TW201136741A - Aluminum and resin composite article excellent in weatherability, and method for manufacturing same - Google Patents

Abstract

To provide an aluminum and resin composite article which not only shows an extremely high adhesion strength and airtightness between an aluminum alloy-made aluminum shaped body and a resin molded article both being integrally joined to each other, keeps the excellent adhesion strength and airtightness of the aluminum-resin joined surface under the severe environment concerning temperature, humidity, dust, corrosive substance and the like, and shows excellence in corrosion resistance, durability and thermal resistance, but also can exhibit excellent performance in weatherability and tensile strength of the joined surface of the aluminum and resin, and to provide a method for manufacturing the same. The aluminum and resin composite article contains the aluminum shaped body having an uneven part on the surface, and the resin molded body whose resin is butt-bonded to the aluminum shaped body. On the surface of the aluminum shaped body, an aluminum film is formed on the outermost surface of the uneven part, and a plurality of recessed parts resulting from the uneven part are formed. The resin penetrates the recessed parts of the resin molded body to make solidified fitting-in parts. The aluminum and resin composite article showing the excellent weatherability is constructed by the mutual engagement by the recessed parts and the fitting-in parts.

Description

201136741 六、發明說明 【發明所屬之技術領域】 本發明係關於鋁合金製的鋁形狀體與在該鋁形狀體之 表面上樹脂成形體被一體設置的鋁•樹脂複合品及其製造 方法，不單僅鋁.樹脂接合面的密著強度及氣密性優異， 耐蝕性或耐候性、進而鋁•樹脂接合面的拉伸強度亦優， 雖未特別限定者，其係關於汽車用各種感應器零件、家電 機器用各種轉換器零件、各種產業機器用電容器零件等爲 代表’可適宜使用於寬廣領域的鋁.樹脂複合品及其製造 方法。 【先前技術】 在汽車用各種感應器零件、家電機器用各種轉換器零 件、各種產業機器用電容器零件等領域、尤其汽車用零件 等領域中’多有在溫度或濕度、粉塵、或二氧化硫或氮氧 化物等起因的酸性雨或在沿海處來自海的海鹽粒子等腐蝕 性物質等存在的嚴苛環境下使用之場合，關於此等感應器 零件、轉換器零件、電容器零件等，在如此嚴苛環境下的 耐蝕性及耐候性之提升、耐久性及耐熱性之提升、氣密性 之提升等成爲重要課題。 以往，作爲金屬與樹脂之接合技術，使用接著劑的方 法爲一般的技術，但由作業效率、零件件數的削減'製品 形狀的簡單化、耐久性等觀點，更合宜於工業上之接合方 法，可舉例如使金屬零件設置在射出成形用模具，於該模 -5- 201136741 具內射出熔融樹脂後充塡，使樹脂固定於金屬零件的嵌入 件成形之方法等。而且，爲了使此等金屬零件與樹脂間的 接合更廉價地進行、更提升接著力，亦知有在與樹脂接合 的金屬零件的表面進行特定的表面處理之方法。 例如專利文獻1中，提案表面粗度爲5μπι〜50μιη， 且由在此表面具有Ιμπι以下的微細凹部或凸部的鋁合金 形狀物、與侵入該鋁合金形狀物的凹部或凸部被固著之特 定的熱可塑性樹脂組成物所構成的複合體。 又，專利文獻2中，揭示浸漬氨、肼、及水溶性胺化 合物所選出的1種以上之水溶液而得，且由表面形成有數 平均內徑10〜80nm之極微細凹部的鋁合金零件、與在其 表面以射出成形固著的熱可塑性合成樹脂組成物零件所構 成的金屬樹脂複合體。 進一步，專利文獻3中，揭示由施加由耐酸鋁處理、 未封孔耐酸鋁處理、酸蝕刻處理、鋅鍍敷鉻酸鹽處理、及 噴砂處理所選出的任一之底層處理的金屬板、與藉由嵌入 件射出成形法無接著劑而一體化的熱可塑性材料所構成之 成型體。 又’專利文獻4中’提案在鋁薄板上以化學的蝕刻法 或電解蝕刻法設置微細粗面層，接著使矽酮樹脂射出而製 造矽酮樹脂-金屬複合體之方法。 進而，專利文獻5中’揭示將金屬零件表面化學蝕刻 ’接著使用熱可塑性樹脂材料進行射出成形以製造金屬嵌 入件樹脂複合成形品之方法。 -6 - 201136741 又’專利文獻6中，揭示使鋁或鋁合金等金屬零件表 面進行溫水處理後’在其表面形成含羥基皮膜，接著藉由 使用熱可塑性樹脂材料進行射出成形，可達成金屬材與熱 可塑性樹脂間之足夠接合強度的金屬嵌入件樹脂複合成形 品的製造方法。 進一步’專利文獻7中，揭示於表面粗度（Rmax) 約8〜18μιη之鋁或鋁合金上，透過有機樹脂或有機—無 機複合樹脂接著金屬箔，而作爲可達成絶緣性樹脂與鋁板 間之良好密著性的鋁芯貼金屬箔層合板。 然而，即使此等任一的場合，暴露在嚴苛環境下時之 金屬-樹脂之界面的密著強度及氣密性未必足夠，且在專 利文獻1、2、4、5中，因蝕刻後表面基本上爲A1質地者 ’耐蝕性亦不充分，故要求開發在金屬•樹脂接合面的密 著強度及氣密性上不僅更優，在耐蝕性或耐候性、進而金 屬•樹脂接合面的拉伸強度上亦優的金屬-樹脂複合體。 因此本發明者們首先著眼於作爲金屬材料的鋁合金、 探討該鋁合金製的鋁形狀體與一體設置於該表面的樹脂成 形體間之界面的密著強度及氣密性極高、即使在嚴苛環境 下亦可發揮優異密著強度及氣密性、進而優異耐久性或耐 熱性的鋁·樹脂複合品，結果發現藉由在鋁形狀體之表面 形成具有具備某特定表面形狀的凹狀部的凹凸部，而鋁形 狀體與樹脂成形體間的密著性或氣密性顯著提升，關於得 到的成果在日本以特願 2008- 1 53,805號及特願 2008-153,806號提出申請。 201136741 [先前技術文獻] [專利文獻] [專利文獻1] W02004/ 04 1,533號公報 [專利文獻2] 特開2007- 1 8 2,07 1號公報 [專利文獻3] 特開2000- 1 27,1 99號公報 [專利文獻4] 特開2000- 1 76,962號公報 [專利文獻5] 專利第3,46 7,47 1號公報 [專利文獻6] 特開200 8- 1 62，1 1 5號公報 [專利文獻7] 特開平1 -27 5,03 6號公報 【發明內容】 [發明所欲解決課題] 本發明者們除上述成果外，進一步，對於製造、提供 在溫度或濕度、粉塵、腐蝕性物質等嚴苛環境下亦維持優 異的鋁•樹脂接合面的密著強度及氣密性，且不僅維持優 異耐蝕性，在耐候性或鋁•樹脂接合面的拉伸強度上亦可 發揮優異性能的鋁·樹脂複合品，進行努力硏究，結果發 現藉由經蝕刻處理而在鋁形狀體之表面形成具有具備某特 定表面形狀的凹狀部的凹凸部，同時在該凹凸部的最表面 ’再形成含來自鋁皮膜形成處理的Al(OH)3、AIO(OH)、 Al2〇3、A1(P04)、A12(HP04)3、A1(H2P04)3、及 A10Si〇2 中選出的任一種以上之鋁化合物的鋁皮膜，不僅鋁形狀體 與樹脂成形體間的密著性、氣密性及耐蝕性提升，耐候性 或鋁•樹脂接合面的拉伸強度亦顯著提升，而完成本發明 201136741 因此，本發明之目的在於提供一體接合的鋁合金製的 鋁形狀體與樹脂成形體間之界面密著強度及氣密性極高、 在溫度或濕度、粉塵、腐蝕性物質等嚴苛環境下維持優異 的鋁·樹脂接合面的密著強度及氣密性，且不僅耐蝕性、 耐久性、耐熱性優異，在耐候性或鋁.樹脂接合面的拉伸 強度上亦可發揮優異性能的鋁.樹脂複合品。 又，本發明之其他目的在於提供可製造如此鋁形狀體 與樹脂成形體間之界面密著強度及氣密性極高、嚴苛環境 下亦維持優異的鋁.樹脂接合面的密著強度及氣密性，且 不僅耐蝕性、耐久性、耐熱性優異，在耐候性或鋁.樹脂 接合面的拉伸強度上亦可發揮優異性能的鋁·樹脂複合品 之鋁•樹脂複合品的製造方法。 [解決課題之手段] 亦即，本發明爲含有於表面之一部份或全部具有凹凸 部之鋁合金製的鋁形狀體、與於該鋁形狀體之一表面，樹 脂以對接狀態結合的樹脂成形體的鋁·樹脂複合品，其特 徵係在前述鋁形狀體之表面，於前述凹凸部的最表面形成 含來自鋁皮膜形成處理的 Al(OH)3、AIO(OH)、Al2〇3、 Α1(Ρ〇4)、A12(HP04)3、A1(H2P04)3、及 A10Si02 中選出的 任一種以上之鋁化合物的鋁皮膜，同時形成該凹凸部構成 的複數的凹狀部，又，在前述樹脂成形體，於前述複數的 凹狀部內形成前述樹脂進入後固化的複數的嵌入部，藉由 -9- 201136741 前述凹狀部與前述嵌入部而鋁形狀體與樹脂成形 止的耐候性優異的鋁·樹脂複合品。 又，本發明爲含有於表面之一部份或全部具 之鋁合金製的鋁形狀體、與設置於該鋁形狀體之 脂成形體的複合品，其特徵係 於前述鋁形狀體之表面，於前述凹凸部的最 含來自鋁皮膜形成處理的 Al(OH)3、AIO(OH)、 Al(PO〇、A12(HP04)3、Al(H2P〇4)3、及 A10Si02 任一種以上之鋁化合物的鋁皮膜，同時形成該凹 的複數的凹狀部， 前述各凹狀部在鋁形狀體之厚度方向剖面中 厚度方向，且通過凹凸部的最高部的頂線與通過 底線間之中線中，以掃瞄型電子顯微鏡觀察測定 爲Ο.ίμιη以上30μηι以下的大小、其深度爲〇. 30μηι以下的大小，又， 於前述樹脂成形體形成前述樹脂進入前述複 部內固化的複數的嵌入部， 藉由前述凹狀部與前述嵌入部而鋁形狀體與 體相互卡止之耐候性優異的鋁·樹脂複合品。 而且，本發明爲鋁合金製的鋁形狀體、與在 體之表面含樹脂成形體的複合品的製造方法，其 由使鋁合金材進行蝕刻處理後於表面的一部份或 具有凹凸部構成的複數的凹狀部之鋁合金材、接 該鋁合金材的凹凸部表面施加鋁皮膜形成處理後 體相互卡 有凹凸部 表面的樹 表面形成 Α12〇3、 中選出的 凸部構成 垂直於該 最深部的 的開口寬 Ιμπι以上 數的凹狀 樹脂成形 該鋁形狀 特徵係藉 全部形成 著至少對 ，在該凹 -10- 201136741 凸部的最表面形成含有來自鋁皮膜形成處理的Α1(ΟΗ)3、 AIO(OH)、Al2〇3、Al(P〇4)、A12(HP04)3、Al(H2P〇4)3、及 A10Si02中選出的任一種以上之鋁化合物的鋁皮膜而形成 鋁合金製的鋁形狀體，又，在樹脂成形體之成形時使樹脂 進入鋁形狀體之各凹狀部內固化的樹脂成形體之嵌入部成 形，鋁形狀體之凹狀部與樹脂成形體之嵌入部相互卡止以 製造鋁形狀體與樹脂成形體結合爲一體的鋁•樹脂複合品 之耐候性優異的鋁•樹脂複合品的製造方法。 〔關於鋁·樹脂複合品〕 本發明中，形成鋁形狀體用的鋁合金材方面，具體上 可舉例如將純A1系的1〇〇〇系、Al-Cu系的2000系、A1· Μπ 系的 3 000 系、Al-Si 系的 4000 系 ' Al-Mg 系的 5000 系、ADC5、及 ADC6、Al-Mg-Si 系的 6000 系、Al-Zn-Mg 系的 7000 系、Al-Fe 系的 8000 系、Al-Si-Mg 系的 ADC3 、Al-Si-Cu 系的 ADC10、ADC10Z、ADC12、及 ADC12Z 、Al-Si-Cu-Mg系的ADC14等材質所構成的材料適當加工 爲所期望的形狀而得之加工材、進而適當組合此等加工材 而得的組合材等。 又’本發明中，因鋁形狀體之表面的凹凸部而在該錯 形狀體之表面形成之複數的凹狀部可爲其開口緣部係無端 的周緣部般穴狀或孔狀者（具無端開口緣部的凹狀部）或 開口緣部係具兩端部般狹縫狀或溝狀者（具有端開口緣部 的凹狀部）’進而亦可混有此等具無端開口緣部的穴狀或 -11 - 201136741 孔狀者與具有有端開口緣部的狹縫狀或溝狀者。 而且，關於鋁形狀體之複數的凹狀部，較佳爲其一部 份或全部中，形成由凹狀部的開口緣部的一部分或全體朝 向開口寬方向中心之呈雪簷狀突出的突出部，藉此，凹狀 部其開口寬變得比其內部的寬度尺寸狹窄、如此進入凹狀 部內固化的樹脂成形體之嵌入部與凹狀部間形成無法相互 脫離的卡止構造，在鋁成形體之凹狀部或樹脂成形體之嵌 入部的任一者或兩者不被破壞下不會脫離，鋁成形體與樹 脂成形體間的密著強度或氣密性更提升。 進一步，如此在鋁形狀體之複數的凹狀部中，於其一 部份或全部的開口緣部形成上述般雪簷狀的突出部，則於 此等凹狀部內樹脂成形體之嵌入部不一定需要以密著狀態 嵌合，例如基於鋁形狀體與樹脂成形體間的線膨脹係數的 差與環境溫度，此等鋁形狀體與樹脂成形體間即使產生不 可避免的極微小間隙，在此等鋁形狀體與樹脂成形體間仍 可維持優異密著強度或氣密性。 進一步，本發明中，於上述鋁形狀體之凹凸部的最表 面形成含來自鋁皮膜形成處理的 Α1(ΟΗ)3、AIO(OH)、 Al2〇3、A1(P04)、Al2(HP〇4)3、A1(H2P04)3、及 A10Si〇2 中選出的任一種以上之鋁化合物的鋁皮膜，因該鋁皮膜在 凹凸部所形成的複數的凹狀部的最表面，形成具有與樹脂 化學鍵結力之官能基、或具微細凹凸形狀的水鋁礦皮膜， 所以進入具如此特定表面形狀的凹狀部內固化的樹脂成形 體之嵌入部，在與凹狀部間，不僅形成穏固的物理的卡止 12- 201136741 構造’亦形成無法相互脫離的化學鍵結，鋁成形體之凹狀 部或樹脂成形體之嵌入部的任一者或兩者不被破壞下不會 脫離’鋁成形體與樹脂成形體間的密著強度或氣密性更提 升。 進一步’具有上述特定表面形狀同時於凹凸部（尤其 其凹狀部）之最表面具有鋁皮膜的鋁形狀體，與僅具有經 蝕刻處理的特定表面形狀場合相比較，除耐蝕性顯著提升 外’耐候性或鋁•樹脂接合面的拉伸強度顯著提升，即使 在將如此鋁形狀體在非常嚴苛環境下放置，之後，使樹脂 進入凹狀部內固化之場合，在鋁形狀體與樹脂成形體間維 持優異密著強度或氣密性。 進而’關於具有上述表面性狀的鋁形狀體與樹脂成形 體結合爲一體的鋁·樹脂複合品，與僅蝕刻處理的鋁形狀 體與樹脂成型體結合爲一體的鋁.樹脂複合品相比較，不 僅密著強度、氣密性提升’且可製造能發揮顯著耐蝕性的 鋁·樹脂複合品。 本發明中，因鋁形狀體之表面的凹凸部而形成的複數 的凹狀部，參考該鋁形狀體之剖面爲模式所示的圖1來說 明’在鋁形狀體1之厚度方向剖面，垂直該厚度方向，且 通過凹凸部的最高部的頂線（TL)與通過最深部的底線（BL) 間的中線（H L)中，以掃瞄型電子顯微鏡觀察測定的開口寬 (d)在Ο.ίμιη以上30μηι以下、較佳爲〇.5gm以上2〇pm# 下、更佳爲Ιμπι以上ΙΟμιη以下的大小，且深度爲〇1μηι 以上30μηι以下、較佳爲0·5μηι以上20μηι以下的大小爲 -13- 201136741 佳。該凹狀部的開口寬（d)若比〇.1μιη窄 融樹脂變得難以進入，鋁形狀體1與樹脂 產生微小空隙，而變得難以得到優異密著 相反地’若比30μηι寬，則在鋁成形體i 刻處理）時，溶解反應過度進行，產生材 材料的板厚減少量增加的問題，成爲產生 製品而生產性降低的原因。又，關於深度 ’則變得難以得到足夠樹脂成形體2之嵌 使其比30μηι深，則在鋁成形體1之表面 )時溶解反應過度進行，產生材料表面的 厚減少S增加的問題。 本發明中，關於因鋁形狀體之表面的 複數的凹狀部的密度，在每邊O.lmm，| 20μιη及深度0.5μιη〜20μιη之範圍內的1 大小者以5〜200個左右的範圍存在爲佳。 又，本發明之鋁形狀體中，在其凹狀 狀的突出部較佳爲鋁•樹脂一體成形品的 ，由其樹脂成形體側向鋁形狀體側，使沿 的觀察線相互以〇. 1 μΐΏ之間隔拉伸時，1 少1個以上的由樹脂-鋁-樹脂所形成的 層合部的鋁形狀體部分之厚度爲0.1 μπι以 範圍者爲佳，在鋁·樹脂一體成形品上， 出部在1 〇〇〇支觀察線之範圍內存在1個 進而，鋁形狀體之複數的凹狀部，其 ，射出成形時熔 成形體2之界面 強度或氣密性， 之表面處理（蝕 料表面的缺損或 材料強度不足之 ，若比〇. 1 μ m淺 入部，相反地， 處理（蝕刻處理 缺損或材料的板 凹凸部所形成的 開口寬 0.5μηι〜 種或2種以上之 部所形成的雪簷 厚度方向剖面中 厚度方向的多數 觀察線上形成至 層合部，且以該 上30μιη以下的 如此雪簷狀的突 (上爲佳。 一部份或全部中 -14- 201136741 ，於內部的壁面亦可具有形成有至少 部的雙重凹狀部構造，又，於內部的 至少1個以上之內部突起部的內部凹 等雙重凹狀部構造或內部凹凸構造亦 複數的凹狀部的一部份或全部中，藉 部構造或內部凹凸構造，鋁形狀體之 之嵌入部相互強固地結合，發揮鋁形 的更優異密著強度或氣密性。 本發明中，在鋁形狀體之表面的 成的鋁皮膜之厚度，爲了在耐候性或 伸強度中發揮優異性能，以0.0 0 1 μ m 圍者爲佳' 較佳爲0.003μηι以上 0.006μηι 以上 5μιη 以下。但，鋁 (Α12〇3)時，其厚度以〇.ΐμιη以上爲 達0.01μηι(在氧化鋁皮膜（α1203 )之 耐候性之效果變得不能充分發揮，比 形狀體之表面的凹凸部被皮膜包埋的 強度或氣密性降低。 〔關於鋁.樹脂複合品的製造方 本發明中，製造如此鋁•樹脂複 面形成具有上述複數的所期望的凹狀 法可舉例如於鋁合金材施加蝕刻處理 面形成凹凸部’並形成具有該凹凸部 1個以上之內部凹狀 壁面亦可具有形成有 凸構造，進一步，此 可並存。鋁形狀體之 由存在如此雙重凹狀 凹狀部與樹脂成形體 狀體與樹脂成形體間 凹凸部的最表面所形 鋁·樹脂接合面的拉 以上30μιη以下的範 8μηι以下、更佳爲 皮膜爲氧化鋁皮膜 佳。鋁皮膜之厚度未 場合未達〇· 1 μηι )， 30μιη厚，則產生鋁 問題，接合面的拉伸 法〕 合品時，首先，在表 部之鋁形狀體，其方 後在表面的一部或全 構成的複數的凹狀部 -15- 201136741 之鋁形狀體的方法。 而且，該鋁合金材的蝕刻處理使用的蝕刻液，雖可舉 例如鹽酸、磷酸、硫酸、乙酸、草酸、抗壞血酸、安息香 酸、酪酸、檸檬酸、甲酸、乳酸、異丁基酸、蘋果酸、丙 酸、酒石酸等酸水溶液所成的蝕刻液，但在形成具有開口 寬及深度爲所期望的大小之複數的凹狀部、或在凹狀部的 一部份或全部的開口緣部，向開口寬方向中心形成突出的 雪簷狀的突出部等、爲了使表面所形成的凹狀部控制在所 期望的形狀及大小，酸水溶液使用氧化力較弱的酸水溶液 ，又，在如此氧化力較弱的酸水溶液中爲了使鋁合金材的 表面所形成之氧化皮膜溶解，必需使用含特定濃度的鹵素 離子的蝕刻液。 亦即，蝕刻液，以使用於氧化力較弱的酸水溶液中， 含有特定濃度範圍的由氯離子（cr)、氟離子（FJ、及碘離 子（Γ)所選出之任1種或2種以上之鹵素離子之蝕刻液爲 佳。而且，使用含如此鹵素離子之氧化力較弱的酸水溶液 、於該蝕刻液中浸潰鋁合金材，則首先蝕刻液中之鹵素離 子溶解鋁合金材表面的氧化皮膜，之後溶解內部的鋁合金 後進而侵蝕鋁合金材內部，此時，因相較於表面的氧化皮 膜而言內部的鋁合金更易被侵蝕（易溶解），故藉由設定 蝕刻液的組成或蝕刻處理的條件等，對表面所形成之凹凸 部起因的凹狀部，可使其開口寬或深度等控制在所期望的 大小、或於其一部份或全部的開口緣部形成向開口寬方向 中心突出之雪簷狀的突出部。 -16 - 201136741 以該目的所使用的蝕刻液’具體上可舉例如作爲酸水 溶液，酸濃度〇. 1重量％以上80重量％以下、較佳爲0·5 重量％以上5 0重量％以下的鹽酸水溶液、磷酸水溶液、稀 硫酸水溶液、乙酸水溶液等或酸濃度5重量％以上3 0重 量％以下、較佳爲1 0重量％以上2 0重量％以下的草酸水 溶液等，又，作爲爲了於此等酸水溶液中導入鹵素離子而 添加之鹵素化物，可舉例如氯化鈉、氯化鉀、氯化鎂 '氯 化鋁等氯化物或氟化鈣等氟化物或溴化鉀等溴化物等，較 佳爲考量安全性等之氯化物。而且，關於該蝕刻液中之鹵 素離子濃度，通常爲0.5公克/公升（g/L)以上3 00g/L 以下、較佳爲lg/L以上100g/L以下，未達〇.5g/L則鹵素 離子之效果小，而產生於開口緣部不形成具雪簷狀的突出 部之凹狀部的問題，又，超過3 00g/L之場合，因鋁成形 體之表面處理（蝕刻處理）時，溶解反應急遽進行，產生 凹狀部的控制變得困難之問題。 又，本發明中，作爲在鋁形狀體之表面形成所期望的 凹狀部用的蝕刻液，硝酸或超過8 0重量％之濃度的濃硫 酸等氧化力較強的酸水溶液或氫氧化鈉或氫氧化鉀等鹼的 水溶液不適當。氧化力較強的酸水溶液對鋁合金具有皮膜 生成能力’且於鋁形狀體之表面形成強固氧化皮膜，以鹵 素離子溶解氧化皮膜變得困難。又，氫氧化鈉或氫氧化鉀 等鹼水溶液的對鋁合金溶解機轉爲全面溶解型，即使添加 鹵素離子之場合’其傾向不變，形成具有所期望的形狀或 大小之凹狀部變得困難。 -17- 201136741 本發明中，關於使用上述蝕刻液將鋁合金材的表面蝕 刻處理時的處理條件，因使用蝕刻液的種類、酸濃度、鹵 素離子濃度等或鋁形狀體所要求之複數的凹狀部的數目或 大小等而相異，但通常在鹽酸水溶液的場合，以浴溫20 〜8 0°C、浸漬時間1〜30分鐘，在磷酸水溶液的場合，以 浴溫30〜80t、浸漬時間1〜5分鐘，在硫酸水溶液的場 合，以浴溫40〜80°C、浸潰時間2〜8分鐘，在草酸水溶 液的場合，以浴溫50〜80°C、浸漬時間1〜3分鐘，在乙 酸水溶液的場合，以浴溫5 0〜8 0 °C、浸漬時間1〜3分鐘 之範圍爲佳。使用蝕刻液的酸濃度或浴溫愈高，則蝕刻處 理之效果愈變得顯著，變得可短時間處理，但關於浴溫， 未達20 °C則溶解速度慢，生成具有足夠大小（開口寬及 深度）的凹狀部需長時間，又，在超過80°C之浴溫，溶 解反應急速進行，凹狀部的開口寬及深度之控制變得困難 ，浸漬時間方面，未達1分鐘則難以控制凹狀部的開口寬 及深度，相反地超過3 0分鐘之浸漬時間，則成爲生產性 降低的原因。 又，本發明中，如上述於鋁合金材施加鈾刻處理形成 具有凹狀部的鋁形狀體時，依必要，於該蝕刻處理前的鋁 合金材表面，以脫脂或表面調整、除去表面附著物•污染 物等爲目的，亦可施加由以酸水溶液之酸處理、及/或以 鹼溶液之鹼處理所成的前處理 在此，該前處理使用的酸水溶液，可使用例如以市售 酸性脫脂劑調製者，使用硫酸、硝酸、氟化氫、磷酸等無 -18- 201136741 機酸或乙酸、檸檬酸等有機酸或混合此等酸得到的混合酸 等酸試藥所調製者等’又’作爲鹼水溶液，可使用例如以 市售鹼性脫脂劑調製者、以苛性鈉等鹼試藥調製者、或混 合此等者而調製者等。 關於使用上述酸水溶液及/或鹼水溶液進行的前處理 的操作方法及處理條件’可與以往使用此種之酸水溶液或 鹼水溶液進行的前處理的操作方法及處理條件相同，例如 可藉由浸漬法、噴塗法等方法進行。 如此’蝕刻處理完畢後，本發明中，在經蝕刻處理所 形成的凹凸部的最表面施加爲了形成含有Al(OH)3、 aio(oh)、ai2o3、Α1(Ρ〇4)、A12(HP04)3、ai(h2po4)3、及 A10Si02中選出的任一種以上之鋁化合物之鋁皮膜用的鋁 皮膜形成處理。作爲該鋁皮膜形成處理使用的處理溶液， 可形成含如此鋁化合物之鋁皮膜即可，並無特別限制，但 可舉例如離子交換水、蒸餾水、矽烷耦合劑、磷酸一氫銨 溶液、磷酸二氫銨溶液、磷酸溶液等。 而且，施加上述鋁皮膜形成處理後，依必要可進行水 洗處理，在該水洗處理，可使用工業用水、地下水、自來 水、離子交換水等，因應欲製造鋁形狀體而適宜選擇。進 一步，關於施加鋁皮膜形成處理的鋁合金材，依必要雖可 進行乾燥處理，該乾燥處理，除可以在室溫放置之自然乾 燥外，亦可使用氣流、吹風機、烤箱等進行強制乾燥。 關於該鋁皮膜形成處理的處理條件，因使用處理溶液 而相異，具體上，在處理溶液爲離子交換水或蒸餾水之場 -19- 201136741 合，以於50°C以上之溫水進行60秒以上之浸漬處理、 0.1 MPa以上之加壓下進行1分鐘以上之水蒸氣處理爲 ，處理溶液爲磷酸離子、磷酸一氫離子、磷酸二氫離子 任一種以上之磷酸離子種以0.1〜l〇〇g/L之比例含有的 酸水溶液系的場合，以在處理溶液中30秒〜30分鐘浸 後、以80〜400°C的熱風乾燥30秒〜30分鐘爲佳，又 處理溶液爲矽烷耦合劑以0.1〜l〇〇g/L之比例含有之溶 的場合，以於處理溶液中，30秒〜30分鐘浸漬後，以 °C〜400°C的熱風乾燥30秒〜30分鐘爲佳。 藉由上述蝕刻處理及鋁皮膜形成處理、或前處理、 刻處理、及鋁皮膜形成處理得到的鋁形狀體之表面，形 有蝕刻處理造成之凹凸部，且其表面的60度表面光澤 (sugatest製小型光澤計之測定）較佳爲60以下。該 面光澤度超過60時，熱可塑性樹脂之射出成形時，熔 樹脂無法充分進入鋁形狀體之凹狀部內，鋁形狀體與樹 成形體間無法得到足夠接合強度。 又，使經上述蝕刻處理及鋁皮膜形成處理、或經前 理、蝕刻處理、及鋁皮膜形成處理得到的鋁形狀體之表 以SEM或光學顯微鏡用倍率1 000倍進行剖面觀察，關 得到的剖面觀察照片，較佳爲鋁形狀體之表面積係經蝕 處理形成凹凸部前之鋁合金材的表面積的1.2倍以上 倍以下。該表面積增加率未達1 .2倍、或超過1 〇倍之 合，樹脂無法充分進入鋁形狀體之凹狀部內，鋁形狀體 樹脂成形體間無法得到足夠接合強度。 或 佳 之 磷 漬 液 80 蝕 成 度 表 融 脂 處 面 於 刻 10 場 與 -20- 201136741 接著’爲了得到本發明之鋁.樹脂複合品，於以上般 得到的鋁形狀體之表面塗佈接著劑後，接合金屬或樹脂、 或於得到的鋁形狀體與金屬間透過樹脂，使此等以熱壓機 施加熱與壓力進行接合、或使得到的鋁形狀體裝設於射出 成形用模具內，將熔融於該模具內的特定熱可塑性樹脂射 出使固化、亦即藉由使用鋁形狀體的樹脂之複合化，製造 目的鋁形狀體與樹脂之複合品。 在此’關於製造本發明之鋁•樹脂複合品用的樹脂， 雖可各種之熱可塑性樹脂單獨使用，但考量本發明之銘. 樹脂複合品追求之物性、用途、使用環境等，熱可塑性樹 脂，較佳可舉例如聚丙烯樹脂、聚乙烯樹脂、丙烯腈.丁 二烯.苯乙烯共聚合物（ABS)、聚碳酸酯樹脂、聚醯胺 樹脂、聚苯硫醚（PPS)等聚伸芳基硫化物樹脂、聚縮醛 樹脂、液晶性樹脂、聚乙烯對苯二甲酸酯（p E T )或聚對 苯二甲酸丁二酯（PBT)等聚酯系樹脂、聚縮醛樹脂、聚 釀亞肢樹脂、間規聚苯乙燃樹脂等或此等熱可塑性樹脂之 2種以上之混合物’又’爲了使鋁形狀體與樹脂成形體間 的密著性、機械的強度、耐熱性、尺寸安定性（耐變形、 彎曲等）、電氣的性質等性能更改善，更佳爲可於此等熱 可塑性樹脂添加纖維狀、粉粒狀、板狀等充塡劑或各種之 彈性體成分。 又’作爲於熱可塑性樹脂添加之充塡劑，例如以玻璃 纖維、碳纖維、金屬纖維、石綿纖維、硼纖維等無機質纖 維充塡劑或聚醯胺、氟樹脂、丙烯酸樹脂等高熔點有機質 -21 - 201136741 纖維充塡劑或石英粉末、玻璃珠粒、玻璃粉、碳酸鈣爲代 表的無機粉體類等粉狀充塡劑或玻璃薄片、滑石或雲母等 砂酸鹽類等板狀充塡劑等，以相對熱可塑性樹脂1 00重量 份而言250重量份以下爲佳、較佳爲20重量份以上220 重量份以下、更佳爲3 0重量 圍添加。該充填劑的添加量超 低且變得難以進入鋁形狀體之 度，產生招致機械特性降低之 又，作爲添加於熱可塑性 甲酸乙酯系 '核殻型、烯烴系 系等彈性體，考量射出成形時 等來選擇，又，相對熱可塑性 重量份以下、較佳爲3〜25重 成分之添加Μ超過30重量份 度之效果、產生機械特性降低 配效果，在熱可塑性樹脂使用 〇 進一步，在製造本發明之 性樹脂，因應所要求性能，可 脂添加的習知添加劑，亦即難 、抗氧化劑或紫外線吸收劑等 滑劑、脫膜劑、結晶化促進劑 本發明中，關於將鋁形狀 進行熱可塑性樹脂之射出成形 份以上100重量份以下的範 過25 0重量份，則流動性降 凹部，無法得到良好密著強 問題。 樹脂之彈性體成分，如胺基 、聚酯系、醯胺系、苯乙烯 的熱可塑性樹脂之熔融溫度 樹脂100重量份而言在30 量份的範圍使用。該彈性體 ，則無法見到更提升密著強 等問題。該彈性體成分之搭 聚酯系樹脂之場合尤其顯著 鋁·樹脂複合品用的熱可塑 適宜添加一般於熱可塑性樹 燃劑、染料或顏料等著色劑 安定劑、可塑劑、潤滑劑、 、結晶核劑等。 體設置在射出成形用模具內 ，雖可採用所使用的熱可塑 -22- 201136741 性樹脂要求的一般成形條件，但射出成形時熔融的熱可塑 性樹脂確實進入鋁形狀體之凹狀部內後固化係爲重要，以 使模具溫度或料筒溫度在熱可塑性樹脂之種類或物性、更 而在成形循環允許範圍下設定較高爲佳，特別關於模具溫 度，必需下限溫度在9 0 °C以上、較佳爲1 3 0。(：以上，但上 限因應使用熱可塑性樹脂之種類，以從1 0 0 °C至比該熱可 塑性樹脂之熔點或軟化點（添加彈性體成分之場合，高者 的熔點或軟化點）低20°C左右的溫度爲止的範圍爲佳。 又，下限模具溫度爲從熱可塑性樹脂之熔點至不低於1 4 〇 C進行設定爲佳。 進一步’關於製造本發明之鋁·樹脂複合品用的樹脂 ’除上述熱可塑性樹脂以外，亦可使用熱硬化性樹脂、常 溫硬化性樹脂、各種接著劑等。作爲熱硬化性樹脂，可舉 例如環氧系樹脂等’又，作爲常溫硬化性樹脂，可舉例如 聚醋系樹脂等。進一步’接著劑方面，可舉例如腈橡膠系 、合成橡膠系、環氧系、氰基丙烯基系、氯化乙烯系、塑 膠系、熱熔系等。 [發明之效果] 本發明之鋁•樹脂複合品，鋁形狀體與樹脂成形體間 的界面（鋁/樹脂界面）之密著強度或氣密性與僅經蝕刻 處理場合比較更爲高、且即使暴露在嚴苛腐蝕環境，可維 持其優異抗者強度 '氣密性及耐鈾性，且鋁之腐蝕造成的 外觀變化亦可長期間維持，係可長期維持高信賴性者。因 -23- 201136741 此，本發明之鋁·樹脂複合品，例如以汽車用各種感應器 零件、家電機器用各種轉換器零件、各種產業機器用電容 器零件等爲代表，可適用於寬廣領域中之金屬-樹脂一體 成形零件，特別適用於從鋁形狀體之一部份的表面，樹脂 成形體以對接狀態突出而要求高結合強度的金屬一樹脂一 體成形零件。 又，根據本發明之鋁•樹脂複合品的製造方法，製造 時藉由測定鋁成形體之表面光澤度或表面粗度，可預想得 到的製品的密著強度，其製造時除品質管理變得容易外， 變得可製造在各製品上密著強度幾乎無不均的高信賴性的 製品。 [實施發明之最佳形態] 以下，基於實施例及比較例，將本發明之較佳實施形 態具體說明。又，本發明不限於下述記載之例。 【實施方式】 [實施例1〕 〔鋁形狀體之調製〕 從厚度lmm之鋁合金（JISA 1050-H24)板切出具有 50mmx50mm之大小的3個鋁片（鋁合金材），對此等鋁 片’施加首先在30wt%硝酸水溶液中，常溫、5分鐘浸漬 後，以離子交換水充分水洗，接著於5 w t %気氧化鈉溶液 、50°C、1分鐘浸漬後，進行水洗，進一步，於30wt%硝 -24- 201136741 酸水溶液、常溫、3分鐘浸漬後，進行水洗之前處理。 接著，對上述前處理後之鋁片施加以在2.5wt%鹽酸 水溶液中，作爲水溶性無機鹵素化合物使用添加54g/L的 氯化鋁六水合物（A1C13 · 6H20 )後調製的蝕刻液（氯離 子濃度：48g/L ) ’於該蝕刻液中以66°C、4分鐘浸漬後 ，進行水洗的方法進行蝕刻處理。 更進而，藉由施加在30wt%硝酸水溶液中常溫下、3 分鐘浸漬後，進行水洗，且在80 °C的熱水中浸漬20分鐘 之水合處理，在經上述蝕刻處理所形成的鋁片表面的凹凸 部的最表面，施加形成鋁皮膜[AIO(OH)〕的鋁皮膜形成處 理，製作3個鋁試驗片（鋁形狀體）。 〔鋁試驗片（鋁形狀體）表面的凹狀部觀察〕 關於得到的各鋁試驗片，將其厚度方向剖面中某領域 之剖面用掃瞄型電子顯微鏡（日立製FE-SEM、S-4500形 )觀察，首先，決定鋁形狀體之厚度方向剖面中，垂直該 厚度方向且通過凹凸部的最高部的頂線（TL)，接著大致同 上述，決定垂直於鋁形狀體之厚度方向且通過凹凸部最深 部的底線，進一步，從頂線（TL)對底線（BL)在垂直方向拉 線段，通過該線段之中間部且與頂線（TL)[或底線（BL)〕 平行拉出的中線（HL)上之鋁形狀體與鋁形狀體間存在之空 隙之距離爲凹狀部的開口寬（d)，觀察起因鋁試驗片表面 的凹凸部所形成的凹狀部的形狀與大小（開口寬及深度） 且進行測定。 -25- 201136741 在所觀察各鋁試驗片（鋁形狀體）之某領域剖面，例 如圖1之鋁形狀體之剖面複製圖所示般，又，以該圖1爲 觀念的凹狀部3之形狀的典型例如圖2所示，爲具有由開 口緣部的一部分向開口寬方向中心突出爲雪簷狀的突出部 之凹狀部（形狀a:圖2 (a)作參考）、具有由開口緣部的 全體向開口寬方向中心突出爲雪簷狀的突出部的凹狀部（ 形狀b :圖2(b)作參考）、內部更具有形成有凹狀部的雙 重凹狀部構造之凹狀部（形狀c:圖2(c)作參考）、及於 內部的壁面具有形成有內部突起部的內部凹凸構造之凹狀 部（形狀d :圖2(d)作參考），在該實施例1中，觀察到 全部形狀a〜d之凹狀部。又，關於如此凹狀部3之形狀 、各鋁試驗片係相同，且即使各鋁試驗片中之觀察場所改 變亦相同。 在此，關於所觀察凹狀部的形狀的評估，具有上述形 狀a〜d之任1個或2個以上之場合評估爲良好（〇）， 又，形狀a〜d皆不存在之場合評估爲不良（X)。又，在 以下所示實施例2〜18及比較例1〜3中對所觀察凹狀部 的形狀亦以同樣基準進行評估。 又，所測定各鋁試驗片某領域之剖面中，所觀察凹狀 部的大小（開口寬及深度）及其比例爲每0· 1 mm邊長四 方形，開口寬0.1 μηι〜Ιμηι之凹狀部爲10個〜100個，開 口寬爲Ιμηι〜ΙΟμηι之凹狀部爲1〜1〇個，開口寬爲Ιίμηι 〜30μιη之凹狀部爲1〜3個，深度在Ο.ίμιη〜30μηι之範 圍內。又，關於形成雙重凹狀部構造之內部的凹狀部的大 -26- 201136741 小（開口寬及深度）及其比例’大致同上述，每〇 · 1 m m 邊長四方形，開口寬O.lpm〜Ιμιη之凹狀部爲10個〜50 個，開口寬爲Ιμιη〜ΙΟμιη之凹狀部爲1〜50個’開口寬 爲Ιίμηι〜30μΐΏ之凹狀部爲1〜2個’深度爲Ο.ίμηι〜 2 Ομιη之範圍內。關於該凹狀部的大小、各鋁試驗片亦相 同，又，即使各鋁試驗片中之觀察場所改變幾乎無變化。 在此，關於所觀察凹狀部的大小的評估，在開口寬 0.1〜30μϊη及深度0.1〜30μιη之範圍內時，評估爲良好（ 〇），若不是則評估爲不良（X )。又，以下所示實施例 2〜1 8及比較例1〜3中所觀察凹狀部的大小亦以同樣基 準評估。 〔鋁試驗片（鋁形狀體）之表面光澤度的評估〕 對得到的3個鋁試驗片，各自使用小型光澤計（ sugatest製）測定表面的60度光澤度，算出所測定3個 値的平均値作爲鋁試驗片之60度光澤度。結果爲26。 〔鋁試驗片（鋁形狀體）之表面積增加率的評估〕 對得到的3個鋁試驗片，各自以SEM或光學顯微鏡 用倍率1 000倍進行剖面觀察，對得到的剖面觀察照片使 用影像處理軟體（ImageJ )測定鋁形狀體之表面的表面積 。對未處理的鋁合金材，各自求得到的各鋁試驗片表面的 表面積增加的比例，算出得到的3個値的平均値，定義爲 表面積增加率。結果爲3 · 4 8倍。 -27- 201136741 〔鋁試驗片（鋁形狀體）之最表面的平均皮膜厚度之 測定〕 對得到的3個鋁試驗片，各自經T E M ( FEI製 TECNAI G2 F20 S-TWIN )以倍率10萬倍〜30萬倍進行 剖面觀察，由得到的剖面觀察照片測定在鋁試驗片表面形 成的皮膜之厚度，II出所測定3個値的平均値作爲平均皮 膜厚度。結果爲〇.3μΠ1。 〔關於評估用試驗體之posiTEST試驗、耐候性試驗 (鹽水噴霧試驗）、及樹脂•鋁·樹脂之層合部的觀察評 估〕 1.評估用試驗體之調製 (1) 試驗體調製用端子之調製 關於鋁製的posiTEST試驗用端子（DeFelsko公司製 :尺寸：20πιηιφ，JISA 1100)，同上述銘試驗片（銘形 狀體）之場合，施加前處理、蝕刻處理及鋁皮膜形成處理 ，製作用以製作在以下的posiTEST試驗及耐候性試驗（ 鹽水噴霧試驗）使用之評估用試驗體之試驗體調製用端子 〇 (2) 評估用試驗體[經接著劑的樹脂（接著劑）之接 合〕之調製 圖3所示，使上所得到的鋁試驗片（鋁形狀體）1與 試驗體調製用端子5透過二液混合型之環氧系急速硬化接 -28- 201136741 著劑（Huntsman Advanced Materials 公司製商品名·· ARALDITE RAPID ) 4接合後，使用熱壓機（S Ο N E製 AH-2003 )在押著壓力O.IMPa下進行常溫加壓，使其持 續維持24小時壓著，接著，將從鋁試驗片1與端子5間 的接合面夾出的多餘接著劑4，在接著劑固化後，使用切 斷機由接合面分離，使以接合面成爲3.14cm2之方式調整 ，製作鋁·接著劑·鋁試驗片（評估用試驗體）。 (3) 評估用試驗體（以加熱壓著的樹脂接合）之調 製 圖4所示，於上所得到的鋁試驗片（鋁形狀體）1上 ，使聚苯硫醚樹脂（東麗製）之顆粒（樹脂）6以 0.04g/cm2之方式乘載，在其上設置試驗體調製用端子5 ，使用熱壓機（S ONE製 AH-2003)，以押著壓力 O.IMPa、金屬板溫度 3 00 °C進行熱壓著，製作樹脂以 3.14cm2接合面積固著的鋁·樹脂.鋁試驗片（評估用試 驗體）。 (4) 評估用試驗體（以射出成形的樹脂接合）之調 製 圖5所示，使上所得到的鋁試驗片（鋁形狀體）丨設 置於圖示外之射出成形機（NISSEI公司製ST10R2V)之 模具內’作爲熱可塑性樹脂使用聚苯硫醚樹脂（東麗製） ，以射出時間5秒、射出速度80mm/秒、保壓力lOOMPa 、成形溫度3 20°C、及模具溫度160°C的成形條件進行射 出成形’在鋁試驗片1之上面使樹脂製端子7 —體成形， -29- 201136741 在鋁試驗片1之上面製作樹脂製端子7之接合面積爲 3 · 1 4cm2的鋁•樹脂試驗片（評估用試驗體）。 2 ·耐候性試驗（鹽水噴霧試驗；S S T 1 0 0 0 h r ) 關於上所調製的3種之評估用試驗體、鋁.接著劑. 鋁試驗片、鋁·樹脂.鋁試驗片、及鋁•樹脂試驗片，使 各評估用試驗體導入鹽水噴霧試驗機（Sugatest製 CASSER-23L-ISO) ，1 000小時經過後由試驗機取出評估 用試驗體，進行外觀觀察。該外觀觀察中，評估除接合部 外的部位之試驗片側的表面白鏽產生數，結果在任一的評 零 爲 比白 又 估階〇 評三爲 形之皆 情化估 色變評 變著的 之顯觀 面有外 表：, 行 X 體 進匕驗 ,化試 變用 有估 稍ί : 的 △ 1 ' 化 變 體無 驗： 試〇 用以 估’ 任 在 果 結 估 評 段 3.posiTEST試驗機之接合面的拉伸強度評估 對上述耐候性試驗後之各評估用試驗體，使用 posiTEST試驗機（DeFelsko公司製），依據 ASTM D4541 (ISO 4624)試驗法，測定鋁·樹脂接合面的拉伸強 度（端子尺寸：20mm炉、分解能：±〇.〇lMPa、精度：土 1%、及測定範園：〇〜20 MPa)。該posiTEST試驗中， 如圖6所示，在posiTEST試驗機之執行機構8透過端子 固定用夾具9，連結評估用試驗體之端子5 (或7)部分 後，以馆浦加壓，測定端子5 (或7)部分至由鋁試驗片 (鋁形狀體）1剝離爲止的荷重（剝離荷重）’又’調查 剝離後之鋁試驗片1之接合部的剝離狀態° -30- 201136741 評估用試驗體之剝離荷重，在鋁·接著劑•鋁試驗片 之場合爲6.3MPA，在鋁•樹脂·鋁試驗片之場合爲 5.7MPA，又，鋁.樹脂試驗片之場合爲5.5MPA。又，對 所觀察到的剝離狀態，於鋁試驗片之接合面，評估方式： 接著劑或樹脂全面殘存之場合評估爲良好（〇），又，在 鋁試驗片側僅一部份殘留場合爲部分良好（△)、在鋁試 驗片側無殘留場合（界面剝離）之場合爲不良（X )，而 結果皆良好（〇）。 4.樹脂•鋁·樹脂之層合部的觀察評估 又，圖7所示，關於上所調製的3種之評估用試驗體 、鋁·接著劑·鋁試驗片、鋁·樹脂•鋁試驗片、及鋁· 樹脂試驗片，各自由其鋁試驗片向在其上層合的樹脂（接 著劑）於厚度方向切斷，使該厚度方向剖面以SEM或光 學顯微鏡用倍率1 〇〇〇倍觀察，對得到的剖面觀察照片， 將由樹脂成形體2側向鋁形狀體1側沿厚度方向延伸的多 數的觀察線（OL)相互以0.1 μιη之間隔隔開時，在1觀察線 (OL)上存在由樹脂（接著劑）-鋁-樹脂（接著劑）所成 的至少1個以上之層合部，且該層合部的鋁形狀體部分之 厚度爲Ο.ΐμπι以上30μιη以下的範圍，以1000支觀察線 (OL )之範圍內存在1個以上之比例的場合評估爲良好（ 〇），如此層合部在1〇〇〇支觀察線（〇L)之範圍內連1個 也不存在者爲不良（X)進行評估，結果，任一的場合皆 爲良好（〇）。又，關於以下的實施例2〜18及比較例1 〜3亦以同樣基準評估。 -31 - 201136741 [實施例2〜5〕 除作爲鋁皮膜形成處理’取代實施例1之80 °C 20分 鐘之熱水浸漬的水合處理，使用下述表1所示處理液，以 下述表1處理條件調製鋁試驗片（鋁成形體）及試驗體調 製用端子以外，以與上述實施例1同樣地，調製評估用試 驗體（鋁.接著劑·鋁試驗片、鋁.樹脂.鋁試驗片、及 鋁·樹脂試驗片），又’與上述實施例1之場合相同，實 施耐候性試驗（鹽水噴霧試驗）、posiTEST試驗、及樹 脂•鋁·樹脂之層合部的觀察評估。 結果與實施例1之結果一同如表2所示。 [表1] 實施例 No. 鋁皮膜形成處理 處理後之 乾燥條件 處理液組成(水溶液） 浸漬 條件 主要成分 濃度 (g/L) 溫度 (0〇 時間 (分） 溫度 (0〇 時間 (分） 2 磷酸 2 25 1 200 5 3 磷酸一氫銨 2 25 1 200 5 4 磷酸二氫銨 2 25 1 200 5 5 矽烷耦合劑 10 25 1 120 5 (注）矽烷耦合劑：；8-(3,4-環氧環己基)乙基三甲氧基矽烷 (信越矽酮公司製：KBM303) [實施例6〕 除作爲製作鋁片的鋁合金板，使用JIS A5052-H34以 外’以與上述贲施例1同樣地，製作鋁試驗片（鋁形狀體 )同時製作端子。接著與上述實施例1同樣地製作評估用 試驗體（鋁·接著劑·鋁試驗片、鋁•樹脂·鋁試驗片、 -32- 201136741 及鋁.樹脂試驗片）’又，與上述實施例1之場合相同， 實施耐候性試驗（鹽水噴霧試驗）、posiTEST試驗、& 樹脂·鋁·樹脂之層合部的觀察評估。 結果與實施例1之結果一同如表2所示。 [實施例7〕 除作爲製作鋁片的鋁合金板，使用JIS A3 003-H 24以 外，以與上述實施例1同樣地，製作鋁試驗片（鋁形狀體 )同時製作端子。接著與上述實施例1同樣地製作評估用 試驗體（鋁·接著劑·鋁試驗片、鋁·樹脂·鋁試驗片、 及鋁.樹脂試驗片），又，與上述實施例1之場合相同， 實施耐候性試驗（鹽水噴霧試驗）、P〇siTEST試驗、及 樹脂·鋁·樹脂之層合部的觀察評估。 結果與實施例1之結果一同如表2所示。 [實施例8〕 與上述實施例1同樣地製作鋁試驗片同時製作端子’ 接著與上述實施例1同樣地製作評估用試驗體（鋁•接著 劑•鋁試驗片、鋁.樹脂.鋁試驗片、及鋁·樹脂試驗片 )，不實施耐候性試驗（鹽水噴霧試驗）’與上述實施例 1之場合同樣地實施posiTEST試驗’進一步實施樹脂 •鋁·樹脂之層合部的觀察評估。 結果與實施例1之結果一同如表2所示。 比較檢討上述實施例1之試驗結果與該實施例8之試 -33 - 201136741 驗結果’可知本發明之鋁•樹脂複合品即使暴露在如耐候 性試驗的條件後，與暴露於該條件前同樣地維持優異的鋁 •樹脂接合面的拉伸強度。 [實施例9〕 與上述實施例1同樣地製作鋁試驗片（鋁形狀體）， 又，製作端子。接著，對製作的鋁試驗片實施耐候性試驗 (鹽水噴霧試驗），之後，水洗後以1 〇〇°C的熱風進行5 分鐘乾燥，接著與0施例1同樣地製作評估用試驗體（鋁 •接著劑•鋁試驗片、鋁•樹脂•鋁試驗片、鋁·樹脂試 驗片）。 對如此製作的評估用試驗體，與上述實施例1之場合 相同地實施posiTEST試驗進行評估，一倂評估上述耐候 性試驗〔（鹽水噴試驗）〕結果，同時與上述實施例1 同樣地實施樹脂•鋁·樹脂之層合部的觀察評估。 結果與實施例1之結果一同如表2所示。 使該實施例9之試驗結果與上述實施例1之各試驗結 果進行比較、檢討，可知本發明中蝕刻處理後經鋁皮膜處 理的鋁形狀體（鋁試驗片）本身顯示優異耐候性，加工爲 鋁·樹脂複合品前即使長時間暴露於嚴苛環境下依然可得 到優異的鋁·樹脂接合面的拉伸強度、其操作性優異。 [©施例1 〇〕 藉由與實施例1同樣地進行前處理與蝕刻處理，進而 -34- 201136741 在3 0 wt %硝酸水溶液中常溫下、3分鐘浸漬後 ’接著施加於1〇〇 °C的熱水中進行1分鐘浸漬 而進行鋁皮膜形成處理，與上述實施例1同樣 驗片（鋁形狀體）’同時與實施例1之場合同 子。 接著’使用得到的鋁試驗片與端子，與上 同樣地調製評估用試驗體（鋁.接著劑·鋁試 樹脂.鋁試驗片、及鋁.樹脂試驗片），又， 例1之場合相同地、實施posiTEST試驗、耐 鹽水噴霧試驗）、及樹脂.鋁.樹脂之層合部 〇 結果延續表2如表3所示。 [實施例Π〕 與實施例1同樣地進行前處理與蝕刻處 3 Owt%硝酸水溶液中以常溫進行3分鐘浸漬後 水洗’接著在硫酸濃度160g/L的溶液中、溶i 流電壓20V之條件下實施陽極氧化處理（鋁 理），形成皮膜厚度5μπι及孔數1 〇16個/m2的 膜（Al2〇3之鋁皮膜）後、水洗，以12CTC的 分鐘乾燥’製作鋁試驗片（鋁形狀體），又， 端子。 接著’使用得到的鋁試驗片與端子，與上 同樣地調製評估用試驗體（鋁.接著劑.鋁試 ，進行水洗 之水合處理 地製作鋁試 樣地製作端 述實施例1 驗片、鋁· 與上述實施 候性試驗（ 的觀察評估 理，進而在 ，充分進行 昆1 8 t及直 皮膜形成處 陽極氧化皮 熱風進行5 同樣地製作 述實施例1 驗片、鋁· -35- 201136741 樹脂•鋁試驗片、及鋁·樹脂試驗片），又，與上述實施 例1之場合相同地，實施posiTEST試驗、耐候性試驗（ 鹽水噴霧試驗）、及樹脂.鋁.樹脂之層合部的觀察評估 〇 結果延續表2如表3所示。 [U施例12〕 與實施例1同樣地進行前處理與蝕刻處理，進而在 3 Owt%硝酸水溶液中常溫下、3分鐘浸漬後，進行水洗， 接著，藉由在〇.5MPa加壓下進行20分鐘的水蒸氣處理（ 鋁皮膜形成處理），形成緻密A10(0H )之鋁皮膜，製作 鋁試驗片（鋁形狀體），同時同樣地製作端子。 接著，使用得到的鋁試驗片與端子，與上述實施例1 同樣地調製評估用試驗體（鋁·接著劑.鋁試驗片、鋁. 樹脂·鋁試驗片、及鋁•樹脂試驗片），又，與上述實施 例1之場合相同地，實施posiTEST試驗、耐候性試驗（ 鹽水噴霧試驗）、及樹脂•鋁·樹脂之層合部的觀察評估 〇 結果延續表2如表3所示。 [實施例1 3〕 除熱可塑性樹脂使用聚丁烯對苯二甲酸酯樹脂（東麗 製）以外，以與上述實施例1同樣地，製作鋁試驗片與端 子，並製作鋁·樹脂試驗片（評估用試驗體）’不對得到 -36- 201136741 的評估用試驗體實施鹽水噴霧試驗，而實施posiTEST試 驗及樹脂·鋁·樹脂之層合部的觀察評估。 結果延續表2如表3所示。 [實施例1 4〕 與實施例1同樣地進行前處理後，使用於50wt%磷酸 水溶液中添加50g/L的氯化鈉調製的蝕刻液（氯離子濃度 :30g/L) ，66t、4分鐘之條件下進行浸漬該蝕刻液之 蝕刻處理，進而水洗後於3 0 w t %硝酸水溶液中以常溫進行 3分鐘浸漬後，再進行水洗，接著實施1 00 °C的熱水中浸 漬1分鐘的水合處理（鋁皮膜形成處理），與上述實施例 1同樣地製作鋁試驗片（鋁形狀體），同時與實施例1之 場合同樣地製作端子。 接著，使用得到的鋁試驗片與端子，與上述實施例1 同樣地調製評估用試驗體（鋁·接著劑·鋁試驗片、鋁· 樹脂·鋁試驗片、及鋁·樹脂試驗片），又，與上述實施 例1之場合相同地，實施posiTEST試驗、耐候性試驗（ 鹽水噴霧試驗）、及樹脂•鋁·樹脂之層合部的觀察評估 〇 結果延續表2如表3所示。 [實施例1 5〕 與實施例1同樣地進行前處理後，使用於1 0 w t %硫酸 水溶液中添加50g/L的氯化鈉調製的蝕刻液（氯離子濃度 -37- 201136741 ：30g/L)，在66°C、4分鐘之條件下進行浸漬該蝕刻液 之蝕刻處理，進而水洗後’在3 0wt%硝酸水溶液中常溫下 、3分鐘浸潰後’進行水洗’接著SI施1 〇〇°C的熱水中浸 漬1分鐘的水合處理（鋁皮膜形成處理），與上述實施例 1同樣地製作鋁試驗片（鋁形狀體），同時與實施例1之 場合同樣地製作端子。 接著，使用得到的鋁試驗片與端子，與上述實施例1 同樣地調製評估用試驗體（鋁·接著劑•鋁試驗片、鋁· 樹脂•鋁試驗片、及鋁•樹脂試驗片），又，與上述實施 例1之場合相同地，實施posiTEST試驗、耐候性試驗（ 鹽水噴霧試驗）、及樹脂•鋁•樹脂之層合部的觀察評估 〇 結果延紹表2如表3所示。 [實施例16〕 與1JT施例1同樣地進行前處理後，使用於30wt%草酸 水溶液中添加50g/L的氯化鈉調製的蝕刻液（氯離子濃度 :30g/L)，在66°C、4分鐘之條件下進行浸漬該蝕刻液 之蝕刻處理，進而水洗後，在3 Owt%硝酸水溶液中常溫下 、3分鐘浸漬後，進行水洗，接著實施1 00°C的熱水中浸 漬1分鐘的水合處理（鋁皮膜形成處理），與上述實施例 1同樣地製作鋁試驗片（鋁形狀體），同時與實施例1之 場合同樣地製作端子。 接著，使用得到的鋁試驗片與端子，與上述實施例1 -38- 201136741 同樣地調製評估用試驗體（鋁·接著劑·鋁試驗片、鋁· 樹脂•鋁試驗片、及鋁•樹脂試驗片），又，與上述實施 例1之場合相同地，實施posiTEST試驗、耐候性試驗（ 鹽水噴霧試驗）、及樹脂·鋁·樹脂之層合部的觀察評估 〇 結果延續表2如表3所示。 [實施例1 7〕 與實施例1同樣地進行前處理後，使用2.5wt%鹽酸 水溶液中添加50g/L的氯化鈉（NaCl )調製的蝕刻液（氯 離子濃度：54g/L )，在66t、4分鐘之條件下進行浸漬 該蝕刻液之鈾刻處理，進而水洗後，在3 0 w t %硝酸水溶液 中常溫下、3分鐘浸漬後’進行水洗，接著實施丨⑽艺的 熱水中浸漬1分鐘的水合處理（鋁皮膜形成處理），與上 述實施例1同樣地製作鋁試驗片（鋁形狀體），同時與實 施例1之場合同樣地製作端子。 接著’使用得到的鋁試驗片與端子，與上述實施例1 同樣地調製評估用試驗體（鋁.接著劑.鋁試驗片、鋁· 樹脂·鋁試驗片、及鋁.樹脂試驗片），又，與上述實施 例1之場合相同地’實施posiTEST試驗、耐候性試驗（ 鹽水噴霧試驗）、及樹脂.鋁.樹脂之層合部的觀察評估 〇 結果延續表2如表3所示。 -39- 201136741 [贸施例18〕 與贲施例1同樣地進行前處理 3 Owt%硝酸水溶液中以常溫進行3分 水洗，接著在硫酸濃度160g/L的溶 流電壓20V之條件下實施陽極氧化 理），形成皮膜厚度Ιμπι及孔數101 膜（αι2ο3之鋁皮膜）後、水洗，以 分鐘乾燥，製作鋁試驗片（鋁形狀體 端子。 接著，使用得到的鋁試驗片與端 同樣地調製評估用試驗體（鋁•接著 樹脂•鋁試驗片、及鋁·樹脂試驗片 例1之場合相同地，责施Ρ 〇 s i T E S Τ 鹽水噴霧試驗）、及樹脂•鋁•樹脂 〇 結果延續表2如表3所示。 與蝕刻處理，進而在 鐘浸漬後，充分進行 交中、溶溫1 8 °C及直 處理（鋁皮膜形成處 S個/m2的陽極氧化皮 120°C的熱風進行5 )，又，同樣地製作 子，與上述實施例1 劑·鋁試驗片、鋁· )，又，與上述實施 試驗、耐候性試驗（ 之層合部的觀察評估 -40- 201136741 gigs XS3I0.[Technical Field] The present invention relates to an aluminum-shaped body made of an aluminum alloy and an aluminum-resin composite which is integrally provided on the surface of the aluminum-shaped body, and a method for producing the same, and a method of manufacturing the same Aluminum only. The resin joint surface is excellent in adhesion strength and airtightness, and is excellent in corrosion resistance, weather resistance, and tensile strength of the aluminum-resin joint surface. Although it is not particularly limited, it is related to various sensor parts and home electric appliances for automobiles. It is represented by a variety of converter parts, capacitor parts for various industrial machines, etc. It can be used in a wide range of aluminum. Resin composite and its manufacturing method. [Prior Art] In the fields of various sensor parts for automobiles, various converter parts for home electric appliances, capacitor parts for various industrial equipment, and other parts for automobiles, especially in the fields of temperature or humidity, dust, or sulfur dioxide or nitrogen. In the case of acid rain such as oxides or corrosive substances such as sea salt particles from the sea, such as marine materials, such sensor parts, converter parts, and capacitor parts are so severe. Corrosion resistance and weather resistance in the environment, improvement in durability and heat resistance, and improvement in airtightness have become important issues. Conventionally, as a bonding technique between a metal and a resin, a method using an adhesive is a general technique, but it is more suitable for industrial bonding methods from the viewpoints of reduction in work efficiency and number of parts, simplification of product shape, durability, and the like. For example, a method in which a metal part is placed in a mold for injection molding, and the mold is molded in a mold, and the resin is fixed in a mold, and the resin is fixed to a metal part. Further, in order to make the joining between the metal parts and the resin more inexpensive and to improve the adhesion, a method of performing a specific surface treatment on the surface of the metal part joined to the resin is also known. For example, Patent Document 1 proposes a surface roughness of 5 μm to 50 μm, and an aluminum alloy shape having a fine concave portion or a convex portion having a diameter of Ιμπ or less on the surface thereof and a concave portion or a convex portion invading the aluminum alloy shaped object are fixed. A composite of a specific thermoplastic resin composition. Further, Patent Document 2 discloses an aluminum alloy component obtained by impregnating an aqueous solution of one or more selected from the group consisting of ammonia, hydrazine, and a water-soluble amine compound, and having an extremely fine concave portion having a number of average inner diameters of 10 to 80 nm formed on the surface thereof, and A metal resin composite comprising a thermoplastic resin synthetic resin component which is formed by injection molding on its surface. Further, Patent Document 3 discloses a metal sheet which is treated by applying an underlayer which is selected by an alumite treatment, an unsealed alumite treatment, an acid etching treatment, a zinc plating chromate treatment, and a grit blasting treatment, and A molded body composed of a thermoplastic material which is integrated by an insert injection molding method without an adhesive. Further, in Patent Document 4, a method of forming a fine rough surface layer by a chemical etching method or an electrolytic etching method on an aluminum thin plate, and then ejecting the fluorenone resin to produce an fluorenone resin-metal composite is proposed. Further, in Patent Document 5, a method of chemically etching a surface of a metal part is disclosed, followed by injection molding using a thermoplastic resin material to produce a metal-inserted resin composite molded article. -6 - 201136741 Further, in Patent Document 6, it is disclosed that after the surface of a metal part such as aluminum or aluminum alloy is subjected to warm water treatment, a hydroxyl-containing film is formed on the surface thereof, and then a metal is formed by injection molding using a thermoplastic resin material. A method of producing a metal insert resin composite molded article having sufficient joint strength between a material and a thermoplastic resin. Further, in Patent Document 7, it is disclosed that aluminum or an aluminum alloy having a surface roughness (Rmax) of about 8 to 18 μm is passed through an organic resin or an organic-inorganic composite resin followed by a metal foil to obtain an insulating resin and an aluminum plate. Good adhesion aluminum core metal foil laminate. However, in any of these cases, the adhesion strength and airtightness of the metal-resin interface when exposed to a severe environment are not necessarily sufficient, and in Patent Documents 1, 2, 4, and 5, after etching In the case where the surface is substantially A1, the corrosion resistance is not sufficient. Therefore, it is required to develop not only the adhesion strength and the airtightness of the metal/resin joint surface but also the corrosion resistance or weather resistance, and further the metal/resin joint surface. A metal-resin composite excellent in tensile strength. Therefore, the inventors of the present invention paid attention to the aluminum alloy as a metal material, and the adhesion strength and airtightness of the interface between the aluminum alloy body made of the aluminum alloy and the resin molded body integrally formed on the surface were extremely high, even in the case of An aluminum-resin composite which exhibits excellent adhesion strength and airtightness, and further excellent durability or heat resistance in a severe environment. As a result, it has been found that a concave shape having a specific surface shape is formed on the surface of the aluminum-shaped body. In the case of the concave-convex portion, the adhesion between the aluminum-shaped body and the resin-molded body and the air-tightness are remarkably improved, and the results of the application are disclosed in Japanese Patent Application