電池負栢隹 器使用時，將銅箔薄壁化可 、。之集電 點考量，典型上為2〜5〇//m 頁之電池。由該觀 # m、更典型為5〜2〇 2.表面處理 左右。 表面處理，係使用唑系 生^ 合物及石夕燒偶合劑的π人％ 進仃。表面處理，係藉由如 《則的此合液 及噴霧等使混合液接觸於銅 精由，又，貝、塗布 物質之密合性的至少一面， 下面中要求與負極活性 後’進行乾燥以使唑系化合 7 201216546 物及：：：合劑與銅荡表面的銅反應’而固定於銅 引用唑系化合物之防鏽性，藉由其與 偶合劑之混人思 、7規 別i浞。層，以均衡提升對負極活性物質之 防鏽性。由該勸點 覜點，唑系化合物，較佳為—般已知呈有輯 — 并二唑系化合物。又，苯并三唑系化合物， 、’’、、限疋，於上述本發明之目的上任一種皆可。笨并二坐 系化：物，“σ1，2,3_苯并三唾、丨一甲基笨并三：、 羧基苯并一唑' 1 ~ [Ν，Ν-雙（2—乙基己基）胺基甲基]苯 并二唑、曱笨基三唑、萘并三唑、5 —硝基笨并三唑、及 啡。井三唑等苯并三唑系化合物。 往石夕烧偶合劑，係於分子内同時具有與有機材料反應鍵 結之Β能基、及與無機材料反應鍵結之官能基的有機矽化 〇物。與有機材料反應鍵結之官能基，可舉例如乙烯基、 %氧基、苯乙烯基、丙烯氧基、曱基丙烯氧基、胺基、Ν— 笨基胺基丙基、脲基、氣丙基、酼基、異氰酸酯基、硫基 (sulfide group)、己基、咪唑基等，以分子内含Ν者為佳， 特佳為咪唑基《與無機材料反應鍵結之官能基，可舉例如 氣基荨鹵素基、烧氧基、乙醯軋基、異丙稀氧基（iS〇pr〇pen〇xy) 等。矽烷偶合劑亦可組合2種以上使用。 石夕烧偶合劑之具體例，可舉例如3 —胺基丙基三甲氧基 石夕院' 3—胺基丙基三乙氧基石夕烧、N—2 —（胺基乙基）一3 —胺基丙基甲基二曱氧基矽烷、N— 2 —(胺基乙基）_3—胺 基丙基三曱氧基石夕烧、N—2—(胺基乙基）一 3_胺基丙基三 乙氧基石夕烧、N—苯基一3 —胺基丙基三曱氧基石夕烧、n—（乙 8 201216546 烯基苄基）—2 —胺基乙基一 3一胺基丙基、三曱氧基矽烷、 N (對乙稀基苄基）一N —(三甲氧基矽基丙基）乙二胺、3 — 環氧丙氧基丙基三曱氧基矽烷、3一環氧丙氧基丙基甲基二 甲氧基石夕院、3~環氧丙氧基丙基三乙氧基矽烷、3 —環氧 丙氧基丙基甲基二乙氧基矽烷、2 — (3，4 —環氧基環己基）乙 基二甲氧基石夕燒、雙（3 —(三乙氧基矽基）丙基）二硫化物、雙 (3 (二乙氧基矽基）丙基）四硫化物、乙烯基三乙醯氧基矽 院、乙稀基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基 二異丙氧基石夕烷、乙烯基三氣矽烷、烯丙基三甲氧基矽烷、 二稀丙基二甲基矽烷、3—甲基丙烯氧基丙基三甲氧基矽 院、3 —甲基丙烯氧基丙基甲基二甲氧基矽烷、3一甲基丙 稀氧基丙基三乙氧基矽烷、3一甲基丙烯氧基丙基曱基二乙 氧基石夕烧、3 —丙烯氧基丙基三曱氧基矽烷、3一巯基丙基 三甲氧基矽烷、3—巯基丙基曱基二曱氧基矽烷、3一酼基 丙基三乙氧基矽烷、3 —酼基丙基三甲氧基矽烷、n_(1,3 —二甲基亞丁基）一3—胺基丙基三乙氧基矽烷、對苯乙烯基 三曱氧基矽烷、3 —脲基丙基三乙氧基矽烷、3 —氣丙基三 曱氧基矽烷、及3—異氰酸酯基丙基三乙氧基矽烷。 於本發明可使用之矽烷偶合劑，亦可例示如日本特開 平6— 256358號公報所記載之以唑系化合物與環氧矽烷系 化合物之反應所得之矽烷偶合劑，將其全部内容援用於本 說明書。 玉衣氧碎烧糸化合物’特佳為以下之通式- ^2^Η-〇Η2〇 (CHz) 3Si (OR1) nR2(3-n) 〇 201216546 (式中’ Rl、R2可為相同或相異之氫或碳數4卜3的 …η為i〜3。）所示之環氧矽烷偶合劑(例如。 :氧基丙基三甲氧基钱卜坐系化合物，特佳為笨并^ 於本發明所制之錢偶合劑，特佳為由該等 偶5劑與咪唾之反應所得之㈣石夕烧。。坐系化合物盘 石夕坑糸化合物之反應，可以日本特開平6— 256说號公報 所說明之條件來進行。例如，以 ^ ϋ，對唑系化合物 莫耳，滴下(Μ〜10莫耳之環氧石夕院系化合物，使其反應 5分鐘〜2小時，此時，溶劑並 〜 _ „ 寸引南要亦可使用氣仿、 一 σ可烧、甲醇、乙醇等有機溶劑。 而二’為了提升與負極活性物質之密合性、防鏽性， 而於銅治表面形成錢偶合劑之有機被膜，但若斑藉唾系 化合物之表面處理相比’防鏽性較差。另—方面，：銅绪 處理上’係廣泛使用嗤系化合物，若與矽烷偶合處 目t，雖具有較優異之防錄性，但活性物質密合性。 :乍為糊取該等兩者之優點的方法，而考量於—表面 再進2另-表面處理’亦即進行表面塗布或重疊塗布。然 =於以哇系化合物進行表面處理後’再以石夕烧偶合劑 進行表面處理時"坐系化合物之防鑛性會降低，又，合於 以碎烧偶合劑進杆病· &走^田/么 鬆订表面處理後，再以㈣化合物進行表面 人理時▲’以石夕烧偶合劑進行表面處理所產生之活性物質密 &性的效果會降低，因此’無法兼顧密合性與防鏽性。因 it =本發明，藉由以矽烷偶合劑與唑系化合物之混合液 進行-次表面處理，可兼顧以石夕炫偶合劑進行表面處理所 10 201216546 得之密合性、與以唑系化合 並且，當以_…二=處_得之防鏽性。 面處理時，僅雲#八/ 糸化合物之混合液進行表 分之效果t 獨㈣時更低之濃度即可得充 效果。亦即，發現以該表面處 混合層的平均厚度即使薄，亦 〔成之銅治表面之 性。又，若係$人麻μ 才了侍到充分之密合性及防鏽 社〜 均厚度薄’則由於超音波炼接性 佳，而旎均衡具備優里 此處，負極活性物質及超音 .係乂黏合劑賦予接著性。哕斑 & d會對負極活性物質斑 x 響。黏合劑之種類Λ fl的密合性造成影 之黏合劑的溶劑系、與使用以 ，..、代表 表之黏合劑的水系。當初雖—直-稀橡膠)為代 田初雖直使用溶劑系黏合 於成本與環境面上的考 — 一 欠糸黏合劑之使用持續增加。 …’水系黏合劑，與溶劑系黏合劑相較 ，密合性較差的問題。對於此種問題，已知有= 進負極聚料、塗布條件來確保密合性。相對於此，二 之表面處理’於溶劑系黏合劑及水系黏合劑兩者 果特別疋對於密合性低的水系黏合劑有效。因此， ^由改進負極漿料、塗布條件等來確保密合性，製造^ 之間於=偶合劑與嗤系化合物所形成之混合層與㈣ '、〇再形成以唑系化合物所構成之中間層。於誃π 合’由於最表面存在有矽烷偶合劑與唑系化合 混合層，故除了如上述可均衡具備優異之密合性、防= 201216546 及超音波炼接性外，並且由於 。坐系化合物所構成之中間層， 亦可形成鉻酸處理層作為中間 防鏽性，故藉由設置以鉻酸處 加提升防鏽性。並且，例如， 合處理，於其上設置混合層， 化合物所形成之混合層與銅箱 更加提升密合性。 混合層與銅箔之間形成有以 故能更加提升防鏽性。又’ 層。鉻酸處理層由於亦具有 理層所形成之中間層，可更 亦可對銅箔表面進行矽烷偶 來代替在石夕院偶合劑與哇系 之間設置中間層。藉此，可 以矽烷偶合劑與。坐系化合物之混合液所形成之混合 層，難以正綠地解明其構造，但作為化學構造解析，藉由 將銅绪表面以傅立葉轉換型紅外線光譜儀（ft_ir裝置）進 行分析，檢測出Sl-〇H基、Si—0_Sl基，以飛行時間二 次離子質譜儀（T0F—SIMS裝置）可檢測出唑系化合物。而 藉由。亥等檢測結果確認矽烧偶合劑與唑系化合物的存在 後，再組合X射線光電子光譜儀（xps裝置）與氬濺鍍進行 深度方向之元素分析，藉由各元素之分布情形來判定是 否形成有矽烷偶合劑與唑系化合物之混合液所形成之混合 層、或是否形成有石夕烧偶合劑與嗤系化合物之單獨之層。 又，藉由該深度方向之元素分析，來決定混合層之厚度。 以XPS裝置檢測si及N ’且以c檢測量大於背景程度之深 度範圍作為混合層的厚度’並對其測量複數部位，而將其 平均值D Q作為混合層的平均厚度。混合層之平均厚度，由 謀求密合性、防鏽性及超音波熔接性共存的觀點考量， 以1 ·〇〜5 ·〇nm為佳、1.5〜4·〇nm為更佳。又，即使當混人 12 201216546 層與銅箔之間進一步形成有中間層時’混合層及中間層之 合計的平均厚度，同樣地以1.0〜5.0nm為佳、i.5〜4 〇njn 為更佳。又，當形成有混合層與中間層時，該等厚度之比 例’以混合層較大為佳。於圖2，顯示測定有機被膜之厚声 時所得之XPS裝置所測得之n、Si、C之縱深分析之例。 石夕烧偶合劑及唑系化合物，可溶解於乙醇或水等溶劑 來使用。 又，一般而言，若提高矽烷偶合劑及唑系化合物的濃 度’則所形成之有機被膜會變厚，若減低濃度則會變薄。 以PH6.0〜9·0(較佳為pH6 5〜8 〇)之範圍來處理混合有兩 者之溶液，藉此形成矽烷偶合劑及唑系化合物的混合層。 表面處理所使用之矽烷偶合劑及唑系化合物的混合液 中，矽烷偶合劑濃度，為1χ1〇-4〜3〇χ1〇—ν〇ΐ/[，較佳為 3xl〇-4〜15xl0-Vol八，唑系化合物之濃度，為Μ" 〜20xl(TV〇1/L’ 較佳為 2x1〇_4〜i〇x1〇_v〇^l。藉由 以。玄等/農度範圍之混合液來進行表面處理，可形成密合 丨生、防鏽性及超音波熔接性之均衡良好的混合層。 可使用藉由以本發明之銅箔作為材料之集電器、與形 成於其上之活性物質層所構成的負極，藉由慣用手段來製 作鐘離子電池。领輸兩 主播 離子電池，包含以電解質中之鋰離子負 貝導電的鋰離子—次雷妯 池用及鋰離子二次電池。負極活性 錫合金、鋰一链合金、鋰—銦合金等 :質並無限定，可舉例如碳、心錫、鍺、m 二氧化錫、鈦酸鋰、氮化鋰、固溶有銦之氧化錫、 13 201216546 [實施例] 以下’揭示本發明之實施例，但該等係為了更加理解 本發明而提供者，並非用來限定本發明。 (實施例1) 為了探討以唑系化合物及矽烷偶合劑之混合劑所進行 之表面處理對特性所造成的影響，以如下之條件製作實施 例及比較例。將各種條件及試驗結果示於後述之表1。 [壓延銅箔之製造] 製造厚度20〇mm、寬度600mm之精銅的鑄錠，以熱軋 壓延至10mm。 接著’反覆進行退火與冷軋，最後以冷軋，使工作輥 徑為60mm、工作輥表面粗糙度Ra為0.03 v m、最後道次 (final pass)之壓延速度為4〇〇m/分、加工度為2〇%，精加 工成厚度10#m。壓延油的黏度為9〇cSt(25t)。所得之壓 延鋼箔之Ra為O.ii M m。 [電解銅箔之製造] 使用日本特許第41 1524〇號之實施例所記載之電解液 進行電解，製造i〇ym之電解銅箔。所得之電解銅箔之Ra 為 〇. 12 /z m。 [表面處理] 〇〇準備表1所記載之濃度的唑系化合物及矽烷偶合劑各 早獨之水溶液、及混合有兩者之混合液，將上述所製造之 板厚10 // m之壓延銅箔及電解銅箔浸潰於其中3秒鐘後， 以乾燥機進行乾燥。接著，進行於活性物質之塗布及密合 14 201216546 性評價"坐系化合物’係使用苯并三嗤（以下，稱為 BTA)’㈣偶合劑，係使用日鑛金屬股份有限公司製之味 唑矽烷(IS- 1000)’僅實施例卜8使用信越化學工業股份 有限公司製之N-(2—胺基乙基）—3 一胺基丙基三甲氧^ 矽烷。 [防鏽性] (1) 將銅箔裁切成3〇mmx60mm之大小。 (2) 將試樣（1)置入硫化氫暴露試驗機（Η』：3ppm、 °C、50RH%) ’ 保持 2〇 分鐘。 (3) 將試樣從（2)之試驗機取出，確認銅羯表面之色調。 (4) 將試驗後之銅箔表面的色調與試驗前相同者評價 為「〇」，與試驗前相比，變色成淡紅褐色者評價為「△」、 表面整體變色成紫色或藍色者則評價為「χ」。 」 [與活性物質之密合性] (1) 將平均粒徑9 # m之人工石墨與聚偏二氟乙烯以重 量比1 : 9混合，將其分散於溶劑N 一曱基—2 —吡咯烷酮。 (2) 將上述之活性物質塗布於銅箔表面。 (3) 將塗布有活性物質之銅箔以乾燥機加熱9(Γ(： χ3〇分 鐘。又，此時矽烷偶合劑，由於在銅表面未鍵結有OH基， 故幾乎不會因與未反應之矽烷偶合劑的脫水反應而與銅表 面發生反應。 (4) 乾燥後’裁切成2〇mm見方，施加1 5噸/ mm2x2〇 秒鐘之荷重。 (5) 對上述樣品’以切刀形成棋盤格狀之割痕，貼上市 15 201216546 售之黏著膠帶（Cellotape(註冊商標）），放置重量2kg之滾輪 來回行進1次以壓接黏著膠帶。 (6)剝下黏著膠帶，殘留於銅箔上之活性物質，將表面 之影像載入PC，以二元化（binarization)區分鋼表面之金屬 光澤。P刀與殘留活性物質之黑色部分，計算出活性物質之 殘留率。殘留率，取各樣品三個的平均值。活性物質密合 性之判定，將殘留率未達50%評價為「χ」，5〇%以上、 未達70%評價為「△」，7〇%以上、未達9〇%評價為「〇」， 90%以上則評價為「◎」。 [超音波熔接性] (1) 將銅箔裁切成l〇〇mnixl50mm之大小，重疊30片。 (2) 於Branson公司製之致動器（型號：mtraweld l2〇e) 女裝震盡頭（h〇rn)(間距〇.8mm、高度〇 4mm)。砧（辦⑴係 使用0.2mm間距。 〇)熔接條件，為壓力40psi、振幅60"m、振動數 20kHz、熔接時間〇丨秒。 (4)以上述條件熔接後，將銅羯一片一片剝離時，當 21片以上之銅箔於熔接部分破裂時評價為「◎」、1 1〜 片之銅落於熔接部分破裂時評價為「〇」、Η。片之銅笔 :熔接部分破裂時評價為「△」、銅帛！片也無破裂時評 秘為「X」。又，在將銅箔剝離之前，以立體顯微鏡以扣 倍放大觀察接觸於震盛頭之最表層之銅箱的炫接部分，於 確認未產生裂痕後，實施剝離試驗。 、 [有機被膜之判定] 16 201216546 進行有機被膜為混合層、或混合層與中間層、或 以石夕院偶合劑或BTA單獨所形成之層的判^。具體而士， 係^傅立葉轉換型紅外線光譜儀（ft、ir裝置）對銅^面 進行分析，藉此檢測Si — 〇H基、Si~ n e. ^ Α ^ 〇— Si基，以飛行時 間二:人離子質譜儀⑽-S題裝置）檢測哇系化合物。而 由該等檢測結果確認矽烷偶合劑與唑系化合物的存在。並 且組合X射線光電子光譜儀（XPS裝置）與氯韻，進行深产 方向之元素分析，#由各^之分布情形，決定有機㈣ 為（A)混合層、或（B)混合層與中間層、或（c)以石夕燒偶合劑 所形成之單獨層、或（D)以BAT所形成之單獨層。 [有機被膜之厚度] 有機被膜（混合層、混合層與中間層、或者以錢偶人 劑或BTA單獨所形成之層)之厚度，係一細，—邊： XPS裝置對㈣之深度方向進行元素分析，檢測〜及N， 且將C檢測量大於背景程度之深度範圍（si〇2換算）作為有 機被膜厚度’將任意、5處之平均值作為有機被 均值。 卞 .裝置：XPS裝置（ULVAC—削公司，型式56〇〇Mc) •真空度：5.7x10-7pa 。· X射線：單色ΑΙΚα、X射線輸出21〇w、入射角45 ° 、取出角45。 •離子射線：離子種類Ar、加速電壓3kv、掃瞄面積 3mmx3mm、濺鍍速度 2.3nm/min(Si〇2 換算） 17 201216546 【I ΐ 超音波熔接性 ◎ ◎ 〇 ◎ < <] ◎ 〇 ◎ ◎ 〇 ◎ ◎ < X ◎ 〇 <1 ◎ ◎ 密合性 〇 ◎ ◎ ◎ ◎ ◎ 〇 ◎ 〇 ◎ ◎ X X X X X <1 〇 <3 X 防鏽性 < 〇 〇 〇 〇 〇 〇 〇 < O 〇 X X < 〇 X X X X < 有機被膜厚度 nm r-H 00 ♦~Η \〇 rn CN cn 00 r- Os 00 ro m \q 寸 CN o CO 寸’ <N r- <N H r-H <N < < < < <3 < CQ < < < < 1 Q Q Q u U U D+C C+D BAT；濃度 xlO"4mol/L <Ν o CN <N O CN 1 <N o o 1 1 1 CN 〇 矽巧濃度 xlO_?mol/L ΓΛ ro m ΓΊ m 1 1 1 1 cn m m 箔種類 壓延銅箔 電解銅箔 壓延銅箔 6 τ~Ή 1 Τ-Η <N 1 ΓΟ 1 寸 1 1 1 1-7* I to 1 T-H Os 1 〇 T 1-H 1 t-H (N T m T 寸 T | 1-15 I T 卜 T 00 T 1 并 1 實施例 比較例 (V χ£^π^^…Q, (^^)^驗蛛…u/^s£-&-^^^?.§r .ρα,^φ^Γ. y :遲^奪·^For visual purposes or requirements, the characteristics of 降, 降, 奋#, and J 乂 适当 are appropriately selected. For example, when rolling copper ruthenium, it is possible to provide 纯度1 and ^ a + such as copper of purity (oxygen-free copper or refined copper 4), and added with Ni, Si, Sn, Zn, Ag, Fe, Zr, p A copper alloy of at least one element in a cage. The thickness of the copper foil is not particularly limited. Generally, it is 丨~]〇n, and the characteristics are suitable. # m, but when used as a lithium secondary battery negative cymbal, the copper foil can be thinned. The collector point is typically 2 to 5 〇 / / m page of the battery. From the view # m, more typically 5~2〇 2. Surface treatment around. The surface treatment was carried out using π% by weight of the azole compound and the Shixi sinter coupling agent. For the surface treatment, the mixture is brought into contact with the copper essence by the liquid mixture and the spray, and at least one side of the adhesion between the shell and the coating material is required. The azole-based compound 7 201216546 and the ::: mixture react with the copper on the copper-plated surface to fix the rust-preventing property of the copper-labeled azole compound, which is mixed with the coupling agent and 7 gauges. The layer is used to balance the rust resistance of the negative active material. From this point of view, the azole compound is preferably generally known as a bis-oxazolyl compound. Further, the benzotriazole-based compound, ’’, and 疋 疋 may be used in any of the above objects of the present invention. Stupid and two-seat: ", σ1,2,3_benzotris, 丨-methyl stupid and three:, carboxybenzo-azole" 1 ~ [Ν, Ν-bis (2-ethylhexyl) Aminomethyl]benzoxazole, hydrazinotriazole, naphthotriazole, 5-nitrobenzatriazole, and morphine. benzotriazole compounds such as triazoles. The mixture is an organic deuterated substance having a functional group bonded to an organic material and a functional group bonded to the inorganic material in the molecule, and a functional group reactive with the organic material, for example, a vinyl group. , % oxy, styryl, propyleneoxy, decyl propyleneoxy, amine, hydrazine - phenylaminopropyl, ureido, propyl, decyl, isocyanate, sulfide group , hexyl group, imidazolyl group, etc., preferably containing a ruthenium in the molecule, particularly preferably an imidazolyl group, a functional group reactive with an inorganic material, such as a gas-based fluorene group, an alkoxy group, an acetonitrile group, Isopropyloxy (iS〇pr〇pen〇xy), etc. The decane coupling agent may be used in combination of two or more kinds. Specific examples of the sulphur coupling agent may, for example, be a 3-amine. Propyltrimethoxy shixiyuan '3-aminopropyltriethoxy oxalate, N-2-(aminoethyl)-3-aminopropylmethyldimethoxy decane, N-2 (Aminoethyl)_3-aminopropyltrimethoxylate, N-2-(aminoethyl)-3-aminopropyltriethoxylate, N-phenyl-3 Aminopropyltrimethoxylate, n-(ethyl 8 201216546 alkenylbenzyl)-2-aminoethyl-3-aminopropyl, trimethoxydecane, N (p-ethylbenzyl) Base)-N-(trimethoxymethyl propyl) ethylenediamine, 3-glycidoxypropyltrimethoxy decane, 3-glycidoxypropylmethyldimethoxy sylvestre , 3~glycidoxypropyltriethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, 2-(3,4-epoxycyclohexyl)ethyldimethyl Oxime, bis(3-(triethoxyindolyl)propyl) disulfide, bis(3(diethoxyindolyl)propyl)tetrasulfide, vinyltriethylphosphonium oxime Home, ethylene trimethoxy decane, vinyl triethoxy decane, vinyl diiso Propoxy alkane, vinyl trioxane, allyl trimethoxydecane, dipropyl dimethyl decane, 3-methyl propyloxypropyl trimethoxy fluorene, 3-methyl propylene oxide Propyl propyl dimethoxy decane, 3-methylpropoxy methoxy triethoxy decane, 3-methyl propylene oxypropyl decyl diethoxy sulphur, 3- propyleneoxy Propyl trimethoxy decane, 3-mercaptopropyltrimethoxy decane, 3-mercaptopropyl decyl decyloxydecane, 3-mercaptopropyltriethoxy decane, 3-mercaptopropyltrimethyl Oxydecane, n_(1,3-dimethylbutylene)-3-aminopropyltriethoxydecane, p-styryltrimethoxydecane, 3-ureidopropyltriethoxydecane 3 - gas propyl trimethoxy decane, and 3-isocyanate propyl triethoxy decane. In the decane coupling agent which can be used in the present invention, a decane coupling agent obtained by reacting an azole compound with an epoxy decane compound as described in JP-A-6-256358, the entire contents of which are incorporated herein by reference. Instructions. The jade ash-burning bismuth compound is particularly preferred as the following formula - ^2^Η-〇Η2〇(CHz) 3Si (OR1) nR2(3-n) 〇201216546 (wherein Rl, R2 may be the same or Divalent hydrogen or carbon number 4 卜 ... η is i~3.) shown as an epoxy decane coupling agent (for example: oxypropyl trimethoxy sulphate compound, especially good stupid and ^ The money coupling agent prepared by the invention is particularly preferably obtained by the reaction of the above 5 agents with the sodium saliva. (4) Shi Xizhuo. The reaction of the stagnation compound Panshi Xikeng compound can be carried out in Japanese Patent Application No. 6-256 The conditions described in the bulletin are carried out. For example, by using ϋ, the azole compound Mox, dripping (Μ~10 mol of the epoxy stone compound, reacting it for 5 minutes to 2 hours, at this time , Solvent and ~ _ „ Inch can also use gas imitation, σ can be burned, methanol, ethanol and other organic solvents. And two 'in order to improve the adhesion with the negative active material, rust resistance, and The surface forms an organic film of the money coupling agent, but if the surface treatment of the spot by the salivary compound is inferior to the 'rust resistance', another aspect: the copper thread In the above, the lanthanide compound is widely used, and if it is coupled with decane, it has excellent anti-recording property, but the active material is intimate. 