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TW201132801A - Surface treatment agent for laminated metal material and method for producing laminated metal material - Google Patents

Surface treatment agent for laminated metal material and method for producing laminated metal material Download PDF

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Publication number
TW201132801A
TW201132801A TW099137244A TW99137244A TW201132801A TW 201132801 A TW201132801 A TW 201132801A TW 099137244 A TW099137244 A TW 099137244A TW 99137244 A TW99137244 A TW 99137244A TW 201132801 A TW201132801 A TW 201132801A
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Taiwan
Prior art keywords
compound
surface treatment
metal material
treatment agent
film
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TW099137244A
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Chinese (zh)
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TWI532880B (en
Inventor
Takanobu Saito
Takashi Ishikawa
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Nihonparkerizing Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
    • C09D5/084—Inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
    • C23C22/44—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also fluorides or complex fluorides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/20—Use of solutions containing silanes

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Laminated Bodies (AREA)

Abstract

Provided is a metal surface treatment agent for forming on the surface of a metal material a surface treatment film capable of imparting high corrosion resistance to the metal material and strong adhesiveness in that a laminated film or extrusion laminated resin will not peel off. The metal surface treatment agent comprises silane coupling agent (A), cationic urethane resin (B), Zr compound (C1), Ti compound (C2), and fluorine-containing inorganic compound (D), and has an (A)/(B) mixture ratio by weight of 1/50 to 20/1, a (C)/(B) mixture ratio by weight of 1/100 to 1/2 (where the weight of (C) is the total of (C1) and (C2)), a (fluorine atom)/(B) mixture ratio by weight of 1/1,000 to 2/1, and a (C1)/(C2) mixture ratio by weight of 1/10 or greater but less than 2/1.

Description

201132801 六、發明說明 【發明所屬之技術領域】 本發明關於用於形成表面處理皮膜的層合金屬材料用 之表面處理劑及層合金屬材料的製造方法，該表面處理皮 膜係提高金屬材料的表面與層合薄膜的密接性（包含加工 密接性）’更且提高層合有薄膜的金屬材料之耐蝕性（尤其 耐強酸性及耐強鹼性）。 更詳細地，關於用於形成表面處理皮膜的層合金屬材 料用之表面處理劑及層合金屬材料的製造方法，該表面處 理皮膜係在鋁系金屬箔及不銹鋼系金屬箔等的金屬材料之 表面上層合樹脂薄膜後，即使在施予深拉加工、減薄拉延 加工或張拉加工等的嚴酷成形加工時，也可賦予高的密接 性而使得其層合薄膜不剝離，更且物品（成形加工品）具有 優異的耐蝕性。 【先前技術】 層合加工係在金屬材料的表面上加熱壓黏（或經由接 著劑而壓黏）樹脂製的薄膜（以下稱爲樹脂薄膜或層合薄膜） 之加工手段，作爲以表面保護或圖案設計性賦予爲目的之 金屬材料表面的被覆方法之一個，使用於各式各樣的領域 中。此層合加工係將樹脂組成物塗佈、烘烤乾燥而形成樹 脂皮膜之方法，即與塗裝相比，烘烤乾燥時所產生的溶劑 及二氧化碳等之廢氣或溫暖化氣體之發生量少。因此，於 環保方面係較佳，其用途係擴大，例如使用於以鋁薄板 -5- 201132801 材、鋼薄板材、包裝用鋁箔或不銹鋼箔等當作原料材的食 品用罐之本體或蓋材、食品用容器或乾電池容器等。 特別地於最近’作爲攜帶電話、電子筆記本、筆記型 個人電腦、攝影機等中所用的行動電話用鋰離子蓄電池之 外裝材’較宜使用輕量且障壁性高的鋁箔及不銹鋼箔等的 金屬箔’層合加工係適用於如此的金屬箔。又，作爲電動 汽車或混合動力汽車的驅動能量，有檢討鋰離子蓄電池， 惟作爲其外裝材，亦檢討經層合加工的金屬涪。 如此的層合加工中所用的層合薄膜，由於在貼合於直 接金屬材料後，進行加熱壓黏，故與塗佈樹脂組成物，然 後進行加熱乾燥的一般樹脂皮膜相比，具有可抑制材料的 浪費、針孔（缺陷部）少及加工性優異等之優點。作爲層合 薄膜的材料，一般使用聚對苯二甲酸乙二酯及聚萘二甲酸 乙二酯等的聚酯系樹脂、或聚乙烯及聚丙烯等的聚烯烴。 於金屬材料的表面（亦僅稱金屬表面）上層合加工層合 薄膜之際，爲了提高層合薄膜與金屬表面的密接性及耐触 性’於將金屬表面脫脂洗淨後，通常施予磷酸鉻酸鹽等的 化成處理。然而，如此的化成處理係在處理後必須有去除 多餘的處理液之洗淨步驟，由於洗淨步驟所排出的洗淨水 之廢水處理係花費成本。特別地，磷酸鉻酸鹽等的化成處 理由於使用含六價鉻的處理液，從近年來環境的關懷來 看，係有迴避的傾向。 另一方面，若對金屬表面不施予化成處理等的處理而 進行層合加工，則有層合薄膜自金屬表面剝離或對金屬材 -6- 201132801 料發生腐蝕之問題。例如，於食品用容器或包裝材中’在 層合加工後的容器或包裝材中加入內容物後，施予以殺菌 爲目的之加熱處理，但在該加熱處理時層合薄膜會自金屬 表面剝離。又，鋰離子蓄電池的外裝材等係在其製造步驟 中接受加工度高的加工。如此的外裝材若被長期使用，則 大氣中的水分滲入內部，此與電解質反應而生成氫氟酸， 其穿透層合薄膜，而發生金屬表面與層合薄膜之剝離，同 時有腐蝕金屬表面之問題。 對於如此的問題，有各種的提案，其爲在層合加工之 前，形成用於提高層合薄膜對金屬表面的密接性之皮膜的 方法。 例如，專利文獻1中提案於鋁合金條的單面上形成化 成處理膜，在該化成處理膜上被覆樹脂薄膜而構成的深 拉•減薄拉延罐用鋁合金之製造方法。此化成處理膜係以 含有由鉻系、鈦系及銷系所選出的一種金屬成分之化成處 理液所形成的膜，藉由金屬附著量而改變與樹脂薄膜的密 接性和耐触性，該金屬附著量較佳爲5〜5 0 m g / m2之情 況。 又，專利文獻2中提案用於形成表面處理皮膜的接著 基底用之表面處理劑’該表面處理皮膜係提高金屬表面與 層合薄膜之層間的密接性，更且提高層合有薄膜的金屬材 料之耐蝕性。此表面處理劑較佳爲含有胺化酚聚合物與由 Ti、Zr、Hf' Mo' W、Se、Ce、Fe、Cu、Zn、V 及 3 價 Cr所選出的至少1種之金屬化合物，pH係在i_5〜6.0的 201132801 範圍。 再者，專利文獻3中提案一種表面處理劑，其不是用 於形成提高金屬表面與層合薄膜之密接性的表面處理皮膜 之表面處理劑，而是用於形成提高金屬表面上所塗佈形成 的塗裝膜之密接性的塗裝基底膜之表面處理劑。此表面處 理劑係含有矽烷偶合劑（A)、陽離子性胺甲酸乙酯樹脂 (B)、Zr化合物及/或Ti化合物（C)以及含氟的無機化合物 (D)之預塗金屬材料用表面處理劑，（A)/(B)的質量比爲 1/50〜20/1，（Zr及/或Ti原子）/(B)的質量比爲1/1，〇〇〇〜 1/2，且氟原子/(B)的質量比爲1/1，〇〇〇〜2/1。 先前技術文獻 專利文獻 專利文獻1:特開2005-120422號公報 專利文獻2 :特開2 0 0 3 - 1 3 8 3 8 2號公報 專利文獻3 :特開2006-3 2 8445號公報 【發明內容】 發明所欲解決的問題 特別地於最近，對攜帶電話、電子筆記本、筆記型個 人電腦或攝影機等中所用的攜帶用鋰離子蓄電池、或作爲 電動汽車或混合動力汽車的驅動能量的鋰離子蓄電池之外 裝材等，要求高的加工性與耐蝕性。因此，於對如此的金 屬材料進行層合加工之前所形成的表面處理皮膜中，比以 往還增加，要求對金屬材料的高密接性及耐蝕性。 -8- 201132801 本發明係可回應最近的高水平之要求者，其目的在於 是供用於形成表面處理皮膜的層合金屬材料用表面處理 劑’其係在金屬材料的表面上層合樹脂薄膜後，即使在施 予深拉加工、減薄拉延加工或張拉加工等的嚴酷成形加工 時’也可賦予高的密接性與高的耐蝕性，而使得其層合薄 膜不剝離。又，本發明之另一目的在於提供層合金屬材料 的製造方法，該層合金屬材料具有以如此表面處理劑所形 成的表面處理皮膜。 解決問題的手段 本發明者檢討上述專利文獻3中記載的塗裝基底膜用 表面處理劑是否亦可使用作爲層合金屬材料用的表面處理 劑，發現照原樣地係無法形成密接性與耐蝕性優異的表面 處理皮膜，藉由將特定的成分規定在特定的範圍內才可達 成，終於完成本發明。 