No. 2008-153,805 and Japanese Patent Application No. 2008-153,806. [Patent Document 1] [Patent Document 1] WO042004/04, No. 1,533 [Patent Document 2] Japanese Laid-Open Patent Publication No. 2007- 1 8 2, No. 07 1 [Patent Document 3] JP-A-2000-127 [Patent Document 4] Japanese Laid-Open Patent Publication No. Hei. No. 2000-176, No. [Patent Document 7] Japanese Unexamined Patent Publication No. Hei No. Hei. No. Hei. No. Hei. In the harsh environment such as corrosive substances, the adhesion strength and airtightness of the excellent aluminum/resin joint surface are maintained, and not only excellent corrosion resistance but also weather resistance or tensile strength of the aluminum/resin joint surface can be exhibited. In an effort to improve the aluminum-resin composite product having excellent performance, it has been found that the uneven portion having a concave portion having a specific surface shape is formed on the surface of the aluminum-shaped body by etching treatment, and the uneven portion is formed at the same time. Surface 'reformation contains Al(OH)3, A from aluminum film formation treatment Aluminum film of any one or more of aluminum compounds selected from IO(OH), Al2〇3, A1(P04), A12(HP04)3, A1(H2P04)3, and A10Si〇2, not only aluminum shaped body and resin formed The adhesion between the body, the airtightness and the corrosion resistance are improved, and the weather resistance or the tensile strength of the aluminum-resin joint surface is also remarkably improved, and the present invention is completed in 201136741. Therefore, the object of the present invention is to provide an integrally joined aluminum alloy. The interface between the aluminum body and the resin molded body is extremely high in adhesion strength and airtightness, and maintains excellent adhesion strength and gas of the aluminum/resin joint surface in a severe environment such as temperature, humidity, dust, and corrosive substances. Tightness, and not only excellent in corrosion resistance, durability, heat resistance, in weather resistance or aluminum. Aluminum can also exhibit excellent properties in tensile strength of the resin joint. Resin composite. Further, another object of the present invention is to provide an aluminum which is excellent in interfacial adhesion strength and airtightness between such an aluminum-shaped body and a resin molded body, and which is excellent in a severe environment. The adhesion strength and airtightness of the resin joint surface are excellent not only in corrosion resistance, durability, heat resistance, but also in weather resistance or aluminum. A method for producing an aluminum/resin composite of an aluminum/resin composite which exhibits excellent properties in tensile strength of a resin joint surface. [Means for Solving the Problem] In other words, the present invention is an aluminum-shaped aluminum alloy body having a part or all of the surface having an uneven portion, and a resin bonded to the surface of the aluminum-shaped body in abutting state. The aluminum-resin composite of the molded body is characterized in that on the surface of the aluminum-shaped body, Al(OH)3, AIO(OH), Al2〇3, which are formed from the aluminum film forming treatment, are formed on the outermost surface of the uneven portion. An aluminum film of any one or more of the aluminum compounds selected from the group consisting of Α1 (Ρ〇4), A12 (HP04)3, A1(H2P04)3, and A10SiO2, and forming a plurality of concave portions formed by the uneven portions, and In the resin molded body, a plurality of embedded portions in which the resin is post-cured are formed in the plurality of concave portions, and the weather resistance between the aluminum-shaped body and the resin is improved by the concave portion and the embedded portion in -9-201136741 Aluminum resin composite. Further, the present invention is a composite product of an aluminum-shaped body made of an aluminum alloy partially or wholly on one surface and a fat-formed body provided on the aluminum-shaped body, and is characterized in that it is on the surface of the aluminum-shaped body. The aluminum or the like containing the aluminum film formation treatment, such as Al(OH)3, AIO(OH), Al (PO〇, A12(HP04)3, Al(H2P〇4)3, and A10Si02 The aluminum film of the compound simultaneously forms the concave plurality of concave portions, and the concave portions are in the thickness direction in the thickness direction cross section of the aluminum body, and pass through the line between the top line of the highest portion of the uneven portion and the bottom line In the middle, the observation by scanning electron microscope is Ο. Ίμιη above 30μηι below the size, its depth is 〇.  In addition to the size of 30 μm or less, the resin molded body is formed into a plurality of embedded portions in which the resin is cured in the plurality of portions, and the aluminum-shaped body and the body are locked to each other by the concave portion and the embedded portion, and the weather resistance is excellent. Aluminum resin composite. Further, the present invention is a method for producing a composite of an aluminum alloy body made of an aluminum alloy and a resin molded body on the surface of the body, which is formed by etching a portion of the aluminum alloy material or having a concave or convex portion on the surface. The aluminum alloy material of the plurality of concave portions and the surface of the concave-convex portion of the aluminum alloy material are formed by the aluminum film forming process, and the surface of the tree surface on which the concave and convex portions are stuck with each other forms a Α12〇3, and the selected convex portion is perpendicular to the The deepest opening is formed by a concave resin having an opening width of πμπι or more. The aluminum shape is formed by at least a pair, and the 最1 (ΟΗ) containing the aluminum film forming treatment is formed on the outermost surface of the concave -10-201136741 convex portion. 3. Aluminium film of any one or more aluminum compounds selected from AIO(OH), Al2〇3, Al(P〇4), A12(HP04)3, Al(H2P〇4)3, and A10SiO2 to form an aluminum alloy In the molding of the resin molded body, the resin is molded into the embedded portion of the resin molded body in which the concave portion of the aluminum-shaped body is solidified, and the concave portion of the aluminum-shaped body and the embedded portion of the resin molded body are formed. Mutual lock A method for producing an aluminum resin composite having excellent weather resistance of an aluminum resin composite in which an aluminum body and a resin molded body are integrated. [Aluminum-resin composite product] In the present invention, the aluminum alloy material for forming an aluminum-shaped body may, for example, be a pure A1-based monoterpene system or an Al-Cu-based 2000 system or A1·Μπ. Series 3,000, Al-Si 4000 system, Al-Mg 5000, ADC5, ADC6, Al-Mg-Si 6000, Al-Zn-Mg 7000, Al-Fe Materials such as 8000-series, Al-Si-Mg-based ADC3, Al-Si-Cu-based ADC10, ADC10Z, ADC12, and ADC12Z, and Al-Si-Cu-Mg-based ADC14 are appropriately processed. A processed material obtained from a desired shape, and a composite material obtained by appropriately combining such processed materials. Further, in the present invention, the plurality of concave portions formed on the surface of the deformed body due to the uneven portion on the surface of the aluminum-shaped body may be a hole-shaped or hole-like portion of the peripheral edge portion of the opening edge portion (with The concave portion of the end opening portion or the opening edge portion may have a slit shape or a groove shape at both end portions (a concave portion having an end opening edge portion)', and may be mixed with such an endless opening edge portion The hole shape or -11 - 201136741 The hole-shaped person and the slit-shaped or groove-shaped one having the end opening edge. Further, in the concave portion of the plurality of aluminum-shaped bodies, it is preferable that a part or all of the opening edge portion of the concave portion protrudes in a snow-like shape toward the center in the opening width direction. In this way, the width of the opening of the concave portion is narrower than the width of the inner portion of the concave portion, and the locking portion that can be separated from each other between the fitted portion and the concave portion of the resin molded body that has been cured in the concave portion is formed in the aluminum. Either or both of the concave portion of the molded body or the embedded portion of the resin molded body are not broken without being broken, and the adhesion strength or airtightness between the aluminum molded body and the resin molded body is further improved. Further, in the concave portion of the plurality of aluminum-shaped bodies, the above-described snow-like protruding portion is formed at one or all of the opening edge portions of the aluminum-shaped body, and the embedded portion of the resin molded body in the concave portion is not It is necessary to fit in a closed state, for example, based on the difference in linear expansion coefficient between the aluminum body and the resin molded body, and the ambient temperature, and even if an inevitable minute gap occurs between the aluminum body and the resin molded body, Excellent adhesion strength or airtightness can be maintained between the aluminum body and the resin molded body. Further, in the present invention, Α1(ΟΗ)3, AIO(OH), Al2〇3, A1(P04), and Al2 (HP〇4) containing the aluminum film forming treatment are formed on the outermost surface of the uneven portion of the aluminum body. (3) an aluminum film of any one or more of the aluminum compounds selected from A1 (H2P04)3 and A10Si〇2, which has a chemical bond with the resin due to the outermost surface of the plurality of concave portions formed on the uneven portion of the aluminum film The functional group of the junction force or the gibbonic film having a fine concavo-convex shape, so that the embedded portion of the resin molded body which is solidified in the concave portion having such a specific surface shape not only forms a tamping physics with the concave portion The locking 12-201136741 structure also forms a chemical bond that cannot be separated from each other, and either or both of the concave portion of the aluminum molded body or the embedded portion of the resin molded body are not broken without being separated from the 'aluminum formed body and The adhesion strength or airtightness between the resin molded bodies is further improved. Further, an aluminum-shaped body having the above-described specific surface shape and having an aluminum film on the outermost surface of the uneven portion (particularly, the concave portion) has a markedly improved corrosion resistance as compared with the case of having only a specific surface shape subjected to etching treatment. The weather resistance or the tensile strength of the aluminum-resin joint surface is remarkably improved, even after the aluminum body is placed in a very severe environment, and then the resin is allowed to enter the concave portion, the aluminum body and the resin molded body are formed. Excellent adhesion strength or air tightness is maintained between. Further, the aluminum-resin composite in which the aluminum-shaped body having the above-mentioned surface properties is integrated with the resin molded body is integrated with the aluminum-shaped body and the resin molded body which are only etched. In comparison with the resin composite, not only the adhesion strength and the airtightness are improved, but also an aluminum/resin composite which can exhibit significant corrosion resistance can be produced. In the present invention, a plurality of concave portions formed by the uneven portions on the surface of the aluminum-shaped body are described with reference to FIG. 1 in which the cross section of the aluminum-shaped body is schematically shown in the thickness direction of the aluminum-shaped body 1. In the thickness direction, the opening width (d) measured by a scanning electron microscope is observed in the center line (HL) between the top line (TL) passing through the highest portion of the uneven portion and the bottom line (BL) passing through the deepest portion. Hey. Ίμιη is above 30μηι, preferably 〇. 5gm or more and 2〇pm# are more preferably Ιμπι or more ΙΟμιη or less, and the depth is 〇1μηι or more and 30μηι or less, preferably 0·5μηι or more and 20μηι or less, preferably -13-201136741. The opening width (d) of the concave portion is greater than 〇. 1 μιηη narrow-melt resin becomes difficult to enter, and the aluminum-shaped body 1 and the resin cause minute voids, and it becomes difficult to obtain excellent adhesion. Conversely, if it is wider than 30 μm, the dissolution reaction is excessively performed when the aluminum molded body is processed. The problem that the amount of reduction in the thickness of the material to be produced is increased is a cause of deterioration in productivity due to the production of the product. When it is difficult to obtain a sufficient depth of the resin molded body 2 to be deeper than 30 μm, the dissolution reaction is excessively performed on the surface of the aluminum molded body 1 and the thickness reduction S of the material surface is increased. In the present invention, the density of the plurality of concave portions due to the surface of the aluminum-shaped body is on each side. Lmm, | 20μιη and depth 0. It is preferable that the size of 1 in the range of 5 μm to 20 μm is present in the range of about 5 to 200. Further, in the aluminum-shaped body of the present invention, the concave portion of the concave shape is preferably an aluminum-resin integrally molded product, and the resin molded body is laterally directed to the aluminum-shaped body side so that the observation lines along the edges are mutually entangled.  When the stretching is performed at intervals of 1 μΐΏ, the thickness of the aluminum-shaped body portion of the laminated portion formed of the resin-aluminum-resin which is less than one is 0. In the case of the aluminum-resin integrally molded article, the outer portion of the aluminum-resin integrally molded product has one concave portion in the range of the one-inch observation line and the aluminum-shaped body, and the injection-molded portion is formed at the time of injection molding. The interface strength or airtightness of the melted body 2, the surface treatment (the defect of the etched surface or the strength of the material is insufficient, if compared.  