乍 is a method of obtaining the advantages of the two, and the method is considered. - Surface re-entry 2 - Surface treatment - that is, surface coating or overlap coating. After = surface treatment with wow compound - 'When surface treatment with Shi Xi siu coupler" " sling compound anti-mine The sexuality will be reduced, and it will be combined with the smear of the smear and the smear of the smear and the surface treatment of the smear and the smear, and then the surface treatment of the (4) compound. The effect of the resulting active material is reduced, so that the adhesion and rust resistance cannot be achieved. Since it = the present invention, the surface treatment is carried out by using a mixture of a decane coupling agent and an azole compound. It can be used for the surface treatment of the Shi Xi Xuan coupling agent. 201216546 The adhesion is obtained, and it is combined with the azole system, and when it is _... two = _ _ rust resistance. / 糸 compound mixture for the effect of the score t (4), when the concentration is lower, the effect can be obtained. That is, it is found that even if the average thickness of the mixed layer at the surface is thin, it is also the nature of the copper to cure the surface. The full adhesion and anti-rust society ~ the thin thickness of the whole is good because of the supersonic refining, and the balance of the yttrium is excellent, the negative active material and the supersonic. & d will ring the negative active material spot x. The type of adhesive Λ fl adhesion causes the solvent of the adhesive, and the water system used to represent the adhesive of the table. -Thin rubber) Tested for the cost and environmental aspects of the use of solvent in the case of Daisaku, the use of a binder. ...'Water-based adhesives have a poor adhesion compared to solvent-based adhesives. For such a problem, it is known to enter the negative electrode aggregate and the coating conditions to ensure adhesion. On the other hand, the surface treatment of both of the solvent-based adhesive and the water-based adhesive is particularly effective for a water-based adhesive having low adhesion. Therefore, the adhesion is ensured by the improvement of the negative electrode slurry, the coating conditions, and the like, and the mixed layer formed between the = coupling agent and the lanthanoid compound and (4) ', and the yttrium is formed in the middle of the azole compound. Floor. Since 矽 π ’ 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The intermediate layer composed of the cradle compound can also form a chromic acid-treated layer as an intermediate rust preventive property, so that rust resistance can be improved by providing chromic acid. Further, for example, in combination treatment, a mixed layer is provided thereon, and the mixed layer formed of the compound and the copper box are more improved in adhesion. The mixed layer is formed between the copper foil and the rust preventive property is further improved. And the layer. Since the chromic acid treatment layer also has an intermediate layer formed by the physical layer, it is also possible to carry out a decane coupling on the surface of the copper foil instead of providing an intermediate layer between the Shi Xiyuan coupling agent and the Wow system. Thereby, a decane coupling agent can be used. The mixed layer formed by the mixture of the stagnation compounds is difficult to explain the structure in a green color. However, as a chemical structure analysis, the surface of the copper surface is analyzed by a Fourier transform infrared spectrometer (ft_ir device) to detect Sl-〇H. The azole compound can be detected by a time-of-flight secondary ion mass spectrometer (T0F-SIMS device) based on the Si-O_Sl group. And by. After confirming the presence of the sputum coupling agent and the azole compound, the X-ray photoelectron spectroscopy (xps device) and argon sputtering were used to perform elemental analysis in the depth direction, and the distribution of each element was used to determine whether or not A mixed layer formed of a mixture of a decane coupling agent and an azole compound, or a separate layer of a ceramsite coupling agent and a lanthanoid compound. Further, the thickness of the mixed layer is determined by elemental analysis in the depth direction. The si and N' were detected by the XPS apparatus and the depth range in which the amount of c detection was larger than the background was taken as the thickness of the mixed layer', and the complex portion was measured, and the average value D Q was taken as the average thickness of the mixed layer. The average thickness of the mixed layer is preferably from 1 〇 to 5 · 〇 nm, and more preferably from 1.5 to 4 〇 nm, from the viewpoint of coexistence of adhesion, rust resistance, and ultrasonic fusion. Further, even when an intermediate layer is further formed between the layer of 201216546 and the copper foil, the average thickness of the mixed layer and the intermediate layer is preferably 1.0 to 5.0 nm, and i.5 to 4 〇njn is Better. Further, when the mixed layer and the intermediate layer are formed, the ratio of the thicknesses is preferably larger as the mixed layer. Fig. 2 shows an example of the depth analysis of n, Si, and C measured by the XPS apparatus obtained by measuring the thick sound of the organic film. The Shixia coupling agent and the azole compound can be dissolved in a solvent such as ethanol or water. Further, in general, when the concentration of the decane coupling agent and the azole compound is increased, the organic film formed becomes thick, and when the concentration is lowered, the thickness is reduced. The solution in which the two are mixed is treated in a range of pH 6.0 to 9.0 (preferably pH 6 5 to 8 Torr) to form a mixed layer of a decane coupling agent and an azole compound. The concentration of the decane coupling agent in the mixture of the decane coupling agent and the azole compound used for the surface treatment is 1χ1〇-4~3〇χ1〇—ν〇ΐ/[, preferably 3xl〇-4~15xl0-Vol 8. The concentration of the azole compound is Μ " 〜20xl (TV〇1/L' is preferably 2x1〇_4~i〇x1〇_v〇^l. By the mixture of Xuan et al/farm range The liquid is subjected to a surface treatment to form a mixed layer having a well-balanced adhesion, rust preventive property, and ultrasonic fusion property. A current collector formed by using the copper foil of the present invention as a material and formed thereon can be used. A negative electrode composed of an active material layer is used to produce a clock ion battery by a conventional means. The two main ion batteries are led to contain a lithium ion-based thunder pool and a lithium ion secondary battery which are electrically conductive with a lithium ion in the electrolyte. The negative electrode