爲了解決上述問題，本發明的層合金屬材料用表面處 理劑之特徵爲含有矽烷偶合劑（A)、陽離子性胺甲酸乙酯 樹脂（B)、Zr化合物（Cl)、Ti化合物（C2)及含氟的無機化 合物（D)，配合比（A)/(B)以重量比表示爲1/50以上20/1 以下，配合比（C)/(B)以重量比表示爲1/100以上1/2以下 (惟，（C)的重量係（C1)與（C2)的合計），配合比（氟原子）/(B) 以重量比表示爲1 / 1 000以上2/1以下，而且配合比 (C1)/(C2)以重量比表示爲1/10以上且未達2/1。 於本發明的層合金屬材料用表面處理劑中，前述陽離 -9 - 201132801 子性胺甲酸乙酯樹脂（B)含有由二級胺基及三級胺基所選 出的胺基性官能基。 於本發明的層合金屬材料用表面處理劑中，前述矽烷 偶合劑（A)全體的5質量％以上係具有由一級胺基、二級 胺基、三級胺基及四級銨基所選出的胺基性官能基之矽烷 偶合劑。 於本發明的層合金屬材料用表面處理劑中，前述Zr 化合物（Cl)及前述Ti化合物（C2)係氟化物或氟酸或氟酸 鹽。 爲了解決上述問題，本發明之層合金屬材料的製造方 法之特徵爲在金屬材料表面塗佈乾燥上述本發明之層合金 屬材料用表面處理劑，以形成〇.〇1〜lg/m2的皮膜，接著 層合聚酯系樹脂、聚乙烯系樹脂、聚丙烯系樹脂或此等的 改性樹脂。 於本發明之層合金屬材料的製造方法中，前述金屬材 料係鋁系或不銹鋼系的金屬箔。 發明的效果 若藉由本發明的層合金屬材料用表面處理劑，則可達 成與層合薄膜的密接性（包含加工密接性）及耐蝕性（尤其 耐強酸性及耐強鹼性）優異之製作層合金屬材料、層合金 屬谷器或層合金屬包裝材用的表面處理劑之優異效果。 又，若藉由本發明的層合金屬材料用表面處理劑，則不具 有六價鉻，亦考慮近年之環境問題的完全無鉻，達成環境 -10- 201132801 負荷少的效果。又，若藉由本發明之層合金屬材料的製造 方法，則達成可提供密接性及耐蝕性優異的金屬容器或包 裝材之優異效果。 【實施方式】 實施發明的形態 以下詳細說明本發明的層合金屬材料用表面處理劑及 層合金屬材料的製造方法。再者，於本申請案中，重量比 與質量比、重量與質量係皆同義。 [層合金屬材料用表面處理劑] 本發明的層合金屬材料用表面處理劑（以下亦僅稱 「表面處理劑」）係含有矽烷偶合劑（A)、陽離子性胺甲酸 乙酯樹脂（B)、Zr化合物（Cl)、Ti化合物（C2)及含氟的無 機化合物（D)當作必要成分。再者，含氟的無機化合物（D) 係可當作單獨的化合物進行配合，也可爲含有氟的Zr化 合物（C1)或Ti化合物（C2)。於Zr化合物（C1)或Ti化合物 (C2)含有氟時，含有氟的Zr化合物（C1)或Ti化合物（C2) 亦可稱爲含氟的無機化合物（D)。藉由將如此的表面處理 劑塗佈於金屬表面上及使乾燥，可形成作爲層合金屬材料 用的基底皮膜之較佳表面處理皮膜。 (矽烷偶合劑） 矽烷偶合劑（A)藉由水解所生成的矽烷醇基之_〇h的 -11 - 201132801 活性係高，與母材的金屬材料Μ經由氧原子而進行- Si-〇_ Μ的強固化學鍵結。此化學鍵結係特別有助於與金屬材料 Μ的良好密接性。又，矽烷偶合劑（Α)係藉由與作爲上層 設置的層合薄膜中所含有的有機官能基之反應，而亦有助 於與層合薄膜的密接性提高。於矽烷偶合劑（Α)中導入以 極性強的0、Ν等當作構成元素的官能基時，進一步提高 與層合薄膜的密接性。 作爲矽烷偶合劑（Α)，例如可舉出γ-胺基丙基三甲氧 基矽烷、γ -胺基丙基三乙氧基矽烷、Ν -苯基-3-丙基三甲 氧基矽烷Ν-苯基-3-丙基三乙氧基矽烷、Ν-(2-胺基乙基） 胺基丙基三甲氧基矽烷、Ν-(2-胺基乙基）胺基丙基甲基二 甲氧基矽烷、Ν-(2-胺基乙基）胺基丙基三乙氧基矽烷、Ν-(2-胺基乙基）胺基丙基甲基二乙氧基矽烷、Ν-(2-胺基乙基） 胺基丙基甲基二甲氧基矽烷、γ-甲基丙烯醯氧基丙基三甲 氧基矽烷、γ-甲基丙烯醯氧基丙基甲基二甲氧基矽烷、γ-甲基丙烯醯氧基丙基三乙氧基矽烷、γ-甲基丙烯醯氧基丙 基甲基二乙氧基矽烷、Ν-β-(Ν-乙烯基苄基胺基乙基）-3-胺 基丙基三甲氧基矽烷、Ν-β-(Ν-乙烯基苄基胺基乙基）-3-胺 基丙基甲基二甲氧基矽烷、Ν-β-(Ν-乙烯基苄基胺基乙 基）-3·胺基丙基三乙氧基矽烷、Ν-β·(Ν-乙烯基苄基胺基乙 基）-3-胺基丙基甲基二乙氧基矽烷、γ-環氧丙氧基丙基三 甲氧基矽烷、γ-環氧丙氧基丙基甲基二甲氧基矽烷、γ-環 氧丙氧基丙基三乙氧基矽烷、γ-環氧丙氧基丙基甲基二乙 氧基砂院、γ -疏基丙基三甲氧基砂院、γ -疏基丙基甲基二 -12- 201132801 甲氧基矽烷、γ-巯基丙基三乙氧基矽烷、γ-毓基丙基甲基 二乙氧基矽烷、甲基三甲氧基矽烷、二甲基二甲氧基矽 烷、甲基三乙氧基矽烷、二甲基二乙氧基矽烷、乙烯基三 乙醯氧基矽烷、γ-氯丙基三甲氧基矽烷、γ-氯丙基甲基二 甲氧基矽烷、γ-氯丙基三乙氧基矽烷、γ-氯丙基甲基二乙 氧基矽烷、六甲基二矽氮烷、γ-苯胺基丙基三甲氧基矽 烷、γ-苯胺基丙基甲基二甲氧基矽烷、γ-苯胺基丙基三乙 氧基矽烷、γ-苯胺基丙基甲基二乙氧基矽烷、異氰酸酯基 丙基三甲氧基矽烷、異氰酸酯基丙基三乙氧基矽烷、脲基 丙基三乙氧基矽烷、雙（三甲氧基矽烷基）胺基乙烯基三甲 氧基矽烷、乙烯基甲基二甲氧基矽烷、乙烯基三乙氧基矽 烷、乙烯基甲基二乙氧基矽烷、十八基二甲基[3-(三甲氧 基矽烷基）丙基]銨氯化物、十八基二甲基[3-(甲基二甲氧 基矽烷基）丙基]銨氯化物、十八基二甲基[3-(三乙氧基矽 烷基）丙基]銨氯化物、十八基二甲基[3-(甲基二乙氧基矽 烷基）丙基]銨氯化物、γ-氯丙基甲基二甲氧基矽烷、γ-锍 基丙基甲基二甲氧基矽烷、甲基三氯矽烷、二甲基二氯矽 烷、三甲基氯矽烷等。 矽烷偶合劑（Α)係具有與作爲上層所層合的層合薄膜 (後述的樹脂薄膜或壓出層合樹脂）之相容性，取決於組 合’性能係有不出現符合期待的案例。於以表面處理劑當 作層合金屬材料用的本發明之用途中，採用具有胺基的矽 烷偶合劑（Α)時，與層合薄膜的相容性良好。因此，於本 發明的表面處理劑中，矽烷偶合劑（Α)較佳爲含有至少1 -13- 201132801 種（1種或2種以上）的具胺基性官能基者。 此處，所謂的胺基性官能基，就是由—級胺基、二級 胺基、三級胺基及四級銨基所選出的官能基。再者，作爲 具有四級銨基時的相對離子，可舉出以氯離子爲首的鹵素 離子、磷酸離子、硝酸離子、硫酸離子、有機酸離子等。 更佳的胺基官能基係三級胺基。其理由係因爲與層合薄膜 的密接性亦良好，但於工業上使用時，作爲表面處理劑的 安定性（儲存安定性）係重要。根據此觀點，本發明者發現 賦予高的密接性，且具有優異的儲存安定性和伴隨其的操 作安定性之三級胺基係最佳。 如此具有至少1種的胺基性官能基之矽烷偶合劑，對 於矽烷偶合劑（A)全體而言的含量較佳爲5質量％以上， 更佳爲1 〇質量％以上，特佳爲20質量％以上。具有如此 含量的矽烷偶合劑（A)，係可消除由於層合薄膜之種類而 可能發生的與層合薄膜之密接性、耐蝕性等之不利影響， 或抑制在最小限度。 混合2種以上使用矽烷偶合劑（A)時，較佳爲使用具 有互相反應而生成新的鍵結之官能基的矽烷偶合劑（A)。 藉由如此作，可進一步提高薄膜密接性（加工密接性），亦 可提高耐蝕性。例如，作爲與具有一級胺基及/或二級胺 基的矽烷偶合劑反應而生成新的縮合之矽烷偶合劑，較佳 爲（i)具有環氧丙基當作前述官能基的矽烷偶合劑，而且較 佳可舉出（Π)具有或能生成羥基當作前述官能基的矽烷偶 合劑（例如具有環氧丙基當作官能基的矽烷偶合劑）與具有 -14- 201132801 異氰酸酯基當作前述官能基的矽烷偶合劑之倂用。如後者 (ii)之具有互相反應而生成鍵結的官能基之矽烷偶合劑彼 此的配合比例，係沒有必要互相的官能基爲不多不少之反 應量，一方的官能基（例如一級胺基或二級胺基）與另一方 的官能基（例如環氧丙基）之當量比較佳爲50:1〜1:50之範 圍，更佳爲30:1〜1:30之範圍。 (陽離子性胺甲酸乙酯樹脂） 陽離子性胺甲酸乙酯樹脂（B)係水溶性或水系乳液形 態者。陽離子性胺甲酸乙酯樹脂（B)在水中溶解或分散， 係可以自溶解性或自分散性爲基礎而達成，而且亦可藉由 陽離子性界面活性劑（例如烷基四級銨鹽等）及/或非離子性 界面活性劑（例如烷基苯基醚等）的存在而分散。如此的陽 離子性胺甲酸乙酯樹脂（B)係對所得到的表面處理皮膜賦 予柔軟性，而且有助於層合薄膜的密接性之提高，結果發 揮有效地提高加工密接性之作用。 陽離子性胺甲酸乙酯樹脂（B)只要是具有由二級胺 基、三級胺基及四級銨鹽中所選出的至少1種（1種或2 種以上）之陽離子性官能基者，則所構成的單體成分之多 元醇及聚異氰酸酯成分及聚合方法係沒有特別的限定。其 中，較佳爲至少具有三級胺基者。另一方面，一級胺基由 於反應性激烈，馬上與環氧丙基等反應，故在藥劑的安定 性或密接性顯著降低之點係不宜，可不含有。於陽離子性 官能基之中，三級胺基的比例較佳爲3 0〜1 00%，更佳爲 -15- 201132801 60%〜100%，藉由使三級胺在此範圍，尤其在層合金屬材 料用途的表面處理皮膜中，可提高其密接性。 陽離子性胺甲酸乙酯樹脂（B)，例如係可藉由習知的 方法使六亞甲基二異氰酸酯（HDI)、二環己基甲烷二異氤 酸酯（HMD I)、異佛爾酮二異氰酸酯（ip DI)等的脂肪族、脂 環式或芳香族二異氰酸酯與聚酯多元醇、聚醚多元醇、聚 碳酸酯多元醇等之在鏈中導入有胺基的多元醇進行聚合， 以硫酸烷酯等將胺一部皆四級化而得。作爲陽離子性官能 基的氮上之取代基，可舉出氫、烷基、芳基、烯基、炔 基、羥烷基等的取代基，惟不受此等所限定。於表面處理 劑中，可混合2種以上的陽離子性胺甲酸乙酯樹脂（B)。 於上述中，作爲脂肪族、脂環式或芳香族聚異氰酸 酯，可舉出四亞甲基二異氰酸酯、六亞甲基二異氰酸酯、 離胺酸二異氰酸酯、氫化苯二甲基二異氰酸酯、I，4·伸環 己基二異氰酸酯、4,4’-二環己基甲烷二異氤酸酯、2,4，-二環己基甲烷二異氰酸酯、異佛爾酮二異氰酸酯、3，3，-二 甲氧基-4，4’-伸聯苯基二異氰酸酯、1,5-萘二異氰酸酯、 1,5-四氫萘二異氰酸酯、2，4-甲苯二異氰酸酯、2，6-甲苯 二異氰酸酯、4，4’-二苯基甲烷二異氰酸酯、2，4’-二苯基 甲烷二異氰酸酯、伸苯基二異氰酸酯、苯二甲基二異氰酸 酯、四甲基苯二甲基二異氰酸酯等。於此等之中，使用四 亞甲基二異氰酸酯、六亞甲基二異氰酸酯、離胺酸二異氰 酸酯、氫化苯二甲基二異氰酸酯、1，4-伸環己基二異氰酸 酯、4,4’-二環己基甲烷二異氰酸酯、2,4’-二環己基甲烷 -16- 201132801 二異氰酸酯、異佛爾酮二異氰酸酯等的脂肪族或脂環式聚 異氰酸酯化合物時，由於得到耐藥品性與防蝕性優異的表 面處理皮膜而較佳。 於上述中，作爲多元醇，例如可舉出乙二醇、二乙二 醇、三乙二醇、1，2-丙二醇、1,3-丙二醇、新戊二醇、 1,2-丁 二醇、1，3-丁 二醇、1,4-丁二醇、己二醇、雙酚 A、 氫化雙酚A、三羥甲基丙烷、1,2-丙二醇、1，3-丙二醇、 2-甲基-1,3-丙二醇、2-丁基-2-乙基-1，3-丙二醇、1,4-丁二 醇、新戊二醇、3-甲基-2,4-戊二醇、2,4-戊二醇、1,5-戊 二醇、3-甲基-1,5-戊二醇、2-甲基-2,4-戊二醇、2,4-二乙 基-1，5-戊二醇、1，6-己二醇、1，7-庚二醇、3,5-庚二醇、 1,8-辛二醇、2 -甲基-1，8-辛二醇、1，9 -壬二醇、1,10-癸二 醇等的脂肪族二醇化合物、三羥甲基乙烷、三羥甲基丙 烷、己糖醇類、戊糖醇類、甘油、二甘油、聚甘油、季戊 四醇、二季戊四醇、四羥甲基丙烷等的3價以上之脂肪族 或脂環族醇化合物等。 於上述中，作爲聚醚多元醇，例如可舉出乙二醇、二 乙二醇 '三乙二醇等的環氧乙烷加成物、丙二醇、二丙二 醇、三丙二醇等的環氧丙烷加成物、上述多元醇的環氧乙 烷及/或環氧丙烷加成物、聚丁二醇等。 