1 μ m shallow entrance, conversely, treatment (etching defect or the opening of the plate of the material is formed by the width of the opening 0. A plurality of observation lines in the thickness direction of the ferrule thickness direction cross section formed by the 5 μηι~ species or the two or more types are formed in the merging portion, and the sleigh-like protrusions of 30 μm or less are preferable. In the inner wall surface, the inner wall surface may have a double concave portion structure in which at least one portion is formed, and a double concave portion structure such as an inner concave portion of at least one inner protrusion portion inside or In a part or all of the concave portion having a plurality of internal concavo-convex structures, the embedded portion of the aluminum-shaped body is strongly bonded to each other in a part or all of the concave portion, and the aluminum-shaped superior adhesion strength or airtightness is exhibited. In the present invention, the thickness of the aluminum film formed on the surface of the aluminum-shaped body is such that it exhibits excellent performance in weather resistance or tensile strength. 0 0 1 μ m is better than 'best'. 003μηι or more 0. 006μηι is above 5μιη. However, when aluminum (Α12〇3), its thickness is 〇. Ϊ́μιη is above 0. 01μηι (the effect of weather resistance in the alumina film (α1203) is not sufficiently exhibited, and the strength or airtightness of the uneven portion on the surface of the shape body is reduced by the film. [About aluminum. In the present invention, in order to produce a desired concave shape having the above-mentioned plural number in the above-described aluminum-resin composite surface, for example, an uneven portion is formed by applying an etching treatment surface to an aluminum alloy material, and the uneven portion 1 is formed. More than one of the inner concave wall surfaces may have a convex structure formed, and further, this may coexist. In the aluminum-shaped body, the aluminum-resin joint surface of the outermost surface of the uneven portion between the resin molded body and the resin molded body is not more than 30 μm, more preferably 30 μm or less, more preferably a film. Good for alumina film. If the thickness of the aluminum film is not up to 〇·1 μηι), if the thickness is 30μιη, the aluminum problem occurs, and the stretching method of the joint surface is as follows. First, in the aluminum body of the surface, the surface is one after the surface. A method of forming an aluminum shaped body of a plurality of concave portions -15-201136741. Further, examples of the etching liquid used for the etching treatment of the aluminum alloy material include hydrochloric acid, phosphoric acid, sulfuric acid, acetic acid, oxalic acid, ascorbic acid, benzoic acid, butyric acid, citric acid, formic acid, lactic acid, isobutyl acid, and malic acid. An etching solution made of an aqueous acid solution such as propionic acid or tartaric acid, but forming a plurality of concave portions having a desired opening width and depth, or an opening edge portion of a part or all of the concave portion In the center of the opening width, a protruding snow-like projection or the like is formed, and in order to control the concave portion formed on the surface to a desired shape and size, the acid aqueous solution uses an aqueous acid solution having a weak oxidizing power, and in this oxidation force In order to dissolve the oxide film formed on the surface of the aluminum alloy material in the weak acid aqueous solution, it is necessary to use an etching liquid containing a specific concentration of halogen ions. That is, the etching solution is used in an aqueous acid solution having a weak oxidizing power, and contains any one or two selected from the group consisting of chloride ion (cr), fluoride ion (FJ, and iodide ion (特定) in a specific concentration range. The above etching liquid of a halogen ion is preferable. Further, when an aluminum alloy material having a weak oxidizing power containing such a halogen ion is used and the aluminum alloy material is impregnated in the etching liquid, first, the halogen ion in the etching liquid dissolves the surface of the aluminum alloy material. After the oxide film is dissolved, the internal aluminum alloy is dissolved to erode the inside of the aluminum alloy material. At this time, since the aluminum alloy inside is more easily eroded (easy to dissolve) than the oxide film on the surface, the etching liquid is set by the etching liquid. The concave portion of the uneven portion formed on the surface, such as the composition or the etching treatment condition, can be controlled such that the opening width or depth is controlled to a desired size, or a part of or all of the opening edge portion is formed. A snow-like projection protruding from the center in the width direction of the opening. -16 - 201136741 The etching liquid used for this purpose 'specifically, for example, is an aqueous acid solution, and the acid concentration is 〇.  1% by weight or more and 80% by weight or less, preferably 0.5% by weight or more and 50% by weight or less of a hydrochloric acid aqueous solution, a phosphoric acid aqueous solution, a dilute sulfuric acid aqueous solution, an acetic acid aqueous solution, or the like, or an acid concentration of 5% by weight or more and 30% by weight or less. An aqueous solution of oxalic acid or the like, which is preferably 10% by weight or more and 20% by weight or less, and a halogen compound added to introduce a halogen ion into the aqueous acid solution, for example, may be, for example, sodium chloride, potassium chloride or magnesium chloride. A chloride such as aluminum chloride or a fluoride such as calcium fluoride or a bromide such as potassium bromide is preferably a chloride which is considered to be safe or the like. Moreover, the concentration of the halogen ion in the etching solution is usually 0. 5 gram / liter (g / L) or more and 300 00g / L or less, preferably lg / L or more and 100g / L or less, not up to 〇. 5g/L has a small effect of halogen ions, and has a problem that the concave portion of the snow-like projection is not formed at the edge of the opening, and in the case of more than 300 g/L, the surface treatment of the aluminum formed body ( In the etching treatment, the dissolution reaction is rapidly progressed, and it becomes difficult to control the concave portion. Further, in the present invention, as an etching solution for forming a desired concave portion on the surface of the aluminum-shaped body, nitric acid or an aqueous acid solution or sodium hydroxide having a strong oxidizing power such as concentrated sulfuric acid having a concentration of more than 80% by weight or An aqueous solution of a base such as potassium hydroxide is not suitable. The acid aqueous solution having a strong oxidizing power has a film forming ability for the aluminum alloy and forms a strong oxide film on the surface of the aluminum body, and it becomes difficult to dissolve the oxide film with halogen ions. Further, an alkali aqueous solution such as sodium hydroxide or potassium hydroxide is converted into a fully soluble type in an aluminum alloy dissolving machine, and even when a halogen ion is added, the tendency is not changed, and a concave portion having a desired shape or size is formed. difficult. -17-201136741 In the present invention, the processing conditions in the case where the surface of the aluminum alloy material is etched using the etching liquid described above are caused by the type of the etching liquid, the acid concentration, the halogen ion concentration, or the like, or a plurality of concave portions required for the aluminum body. The number or size of the parts are different, but usually, in the case of an aqueous hydrochloric acid solution, the bath temperature is 20 to 80 ° C, the immersion time is 1 to 30 minutes, and in the case of the phosphoric acid aqueous solution, the bath temperature is 30 to 80 t, and the immersion is performed. The time is 1 to 5 minutes, in the case of a sulfuric acid aqueous solution, the bath temperature is 40 to 80 ° C, the impregnation time is 2 to 8 minutes, and in the case of an aqueous oxalic acid solution, the bath temperature is 50 to 80 ° C, and the immersion time is 1 to 3 minutes. In the case of an aqueous acetic acid solution, a bath temperature of 50 to 80 ° C and an immersion time of 1 to 3 minutes are preferred. When the acid concentration or the bath temperature of the etching solution is used, the effect of the etching treatment becomes more remarkable, and the treatment becomes short-time, but with respect to the bath temperature, the dissolution rate is slow when the temperature is less than 20 ° C, and the generation is sufficiently large (opening) The concave portion of the width and the depth is required to be long, and at a bath temperature exceeding 80 ° C, the dissolution reaction proceeds rapidly, and the control of the opening width and depth of the concave portion becomes difficult, and the immersion time is less than 1 minute. It is difficult to control the opening width and depth of the concave portion, and conversely, the immersion time exceeding 30 minutes causes a decrease in productivity. Further, in the present invention, when an aluminum alloy having a concave portion is formed by applying an uranium engraving treatment to the aluminum alloy material, if necessary, the surface of the aluminum alloy material before the etching treatment is degreased or surface-adjusted to remove surface adhesion. For the purpose of the substance, the contaminant, etc., a pretreatment by treatment with an acid aqueous solution and/or an alkali solution may be applied. The aqueous acid solution used in the pretreatment may be used, for example, commercially. For the preparation of the acidic degreaser, use an acid reagent such as sulfuric acid, nitric acid, hydrogen fluoride or phosphoric acid, or an acid acid such as acetic acid or citric acid, or a mixed acid obtained by mixing such acids, etc. As the aqueous alkali solution, for example, those prepared by using a commercially available basic degreaser, those prepared by using an alkali reagent such as caustic soda, or those prepared by mixing them may be used. The operation method and treatment conditions of the pretreatment using the aqueous acid solution and/or the aqueous alkali solution can be the same as the operation method and treatment conditions of the prior treatment using such an aqueous acid solution or an aqueous alkali solution, and for example, by impregnation Method, spray method, etc. After the etching process is completed, in the present invention, the outermost surface of the uneven portion formed by the etching treatment is applied to form Al(OH)3, aio(oh), ai2o3, Α1 (Ρ〇4), A12 (HP04). 3) An aluminum film forming treatment for an aluminum film of any one or more of the aluminum compounds selected from ai(h2po4)3 and A10SiO2. The treatment solution used for the aluminum film formation treatment may be formed into an aluminum film containing such an aluminum compound, and is not particularly limited, and examples thereof include ion-exchanged water, distilled water, decane coupling agent, ammonium monohydrogen phosphate solution, and phosphoric acid. Ammonium hydrogen solution, phosphoric acid solution, and the like. Further, after the aluminum film forming treatment is applied, if necessary, a water washing treatment may be carried out, and industrial water, ground water, tap water, ion-exchanged water or the like may be used in the water washing treatment, and an aluminum-shaped body is preferably produced in an appropriate manner. Further, the aluminum alloy material to which the aluminum film forming treatment is applied may be subjected to a drying treatment as necessary, and the drying treatment may be carried out by air drying, a blower, an oven or the like, in addition to being naturally dried at room temperature. The treatment conditions for the aluminum film formation treatment differ depending on the use of the treatment solution. Specifically, the treatment solution is ion exchanged water or distilled water, -19-201136741, and the warm water at 50 ° C or higher is used for 60 seconds. The above impregnation treatment, 0. The steam treatment is carried out for 1 minute or more under a pressure of 1 MPa or more, and the treatment solution is a phosphate ion, a monohydrogen phosphate ion, or a dihydrogen phosphate ion. In the case of an aqueous acid solution containing a ratio of 1 to 10 g/L, it is preferably dried in a hot air at 80 to 400 ° C for 30 seconds to 30 minutes after being immersed in the treatment solution for 30 seconds to 30 minutes. The solution is a decane coupling agent at 0. When the ratio of 1 to l〇〇g/L is dissolved, it is preferably dried in a hot air at a temperature of from ° C to 400 ° C for 30 seconds to 30 minutes after being immersed in the treatment solution for 30 seconds to 30 minutes. The surface of the aluminum-shaped body obtained by the etching treatment, the aluminum film forming treatment, or the pre-treatment, the engraving treatment, and the aluminum film forming treatment is formed with an uneven portion caused by etching treatment, and the surface is 60-degree surface gloss (sugatest) The measurement of the small gloss meter is preferably 60 or less. When the gloss of the surface exceeds 60, the molten resin does not sufficiently enter the concave portion of the aluminum body during the injection molding of the thermoplastic resin, and sufficient joint strength cannot be obtained between the aluminum body and the tree molded body. Further, the surface of the aluminum-shaped body obtained by the above-described etching treatment, aluminum film formation treatment, pre-treatment, etching treatment, and aluminum film formation treatment was observed by SEM or optical microscopy at a magnification of 1,000 times. In the cross-sectional observation photograph, it is preferable that the surface area of the aluminum-shaped body is the surface area of the aluminum alloy material before the embossing treatment to form the uneven portion. 