active tin alloy, the lithium one-chain alloy, the lithium-indium alloy, and the like are not limited, and examples thereof include carbon, tin tin, antimony, m tin dioxide, lithium titanate, lithium nitride, and solid solution indium. Tin Oxide, 13 201216546 [Embodiment] The following 'declares an embodiment of the present invention, but these are for The present invention is not intended to limit the present invention. (Example 1) In order to investigate the influence of surface treatment on the characteristics of a mixture of an azole compound and a decane coupling agent, the following conditions were employed. EXAMPLES AND COMPARATIVE EXAMPLES Various conditions and test results are shown in Table 1 which will be described later. [Production of Rolled Copper Foil] An ingot of a thickness of 20 mm and a width of 600 mm was produced and rolled by hot rolling to 10 mm. The annealing and cold rolling are repeated, and finally, the cold rolling is performed so that the working roll diameter is 60 mm, the surface roughness Ra of the work roll is 0.03 vm, and the final pass speed is 4 〇〇m/min, and the degree of processing is 2〇%, finished to a thickness of 10#m. The viscosity of the calendered oil is 9〇cSt (25t). The Ra of the obtained rolled steel foil is O.ii M m. [Manufacture of electrolytic copper foil] Use Japanese license 41 The electrolytic solution described in the Example of No. 1524 was electrolyzed to produce an electrolytic copper foil of i〇ym. The obtained electrolytic copper foil had Ra of 〇. 12 /zm. [Surface treatment] 〇〇 Prepare the concentration described in Table 1. The azole compound and the decane coupling agent are each an aqueous solution A mixture of the two was mixed, and the rolled copper foil and the electrolytic copper foil having a thickness of 10 // m prepared above were immersed therein for 3 seconds, and then dried in a dryer. Then, the coating was carried out on the active material. And adhesion 14 201216546 Sexual evaluation "sit system compound' uses benzotriazine (hereinafter referred to as BTA)' (four) coupling agent, using the oxazolidine (IS-1000) manufactured by Nippon Mining & Metal Co., Ltd. In the example 8 only, N-(2-aminoethyl)-3 monoaminopropyltrimethoxyoxane manufactured by Shin-Etsu Chemical Co., Ltd. was used. [Rust prevention] (1) Cut the copper foil to a size of 3 mm x 60 mm. (2) Place the sample (1) in a hydrogen sulfide exposure tester (Η: 3ppm, °C, 50RH%) ’ for 2 minutes. (3) Take the sample out of the tester of (2) and check the color tone of the matte surface. (4) The color tone of the surface of the copper foil after the test was evaluated as "〇" in the same manner as before the test, and the color change to pale reddish brown was evaluated as "△", and the entire surface was discolored to purple or blue. The evaluation is "χ". [Adhesion to active material] (1) The artificial graphite having an average particle diameter of 9 # m and polyvinylidene fluoride are mixed at a weight ratio of 1:9, and dispersed in a solvent N-mercapto-2-pyrrolidone . (2) The above active material is applied to the surface of the copper foil. (3) Heat the copper foil coated with the active material in a dryer for 9 (Γ(: χ3〇 min. Also, at this time, the decane coupling agent, since the OH group is not bonded to the copper surface, it is hardly caused by The dehydration reaction of the reaction decane coupling agent reacts with the copper surface. (4) After drying, 'cut into 2 〇 mm square, apply a load of 15 ton / mm 2 x 2 〇 seconds. (5) Cut the above sample The knife forms a checkerboard-shaped cut mark, which is attached to the adhesive tape (Cellotape (registered trademark)) sold on 201216546, and the roller with a weight of 2kg is used to roll back and forth one time to crimp the adhesive tape. (6) Peel off the adhesive tape and leave it on The active material on the copper foil, the image of the surface is loaded into the PC, and the metallic luster of the steel surface is distinguished by binarization. The black portion of the P-knife and the residual active material is used to calculate the residual ratio of the active material. The average value of the three samples was taken. The determination of the adhesiveness of the active material was evaluated as "χ" with a residual ratio of less than 50%, and "〇" was found to be "△" or less than 70%, and not more than 70%. Less than 9〇% is rated as “〇”, and 90% or more is evaluated as “◎” [Supersonic welding] (1) Cut the copper foil into l〇〇mnixl50mm and overlap 30 pieces. (2) Actuator made by Branson (model: mtraweld l2〇e) (h〇rn) (pitch 〇.8mm, height 〇4mm). Anvil (does (1) using 0.2mm pitch. 〇) welding conditions, pressure 40psi, amplitude 60 " m, vibration number 20kHz, welding time leap second. (4) When the copper ruthenium was peeled off one by one after the above-mentioned conditions, when 21 or more copper foils were broken at the welded portion, it was evaluated as "?", and 1 to 1 piece of copper fell when the welded portion was broken. 〇", Η. Piece of copper pen: When the welded part is broken, it is evaluated as "△", and the copper enamel! When the piece is not broken, the evaluation is "X". Also, before the copper foil is peeled off, zoom in with a stereo microscope Observe the splicing portion of the copper box that is in contact with the outermost layer of the Zhenshengtou, and perform the peeling test after confirming that no crack has occurred. [Determination of the organic film] 16 201216546 The organic film is a mixed layer, or a mixed layer and an intermediate layer. Or the judgment of the layer formed by the Shi Xiyuan coupling agent or BTA alone. The body is analyzed by a Fourier transform infrared spectrometer (ft, ir device) to detect the Si- 〇H-based, Si~ n e. ^ Α ^ 〇-Si-based, with flight time two : Human ion mass spectrometer (10)-S device) detects wow compounds, and confirms the presence of decane coupling agent and azole compound by these test results, and combines X-ray photoelectron spectrometer (XPS device) with chlorine rhyme to carry out deep production. Elemental analysis of direction, #determined by the distribution of each ^, the organic (4) is (A) mixed layer, or (B) mixed layer and intermediate layer, or (c) a separate layer formed by Shixia coupling agent, or (D) A separate layer formed by BAT. [Thickness of Organic Film] The thickness of the organic film (the mixed layer, the mixed layer and the intermediate layer, or the layer formed by the singularity agent or BTA alone) is a fine, edge: XPS device is in the depth direction of (4) For elemental analysis, ～ and N were measured, and the depth range (in terms of si 〇 2) in which the amount of C detection was greater than the background was taken as the organic film thickness 'the average value of the five points was taken as the organic mean value.