於上述中，作爲聚酯多元醇，例如可舉出上述多元醇 等與比其化學計算量少的量之多元羧酸或其酯、酐、鹵化 物等的酯形成性衍生物、及/或內酯類或其進行水解開環 而得之羥基羧酸化合物之直接酯化反應及/或酯交換反應 -17- 201132801 所得者。作爲多元羧酸’例如可舉出草酸、丙二酸、琥珀 酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二 酸、十—院二酸、2 -甲基號拍酸、2 -甲基己二酸、3 -甲基 己二酸、3 -甲基戊二酸、2 -甲基辛二酸、3，8_二甲基癸二 酸、3,7-二甲基癸二酸、二聚酸、氫化二聚酸等的脂肪族 二羧酸類’環己烷二羧酸等的脂環式二羧酸類；苯二甲 酸、間苯二甲酸、對苯二甲酸、萘二羧酸等的芳香族二羧 酸類；偏苯三酸'均苯三酸'蓖麻油脂肪酸的三聚物等的 三羧酸類’苯均四酸等的四羧酸等之多羧酸。作爲該酯形 成性衍生物，可舉出此等的多元羧酸之酸酐，該多元羧酸 的氯化物、溴化物等的鹵化物，該多元竣酸的甲醋、乙 酯、丙酯、異丙酯、丁酯、異丁酯、戊酯等的低級脂肪族 酯等。作爲上述內酯類，可舉出γ-己內酯、δ_己內酯、ε-己內酯、γ-戊內酯、δ-戊內酯等的內酯類等。 於上述中，作爲聚碳酸酯多元醇，例如可使用使碳酸 與脂肪酸多元醇進行酯化反應而得者等。具體地，可舉出 如1，3-丙二醇、1,4-丁二醇、1,6-己二醇、二乙二醇、二 乙二醇、聚乙二醇、聚丙二醇或聚丁二醇等的二醇與碳酸 二甲酯或碳酸二苯酯或光氣等的反應生成物等。 於陽離子性胺甲酸乙酯樹脂（Β)中，作爲可溶化劑或 乳化劑的界面活性劑之使用，由於有對金屬材料的密接性 或耐水性造成不利影響之虞，更佳爲不使用如此的界面活 性劑之無皂或抑制其使用量者。 陽離子性胺甲酸乙酯樹脂（Β)的重量平均分子量較佳 -18- 201132801 爲1,000〜1，000,000，更佳爲2,000〜500,00(^重量平均 分子量未達1，〇〇〇時，表面處理皮膜的形成性有變不充分 的傾向，另一方面，重量平均分子量超過ι，οοο,οοο時， 表面處理劑的安定性有降低的傾向。 又，只要是與陽離子性胺甲酸乙酯樹脂（B)相溶者， 則亦可混合丙稀酸系樹脂、醋系樹脂、胺系樹脂、環氧系 樹脂或酣系樹脂等而使用。此等樹脂亦可具有水溶性或水 分散性。只要是與本發明的表面處理可相溶，不使所形成 的皮膜之性能降低者，則沒有特別的限定。又，陽離子 性、陰離子性、非離子性等的樹脂之離子性亦沒有限定。 另外，爲了提高其造膜性，形成更均句的平滑皮膜，亦可 使用有機溶劑。 陽離子性胺甲酸乙酯樹脂（B)與砂院偶合劑（A)的配合 比（A)/(B)以重量比表示較佳爲1/5〇以上20/1以下。藉由 成爲如此的配合比，在與上層的層合薄膜之間可得到優異 的密接性。再者，配合比（A)/(B)的更佳範圍爲1/20以上 1 0/ 1以下，尤佳的範圍爲1 /1 〇以上5/ 1以下。配合比 (A)/(B)未達1/50時，所得之表面處理皮膜的硬度降低， 難以得到充分的加工密接性，而配合比（A)/(B)超過2〇/1 時，反而難以得到與基底金屬的金屬表面之間的密接性， 隔著表面處理皮膜的層合薄膜之密接性會變差。 (Zr化合物與Ti化合物）BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface treatment agent for a laminated metal material for forming a surface treatment film, and a method for producing a laminated metal material, which is used to improve the surface of a metal material. The adhesion to the laminated film (including the process adhesiveness) is improved, and the corrosion resistance (especially strong acid resistance and strong alkali resistance) of the metal material laminated with the film is improved. More specifically, the surface treatment agent for a laminated metal material for forming a surface treatment film and a method for producing a laminated metal material are used for a metal material such as an aluminum-based metal foil or a stainless steel-based metal foil. After laminating the resin film on the surface, even when subjected to a severe forming process such as deep drawing, thin drawing, or drawing, high adhesion can be imparted so that the laminated film is not peeled off, and the article is further (Formed product) has excellent corrosion resistance. [Prior Art] Lamination processing is a method of processing a resin film (hereinafter referred to as a resin film or a laminate film) by heat-pressing (or pressure-adhesive via an adhesive) on the surface of a metal material, as a surface protection or The pattern design imparts one of the coating methods for the intended surface of the metal material, and is used in various fields. This laminating process is a method in which a resin composition is applied and baked to form a resin film, that is, a solvent and a waste gas or a warm gas generated in a baking process are less generated than baking. . Therefore, it is better in terms of environmental protection, and its use is expanded. For example, it is used for the body or cover material of food cans which are used as raw materials for aluminum sheet-5-201132801, steel sheet, packaging aluminum foil or stainless steel foil. , food containers or dry battery containers. In particular, it is more suitable to use a metal such as a lithium ion battery for mobile phones used in mobile phones, electronic notebooks, notebook personal computers, and video cameras, and it is preferable to use a metal such as aluminum foil and stainless steel foil which are lightweight and have high barrier properties. The foil 'lamination process is suitable for such a metal foil. Further, as a driving energy of an electric car or a hybrid car, a lithium ion battery is reviewed, and as a casing material, a metal enamel which has been laminated is also reviewed. Since the laminated film used in such a lamination process is heated and pressure-bonded after being bonded to a direct metal material, it has a suppressable material as compared with a general resin film which is coated with a resin composition and then heat-dried. The waste, the pinhole (defective portion) are small, and the workability is excellent. As the material of the laminated film, a polyester resin such as polyethylene terephthalate or polyethylene naphthalate or a polyolefin such as polyethylene or polypropylene is generally used. When laminating a laminated film on the surface of a metal material (also referred to as a metal surface), in order to improve the adhesion and contact resistance of the laminated film to the metal surface, after the metal surface is degreased and washed, phosphoric acid is usually applied. Chemical treatment of chromate or the like. However, such a chemical conversion process requires a washing step of removing excess processing liquid after the