2 times or more. The surface area increase rate is less than one. 2 times or more than 1 time, the resin does not sufficiently enter the concave portion of the aluminum-shaped body, and sufficient joint strength cannot be obtained between the aluminum-shaped resin molded bodies. Or better phosphorous liquid 80 etch degree table melting fat surface in the engraved 10 field and -20- 201136741 then 'in order to obtain the aluminum of the present invention. In the resin composite, after applying an adhesive to the surface of the aluminum-shaped body obtained as described above, a metal or a resin is bonded, or the obtained aluminum-shaped body and the metal are allowed to pass through the resin, and the heat and pressure are applied by a hot press. The aluminum-shaped body that has been joined or placed is placed in a mold for injection molding, and a specific thermoplastic resin melted in the mold is injected to cure, that is, a composite of a resin using an aluminum-shaped body, thereby producing aluminum. A composite of a shape body and a resin. Here, the resin for the aluminum/resin composite of the present invention can be used alone, but various types of thermoplastic resin can be used alone, but the invention is considered.  The resin composite is intended for physical properties, use, use environment, etc., and thermoplastic resin is preferably, for example, a polypropylene resin, a polyethylene resin, or an acrylonitrile. Butadiene. Styrene copolymer (ABS), polycarbonate resin, polyamide resin, polyphenylene sulfide (PPS), etc., arylene sulfide resin, polyacetal resin, liquid crystal resin, polyethylene terephthalic acid a polyester resin such as an acid ester (p ET ) or polybutylene terephthalate (PBT), a polyacetal resin, a poly-branth resin, a syndiotactic polystyrene resin, or the like, or a thermoplastic resin thereof. The mixture of two or more types is further improved in terms of adhesion between the aluminum body and the resin molded body, mechanical strength, heat resistance, dimensional stability (resistance to deformation, bending, etc.), electrical properties, and the like. It is preferable to add a filler such as a fibrous form, a powder form or a plate form, or various elastomer components to the thermoplastic resin. Further, as a filler for the addition of a thermoplastic resin, for example, an inorganic fiber-filling agent such as glass fiber, carbon fiber, metal fiber, asbestos fiber or boron fiber, or a high-melting organic substance such as polyamine, fluororesin or acrylic resin - 201136741 Powdery filling agents such as fibrous fillers, quartz powders, glass beads, glass powders, calcium carbonates, etc., or plate-like filling agents such as glass flakes, talc or mica The amount is preferably 250 parts by weight or less, preferably 20 parts by weight or more and 220 parts by weight or less, more preferably 30% by weight, based on 100 parts by weight of the thermoplastic resin. The addition amount of the filler is extremely low, and it becomes difficult to enter the aluminum-shaped body, and the mechanical properties are lowered. As an elastomer added to the thermoplastic formic acid-based core-shell type or olefin system, it is considered to be emitted. It is selected at the time of molding, and the effect of adding Μ to 30 parts by weight or less, preferably 3 to 25 parts by weight, to produce a mechanical property reduction effect, and further to use in the thermoplastic resin. A conventional additive capable of producing a resin according to the present invention, which is a fat-addable conventional additive, that is, a lubricant, an antioxidant, or an ultraviolet absorber, a release agent, a crystallization accelerator, etc. When the amount of the injection molding of the thermoplastic resin is not more than 50 parts by weight per 100 parts by weight or less, the fluidity is reduced, and the problem of good adhesion is not obtained. The elastomer component of the resin, such as a melting temperature of a thermoplastic resin of an amine group, a polyester system, a guanamine type or a styrene resin, is used in an amount of 30 parts by weight based on 100 parts by weight of the resin. With this elastomer, it is impossible to see problems such as increasing the density. In the case of the polyester component of the elastomer component, the thermoplastic resin for the aluminum resin composite is particularly preferably added to a colorant stabilizer such as a thermoplastic resin, a dye or a pigment, a plasticizer, a lubricant, and a crystal. Nuclear agents, etc. The body is placed in the injection molding die, and the general molding conditions required for the thermoplastic resin -22-201136741 resin to be used may be used. However, the thermoplastic resin melted during injection molding does enter the concave portion of the aluminum body. It is important that the mold temperature or the barrel temperature is set higher in the type or physical properties of the thermoplastic resin, and more preferably in the allowable range of the molding cycle, especially regarding the mold temperature, the minimum temperature must be above 90 °C. Good for 1 3 0. (: The above, but the upper limit is lower than the type of thermoplastic resin, from 100 ° C to the melting point or softening point of the thermoplastic resin (when the elastomer component is added, the higher the melting point or softening point) The temperature of the lower limit mold temperature is preferably set from the melting point of the thermoplastic resin to not less than 14 〇C. Further, the invention relates to the production of the aluminum/resin composite of the present invention. In addition to the above-mentioned thermoplastic resin, a thermosetting resin, a room temperature curable resin, various adhesives, etc. may be used. Examples of the thermosetting resin include an epoxy resin and the like, and a room temperature curable resin. For example, a polyester resin, a synthetic rubber type, an epoxy type, a cyanopropylene type, a vinyl chloride type, a plastic type, a hot melt system, etc. are mentioned. Advantageous Effects of Invention According to the aluminum resin composite of the present invention, the adhesion strength or airtightness of the interface between the aluminum body and the resin molded body (aluminum/resin interface) is compared with the case of etching only It is high, and even when exposed to severe corrosive environments, it maintains its excellent resistance to 'air tightness and uranium resistance, and the appearance change caused by corrosion of aluminum can be maintained for a long period of time. -23-201136741 The aluminum-resin composite of the present invention is applicable to a wide range of fields, for example, various sensor parts for automobiles, various converter parts for home electric appliances, and various capacitor parts for industrial equipment. The metal-resin integrally formed part is particularly suitable for a metal-resin integrally formed part which is required to protrude from a surface of a part of an aluminum shape body and which is protruded in a butt joint state, and which requires high bonding strength. Further, the aluminum according to the present invention In the method for producing a resin composite, the adhesion strength of the product can be expected by measuring the surface glossiness or the surface roughness of the aluminum molded article at the time of production, and it can be manufactured at the time of manufacture in addition to quality management. Each product has a high-reliability product with almost no unevenness in strength. [Best Mode for Carrying Out the Invention] Hereinafter, based on examples and comparative examples, BEST MODE FOR CARRYING OUT THE INVENTION The present invention is not limited to the examples described below. [Embodiment] [Example 1] [Modulation of aluminum body] Aluminum alloy (JISA 1050-H24) plate having a thickness of 1 mm Three aluminum sheets (aluminum alloy) having a size of 50 mm x 50 mm were cut out, and the aluminum sheets were applied first in a 30 wt% aqueous solution of nitric acid, immersed at room temperature for 5 minutes, and then thoroughly washed with ion-exchanged water, followed by 5 wt. After immersing in a sodium bismuth oxide solution at 50 ° C for 1 minute, it was washed with water, and further immersed in a 30 wt% nitric acid--24-367367 acid aqueous solution at room temperature for 3 minutes, and then subjected to water washing before treatment. The aluminum sheet is applied at 2. In a 5 wt% aqueous hydrochloric acid solution, an etchant (chloride ion concentration: 48 g/L) prepared by adding 54 g/L of aluminum chloride hexahydrate (A1C13 · 6H20 ) was used as the water-soluble inorganic halogen compound in the etching solution. After immersion at 66 ° C for 4 minutes, the method of performing water washing was performed. Further, by applying immersion in a 30 wt% aqueous solution of nitric acid at room temperature for 3 minutes, washing with water, and immersing in hot water at 80 ° C for 20 minutes, the surface of the aluminum sheet formed by the above etching treatment was applied. On the outermost surface of the uneven portion, an aluminum film forming process of forming an aluminum film [AIO(OH)] was applied to prepare three aluminum test pieces (aluminum shaped body). [Observation of the concave portion on the surface of the aluminum test piece (aluminum-shaped body)] With respect to each of the obtained aluminum test pieces, a scanning electron microscope (Hitachi FE-SEM, S-4500) was used for the cross section of a certain area in the thickness direction cross section. First, in the thickness direction cross section of the aluminum body, the top line (TL) passing through the highest portion of the uneven portion in the thickness direction is determined to be perpendicular to the thickness direction of the aluminum body. a bottom line of the deepest portion of the uneven portion, and further, a line segment is drawn from the top line (TL) to the bottom line (BL) in the vertical direction, passes through the middle portion of the line portion, and is pulled out in parallel with the top line (TL) [or the bottom line (BL)] The distance between the gap between the aluminum-shaped body and the aluminum-shaped body on the center line (HL) is the opening width (d) of the concave portion, and the shape and size of the concave portion formed by the uneven portion on the surface of the aluminum test piece are observed. (Opening width and depth) and measuring. -25-201136741 In the cross section of a certain area of the aluminum test piece (aluminum shape) observed, for example, as shown in the cross-sectional view of the aluminum shape of Fig. 1, the concave portion 3 of the concept of Fig. 1 is used. For example, as shown in FIG. 2, the shape is a concave portion having a projection which protrudes from the center of the opening width toward the center of the opening in a snowy shape (shape a: FIG. 2(a) is referred to), and has an opening. The entire edge portion protrudes from the center of the opening width direction into a concave portion of the snow-like protruding portion (shape b: FIG. 2(b) for reference), and the inside has a concave shape of a double concave portion in which a concave portion is formed. a shape (shape c: FIG. 2(c) for reference), and a concave portion having an inner concavo-convex structure in which an inner protrusion is formed on the inner wall surface (shape d: FIG. 2(d) is referred to), and the implementation is performed In Example 1, the concave portions of all the shapes a to d were observed. Further, the shape of the concave portion 3 and the aluminum test piece were the same, and the observation position in each of the aluminum test pieces was changed. Here, the evaluation of the shape of the observed concave portion is evaluated as good (〇) when any one or two of the above-described shapes a to d are evaluated, and the case where the shapes a to d are not present is evaluated as Bad (X). Further, in the following Examples 2 to 18 and Comparative Examples 1 to 3, the shapes of the observed concave portions were also evaluated on the same basis. Further, in the cross section of a certain area of each of the aluminum test pieces, the size (opening width and depth) of the concave portion and the ratio thereof were squared every 0·1 mm, and the opening width was 0. The concave portion of 1 μηι~Ιμηι is 10 to 100, the opening width is 〜μηι~ΙΟμηι, the concave portion is 1~1〇, and the opening width is Ιίμηι 〜30μιη, the concave portion is 1~3, the depth is Hey. Ίμιη~30μηι的范内内. Further, the width of the concave portion forming the inside of the double concave portion structure is small (opening width and depth) and its ratio 'is substantially the same as above, and each side is 1 m square long square, and the opening width is O. The concave portion of lpm~Ιμιη is 10 to 50, and the width of the opening is 〜μιη~ΙΟμιη, and the concave portion is 1 to 50'. The opening width is 1ίμηι~30μΐΏ, and the concave portion is 1~2'. Ίμηι~ 2 Ομιη range. The size of the concave portion and the aluminum test piece were also the same, and the change in the observation place in each of the aluminum test pieces was hardly changed. Here, the evaluation of the size of the observed concave portion is at the opening width of 0. 1~30μϊη and depth 0. When it is within the range of 1 to 30 μm, it is evaluated as good ((), and if not, it is evaluated as bad (X). Further, the sizes of the concave portions observed in Examples 2 to 18 and Comparative Examples 1 to 3 shown below were also evaluated on the same basis. [Evaluation of Surface Gloss of Aluminum Test Pieces (Aluminum Shaped Body)] The obtained aluminum test pieces were each measured for a 60-degree gloss of the surface using a small gloss meter (manufactured by Sugatest), and the average of the three flaws measured was calculated.