卞. Device: XPS device (ULVAC-cutting company, type 56〇〇Mc) • Vacuum degree: 5.7x10-7pa. · X-ray: monochrome ΑΙΚα, X-ray output 21〇w, incident angle 45 °, extraction angle 45. • Ion ray: ion type Ar, acceleration voltage 3kv, scan area 3mmx3mm, sputtering rate 2.3nm/min (Si〇2 conversion) 17 201216546 [I ΐ Ultrasonic fusion ◎ ◎ 〇 ◎ <<] ◎ 〇 ◎ ◎ 〇 ◎ ◎ < X ◎ 〇 <1 ◎ ◎ Adhesive 〇 ◎ ◎ ◎ ◎ ◎ 〇 ◎ 〇 ◎ ◎ XXXXX <1 〇 <3 X rust resistance < 〇〇〇〇〇〇〇 < O 〇 XX < 〇XXXX < organic film thickness nm rH 00 ♦~Η \〇rn CN cn 00 r- Os 00 ro m \q inch CN o CO inch ' <N r- <NH rH < ;N <<<<<3< CQ <<<< 1 QQQ u UU D+C C+D BAT; Concentration xlO"4mol/L <Ν o CN <NO CN 1 <N oo 1 1 1 CN 〇矽巧浓度xlO_?mol/L ΓΛ ro m ΓΊ m 1 1 1 1 cn mm Foil type rolled copper foil electrolytic copper foil rolled copper foil 6 τ~Ή 1 Τ-Η < ; N 1 ΓΟ 1 inch 1 1 1 1-7* I to 1 TH Os 1 〇T 1-H 1 tH (NT m T inch T | 1-15 IT 卜 T 00 T 1 and 1 Example Comparative Example (V χ£^π^^...Q, (^^)^Test the spider...u/^s£-&-^^^?.§r .ρα,^φ^Γ. y: late ^··^
Ii^v9^^tFvlOQ^^*^®Hi^«^^f/i#^?cf^^^^:*oz:II 铟蜮《<^哿冢Φ筚越^^_了^韧螭喵<^^<19^#:*61—1 ^^^^δ--^^肊硪绪丨 el (砩to^^—fN)IN^ί锻命筚^^:*00丨1 Ni^«^^^^^?iw^^IoiT，^:ii^«^^?Fvla W Ί/οε了 olx(N^^ti:*/.—！ 001 201216546 (評價結果） 貫施例1 — 1〜1 — 6及1 — 9〜1 — 11，係使用臌 丁1之用壓延銅箔 或電解銅箔’而以BTA與矽烷偶合劑之混合液進行表面〆 理，再者，BTA與矽烷偶合劑之混合有機被膜厚度在1 〇〜 5.Onm之範圍。因此，熔接性、防鏽性及密合性全部皆顯示 出良好的特性。 實施例1 — 7，係於以BTA進行表面處理後，再以與實 施例1 ~ 1同濃度之BTA與矽烷偶合劑之混合液進行表面處 理，由於在BTA與矽烷偶合劑之混合層與銅箔之間，進一 步存在有BTA之中間層，故與實施例i J相較 〜卜，防鏽 性更佳。又，此處之有機被膜厚度，係上述2層之人叶， 由於處於1.0〜5.Onm之範圍，故熔接性亦良好。關於密合 性’由於混合層位於最表層，故良好。 實施例1 一 8 ’係使用N — (2 —胺基乙基）—3〜胺基丙基 二曱氧基矽烷作為矽烷偶合劑，而與使用咪唑矽烷時同樣 地，熔接性、防鏽性及密合性皆顯示良好的特性。 比較例1—12,未實施表面處理，於表面未存在有機被 膜’熔接性雖良好’但防鏽性與密合性差。 比較例1— 13〜1— 15,係僅以BTA進行表面處理，處 理液濃度愈低，熔接性愈佳’而處理液濃度愈高，防鏽性 愈佳。然而’無論是何種濃度，冑合性皆差，顯示出僅以 BTA的話，無法同時滿足熔接性、防鏽性及密合 比較例1—1 6〜1 一 18，係僅以矽烷偶合劑 理，處理液濃度愈低，熔接性愈佳，而處理液濃度愈高处 19 201216546 “造愈佳 '然而’無論是何種漢度，防鏽性皆差，顯示 出僅以矽烷偶合劑的話’無法同時滿足熔接性、防鏽性及 密合性。 _ 較例1 19，係僅以BTA進行表面處理後，僅以矽 烧偶合劑進行表面處理，未以BTA與㈣偶合劑之混合液 進行表面處理。因此，有機被膜厚度雖在1.G〜5.Gnm之範 防鏽丨生差，顯示出無法同時滿足溶接性、防鑛性及 密合性。 比較例1 —20，係僅以矽烷偶合劑進行表面處理後，僅 以BTA進行表面處理，未以BTA與矽烷偶合劑之混合液進 行表面處理。因此，有機被膜厚度雖在1.0〜5.〇nm之範圍， 但密合性差’顯示出無法同時滿足熔接性、防鏽性及密合 性。 (實施例2) 為了探討有機被膜厚度、與防鏽性及超音波炼接性的 關係’進行以下之實驗作為實施例2。 作為本發明之實施例，形成具有矽烷偶合劑及唑系化 5物之混合層，而其混合層（有機被膜）厚度在1 .〇〜5 . 〇nm 之範圍外的實施例2 — 1及2 _ 2。貫施例2 — 1及2 — 2，係 一邊調整混合液中之唑系化合物及矽烷偶合劑的濃度，一 邊以上述實施例1所記載之方法形成。 更具體而言，於實施例2 — 1，係使用壓延銅箔，混合 液中之矽烷濃度為1.5xl(T4m〇l/L、BAT濃度為lxl0-4m〇1 / 藉此所形成之實施例2 — 1的有機被膜厚度為〇.8nm。 20 201216546 於實施例2 — 2，係使用壓延銅箔，混合液中之石夕烧濃 度為 3.0x10-4mol/L、BAT 濃度為 30xl0—4mol/L。藉此 所形成之實施例2— 2的有機被膜厚度為5.6nm。 又，作為比較例，與上述之實施例1所記載之方法， 製作具有與實施例2— 1及2—2同樣的有機被膜厚度，而 有機被膜僅以°坐系化合物或石夕烧偶合劑之任一者所構成之 比較例2 — 3及2 — 4。 更具體而言’於比較例2 — 3，係使用壓延銅落，僅以 矽烧偶合劑進行表面處理。處理液中之石夕烧濃度為i . 5 χ丨〇 - 4mol/ L。藉此所形成之比較例2 — 3的有機被膜厚度為 〇.9nm。 於比較例2 — 4 ’係使用壓延銅箔，僅以bta進行表面 處理。處理液中之BTA濃度為30xl0_4m〇l/L。藉此所形 成之比較例2 — 4的有機被膜厚度為5 4nm。 將實施例2之試驗條件及評價結果示於表2。 [表2]Ii^v9^^tFvlOQ^^*^®Hi^«^^f/i#^?cf^^^^:*oz:II Indium 蜮 "<^哿冢Φ筚越^^_^^喵<^^<19^#:*61—1 ^^^^δ--^^肊硪绪丨el (砩to^^—fN)IN^ίForging 筚^^:*00丨1 Ni^«^^^^^?iw^^IoiT,^:ii^«^^?Fvla W Ί/οε了olx(N^^ti:*/._! 001 201216546 (Evaluation result) Example 1 — 1~1 — 6 and 1 — 9~1 — 11, using a calendered copper foil or electrolytic copper foil for crucible 1 and surface treatment with a mixture of BTA and a decane coupling agent, and further, BTA and The mixed organic film thickness of the decane coupling agent is in the range of 1 〇 to 5. Onm. Therefore, the weldability, the rust resistance, and the adhesion all show good characteristics. Example 1 - 7, is applied to the surface with BTA After the treatment, the surface treatment is carried out with a mixture of BTA and a decane coupling agent at the same concentration as in Examples 1 to 1. Since the intermediate layer of BTA is further present between the mixed layer of BTA and the decane coupling agent and the copper foil, Therefore, compared with the embodiment i J, the rust prevention property is better. Moreover, the thickness of the organic film here is the range of the human layer of the above two layers, since it is in the range of 1.0 to 5. Onm. Therefore, the weldability is also good. The adhesion is good because the mixed layer is located at the outermost layer. Example 1 - 8 ' uses N - (2 - aminoethyl) - 3 - aminopropyl dioxane Since decane is used as a decane coupling agent, the weldability, rust resistance, and adhesion all show good characteristics similarly to the case of using imidazolium. Comparative Example 1-10, no surface treatment was performed, and no organic film was present on the surface. Although the weldability is good, the rust resistance and adhesion are inferior. Comparative Example 1 - 13 to 1 - 15 is only surface treatment with BTA, the lower the concentration of the treatment liquid, the better the weldability, and the higher the concentration of the treatment liquid, The rust resistance is better. However, 'no matter what the concentration, the chelating property is poor. It shows that only BTA can not satisfy the weldability, rust resistance and adhesion at the same time. Comparative Example 1 -1 6~1-18. It is only treated with decane coupling agent. The lower the concentration of the treatment liquid, the better the weldability, and the higher the concentration of the treatment liquid. 19 201216546 “Good for the better” However, no matter what kind of Han, the rust resistance is poor, showing If only a decane coupling agent is used, it cannot meet the weldability and rust resistance at the same time. And the adhesion. _ Comparative Example 1 19, after only surface treatment with BTA, the surface treatment was only carried out with a simmering coupling agent, and the surface treatment was not carried out with a mixture of BTA and (4) coupling agent. In the range of 1.G to 5.Gnm, the rust prevention was poor, and it was shown that the compatibility, the anti-mining property, and the adhesion could not be satisfied at the same time. Comparative Example 1-20 was only subjected to surface treatment with a decane coupling agent, and only The surface treatment was carried out with BTA, and the surface treatment was not carried out with a mixture of BTA and a decane coupling agent. Therefore, although the thickness of the organic film is in the range of 1.0 to 5. 