treatment, and the waste water treatment of the washing water discharged by the washing step is costly. In particular, the chemical conversion treatment of chromate phosphate or the like has a tendency to avoid from the care of the environment in recent years due to the use of a treatment liquid containing hexavalent chromium. On the other hand, when the metal surface is subjected to a lamination process without a treatment such as a chemical conversion treatment, there is a problem that the laminated film peels off from the metal surface or corrodes the metal material -6-201132801. For example, in a food container or a packaging material, after the contents are added to the container or packaging material after the lamination processing, heat treatment is performed for the purpose of sterilization, but the laminated film is peeled off from the metal surface during the heat treatment. . Further, the exterior material of the lithium ion secondary battery or the like is processed in a high degree of processing in the manufacturing step. When such an exterior material is used for a long period of time, moisture in the atmosphere penetrates into the interior, which reacts with the electrolyte to form hydrofluoric acid, which penetrates the laminated film, and peels off the metal surface and the laminated film, and at the same time corrodes the metal. Surface problem. There are various proposals for such a problem, which is a method of forming a film for improving the adhesion of a laminated film to a metal surface before lamination processing. For example, Patent Document 1 proposes a method for producing an aluminum alloy for deep drawing and thinning cans which is formed by forming a chemical conversion treatment film on one surface of an aluminum alloy strip and coating a resin film on the chemical conversion treatment film. The chemical conversion treatment film is a film formed of a chemical conversion treatment liquid containing a metal component selected from a chromium-based, titanium-based or pin-based system, and the adhesion to the resin film and the contact resistance are changed by the amount of metal adhesion. The amount of metal adhesion is preferably 5 to 50 mg / m 2 . Further, Patent Document 2 proposes a surface treatment agent for forming a surface-treated film for a base material. The surface treatment film improves the adhesion between the metal surface and the layer of the laminated film, and further improves the metal material laminated with the film. Corrosion resistance. The surface treatment agent preferably contains at least one metal compound selected from the group consisting of an aminated phenol polymer and Ti, Zr, Hf' Mo' W, Se, Ce, Fe, Cu, Zn, V and 3-valent Cr. The pH range is in the range of 201132801 of i_5~6.0. Further, Patent Document 3 proposes a surface treatment agent which is not used for forming a surface treatment agent for improving the adhesion of a metal surface to a laminated film, but for forming an improved coating on a metal surface. The surface treatment agent for the coated base film in which the coating film is adhered. The surface treatment agent is a surface for precoated metal materials containing a decane coupling agent (A), a cationic urethane resin (B), a Zr compound and/or a Ti compound (C), and a fluorine-containing inorganic compound (D). The mass ratio of the treatment agent (A)/(B) is 1/50 to 20/1, and the mass ratio of (Zr and/or Ti atom)/(B) is 1/1, 〇〇〇~ 1/2, Further, the mass ratio of the fluorine atom/(B) is 1/1, 〇〇〇~2/1. CITATION LIST PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT 1: JP-A-2005-120422 Patent Document 2 Contents] The problem to be solved by the invention is, in particular, a lithium ion battery for carrying a lithium ion battery used in a mobile phone, an electronic notebook, a notebook personal computer or a video camera, or as a driving energy of an electric car or a hybrid car. High-quality workability and corrosion resistance are required for materials other than batteries. Therefore, in the surface treatment film formed before the lamination processing of such a metal material, the surface treatment film is further increased, and high adhesion to the metal material and corrosion resistance are required. -8- 201132801 The present invention is responsive to the recent high level of requirements, and is intended to provide a surface treatment agent for a laminated metal material for forming a surface treatment film, which is formed by laminating a resin film on the surface of a metal material. Even when subjected to a deep drawing process such as deep drawing, thin drawing, or tension processing, high adhesion and high corrosion resistance can be imparted, so that the laminated film is not peeled off. Further, another object of the present invention is to provide a method for producing a laminated metal material having a surface-treated film formed by such a