値 as a 60-degree gloss of the aluminum test piece. The result is 26. [Evaluation of Surface Area Increasing Rate of Aluminum Test Pieces (Aluminum Shaped Body)] Each of the obtained three aluminum test pieces was observed by a SEM or optical microscope at a magnification of 1,000 times, and an image processing software was used for the obtained cross-sectional observation photograph. (ImageJ) The surface area of the surface of the aluminum shaped body was measured. The ratio of the surface area increase of each of the aluminum test pieces obtained for each of the untreated aluminum alloy materials was calculated, and the average enthalpy of the three enthalpy obtained was calculated and defined as the surface area increase rate. The result was 3 · 4 8 times. -27- 201136741 [Determination of the average film thickness on the outermost surface of an aluminum test piece (aluminum shape)] The obtained three aluminum test pieces were each subjected to TEM (FCEI's TECNAI G2 F20 S-TWIN) at a magnification of 100,000 times. The cross-sectional observation was performed at ~300,000 times, and the thickness of the film formed on the surface of the aluminum test piece was measured from the obtained cross-sectional observation photograph, and the average enthalpy of the three enthalpies measured by II was taken as the average film thickness. The result is 〇. 3μΠ1. [About the posiTEST test, weather resistance test (saline spray test) of the test body for evaluation, and observation and evaluation of the laminate of resin and aluminum resin] 1. Modification of the test body for evaluation (1) Preparation of the terminal for the preparation of the test body For the case of the posiTEST test terminal made of aluminum (manufactured by DeFelsko Co., Ltd.: size: 20πιηιφ, JISA 1100), the same as the above-mentioned test piece (Ming shape) The pre-treatment, the etching treatment, and the aluminum film forming treatment were carried out to prepare a test body preparation terminal 〇 (2) for the evaluation test piece used in the following posiTEST test and weather resistance test (saline spray test). [Preparation of the resin (adhesive) of the adhesive agent] The aluminum test piece (aluminum shape) 1 obtained above and the test body preparation terminal 5 are passed through a two-liquid mixing type epoxy system as shown in Fig. 3 . Rapid hardening -28- 201136741 Ingredients (Hardsman Advanced Materials company name · ARALDITE RAPID) 4 After joining, using a hot press (S Ο NE AH-2003) is holding the pressure O. Under the IMPa, the room temperature is pressurized and maintained for 24 hours, and then the excess adhesive 4 which is sandwiched from the joint between the aluminum test piece 1 and the terminal 5 is used, after the adhesive is cured, the cutter is used. The joint surface is separated so that the joint surface becomes 3. Adjusted in a manner of 14 cm 2 to prepare an aluminum, an adhesive, and an aluminum test piece (test body for evaluation). (3) Preparation of the test test body (joined by a resin which is pressed by heating) As shown in Fig. 4, the polyphenylene sulfide resin (manufactured by Toray Industries, Inc.) was placed on the aluminum test piece (aluminum body) 1 obtained above. The particle (resin) 6 is 0. The test body modulation terminal 5 is placed on the method of 04 g/cm2, and the hot press (AH-2003 manufactured by S ONE) is used to press the pressure O. IMPa, metal plate temperature 3 00 °C for hot pressing, making resin to 3. 14cm2 joint area fixed aluminum resin. Aluminum test piece (evaluation test body). (4) Preparation of the test test body (joined by injection molding) As shown in Fig. 5, the aluminum test piece (aluminum body) obtained above was placed in an injection molding machine (ST10R2V manufactured by NISSEI Co., Ltd.) In the mold, 'polyphenylene sulfide resin (manufactured by Toray Industries, Inc.) was used as the thermoplastic resin, with an injection time of 5 seconds, an injection speed of 80 mm/sec, a holding pressure of 100 MPa, a forming temperature of 3 20 ° C, and a mold temperature of 160 ° C. In the molding conditions, the injection molding was carried out. The resin terminal 7 was molded on the upper surface of the aluminum test piece 1. -29-201136741 On the aluminum test piece 1, a joint area of the resin terminal 7 of 3 · 1 4 cm 2 was produced. Resin test piece (test piece for evaluation). 2 · Weather resistance test (saline spray test; S S T 1 0 0 0 h r ) Three kinds of evaluation test bodies prepared on the top, aluminum. Follow-up agent.  Aluminum test piece, aluminum resin. The aluminum test piece and the aluminum/resin test piece were introduced into the salt spray tester (CASSER-23L-ISO, manufactured by Sugatest), and the evaluation test body was taken out by the test machine after 1 000 hours to observe the appearance. In the observation of the appearance, the number of white rusts on the surface of the test piece on the portion other than the joint portion was evaluated, and as a result, in any of the evaluations, the evaluation was changed from the white to the third. The appearance of the appearance has a appearance:, the X body is tested, and the test is used to estimate the value of the △ 1 'in the variant: the test is used to estimate the 'in the fruit evaluation section 3. Tensile strength evaluation of the joint surface of the posiTEST tester For each evaluation test body after the above weather resistance test, the aluminum/resin joint surface was measured according to the ASTM D4541 (ISO 4624) test method using a posiTEST tester (manufactured by DeFelsko). Tensile strength (terminal size: 20mm furnace, decomposition energy: ± 〇. 〇lMPa, accuracy: soil 1%, and measurement Fanyuan: 〇 ~ 20 MPa). In the posiTEST test, as shown in Fig. 6, the actuator 8 of the posiTEST tester is connected to the terminal 5 (or 7) of the evaluation test body through the terminal fixing jig 9, and then pressurized by the column, and the terminal 5 is measured. (or 7) part to the load (peeling load) from the peeling of the aluminum test piece (aluminum body) 1 and 'investigating the peeling state of the joint portion of the aluminum test piece 1 after peeling off -30-201136741 Test body for evaluation The peeling load is 6. in the case of aluminum, adhesive, aluminum test piece. 3MPA, in the case of aluminum•resin·aluminum test piece 5. 7MPA, again, aluminum. The case of the resin test piece is 5. 5MPA. Further, the observed peeling state was evaluated on the joint surface of the aluminum test piece, and the evaluation method was as follows: the case where the adhesive or the resin remained intact was evaluated as good (〇), and only a part of the aluminum test piece remained as a part. Good (?), when there was no residue on the aluminum test piece side (interfacial peeling), it was bad (X), and the result was good (〇). 4. Observation and evaluation of the laminated portion of the resin, aluminum, and resin, as shown in Fig. 7, three kinds of evaluation test bodies, aluminum, adhesive, aluminum test piece, aluminum resin, aluminum test piece, and Each of the aluminum-resin test pieces was cut in the thickness direction from the aluminum test piece to the resin (adhesive) laminated thereon, and the cross-section in the thickness direction was observed by SEM or optical microscope at a magnification of 1 〇〇〇. In the cross-sectional observation photograph, a plurality of observation lines (OL) extending in the thickness direction from the side of the resin molded body 2 toward the aluminum-shaped body 1 side are 0. When the interval is 1 μm, at least one or more laminated portions made of a resin (adhesive)-aluminum-resin (adhesive) are present on the 1 observation line (OL), and the laminated portion is aluminum. The thickness of the shape body portion is Ο. Ϊ́μπι or more and 30μιη or less, and it is evaluated as good (〇) when there is one or more ratios in the range of 1000 observation lines (OL), so that the laminated portion is in the 1〇〇〇 observation line (〇L) If one of the ranges does not exist, the evaluation is not good (X), and as a result, it is good (〇) in either case. Further, the following Examples 2 to 18 and Comparative Examples 1 to 3 were also evaluated on the same basis. -31 - 201136741 [Examples 2 to 5] In addition to the aluminum film forming treatment, instead of the hydration treatment of the hot water immersion at 80 ° C for 20 minutes in Example 1, the treatment liquid shown in Table 1 below was used, and the following Table 1 was used. A test specimen for evaluation (aluminum was prepared in the same manner as in Example 1 except that the aluminum test piece (aluminum molded body) and the test body preparation terminal were prepared under the treatment conditions. Follower · Aluminum test piece, aluminum. Resin. In the aluminum test piece and the aluminum/resin test piece, the weather resistance test (saline spray test), the posiTEST test, and the observation and evaluation of the laminate of the resin, aluminum, and resin were carried out in the same manner as in the case of the above-described Example 1. The results are shown in Table 2 together with the results of Example 1. [Table 1] Example No.  Drying condition treatment composition after aluminum film formation treatment (aqueous solution) Impregnation conditions Main component concentration (g/L) Temperature (0〇 time (minutes) Temperature (0〇 time (minutes) 2 Phosphoric acid 2 25 1 200 5 3 Phosphoric acid Monoammonium hydroxide 2 25 1 200 5 4 Ammonium dihydrogen phosphate 2 25 1 200 5 5 decane coupling agent 10 25 1 120 5 (Note) decane coupling agent: 8-(3,4-epoxycyclohexyl)ethyltrimethyl Oxydecane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM303) [Example 6] An aluminum test piece (aluminum) was produced in the same manner as in the above-described Example 1 except that JIS A5052-H34 was used as the aluminum alloy plate for producing an aluminum sheet. In the same manner as in the above-mentioned Example 1, a test test body (aluminum, an adhesive, an aluminum test piece, an aluminum resin, an aluminum test piece, -32-201136741, and aluminum) was produced. In the same manner as in the above-mentioned Example 1, the weather resistance test (saline spray test), the posiTEST test, and the observation and evaluation of the laminate of the resin and aluminum resin were carried out. The results are shown in Table 2 together with the results of Example 1. [Example 7] An aluminum test piece (aluminum shape body) was produced in the same manner as in the above-described Example 1 except that JIS A3 003-H 24 was used as the aluminum alloy plate for producing an aluminum sheet, and a terminal was produced. Then, a test object for evaluation (aluminum, an adhesive, an aluminum test piece, an aluminum resin, an aluminum test piece, and aluminum) was produced in the same manner as in the above Example 1. Further, in the same manner as in the case of the above-described Example 1, the weather resistance test (saline spray test), the P〇siTEST test, and the observation and evaluation of the laminated portion of the resin·aluminum resin were carried out. The results are shown in Table 2 together with the results of Example 1. [Example 8] An aluminum test piece was produced in the same manner as in the above-mentioned Example 1, and a terminal was produced. Next, a test piece for evaluation (aluminum, an adhesive, an aluminum test piece, and aluminum) was produced in the same manner as in the above Example 1. Resin. In the aluminum test piece and the aluminum/resin test piece, the weather resistance test (salt spray test) was not carried out, and the posiTEST test was carried out in the same manner as in the case of the above-mentioned Example 1, and the observation and evaluation of the laminate of the resin and the aluminum resin were further carried out. . The results are shown in Table 2 together with the results of Example 1. The results of the test of the above Example 1 and the test result of the test of Example 8 - 33 - 201136741 were compared. It can be seen that the aluminum resin composite of the present invention is the same as that before the exposure to the condition even after exposure to conditions such as weather resistance test. Maintain excellent tensile strength of the aluminum/resin joint. [Example 9] An aluminum test piece (aluminum shaped body) was produced in the same manner as in the above-described Example 1, and a terminal was produced. Then, the produced aluminum test piece was subjected to a weather resistance test (saline spray test), and after washing with water, it was dried by hot air at 1 ° C for 5 minutes, and then a test piece for evaluation was prepared in the same manner as in Example 1 (aluminum). • Adhesive • Aluminum test piece, aluminum • Resin • Aluminum test piece, aluminum·resin test piece). The evaluation test piece prepared in this manner was subjected to the posiTEST test in the same manner as in the case of Example 1, and the results of the above weather resistance test ((saline spray test) were evaluated, and the resin was applied in the same manner as in the above Example 1. • Observation and evaluation of the laminate of aluminum and resin. The results are shown in Table 2 together with the results of Example 1. The test results of the above-mentioned Example 9 were compared with the respective test results of the above-described Example 1, and it was found that the aluminum-shaped body (aluminum test piece) treated with the aluminum film after the etching treatment in the present invention exhibited excellent weather resistance, and was processed into Even when exposed to a severe environment for a long period of time before the aluminum/resin composite, the tensile strength of the excellent aluminum/resin joint surface can be obtained, and the workability is excellent. [Example 1 〇] Pretreatment and etching treatment were carried out in the same manner as in Example 1, and further, -34-201136741 was immersed in a 30 wt% aqueous solution of nitric acid at room temperature for 3 minutes, and then applied to 1 〇〇. In the hot water of C, the aluminum film formation treatment was performed by immersing for 1 minute, and the same test piece (aluminum shape) as in the above-mentioned Example 1 was simultaneously subjected to the contract of Example 1. Next, using the obtained aluminum test piece and terminal, the evaluation test body (aluminum was prepared in the same manner as above). Follower · Aluminum test resin. Aluminum test piece, and aluminum. Resin test piece), again, in the case of Example 1, the posiTEST