〇 nm, the poor adhesion ‘ shows that the weldability, the rust resistance, and the adhesion cannot be satisfied at the same time. (Example 2) In order to investigate the relationship between the thickness of the organic film, the rust preventive property, and the ultrasonic blending property, the following experiment was carried out as Example 2. As an embodiment of the present invention, a mixed layer having a decane coupling agent and an azole-based compound 5 is formed, and the mixed layer (organic film) has a thickness of 1. 〇 〜5. twenty two. Each of Examples 2 to 1 and 2 to 2 was formed by the method described in the above Example 1 while adjusting the concentrations of the azole compound and the decane coupling agent in the mixed solution. More specifically, in Example 2-1, a rolled copper foil was used, and the decane concentration in the mixed solution was 1.5 x 1 (T4 m〇l/L, and the BAT concentration was lx10-4 m〇1 / The organic film thickness of 2 - 1 is 〇.8 nm. 20 201216546 In Example 2 - 2, a rolled copper foil is used, the concentration of the sinter in the mixed solution is 3.0 x 10-4 mol/L, and the BAT concentration is 30 x 10 - 4 mol / L. The thickness of the organic film of Example 2-2 thus formed was 5.6 nm. Further, as a comparative example, the method described in the above Example 1 was produced in the same manner as in Examples 2-1 and 2-1. The thickness of the organic film, and the organic film is only Comparative Examples 2 - 3 and 2 - 4 which are composed of either a sitting compound or a Shi Xi burning coupling. More specifically, in Comparative Example 2 - 3, The calendered copper was used, and only the surface treatment was carried out with a smouldering coupler. The concentration of the sinter in the treatment liquid was i. 5 χ丨〇 - 4 mol / L. The thickness of the organic film of Comparative Example 2-3 formed thereby was 〇.9nm. In Comparative Example 2 - 4 ', a rolled copper foil was used, and only surface treatment was performed with bta. BTA in the treatment liquid The concentration was 30 x 10 4 μm / L. The thickness of the organic film of Comparative Example 2 - 4 thus formed was 5 4 nm. The test conditions and evaluation results of Example 2 are shown in Table 2. [Table 2]
No _ 矽烷濃度 xlO"4mol/L BAT濃度 xlO_4mol/L 有機被膜 有機被膜 厚度 nm 防鏽性 超音波 熔接性 實把例 2-1 1.5 1 A 0.8 △ ◎ 2-2 3.0 30 A 5.6 〇 △— 比較例 2-3 1.5 — C 0.9 X ◎— 2-4 30 D 5.4 〇 X 有機被膜：A…混合層、：B...混合層及中間層、c…單獨 層（石夕烧）、D…單獨層（BTA) (評價結果） 實施例2—1 ’有機被膜厚度未達丨如爪，與實施例工 21 201216546 - Μ目比’防鏽性較差，而若與具有同樣有機被膜厚度之比 較例2 — 3相比，則超音波熔接性優異。 實施例2-2,有機被膜厚度超過5 〇_，與實施例ι —9相比，超音波熔接性較差，^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ 石”八有冋樣有機被膜厚 度之比較例2 — 4相比，則超音波熔接性優異。 (實施例3) 將表3所示之各種銅合金使用作為銅羯基材。此等全 部，係將各元素添加至無氧銅中之溶融液，製造鑄錠，反 覆進行退火及壓延，壓延至厚度6〜20//m，藉此製得。 接著，準備表3所記載之濃度之唑系化合物及矽烷偶 合劑單獨的水溶液、及混合有兩者的水溶液，將以上述方 式所製得之各種銅合金猪浸潰5秒鐘後，以乾燥機乾燥。 接著，進行對活性物質之塗布及密合性評價。 使用1，2,3 —苯并三唑（bAT)作為唑系化合物、使用曰 鑛金屬公司製之咪唑矽烷（IS— 1〇〇〇)作為矽烷偶合劑。 對於防鏽性、活性物質密合性、有機被膜判定及膜厚， 以與實施例1相同方法進行評價，超音波熔接性則以如下 方式進行評價。 5平價結果不於表3。 [超音波熔接性] (1) 將銅箔裁切成l〇〇mmxl50nim之大小，板厚6 e m 時重疊50片’板厚ι〇 " m時重疊3〇片，板厚2〇 # m時則 重疊15片。 (2) 於Branson公司製之致動器（型號：ultraweld L20E) 22 201216546 安裝震盪頭（間距0 8_、高度〇 4mm) 距。 6係使用0.2mm間 (3) 熔接條件，為壓力4〇psi、振 20kHz、炫接時間（M秒。 心、振動數 (4) 以上述條件熔接後，將銅箔一 ^ 35 H - r 1Λ 片剝離時，將板 片以上、板厚⑺以⑺時21片 P時U 4以上之銅落於熔接部 、板厚2〇 「◎」；將板厚一時18〜34 =的情形評價為 片、板厚時6〜10片之銅^反#1〇心時11〜2〇 評價為「〇」；將板“…夺卜心接部分破裂的情形 〜W片、板厚20"m時i〜5h 板厚1〇#111時1 形評價為「△」n片也:鋼>自於熔接部分破裂的情No _ decane concentration xlO " 4mol / L BAT concentration xlO_4mol / L organic film organic film thickness nm rust-proof ultrasonic fusion properties 2-1 1.5 1 A 0.8 △ ◎ 2-2 3.0 30 A 5.6 〇 △ - comparison Example 2-3 1.5 — C 0.9 X ◎— 2-4 30 D 5.4 〇X Organic film: A... mixed layer, : B... mixed layer and intermediate layer, c... separate layer (Shi Xizhu), D... Separate layer (BTA) (evaluation result) Example 2-1 'The thickness of the organic film is not as high as the claw, and the example work 21 201216546 - Μ目 ratio' is less rust-proof, and if compared with the same organic film thickness In comparison with Examples 2 to 3, the ultrasonic fusion properties were excellent. In Example 2-2, the organic film thickness exceeds 5 〇 _, and the ultrasonic fusion property is inferior to that of the embodiment ι -9, ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ” 八 冋 冋 有机 有机 有机 有机 有机In comparison with Comparative Examples 2 to 4, the ultrasonic fusion properties were excellent. (Example 3) Various copper alloys shown in Table 3 were used as the copper-ruthenium base material. All of these were added to the oxygen-free copper. In the molten solution, the ingot is produced, and the ingot is repeatedly annealed and calendered, and rolled to a thickness of 6 to 20/m, thereby obtaining an aqueous solution of the azole compound and the decane coupling agent in the concentration shown in Table 3. And a mixture of the two aqueous solutions, the various copper alloy pigs obtained in the above manner were immersed for 5 seconds, and then dried in a dryer. Next, the application of the active material and the adhesion evaluation were carried out. 2,3 -benzotriazole (bAT) is used as an azole compound and imidazolium (IS-1) manufactured by Yankuang Metal Co., Ltd. as a decane coupling agent. For rust prevention, active substance adhesion, organic The film was judged and the film thickness was evaluated in the same manner as in Example 1, and the ultrasonic wave was used. The weldability was evaluated in the following manner. 5 The parity result is not shown in Table 3. [Supersonic fusion] (1) The copper foil is cut into a size of l〇〇mmxl50nim, and the thickness of 6 em overlaps 50 pieces. Ι〇" m overlaps 3 〇, when the thickness is 2〇# m, it overlaps 15. (2) Actuator made by Branson (model: ultraweld L20E) 22 201216546 Installation shock head (pitch 0 8_, Height 〇 4mm) Distance. 6 series use 0.2mm (3) welding condition, pressure 4〇psi, vibration 20kHz, splicing time (M seconds. Heart, vibration number (4) After welding under the above conditions, copper foil When the sheet is peeled off, the sheet thickness is greater than or equal to the thickness of the sheet (7). When 21 sheets of P are used, the copper of U 4 or more falls on the welded portion and the thickness of the sheet is 2 〇 "◎"; the thickness of the sheet is 18 〜 The case of 34 = is evaluated as a sheet, a plate thickness of 6 to 10 pieces of copper ^ anti #1 〇 heart time 11~2 〇 evaluated as "〇"; the board "... 夺 心 心 心 〜 〜 〜 〜 〜 〜 〜 Plate thickness 20"m when i~5h plate thickness 1〇#111 when 1 shape is evaluated as "△" n piece also: steel > since the weld part is broken