surface treating agent. Means for Solving the Problem The present inventors have examined whether or not the surface treatment agent for a coated base film described in Patent Document 3 can be used as a surface treatment agent for a laminated metal material, and it is found that adhesion and corrosion resistance cannot be formed as it is. The excellent surface treatment film can be achieved by setting a specific component within a specific range, and finally completed the present invention. In order to solve the above problems, the surface treatment agent for laminated metal materials of the present invention is characterized by containing a decane coupling agent (A), a cationic urethane resin (B), a Zr compound (Cl), a Ti compound (C2), and The fluorine-containing inorganic compound (D) has a mixing ratio of (A)/(B) in a weight ratio of 1/50 or more and 20/1 or less, and a mixing ratio (C)/(B) in terms of a weight ratio of 1/100 or more. 1/2 or less (except that the weight of (C) is the total of (C1) and (C2)), and the mixing ratio (fluorine atom) / (B) is expressed by weight ratio of 1 / 1 000 or more and 2 / 1 or less, and The compounding ratio (C1) / (C2) is represented by a weight ratio of 1/10 or more and less than 2/1. In the surface treatment agent for laminated metal materials of the present invention, the aforementioned cation-9-201132801 urethane resin (B) contains an amine functional group selected from a secondary amino group and a tertiary amine group. . In the surface treatment agent for a laminated metal material of the present invention, 5% by mass or more of the entire decane coupling agent (A) is selected from a primary amine group, a secondary amine group, a tertiary amine group, and a quaternary ammonium group. Alkane-based functional decane coupling agent. In the surface treatment agent for a laminated metal material of the present invention, the Zr compound (Cl) and the Ti compound (C2) are fluorides or hydrofluoric acid or hydrofluoric acid salts. In order to solve the above problems, the method for producing a laminated metal material according to the present invention is characterized in that the surface treatment agent for laminating the metal material of the present invention is applied to the surface of the metal material to form a film of 〇.〇1 to lg/m2. Then, a polyester resin, a polyethylene resin, a polypropylene resin, or a modified resin thereof is laminated. In the method for producing a laminated metal material according to the present invention, the metal material is an aluminum-based or stainless steel-based metal foil. According to the surface treatment agent for a laminated metal material of the present invention, it is possible to achieve adhesion to a laminated film (including process adhesion) and corrosion resistance (especially resistance to strong acidity and strong alkali resistance). Excellent effect of surface treatment agents for laminated metal materials, laminated metal grain or laminated metal packaging materials. Further, when the surface treatment agent for a laminated metal material of the present invention does not have hexavalent chromium, it is also considered to be completely chromium-free in consideration of environmental problems in recent years, and the effect of environmental -10-201132801 is small. Moreover, according to the method for producing a laminated metal material of the present invention, an excellent effect of providing a metal container or a packaging material excellent in adhesion and corrosion resistance is achieved. [Embodiment] Mode for Carrying Out the Invention The surface treatment agent for a laminated metal material of the present invention and a method for producing a laminated metal material will be described in detail below. Further, in the present application, the weight ratio is synonymous with the mass ratio, weight and quality. [Surface Treatment Agent for Laminated Metal Material] The surface treatment agent for laminated metal materials of the present invention (hereinafter also referred to simply as "surface treatment agent") contains a decane coupling agent (A) and a cationic urethane resin (B). ), a Zr compound (Cl), a Ti compound (C2), and a fluorine-containing inorganic compound (D) are essential components. Further, the fluorine-containing inorganic compound (D) may be compounded as a single compound, or may be a fluorine-containing Zr compound (C1) or a Ti compound (C2). When the Zr compound (C1) or the Ti compound (C2) contains fluorine, the fluorine-containing Zr compound (C1) or the Ti compound (C2) may also be referred to as a fluorine-containing inorganic compound (D). By coating such a surface treating agent on a metal surface and drying it, a preferred surface treatment film as a base film for a laminated metal material can be formed. (decane coupling agent) decane coupling agent (A) 矽 的h -11 - 201132801 by the hydrolysis of the stanol group is