test, the salt water spray test, and the resin were carried out in the same manner. aluminum. The laminate of the resin 〇 The results are shown in Table 3 as shown in Table 3. [Example Π] In the same manner as in Example 1, pretreatment and etching were carried out in a 3 Owt% nitric acid aqueous solution at room temperature for 3 minutes, followed by water washing, and then in a solution having a sulfuric acid concentration of 160 g/L, a flow rate of 20 V was dissolved. Anodizing treatment (aluminum treatment) was carried out to form a film having a film thickness of 5 μm and a pore number of 1 〇16/m2 (aluminum film of Al2〇3), followed by washing with water, and drying at 12 CTC for 'aluminum test piece (aluminum shape) Body), again, terminal. Next, using the obtained aluminum test piece and terminal, the evaluation test body (aluminum was prepared in the same manner as above). Follow-up agent. In the aluminum test, the aluminum sample was prepared by hydration treatment with water washing. The first example of the test piece, the aluminum, and the above-mentioned performance test (the observation evaluation principle, and further, the k8 8 t and the straight film formation were sufficiently performed. In the same manner as in the above-described first embodiment, the same manner as in the case of the first embodiment described above was carried out in the same manner as in the case of the first embodiment described above. posiTEST test, weather resistance test (saline spray test), and resin. aluminum. Observation and evaluation of the laminate of the resin 〇 The results are shown in Table 3 as shown in Table 3. [U Example 12] Pretreatment and etching treatment were carried out in the same manner as in Example 1, and further immersed in a 3 Owt% nitric acid aqueous solution at room temperature for 3 minutes, followed by water washing, and then, by 〇. Water vapor treatment (aluminum film formation treatment) was carried out for 20 minutes under a pressure of 5 MPa to form a dense aluminum film of A10 (0H), and an aluminum test piece (aluminum shape body) was produced, and a terminal was produced in the same manner. Next, using the obtained aluminum test piece and terminal, the evaluation test body (aluminum·adhesive agent) was prepared in the same manner as in the above Example 1. Aluminum test piece, aluminum.  In the same manner as in the above-described Example 1, the resin-aluminum test piece and the aluminum-resin test piece were subjected to a posiTEST test, a weather resistance test (saline spray test), and a laminate of a resin and an aluminum resin. Observation and evaluation 〇 results Continuation Table 2 is shown in Table 3. [Example 1 3] An aluminum test piece and a terminal were produced in the same manner as in Example 1 except that a polybutylene terephthalate resin (manufactured by Toray Industries, Inc.) was used as the thermoplastic resin, and an aluminum resin test was prepared. The sheet (evaluation test body) was subjected to a salt spray test for the evaluation test body of -36-201136741, and the observation and evaluation of the posiTEST test and the laminate of the resin and aluminum resin were carried out. The results of the continuation of Table 2 are shown in Table 3. [Example 1 4] After pretreatment was carried out in the same manner as in Example 1, an etching solution (chloride ion concentration: 30 g/L) prepared by adding 50 g/L of sodium chloride to a 50 wt% phosphoric acid aqueous solution was used, 66 t, 4 minutes. Under the same conditions, the etching solution was immersed in the etching solution, and after washing with water, the mixture was immersed in a 30 wt% nitric acid aqueous solution at room temperature for 3 minutes, and then washed with water, followed by immersion in hot water at 100 ° C for 1 minute. In the same manner as in the above-described Example 1, an aluminum test piece (aluminum-shaped body) was produced, and a terminal was produced in the same manner as in the case of Example 1. Then, using the obtained aluminum test piece and the terminal, the evaluation test body (aluminum, the adhesive, the aluminum test piece, the aluminum resin, the aluminum test piece, and the aluminum resin test piece) was prepared in the same manner as in the above-described Example 1. In the same manner as in the case of the above-described Example 1, the posiTEST test, the weather resistance test (saline spray test), and the observation and evaluation of the laminate of the resin and the aluminum resin were carried out, and the results are shown in Table 3. [Example 1 5] After pretreatment was carried out in the same manner as in Example 1, an etching solution prepared by adding 50 g/L of sodium chloride to a 10 wt% sulfuric acid aqueous solution (chloride ion concentration - 37 - 201136741 : 30 g / L) was used. The etching treatment of immersing the etching solution was carried out at 66 ° C for 4 minutes, and after water washing, 'washing in a 30% by weight aqueous solution of nitric acid at room temperature for 3 minutes, 'washing with water' followed by SI application 1 〇〇 The hydration treatment (aluminum film formation treatment) was immersed in hot water of ° C for 1 minute, and an aluminum test piece (aluminum-shaped body) was produced in the same manner as in the above-mentioned Example 1, and a terminal was produced in the same manner as in the case of Example 1. Then, using the obtained aluminum test piece and the terminal, the evaluation test body (aluminum, the adhesive, the aluminum test piece, the aluminum resin, the aluminum test piece, and the aluminum resin test piece) was prepared in the same manner as in the above-described Example 1. In the same manner as in the case of the above-described Example 1, the posiTEST test, the weather resistance test (saline spray test), and the observation and evaluation of the laminate of the resin and the aluminum resin were carried out. The results are shown in Table 3. [Example 16] After pretreatment in the same manner as in 1JT Example 1, an etching solution (chloride ion concentration: 30 g/L) prepared by adding 50 g/L of sodium chloride to a 30 wt% aqueous oxalic acid solution was used at 66 ° C. After etching for 4 minutes, the etching solution was immersed in water, and after immersing in a 3 Owt% nitric acid aqueous solution at room temperature for 3 minutes, it was washed with water, and then immersed in hot water at 100 ° C for 1 minute. In the hydration treatment (aluminum film formation treatment), an aluminum test piece (aluminum shape body) was produced in the same manner as in the above-described Example 1, and a terminal was produced in the same manner as in the case of Example 1. Next, using the obtained aluminum test piece and terminal, a test test body (aluminum, an adhesive, an aluminum test piece, an aluminum resin, an aluminum test piece, and an aluminum resin test) was prepared in the same manner as in the above-mentioned Example 1-38-201136741. In the same manner as in the case of the first embodiment, the posiTEST test, the weather resistance test (saline spray test), and the observation and evaluation of the laminate of the resin and the aluminum resin were carried out, and the results are continued as shown in Table 3. Show. [Example 1 7] After pretreatment was carried out in the same manner as in Example 1, 2. An etchant (chloride ion concentration: 54 g/L) prepared by adding 50 g/L of sodium chloride (NaCl) to a 5 wt% aqueous hydrochloric acid solution, and immersing the etching solution in an uranium engraving treatment at 66 t for 4 minutes, followed by washing with water After that, it was washed with water in a 30 wt% aqueous nitric acid solution at room temperature for 3 minutes, and then immersed in hot water for 1 minute in a hot water bath (aluminum film formation treatment) for the first time, in the same manner as in the above-described Example 1. An aluminum test piece (aluminum body) was produced, and a terminal was produced in the same manner as in the case of Example 1. Next, using the obtained aluminum test piece and terminal, the evaluation test body (aluminum was prepared in the same manner as in the above Example 1. Follow-up agent. Aluminum test piece, aluminum resin, aluminum test piece, and aluminum. The resin test piece) was subjected to the posiTEST test, the weather resistance test (saline spray test), and the resin in the same manner as in the above-mentioned Example 1. aluminum. Observation and evaluation of the laminate of the resin 〇 The results are shown in Table 3 as shown in Table 3. -39-201136741 [Third Example 18] Pretreatment was carried out in the same manner as in Example 1 in a 3 wt% aqueous nitric acid solution at room temperature for 3 minutes, followed by a solution having a sulfuric acid concentration of 160 g/L at a solution voltage of 20 V. Oxidation), film thickness Ιμπι and pore number 101 film (aluminum film of αι2ο3), water washing, and drying in minutes to prepare an aluminum test piece (aluminum-shaped body terminal. Next, the obtained aluminum test piece was prepared in the same manner as the end. For the evaluation test body (aluminum, the following resin, the aluminum test piece, and the case of the aluminum/resin test piece 1), the Ρ T T si TES Τ salt spray test, and the resin • aluminum • resin 〇 results continuation table 2 As shown in Table 3, after the etching treatment, and after the immersion in the bell, the cross-linking, the solution temperature is 18 ° C, and the straight treatment is performed (the hot film of 120 ° C of the anodized skin at S/m2 where the aluminum film is formed is performed 5 In the same manner, the preparation was carried out in the same manner as in the above-mentioned Example 1 agent, aluminum test piece, aluminum, and the above-mentioned test and weather resistance test (observation evaluation of the laminated portion -40-201136741 gigs XS3I0.

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S il 一一 ΙΖ vr/-κ 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 蠢 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 -41 - 201136741 m Ci3 剝離 形態 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 f-H • ~4 GO s 測定値 (MPa) LTD CO 〇〇 LO σ> LO 〇〇 CO LO LO 卜 LTD 0¾ ς〇 *—H LO CD C^3 CO CO LTD LTD 00 LO CO CO uo LT^ CO p 嶙 UfD LO LO 03 CO 1 < LTD LO LTD CO cd 卜 LO CO LO m 紙 m 担 & -Ci g 11 <=> <=> 〇 〇 〇 C5 0 〇 CD 1 0 CD Q c? 0 CS 0 CZ> C3 〇) C3 CZ> CZ5 oo C/O 外觀 i化 〇 〇 〇 〇 〇 〇 〇 〇 〇 1 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 樹脂接 合方法 接著劑 熱壓著1 1射出1 m 啤 m 1熱壓著1 1射出1 槲 瑯 熱壓著 1射出I 1射出| 丨接著劑 熱壓著1 1射出 1接著劑 w ϋ 銳 s 蘅 m 逝 熱壓著1 1射出I 1接著劑 熱壓著1 1射出1 m w 雄 熱壓著1 丨射出1 £ m 鯆 is 龜 IQlB -¾ =i 现涵 LTD CO CO CO CO CO CO 1 A10㈣ CO CO A10(0H A10(0H A10 (OH A10 (OH) AKHOH) A10 (OH) CO CO m 瞄呂 CO CO CO cr> CO •^r uo CO Cs3 CO CO CO s CO g CO CN3 CO 層合部 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 60。 光澤度 LO C^O CO ITS CO <75 一 cz> CS3 03 CO CO 插 大小 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 a 形狀 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 1 CN3 OQ I H csi CO "丨·， 03 CO 1 * C<1 CO CN3 CO T" i C<J CO r H CsJ CO » i (>3 CO 〇 F丨丨H 03 CO 2 LO c〇 00 -42 - 201136741 [比較例1〕 與實施例1同樣地進行前處理後，不進行蝕刻處理， 實施與實施例1同樣之水合處理的鋁皮膜形成處理，製作 鋁試驗片（鋁形狀體），同時與實施例1同樣地製作端子 0 接著’與上述實施例1同樣地，製作評估用試驗體（ 鋁.接著劑.鋁試驗片、鋁·樹脂.鋁試驗片、鋁·樹脂 試驗片），對得到的評估用試驗體實施posiTEST試驗及 樹脂•鋁.樹脂之層合部的觀察評估。 結果如表4所示。 [比較例2〕 與實施例1同樣地進行前處理與蝕刻處理後，在 3 Owt%硝酸水溶液中常溫下、3分鐘浸漬後，進行水洗， 接著不進行鋁皮膜形成處理，以1 00eC的熱風進行5分鐘 乾燥，製作鋁試驗片（鋁形狀體），同時與實施例1同樣 地製作端子。 接著，與上述實施例1同樣地，製作評估用試驗體（ 鋁·接著劑•鋁試驗片、鋁•樹脂•鋁試驗片、及鋁.樹 脂試驗片），又，與上述實施例1之場合相同，實施耐候 性試驗（鹽水噴霧試驗）、posiTEST試驗、及樹脂.鋁 •樹脂之層合部的觀察評估。 結果與比較例1之結果一起如表4所示。 -43- 201136741 [比較例3〕 進行實施例1之前處理後，於2 · 5 wt%鹽酸水溶液以 6 6°C進行4分鐘浸溃後、水洗，進—步，在3〇wt%硝酸水 溶液中常溫下、3分鐘浸漬後，進行水洗，以1 〇 〇艺的熱 風進行5分鐘乾燥後’導入鹽水噴霧試驗機，1 〇 〇 〇小時 經過後由試驗機取出試驗片’水洗後，以100 °C的熱風進 行5分鐘乾燥，製作鋁試驗片（鋁形狀體）。又，與實施 例1同樣地各自製作端子、製作鋁.接著劑·鋁試驗片、 鋁•樹脂•鋁試驗片、鋁.樹脂試驗片（評估用試驗體） 。對如此製作的評估用試驗體，與上述實施例〗之場合相 同地實施posiTEST試驗進行評估，—倂評估上述耐候性 試驗（鹽水噴_試驗）之結果，同時與上述實施例1同樣 地實施樹脂.鋁.樹脂之層合部的觀察評估。 結果與比較例1之結果〜起如表4所示。 -44- 201136741 【寸巡 m 剝離 形態 X X X < <] <3 <] <] <] posit m 班 CM »—( οο ci c— 卜 03 C<J C^l c^l CO oa Cn3 0<3 C<l 鐵 u 旺 担 κι [lOOOh 白鏽產生 (f@/cm2) 1 1 1 録 無數 藏 I 無數 Μ 壊 親 璀 litrn 1 1 1 X X X X X X m i 豳 癒 wV\ 1射出1 Μ W 逝 熱壓著 33 罷 m 逝 ii m 丨射出1 i： Μ Μ m m 平均皮膜 厚度Um) οο 0.005 0.005 A1皮膜 (主成分) AUHOH) Α1·2〇3 (自然氧化膜) ai2o3 (自然氧化膜) S5# 胆呂 >-； ΟΟ |· < CO S5 <r<i 層合部 X X X 〇 〇 〇 〇 〇 〇 60° 光澤度 C〇 寸 CO 插 大小 X X X 〇 〇 〇 〇 〇 〇 a 形狀! _1 X X X 〇 〇 〇 〇 〇 〇 ψ· C<I CO Τ '( C<1 CO 03 CO i H CO Ϊα 鎰 m M 盤 d 2 -45- 201136741 【圖式簡單說明】 [圖π 圖1爲複製實施例1的鋁形狀體之厚度方向剖面，說 明凹狀部用的剖面複製圖。 [圖2] 圖2爲表示圖1觀念的凹狀部的形狀的典型例之剖面 說明圖。 [圖3] 圖3爲使用鋁試驗片（鋁形狀體），於posiTEST試 驗用所調製的鋁·接著劑·鋁試驗片（評估用試驗體）正 面圖及側面圖。 [圖4] 圖4爲使用鋁試驗片（鋁形狀體），於posiTEST試 驗用所調製的鋁·樹脂·鋁試驗片（評估用試驗體）正面 圖及側面圖。 [圖5] 圖5爲使用鋁試驗片（鋁形狀體），於posiTEST試 驗用所調製的鋁•樹脂試驗片（評估用試驗體）正面圖及 側面圖。 [圖6] 圖6爲表示在posiTEST試驗時，將評估用試驗體裝 設在posiTEST試驗裝置之執行機構部之狀態的剖面說明 [圖7] -46- 201136741 圖7係用以說明評估用試驗體中之樹脂·鋁·樹脂之 層合部的觀察評估方法的剖面說明圖。 【主要元件符號說明】 1 :鋁形狀體（鋁試驗片） TL :頂線 B L .