v如 也無破裂的情形則評價為「X 又，在將銅箔剝離之前，以 員勹X」。 觸於震盛頭之最表層之鋼②’、微鏡以2G倍放大觀察接 痕後，實施剝離試驗。 、、’'接部分’於確認未產生裂 23 201216546 【e ΐ 超音波 熔接性 ◎ 〇 ◎ < ◎ ◎ ◎ ◎ 0 ◎ 〇 < 密合性 〇 ◎ 〇 ◎ ◎ ◎ ◎ ◎ ◎ 〇 X X j 防鏽性 < 〇 〇 〇 〇 〇 〇 〇 X X 〇 〇 有機被膜 厚度 nm CN τ-Η ro rn Ο； in 寸· ο <Ν vo r-； \q vn 寸’ ίΝ o rn <N 寸· 有機 被膜 C < PQ < < < c < O C+D Q |d+c BAT濃度 xlO_4mol/L 寸 (N (Ν <N <N (N 1 (N o 〇 矽烷濃度 xlO_4mol/L r-Η ro m m m ΓΟ 1 r〇 箔厚 βτη Ο 銅合金之成分 Cu-0.02%Ag Cu-0.12%Sn Cu-0.04%Zr Cu-2.7%Ni-0.8%Si Cu-0.13%Cr Cu-0.18%Fe-0.03%P Cu-0.02%Ag Cu-0.12%Sn d 1 m 3-2 3-3* 寸 1 m IT) m m 3-7 00 ro G\ ro * o 1 m 1 ro * (N 1 實施例 比較例 钡喊«^^^赵^嗖 W 长定1 <^-耜韧^«4-yr?Fvla W 口/οε了 ο I xCN^^ei: * e — ε (VXCQ)_^^..·Q, (^^)^^n^:.u,_s£-6-^^^?i...CQ,^^^.: y :德絮奪杯 寸3 劫^«^^^<19^1了^韧^电^^^冢^筚^^^^:*31丨£ 韧^喵^^哿蘅命筚Ir^Ii^vs<^tFvls3^:*0Ile 201216546 (評價結果） 實施例3 1〜3 — 8 ,係以B T A與；δ夕烧偶合劑之混合液 進仃表面處理，再者，BTA與矽烷偶合劑之混合有機被膜 在1 ·0〜5.〇nm之範圍。因此，熔接性、防鏽性及密合性全 部皆顯示出良好的特性。 比杈例3 — 9，係僅以矽烷偶合劑進行表面處理，故防 鏞性不足。 比較例3 — 1〇，係僅以矽烷偶合劑進行表面處理後，僅 以BTA進仃表面處理，未以BTA與矽烷偶合劑之混合液進 订表面處理。因此，有機被膜厚度雖在1.0〜5.Onm之範圍， 但达、合性差，無法同時滿足熔接性、防鏽性及密合性。 車4 1 3 1 1，係僅以B T A進行表面處理，故密合性 不足。 比較例3 ~~ 12，係僅以BTA進行表面處理後，僅以矽 :元偶。劑進仃表面處理，未以bta與矽烷偶合劑之混合液 圍'亍表面處理。因此，有機被膜厚度雖在1.0〜5.Onm之範 防鏽丨生差，無法同時滿足熔接性、防鏽性及密合性。 (實施例4) 偶八為了探讨當使用水系黏合劑時，以唑系化合物及矽烷 以士則之混〇劑所進行之表面處理對特性所造成的影響， 軍-下之條件製作實施例及比較例。將各種條件及試驗結 禾示於表 4。ν 音… ，壓延銅箔及電解銅箔之製造及防鏽性、超 、、妾丨生有機被臈之判定與厚度之評價，與實施例1 25 201216546 [表面處理] β準備表4所記載之濃度的㈣化合物及錢偶合劑各 別單獨之水溶液、及混人古 混S有兩者之水溶液，將板厚1〇//m 之壓延銅落及電解銅箔浸潰其 + 又貝於再中5秒鐘後，以乾燥機乾 無：接著，進行活性物質之塗布及密合性評價。唑系化合 物係使用BTA ’⑦院偶合劑則是使用日鑛金屬公司製之味 唑矽烷（IS— 1000)。 [與活性物質之密合性] 與活性物質之密合性，係以剝離強度之測定進行評價 ⑴混合水與CMC(缓基甲基、纖維素），並力〇以搜掉。 (2) 將石墨加入上述之混合液，進行_，再加入水。 (3) 將SBR加入上述混合液，…于授#，並加水使黏 度為 3000 〜4000Pa· s。 又，此處，CMC與石墨與SBR之添加比率，以重量比 計為 1 : 98 : 1。 (4) 使用刮刀片將（3)塗布於銅箔表面上至一定厚度。 (5) 依序以60°Cxl0分、120°Cxl〇分進行乾燥。 (6) 施加1.5頓/mm2x20秒鐘之荷重進行加壓。 (7) 將上述樣品裁切成寬度1 5 mm。 (8) 將雙面膠貼於支持板，再將銅箔之活性物質側貼於 雙面膠。 (9) 一邊剝下銅箔，一邊測定剝離強度，並計算出平均 剝離強度。 剝離強度，係以依據JIS C 6471之方法，以剝下角度 26 201216546 90°進行測定。 活性物質密合性之判定，對樣品寬度1 5mm，將平均剝 離強度未達l〇〇mN評價為「X」，lOOmN以上、未達150mN 評價為「△」，150mN以上、未達200mN評價為「〇」、 200mN以上則評價為「◎」。 27 201216546 【寸ΐ 超音波熔接性 ◎ ◎ 〇 〇 < < ◎ ◎ ◎ 〇 ◎ ◎ X ◎ < ◎ 0 密合性 〇 ◎ ◎ ◎ ◎ ◎ 〇 ◎ ◎ ◎ X X X ◎ ◎ 〇 X 防鏽性 < 〇 〇 〇 〇 〇 〇 < 〇 〇 X 0 〇 X X X 〇 有機被膜厚度 nm 1"^ 〇〇 rn (N ΡΊ oo 卜 〇\ ro v〇 寸 <N o r〇 CN 卜 寸· » η <Ν 寸 有機被膜 < < < < < < OQ < < < 1 Q Q U υ D+C C+D 1 BAT濃度 xlO_4mol/L »-Η CN Ο CN <N <N 1 (N o 1 I (Ν Ο 矽烷濃度 xlO_4mol/L m m m r〇 ro cn 1 1 1 m m m 羯種類 壓延銅箔 電解銅箔 壓延銅箔 〇 τ-^ 1 寸 CN 1 寸 1 寸 寸 1 寸 1 寸 v〇 1 寸 1 4-7* 1 00 1 寸 On 1 寸 o T 寸 ι~Η 1 寸 rs 1 寸 m T-H 1 寸 寸 T 寸 1 寸 ν〇 1 寸 * 卜 1 寸 實施例 比較例 韧_«<^?F^<o^w 长^1<^-趣 Ιί^vs^^tFvlg W Ί/οε 了 οιχ(Ν^«^:*Α —寸 (VHOQ) _ 隳5®1-·:α , (¾^) _ 隳 ΐ :ό , _ 葩夺^_^^...3 ' _^?i:· V :璣#_杯v If there is no crack, it is evaluated as "X. Before the copper foil is peeled off, the member 勹X". The peeling test was carried out after touching the steel 2' of the outermost layer of the Zhenshengtou and the micromirror to observe the joint at 2G magnification. , ''Connecting part' is confirmed to have not cracked 23 201216546 [e ΐ Ultrasonic welding ◎ 〇 ◎ ◎ ◎ ◎ ◎ 0 ◎ 〇 密 密 密 密 ◎ ◎ ◎ ◎ ◎ ◎ ◎ 〇 XX j Rust prevention < 〇〇〇〇〇〇〇XX 〇〇 organic film thickness nm CN τ-Η ro rn Ο; in inch · ο <Ν vo r-; \q vn inch' ίΝ o rn <N inch · Organic film C < PQ <<< c < O C+DQ |d+c BAT concentration xlO_4mol/L inch (N (Ν <N <N (N 1 (N o decane concentration xlO_4mol /L r-Η ro mmm ΓΟ 1 r〇 foil thickness βτη 成分 composition of copper alloy Cu-0.02% Ag Cu-0.12%Sn Cu-0.04%Zr Cu-2.7%Ni-0.8%Si Cu-0.13%Cr Cu- 0.18%Fe-0.03%P Cu-0.02%Ag Cu-0.12%Sn d 1 m 3-2 3-3* inch 1 m IT) mm 3-7 00 ro G\ ro * o 1 m 1 ro * (N 1 Example Comparative Example Shouting «^^^赵^嗖W Changding 1 <^-耜韧^«4-yr?Fvla W 口/οε了ο I xCN^^ei: * e — ε (VXCQ) _^^..·Q, (^^)^^n^:.u,_s£-6-^^^?i...CQ,^^^.: y: De 夺 夺 cup cup inch 3 robbing ^« ^^^<19^1^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^筚Ir^Ii^vs<^tFvls3^:*0Ile 201216546 (Evaluation results) Example 3 1~3-8, with a mixture of BTA and δ 烧 偶 coupling agent into the surface treatment, in addition, BTA and The mixed organic film of the decane coupling agent is in the range of 1.00 to 5. 〇 nm. Therefore, all of the weldability, rust resistance, and adhesion show good characteristics. Comparative Example 3 - 9, only decane The coupling agent was surface-treated, so the anti-cracking property was insufficient. Comparative Example 3 - 1〇, after only surface treatment with a decane coupling agent, only BTA was applied to the surface treatment, and the mixture of BTA and decane coupling agent was not ordered. Therefore, although the thickness of the organic film is in the range of 1.0 to 5. Onm, the adhesion and the adhesion are poor, and the weldability, the rust resistance, and the adhesion cannot be satisfied at the same time. The car 4 1 3 1 1 is only surface treated with B T A, so the adhesion is insufficient. Comparative Example 3 ~~12, after only surface treatment with BTA, only 矽: meta-couple. The agent was surface treated and was not treated with a mixture of bta and decane coupling agent. Therefore, although the thickness of the organic film is in the range of 1.0 to 5. Onm, the rust resistance is poor, and the weldability, rust resistance, and adhesion cannot be satisfied at the same time. (Example 4) In order to investigate the influence of the surface treatment on the properties of the azole compound and the decane compound by using the water-based adhesive, the conditions of the military-made conditions and Comparative example. Various conditions and test results are shown in Table 4. ν sound..., the manufacture of rolled copper foil and electrolytic copper foil, and the evaluation of rust prevention, super, and organic organic bedding, and evaluation of thickness, and Example 1 25 201216546 [Surface treatment] β Preparation Table 4 The concentration of the (IV) compound and the money coupling agent separately in the aqueous solution, and the mixed solution of the old-fashioned S, both of which have a thickness of 1 〇//m of the rolled copper and the electrolytic copper foil is immersed in the After 5 seconds, the dryer was dried: Next, the application of the active material and the adhesion evaluation were performed. For the use of the azole compound, the BTA '7 hospital coupling agent is a oxazolidine (IS-1000) manufactured by Nippon Mining & Metal Co., Ltd. [Adhesion to active material] The adhesion to the active material was evaluated by measurement of peel strength. (1) The mixed water and CMC (suppressed methyl group, cellulose) were mixed and searched. (2) Add graphite to the above mixture, carry