high in activity, and the metal material of the base material is carried out via an oxygen atom - Si-〇_ Strong curing bond of bismuth. This chemical bonding system is particularly useful for good adhesion to metallic materials. Further, the decane coupling agent (Α) is also effective in the adhesion to the laminated film by the reaction with the organic functional group contained in the laminated film provided as the upper layer. When a functional group having a strong polarity of 0, ruthenium or the like as a constituent element is introduced into the decane coupling agent (Α), the adhesion to the laminated film is further improved. Examples of the decane coupling agent (Α) include γ-aminopropyltrimethoxydecane, γ-aminopropyltriethoxydecane, and fluorenyl-phenyl-3-propyltrimethoxydecanefluorene- Phenyl-3-propyltriethoxydecane, Ν-(2-aminoethyl)aminopropyltrimethoxydecane, Ν-(2-aminoethyl)aminopropylmethyl dimethyl Oxydecane, Ν-(2-aminoethyl)aminopropyltriethoxydecane, Ν-(2-aminoethyl)aminopropylmethyldiethoxydecane, Ν-(2 -aminoethyl)aminopropylmethyldimethoxydecane, γ-methylpropenyloxypropyltrimethoxydecane, γ-methylpropenyloxypropylmethyldimethoxydecane , γ-methacryloxypropyltriethoxydecane, γ-methylpropenyloxypropylmethyldiethoxydecane, Ν-β-(Ν-vinylbenzylaminoethyl )-3-aminopropyltrimethoxydecane, Ν-β-(Ν-vinylbenzylaminoethyl)-3-aminopropylmethyldimethoxydecane, Ν-β-(Ν -vinylbenzylaminoethyl)-3-aminopropyltriethoxydecane, Ν-β·(Ν-vinylbenzylaminoethyl)-3-aminopropyl Methyldiethoxydecane, γ-glycidoxypropyltrimethoxydecane, γ-glycidoxypropylmethyldimethoxydecane, γ-glycidoxypropyltriethyl Oxydecane, γ-glycidoxypropylmethyldiethoxylate, γ-mercaptopropyltrimethoxy sand, γ-sulfopropylmethyldi-12- 201132801 methoxy Decane, γ-mercaptopropyltriethoxydecane, γ-mercaptopropylmethyldiethoxydecane, methyltrimethoxydecane, dimethyldimethoxydecane, methyltriethoxydecane , dimethyldiethoxydecane, vinyltriethoxydecane, γ-chloropropyltrimethoxydecane, γ-chloropropylmethyldimethoxydecane, γ-chloropropyltriethoxy Base decane, γ-chloropropylmethyldiethoxy decane, hexamethyldioxane, γ-anilinopropyltrimethoxydecane, γ-anilinopropylmethyldimethoxydecane, γ -anilinopropyltriethoxydecane, gamma-anilinopropylmethyldiethoxydecane, isocyanatopropyltrimethoxydecane, isocyanatopropyltriethoxydecane, ureidopropyltriethyl Oxyquinone , bis(trimethoxydecyl)aminovinyltrimethoxydecane, vinylmethyldimethoxydecane, vinyltriethoxydecane, vinylmethyldiethoxydecane,octadecyl Methyl [3-(trimethoxydecyl)propyl]ammonium chloride, octadecyldimethyl[3-(methyldimethoxydecyl)propyl]ammonium chloride, octadecyldimethyl [3-(Triethoxydecyl)propyl]ammonium chloride, octadecyldimethyl[3-(methyldiethoxydecyl)propyl]ammonium chloride, γ-chloropropyl Methyldimethoxydecane, γ-mercaptopropylmethyldimethoxydecane, methyltrichlorodecane, dimethyldichlorodecane, trimethylchlorodecane, and the like. The decane coupling agent (Α) has compatibility with a laminated film (a resin film or an extrusion laminated resin to be described later) laminated as an upper layer, and depending on the combination performance, there is no expectation. In the use of the present invention for using a surface treating agent as a laminated metal material, when a decane coupling agent having an amine group is used, compatibility with a laminated film is good. Therefore, in the surface treatment agent of the present invention, the decane coupling agent (Α) preferably contains at least 1 -13 to 201132801 (one or more) amino group-containing functional groups. Here, the so-called amino-functional functional group is a functional group selected from the group consisting of an amine group, a secondary amino group, a tertiary amino group, and a quaternary ammonium group. Further, examples of the counter ion having a quaternary ammonium group include a halogen ion, a phosphate ion, a nitrate ion, a sulfate ion, an organic acid ion, and the like. More preferred amine functional groups are tertiary amine groups. The reason for this is that the adhesion to the laminated film is also good, but when used industrially, the stability (storage stability) as a surface treatment agent is important. From this point of view, the inventors have found that a tertiary amine group which imparts high adhesion and has excellent storage stability and operational stability accompanying it is preferred. The content of the decane coupling agent having at least one of the amino group-functional groups is preferably 5% by mass or more, more preferably 1% by mass or more, and particularly preferably 20% by mass for the entire decane coupling agent (A). %the above. The decane coupling agent (A) having such a content can eliminate the adverse effect of adhesion to the laminated film, corrosion resistance, and the like which may occur due to the type of the laminated film, or can be minimized. When two or more kinds of the decane coupling agent (A) are used, it is