底線 HL :中線 d :開口寬 OL :觀察線 2 :樹脂成形體 3 :凹狀部 4 :接著劑 5，7 :端子 8 :執行機構 9 :端子固定用夾具 -47-S il one by one vr/-κ 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇 stupid 〇〇〇〇〇〇〇〇〇〇〇〇-41 - 201136741 m Ci3 Peeling form 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇fH • ~4 GO s Measurement 値 (MPa) LTD CO 〇〇LO σ> LO 〇〇CO LO LO 卜LTD 03⁄4 ς〇*—H LO CD C^3 CO CO LTD LTD 00 LO CO CO uo LT^ CO p 嶙UfD LO LO 03 CO 1 < LTD LO LTD CO cd AB LO CO LO m Paper m && -Ci g 11 <=><=> 〇〇〇C5 0 〇CD 1 0 CD Q c? 0 CS 0 CZ&gt ; C3 〇) C3 CZ> CZ5 oo C/O Appearance i 〇〇〇〇〇〇〇〇〇 1 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇 resin bonding method adhesive hot pressing 1 1 Shot 1 m beer m 1 hot pressed 1 1 shot 1 槲琅 hot pressed 1 shot I 1 shot | 丨 adhesive hot pressed 1 1 shot 1 adhesive w ϋ sharp s 蘅m Pressing 1 1 injection I 1 adhesive hot pressing 1 1 shooting 1 mw male heat pressing 1 丨 shooting 1 £ m 鯆is turtle IQlB -3⁄4 = i now LTD LTD CO CO CO CO CO CO 1 A10 (4) CO CO A10 ( 0H A10(0H A10 (OH A10 (OH) AKHOH) A10 (OH) CO CO m Sightseeing CO CO CO cr> CO •^r uo CO Cs3 CO CO CO s CO g CO CN3 CO Laminate 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇60. Gloss LO C^O CO ITS CO <75 a cz> CS3 03 CO CO Insert size 〇〇〇〇〇〇 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇a shape 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇1 CN3 OQ IH Csi CO "丨·, 03 CO 1 * C<1 CO CN3 CO T" i C<J CO r H CsJ CO » i (>3 CO 〇F丨丨H 03 CO 2 LO c〇00 -42 - 201136741 [Comparative Example 1] After the pretreatment was carried out in the same manner as in Example 1, the aluminum film formation treatment of the hydration treatment similar to that of Example 1 was carried out without performing an etching treatment. Test piece (aluminum-shaped body), and terminal 0 was produced in the same manner as in Example 1. Then, in the same manner as in Example 1, an evaluation test body (aluminum, an adhesive, an aluminum test piece, an aluminum resin, an aluminum test piece) was prepared. , aluminum/resin test piece), the evaluation test body was subjected to observation and evaluation of the posiTEST test and the laminate of the resin and aluminum resin. The results are shown in Table 4. [Comparative Example 2] After pretreatment and etching treatment were carried out in the same manner as in Example 1, the mixture was immersed in a 3 Owt% nitric acid aqueous solution at room temperature for 3 minutes, and then washed with water. Then, the aluminum film formation treatment was not performed, and a hot air of 100 ° C was applied. The aluminum test piece (aluminum shape) was produced by drying for 5 minutes, and a terminal was produced in the same manner as in Example 1. Then, in the same manner as in the above-described Example 1, a test test body (aluminum, an adhesive, an aluminum test piece, an aluminum resin, an aluminum test piece, and an aluminum resin test piece) was produced, and in the case of the above-described Example 1, In the same manner, the weather resistance test (saline spray test), the posiTEST test, and the observation and evaluation of the laminate of the resin and aluminum resin were carried out. The results are shown in Table 4 together with the results of Comparative Example 1. -43-201136741 [Comparative Example 3] After the pretreatment of Example 1, the solution was immersed in a 2.6 wt% aqueous hydrochloric acid solution at 6 6 ° C for 4 minutes, washed with water, and further, in a 3 wt% aqueous solution of nitric acid. After immersing at room temperature for 3 minutes, it was washed with water, dried in a hot air of 1 〇〇 art for 5 minutes, and then introduced into a salt spray test machine. After 1 hour, the test piece was taken out by the test machine. After washing, the pressure was 100. The hot air of °C was dried for 5 minutes to prepare an aluminum test piece (aluminum shaped body). Further, in the same manner as in Example 1, a terminal was produced, and an aluminum, an adhesive, an aluminum test piece, an aluminum resin, an aluminum test piece, and an aluminum resin test piece (test piece for evaluation) were produced. The evaluation test body prepared in this manner was subjected to the posiTEST test in the same manner as in the above Example, and the results of the weather resistance test (saline spray test) were evaluated, and the resin was applied in the same manner as in the above Example 1. . Observation and evaluation of the laminate of aluminum. The results and the results of Comparative Example 1 are shown in Table 4. -44- 201136741 [Inch tour m stripping form XXX <<]<3<]<]<] posit m class CM »—( οο ci c— Bu 03 C<JC^lc^l CO oa Cn3 0<3 C<l iron u wang κι [lOOOOh white rust generation (f@/cm2) 1 1 1 recorded countless Tibetan I countless Μ 壊 relative litrn 1 1 1 XXXXXX mi recovered wV\ 1 shot 1 Μ W死 压 33 ii ii ii ii ii i i i 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 平均 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 S5# 胆吕>-; ΟΟ |· < CO S5 <r<i Lamination XXX 〇〇〇〇〇〇60° Gloss C〇Inch CO Insert Size XXX 〇〇〇〇〇〇a Shape! _1 XXX 〇〇〇〇〇〇ψ· C<I CO Τ '( C<1 CO 03 CO i H CO Ϊα 镒m M disk d 2 -45- 201136741 [Simplified illustration] [Figure π Figure 1 is a copy The cross section in the thickness direction of the aluminum body of the first embodiment will be described with reference to the cross section of the concave portion. [Fig. 2] Fig. 2 is a concave view showing the concept of Fig. 1. A cross-sectional view of a typical example of the shape of the shape. [Fig. 3] Fig. 3 is an aluminum test piece (a test piece for evaluation) prepared by using an aluminum test piece (aluminum shape body) for the posiTEST test. Front view and side view. Fig. 4 is a front view and a side view of an aluminum/resin-aluminum test piece (test piece for evaluation) prepared by using the aluminum test piece (aluminum-shaped body) for the posiTEST test. Fig. 5] Fig. 5 is a front view and a side view of an aluminum resin test piece (test piece for evaluation) prepared by using an aluminum test piece (aluminum-shaped body) for the posiTEST test. [Fig. 6] Fig. 6 is a view showing the posiTEST. In the test, the cross section of the state in which the test body is placed in the actuator portion of the posiTEST test device is shown in Fig. 7 - 46 - 201136741. Fig. 7 is a diagram showing the layer of resin, aluminum, and resin in the test body for evaluation. A cross-sectional explanatory view of the observation and evaluation method of the joint. [Explanation of main component symbols] 1 : Aluminum shape body (aluminum test piece) TL : Top line BL . Bottom line HL : Center line d : Opening width OL : Observation line 2 : Resin molded body 3 : Concave portion 4 : Adhesive 5 , 7 : Terminal 8 : Actuator 9 : Terminal fixing clamp -47-

Claims (1)

201136741 七、申請專利範圍 1. —種耐候性優異的鋁•樹脂複合品，其係含有於 表面之一部份或全部具有凹凸部之鋁合金製的鋁形狀體、 與於該鋁形狀體之一表面上樹脂以對接狀態結合的樹脂成 形體之鋁•樹脂複合品，其特徵係在前述鋁形狀體之表 面，在前述凹凸部的最表面形成含有來自鋁皮膜形成處理 的 Al(OH)3、AIO(OH)、Al2〇3、Al(P〇4)、Al2(HP〇4)3、 Al(H2P〇4)3、及A10Si〇2中選出的任一種以上之鋁化合物 之鋁皮膜，同時形成該凹凸部構成的複數的凹狀部，且在 前述樹脂成形體上形成前述樹脂進入前述複數的凹狀部內 固化的複數的嵌入部，藉由前述凹狀部與前述嵌入部而鋁 形狀體與樹脂成形體相互卡止》 2. —種耐候性優異的鋁·樹脂複合品，其係含有於 表面之一部份或全部具有凹凸部之鋁合金製的鋁形狀體、 與設置於該鋁形狀體之表面的樹脂成形體之複合品，其特 徵係於前述鋁形狀體之表面，前述凹凸部的最表面形成含 有來自鋁皮膜形成處理的 Al(OH)3、AIO(OH)、Al2〇3、 ai(po4)、ai2(hpo4)3、ai(h2p〇4)3、及 A10Si02 中選出的 任一種以上之鋁化合物的鋁皮膜，同時形成該凹凸部所構 成的複數的凹狀部， 前述各凹狀部，鋁形狀體之厚度方向剖面，垂直該厚 度方向’且在通過凹凸部的最高部之頂線與通過最深部之 底線間之中線，以掃瞄型電子顯微鏡觀察所測定的開口寬 爲Ο.ίμηι以上30μηι以下的大小、其深度爲Ο.ίμηι以上 -48- 201136741 3 0 μ m以下的大小， 且於前述樹脂成形體，形成前述樹脂進入前述複數的 凹狀部內固化的複數的嵌入部， 藉由前述凹狀部與前述嵌入部而鋁形狀體與樹脂成形 體相互卡止。 3. 如請求項1或2記載之耐候性優異的鋁·樹脂複 合品，其中，在前述鋁形狀體，其複數的凹狀部中之一部 份或全部中，形成由凹狀部的開口緣部的一部分或全體朝 向開口寬方向中心之呈雪簷狀突出的突出部、藉由該突出 部形成鋁成形體之凹狀部與樹脂成形體之嵌入部相互卡止 無法脫離之構造。 4. 如請求項3記載之耐候性優異的鋁·樹脂複合品， 其中， 在鋁·樹脂一體成形品的厚度方向剖面，由其樹脂成 形體側向鋁形狀體側使厚度方向延伸的多數的觀察線相互 以0.1 μιη間隔拉引時，雪簷狀的突出部在1觀察線上至少 存在1個以上之由樹脂一鋁-樹脂所構成的層合部，且該 層合部的鋁形狀體部分之厚度爲〇·1μηι以上30μιη以下的 範圍，且該雪簷狀的突出部在1000支觀察線之範圍內存 在1個以上。 5. 如請求項1〜4 _中任一項記載之耐候性優異的鋁· 樹脂複合品，其中， 鋁形狀體之複數的凹狀部’於其—部份或全部中’於 內部的壁面具有至少1個以上形成有內部凹狀部的雙重凹 -49- 201136741 狀部構造。 6.如請求項1〜4中任--項記載之耐候性優異的鋁· 樹脂複合品，其中， 鋁形狀體之複數的凹狀部，於其一部份或全部中，於 內部的壁面具有至少1個以上形成有內部突起部的內部凹 凸構造。 7-如請求項1〜6中任一項記載之耐候性優異的鋁· 樹脂複合品，其中，鋁形狀體之60度鏡面光澤度爲60以 下。 8. 如請求項1〜7中任一項記載之耐候性優異的鋁· 樹脂複合品，其中，鋁形狀體之表面積爲形成凹凸部前之 鋁合金材表面積的1 .2倍以上1 0倍以下。 9. 一種耐候性優異的鋁·樹脂複合品的製造方法， 其係鋁合金製的鋁形狀體、與該鋁形狀體之表面含樹脂成 形體之複合品的製造方法，其特徵係使鋁合金材進行蝕刻 處理後於表面的一部份或全部形成具有凹凸部構成的複數 的凹狀部之鋁合金材、接著藉由至少對該鋁合金材的凹凸 部表面施加鋁皮膜形成處理後，在該凹凸部的最表面形成 含有 Al(OH)3、AIO(OH)、Al2〇3、Al(P〇4) ' Α12(ΗΡ〇4)3、 Al(H2P〇4)3、及A10Si02中選出的任一種以上之銘化合物 的鋁皮膜而形成鋁合金製的鋁形狀體，又，在樹脂成形體 之成形時，使樹脂進入鋁形狀體之各凹狀部內固化的樹脂 成形體之嵌入部成形，鋁形狀體之凹狀部與樹脂成形體之 嵌入部相互卡止而形成鋁形狀體與樹脂成形體結合爲一體 -50- 201136741 的鋁·樹脂複合品。 1 0 ·如請求項9記載之耐候性優異的鋁.樹脂 的製造方法，其中，鋁形狀體之鋁皮膜係藉由選 5 0°C以上之溫水中浸漬60秒以上；〇.丨MPa以上之 進行1分鐘以上之水蒸氣處理；在含有磷酸離子、 氫離子、磷酸二氫離子中任一種以上之磷酸離子種 〜100g/L之磷酸系水溶液中浸漬30秒〜30分鐘 80〜400 °C的熱風、使進行30秒〜30分鐘乾燥： 有0.1〜100g/L的矽烷耦合劑之溶液中浸漬30秒-鐘後，以80〜400 °C的熱風、使進行30秒〜30 燥；的任1種之鋁皮膜形成處理而形成。 複合品 自：在 加壓下 磷酸一 的 0_ 1 後，以 及在含 - 3 0分 分鐘乾 -51 -201136741 VII. Patent application scope 1. An aluminum resin composite product excellent in weather resistance, which is an aluminum-shaped aluminum alloy body having a part or all of a surface having an uneven portion, and an aluminum-shaped body An aluminum resin composite of a resin molded body in which a resin is bonded in abutting state is characterized in that the surface of the aluminum-shaped body is formed on the outermost surface of the uneven portion and contains Al(OH)3 from the aluminum film forming treatment. , an aluminum film of any one or more of the aluminum compounds selected from the group consisting of AIO(OH), Al2〇3, Al(P〇4), Al2(HP〇4)3, Al(H2P〇4)3, and A10Si〇2, At the same time, a plurality of concave portions formed by the uneven portions are formed, and a plurality of embedded portions in which the resin is solidified in the plurality of concave portions are formed on the resin molded body, and the concave portions and the embedded portions are formed in an aluminum shape. The body and the resin molded body are mutually locked. 2. An aluminum-resin composite product excellent in weather resistance, which is provided in an aluminum-shaped aluminum alloy body having a part or all of the surface having an uneven portion Resin on the surface of an aluminum shaped body The composite of the body is characterized in that the surface of the aluminum-shaped body is formed, and the outermost surface of the uneven portion is formed to contain Al(OH)3, AIO(OH), Al2〇3, ai(po4) from the aluminum film forming treatment, An aluminum film of any one or more of the aluminum compounds selected from ai2 (hpo4)3, ai(h2p〇4)3, and A10SiO2, and a plurality of concave portions formed by the uneven portions, and the respective concave portions, aluminum The thickness direction cross section of the shape body, perpendicular to the thickness direction 'and the line width between the top line passing through the highest portion of the uneven portion and the bottom line passing through the deepest portion, and the opening width measured by a scanning electron microscope observation is Ο. ίμηι The size of the above 30 μηι or less, the depth of which is Ο.ίμηι or more -48-201136741 3 0 μm or less, and the resin molded body is formed into a plurality of embedded portions in which the resin is cured in the plurality of concave portions. The aluminum body and the resin molded body are locked to each other by the concave portion and the fitting portion. 3. The aluminum-resin composite product having excellent weather resistance according to claim 1 or 2, wherein the aluminum-shaped body has an opening formed by a concave portion in one or all of a plurality of concave portions A part of the edge portion or the entire portion of the protruding portion that protrudes toward the center in the width direction of the opening in a snow-like shape, and the concave portion of the aluminum molded body and the fitting portion of the resin molded body are locked from each other by the protruding portion. 4. The aluminum-resin composite product which is excellent in the weather resistance of the aluminum-resin-integrated article, and the cross-section of the aluminum-resin integrally molded product in the thickness direction of the aluminum-resin integrally molded product. When the observation lines are pulled at intervals of 0.1 μm, the snow-like protruding portion has at least one or more laminated portions composed of a resin-aluminum-resin on the observation line, and the aluminum-shaped body portion of the laminated portion The thickness is in the range of 〇·1 μηι or more and 30 μmη or less, and the snow-like protruding portion has one or more in the range of 1,000 observation lines. 5. The aluminum-resin composite product excellent in weather resistance according to any one of claims 1 to 4, wherein the plurality of concave portions of the aluminum-shaped body are in part or all of the inner wall surface. There is at least one double recess-49-201136741-shaped structure in which an internal concave portion is formed. 6. The aluminum-resin composite product excellent in weather resistance according to any one of claims 1 to 4, wherein the plurality of concave portions of the aluminum-shaped body are in part or all of the inner wall surface There is at least one or more internal concavo-convex structure in which internal protrusions are formed. The aluminum-resin composite product excellent in weather resistance according to any one of claims 1 to 6, wherein the aluminum-shaped body has a 60-degree specular gloss of 60 or less. 8. The aluminum-resin composite product having excellent weather resistance according to any one of claims 1 to 7, wherein the surface area of the aluminum-shaped body is 1.2 times or more and 10 times the surface area of the aluminum alloy material before forming the uneven portion. the following. A method for producing an aluminum-resin composite excellent in weather resistance, which is a method for producing a composite of an aluminum-shaped aluminum alloy body and a surface-containing resin molded body of the aluminum-shaped body, characterized in that an aluminum alloy is used After the material is etched, an aluminum alloy material having a plurality of concave portions having irregularities is formed on a part or all of the surface, and then an aluminum film is formed on at least the surface of the uneven portion of the aluminum alloy material. The outermost surface of the uneven portion is formed of Al(OH)3, AIO(OH), Al2〇3, Al(P〇4)' Α12(ΗΡ〇4)3, Al(H2P〇4)3, and A10Si02. The aluminum film of any one of the above-mentioned compounds is formed into an aluminum-shaped aluminum alloy body, and at the time of molding the resin molded body, the resin is molded into the embedded portion of the resin molded body in which the concave portions of the aluminum-shaped body are solidified. The concave portion of the aluminum-shaped body and the fitting portion of the resin molded body are locked to each other to form an aluminum-resin composite in which the aluminum-shaped body and the resin molded body are integrated into one -50 to 201136741. A method for producing an aluminum resin having excellent weather resistance as described in claim 9, wherein the aluminum film of the aluminum body is immersed in warm water of 50 ° C or higher for 60 seconds or more; It is subjected to steam treatment for 1 minute or more; and immersed in a phosphoric acid aqueous solution containing at least one of phosphate ion, hydrogen ion and dihydrogen phosphate ion to 100 g/L for 30 seconds to 30 minutes at 80 to 400 °C. The hot air is dried for 30 seconds to 30 minutes: after immersing in a solution of 0.1 to 100 g/L of a decane coupling agent for 30 seconds - a clock, drying with a hot air of 80 to 400 ° C for 30 seconds to 30 minutes; It is formed by forming an aluminum film of any one of them. Composite product: after 0_1 of phosphoric acid under pressure, and -30 minutes in -3 minutes