out _, and add water. (3) Add SBR to the above mixture, add #, and add water to make the viscosity 3000~4000Pa·s. Here, the ratio of addition of CMC to graphite and SBR is 1 : 98 : 1 by weight. (4) Apply (3) to the surface of the copper foil to a certain thickness using a doctor blade. (5) Drying in order of 60 ° C x 10 min and 120 ° C x l. (6) Apply a load of 1.5 tons/mm2x20 seconds for pressurization. (7) Cut the above sample to a width of 15 mm. (8) Apply the double-sided tape to the support plate, and then attach the active material of the copper foil to the double-sided tape. (9) The peel strength was measured while peeling off the copper foil, and the average peel strength was calculated. The peel strength was measured by a peeling angle of 26 201216546 90° in accordance with the method of JIS C 6471. For the determination of the adhesiveness of the active material, the sample width was 15 mm, and the average peel strength was less than 10 μm. The evaluation was "X", 100 nm or more, and 150 mN was evaluated as "△", and 150 mN or more and less than 200 mN were evaluated as "〇" and 200mN or more are evaluated as "◎". 27 201216546 [Inch ΐ Ultrasonic welding ◎ ◎ 〇〇 << ◎ ◎ ◎ 〇 ◎ ◎ X ◎ < ◎ 0 Adhesive 〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 〇 X rust resistance <〇〇〇〇〇〇< 〇〇X 0 〇XXX 〇Organic film thickness nm 1"^ 〇〇rn (N ΡΊ oo 〇 〇 \ ro v〇 inch<N or〇CN 卜寸· » η < Ν 有机 Organic film <<<<<<<<<<<<<<<<<<<<<><<>><<>><>><>> N 1 (N o 1 I (Ν Ο 矽 浓度 concentration xlO_4mol/L mmmr〇ro cn 1 1 1 mmm 羯 type rolled copper foil electrolytic copper foil rolled copper foil 〇τ-^ 1 inch CN 1 inch 1 inch inch 1 inch 1 inch v 〇1 inch 1 4-7* 1 00 1 inch On 1 inch o T inch ι~Η 1 inch rs 1 inch m TH 1 inch inch T inch 1 inch ν〇1 inch* Bu 1 inch example comparison example tough _«< ;^?F^<o^w 长^1<^-趣Ι ί^vs^^tFvlg W Ί/οε οιχ(Ν^«^:*Α—inch (VHOQ) _ 隳5®1-·: α , (3⁄4^) _ 隳ΐ :ό , _ 葩 ^^^^...3 ' _^?i:· V :玑#_杯
Mi 螭«^^刼 vla^n了趣剖喊Vs<^^f#:^^^^>:-T^: *r-I — 寸 韧 _«<^^i#:伞筚^^3 #*^li^vs^-yrtFvlPQ^^:*9I—t ooz 201216546 (評價結果） 貫施例4 — 1 - 4 一 6及4 ’係使用壓延銅箔 ，Ν /王：¾:闽 泊 或電解鋼箔’而以BTA與矽烷偶合劑之混合液進行表面户 理，再者，BTA與矽烷偶合劑之混合有機被膜在i 〇〜5〇nl 之範圍。因此，熔接性、防鏽性及密合性全部皆顯示出良 好的特性》 實施例4—7,係於以BTA進行表面處理後，再以與實 施例4—丨同濃度之BTA與矽烷偶合劑之混合液進行表面處 理，由於在BTA與矽烷偶合劑之混合層與銅箔之間，進一 步存在有BTA之中間層，故與實施例4一丨相較之下，防鏽 性更佳。又，此處之有機被膜厚度，係上述2層之合計值， 由於處於1.0〜5.〇nm之範圍，故熔接性亦良好。關於密合 ^生由於混合層位於最表層，故良好。 比較例4—η，未實施表面處理，表面未存在有機被 膜’溶接性雖佳，但防鏽性與密合性差。 ^比較例4— 12及4— 13，係僅以ΒΤΑ進行表面處理， -處理液濃度低時熔接性佳，而當處理液濃度高時防鏽性 佳：然而，無論是何種濃度’密合性皆差，顯示出僅以βτα 的話，無法同時滿足熔接性、防鏽性及密合性。 比較例4 — 14〜4— 15，係僅以矽烷偶合劑進行表面處 人田處理液濃度低時熔接性佳，而當處理液濃度高時密 :性佳 '然而，無論是何種濃度’防鏽性皆差，顯示出僅 Μ石夕院偶合劑的話’無法同時滿足熔接性、防鏽性 性。 29 201216546 比較例4—16’係僅以BTA進行表面處理後僅以石夕 劑進行表面處理，未以BTA與彻合劑之混合液 订Φ處理。因此，有機被膜厚度雖在1.0〜5.〇nm之範 ’但防鏽性差’無法同時毅炫接性、防鏽性及密合性。 較例4 1 7 ’係僅以矽烷偶合劑進行表面處理後，僅 二BTA進行表面處理’未以bta與㈣偶合劑之混合液進 :ί:處理。因此’有機被膜厚度雖在I0〜5.〇—之範圍， 密口丨生差，無法同時滿足熔接性、防鏽性及密合性。 【圖式簡單說明】 圖1 ’係顯示鋰離子電池之堆疊構造之示意圖。 圖2係測定有機被膜之厚度時所得之xps之縱深分 U上圖表不N之縱深分析，中圖表示Si之縱深分析、 下圖則表示C之縱深分析。 【主要元件符號說明】 11 正極 12 隔板 13 負極 14、15 片狀端子 30Mi 螭«^^刼vla^n interestingly screaming Vs<^^f#:^^^^>:-T^: *rI — inch tough _«<^^i#: Umbrella 筚^^3 # *^li^vs^-yrtFvlPQ^^:*9I-t ooz 201216546 (Evaluation Results) Example 4 — 1 - 4 A 6 and 4 'Use of rolled copper foil, Ν / Wang: 3⁄4: Mooring or electrolysis The steel foil 'is surface-treated with a mixture of BTA and a decane coupling agent. Further, the mixed organic film of BTA and a decane coupling agent is in the range of i 〇 5 5 〇 nl. Therefore, all the weldability, rust resistance and adhesion show good characteristics. Example 4-7 is after surface treatment with BTA, and then BTA and decane couple at the same concentration as in Example 4 The mixture of the mixture was subjected to surface treatment. Since the intermediate layer of BTA was further present between the mixed layer of BTA and the decane coupling agent and the copper foil, the rust resistance was better than that of Example 4. Moreover, the thickness of the organic film herein is a total value of the above two layers, and since it is in the range of 1.0 to 5. 〇 nm, the weldability is also good. The adhesion is good because the mixed layer is located at the outermost layer. Comparative Example 4 - η, no surface treatment was performed, and the organic film was not present on the surface. The adhesion was good, but the rust prevention property and the adhesion were inferior. ^Comparative Examples 4-12 and 4-13, the surface treatment is only performed with ruthenium, - the weldability is good when the concentration of the treatment liquid is low, and the rust resistance is good when the concentration of the treatment liquid is high: however, regardless of the concentration The properties are poor, and it is shown that only βτα does not satisfy the weldability, rust resistance, and adhesion at the same time. Comparative Example 4 - 14~4-15, the fusion property was good only when the concentration of the human field treatment liquid was low at the surface of the decane coupling agent, and the density was good when the concentration of the treatment liquid was high. However, no matter what concentration The rust resistance is poor, and it is shown that only the Μ石夕院 coupling agent can't satisfy the weldability and rust resistance at the same time. 29 201216546 Comparative Example 4-16' was only surface-treated with BTA after surface treatment with BTA, and was not treated with a mixture of BTA and a mixture. Therefore, the organic film thickness is in the range of 1.0 to 5. 〇nm, but the rust resistance is poor, and the splicing property, the rust preventing property, and the adhesion property cannot be simultaneously achieved. In Comparative Example 4 1 7 ', after only surface treatment with a decane coupling agent, only two BTAs were surface-treated, and the mixture of bta and (iv) coupling agents was not treated. Therefore, although the thickness of the organic film is in the range of I0 to 5. 〇, the denseness of the film is poor, and the weldability, rust resistance, and adhesion cannot be satisfied at the same time. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 ' is a schematic view showing a stacked structure of a lithium ion battery. Fig. 2 is a longitudinal analysis of the depth of the xps obtained when the thickness of the organic film is measured. U is a depth analysis of the graph on the graph. The middle graph shows the depth analysis of Si, and the lower graph shows the depth analysis of C. [Main component symbol description] 11 Positive electrode 12 Separator 13 Negative electrode 14, 15 Chip terminal 30