preferred to use a decane coupling agent (A) having a functional group which reacts with each other to form a new bond. By doing so, the film adhesion (process adhesion) can be further improved, and the corrosion resistance can be improved. For example, as a new condensed decane coupling agent which is reacted with a decane coupling agent having a primary amine group and/or a secondary amine group, (i) a decane coupling agent having a glycidyl group as the aforementioned functional group is preferred. And, preferably, a decane coupling agent having or capable of forming a hydroxyl group as the aforementioned functional group (for example, a decane coupling agent having a glycidyl group as a functional group) and an isocyanate group having -14 to 201132801 are used as The above-mentioned functional group of decane coupling agent is used. The ratio of the ratio of the decane coupling agents having the functional groups which form a bond to each other in the latter (ii) is not necessarily the reaction amount of each other, and the functional group (for example, the primary amino group) The equivalent weight of the functional group (e.g., the epoxy group) to the other functional group (e.g., epoxy propyl group) is preferably in the range of 50:1 to 1:50, more preferably in the range of 30:1 to 1:30. (Cational urethane resin) The cationic urethane resin (B) is a water-soluble or aqueous emulsion. The cationic urethane resin (B) is dissolved or dispersed in water, and can be achieved on the basis of solubility or self-dispersibility, and can also be a cationic surfactant (for example, an alkyl quaternary ammonium salt or the like). And/or dispersed in the presence of a nonionic surfactant (eg, alkyl phenyl ether, etc.). Such a cationic urethane resin (B) imparts flexibility to the obtained surface-treated film and contributes to an improvement in the adhesion of the laminated film, and as a result, it is effective in improving the adhesion of the film. The cationic urethane resin (B) is a cationic functional group having at least one (one or more) selected from the group consisting of a secondary amino group, a tertiary amino group, and a quaternary ammonium salt. The polyol, the polyisocyanate component, and the polymerization method of the monomer component to be formed are not particularly limited. Among them, those having at least a tertiary amino group are preferred. On the other hand, since the primary amine group is highly reactive and immediately reacts with the epoxy propyl group or the like, it is not suitable for the point that the stability or adhesion of the drug is remarkably lowered, and may not be contained. Among the cationic functional groups, the proportion of the tertiary amino group is preferably from 3 to 10%, more preferably from -15 to 201132801, from 60% to 100%, by making the tertiary amine in this range, especially in the layer. In the surface treated film for metal materials, the adhesion can be improved. The cationic urethane resin (B) can be, for example, hexamethylene diisocyanate (HDI), dicyclohexylmethane diisocyanate (HMD I), isophorone II by a conventional method. An aliphatic, alicyclic or aromatic diisocyanate such as an isocyanate (ip DI) is polymerized with a polyol having an amine group introduced in a chain such as a polyester polyol, a polyether polyol or a polycarbonate polyol. An alkyl sulfate or the like is obtained by quaternizing all of the amines. The substituent on the nitrogen of the cationic functional group may, for example, be a substituent such as hydrogen, an alkyl group, an aryl group, an alkenyl group, an alkynyl group or a hydroxyalkyl group, but is not limited thereto. Two or more kinds of cationic urethane resin (B) may be mixed in the surface treatment agent. In the above, examples of the aliphatic, alicyclic or aromatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, leucine diisocyanate, hydrogenated dimethyl diisocyanate, and I. 4. Cyclohexyl diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 2,4,-dicyclohexylmethane diisocyanate, isophorone diisocyanate, 3,3,-dimethoxy 4--4'-Exbiphenyl diisocyanate, 1,5-naphthalene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4, 4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, phenyl diisocyanate, benzodimethyl diisocyanate, tetramethyl benzene diisocyanate, and the like. Among these, tetramethylene diisocyanate, hexamethylene diisocyanate, leucine diisocyanate, hydrogenated dimethyl diisocyanate, 1,4-cyclohexyl diisocyanate, 4, 4'- are used. When an aliphatic or alicyclic polyisocyanate compound such as dicyclohexylmethane diisocyanate or 2,4'-dicyclohexylmethane-16-201132801 diisocyanate or isophorone diisocyanate is obtained, chemical resistance and corrosion resistance are obtained. It is preferred to have an excellent surface treatment film. In the above, examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propanediol, neopentyl glycol, and 1,2-butanediol. , 1,3-butanediol, 1,4-butanediol, hexanediol, bisphenol A, hydrogenated bisphenol A, trimethylolpropane, 1,2-propanediol, 1,3-propanediol, 2- Methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-2,4-pentanediol , 2,4-pentanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 2,4-diethyl -1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 3,5-heptanediol, 1,8-octanediol, 2-methyl-1,8- An aliphatic diol compound such as octanediol, 1,9-nonanediol or 1,10-decanediol, trimethylolethane, trimethylolpropane, hexitol, pentitol, A trivalent or higher aliphatic or alicyclic alcohol compound such as glycerin, diglycerin, polyglycerin, pentaerythritol, dipentaerythritol or tetramethylolpropane. In the above, examples of the polyether polyol include ethylene oxide adducts such as ethylene glycol and diethylene glycol 'triethylene glycol, and propylene oxide additions such as propylene glycol, dipropylene glycol, and tripropylene glycol. The product, the ethylene oxide and/or propylene oxide adduct of the above polyol, polytetramethylene glycol or the like. In the above, the polyester polyol may, for example, be an ester-forming derivative such as a polyvalent carboxylic acid or an ester thereof, an anhydride or a halide which is less than a stoichiometric amount thereof, and/or A direct esterification reaction and/or a transesterification reaction of a lactone or a hydroxycarboxylic acid compound obtained by subjecting it to hydrolysis and ring opening. -17-201132801. Examples of the polyvalent carboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decapine acid, and 2- Methyl acepicric acid, 2-methyladipate, 3-methyladipate, 3-methylglutaric acid, 2-methylsuberic acid, 3,8-dimethylsebacic acid, 3 An alicyclic dicarboxylic acid such as an aliphatic dicarboxylic acid such as 7-dimethylsebacic acid, a dimer acid or a hydrogenated dimer acid, such as cyclohexanedicarboxylic acid; phthalic acid or isophthalic acid; An aromatic dicarboxylic acid such as terephthalic acid or naphthalene dicarboxylic acid; a tetracarboxylic acid such as a terpolymer of trimellitic acid 'trimellitic acid' castor oil fatty acid, or the like, such as tetracarboxylic acid such as pyromellitic acid Polycarboxylic acid. Examples of the ester-forming derivative include an acid anhydride of such a polyvalent carboxylic acid, a halide of a polyvalent carboxylic acid such as a chloride or a bromide, and a methyl vinegar, an ethyl ester, a propyl ester or the like of the polybasic citric acid. A lower aliphatic ester such as propyl ester, butyl ester, isobutyl ester or amyl ester. Examples of the lactones include lactones such as γ-caprolactone, δ-caprolactone, ε-caprolactone, γ-valerolactone, and δ-valerolactone. In the above, as the polycarbonate polyol, for example, an esterification reaction between carbonic acid and a fatty acid polyol can be used. Specific examples thereof include 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, diethylene glycol, polyethylene glycol, polypropylene glycol or polybutylene. A reaction product of a diol such as an alcohol with dimethyl carbonate or diphenyl carbonate or phosgene or the like. In the cationic urethane resin (Β), the use of a surfactant as a solubilizing agent or an emulsifier is more disadvantageous because it has an adverse effect on the adhesion or water resistance of the metal material. The surfactant is soap-free or inhibits its use. The weight average molecular weight of the cationic urethane resin (Β) is preferably from -18 to 201132801, from 1,000 to 1,000,000, more preferably from 2,000 to 500,00 (the weight average molecular weight is less than 1, when 〇〇〇, the surface The formation property of the treatment film tends to be insufficient. On the other hand, when the weight average molecular weight exceeds ι, οοο, οοο, the stability of the surface treatment agent tends to decrease. Further, as long as it is a cationic urethane resin (B) If it is compatible, it may be used by mixing an acrylic resin, an vinegar resin, an amine resin, an epoxy resin, a fluorene resin, etc. These resins may also have water solubility or water dispersibility. The ionic property of the resin such as cationic, anionic or nonionic is not particularly limited as long as it is compatible with the surface treatment of the present invention and does not degrade the performance of the formed film. Further, in order to improve the film forming property and form a smooth film of a more uniform sentence, an organic solvent may be used. The mixing ratio of the cationic urethane resin (B) to the sand compound coupling agent (A) (A)/(B) ) by weight ratio It is preferably 1/5 Å or more and 20/1 or less. By such a mixing ratio, excellent adhesion can be obtained between the laminated film and the upper layer. Further, the mixing ratio (A)/(B) is obtained. A more preferable range is 1/20 or more and 1 0/1 or less, and a preferred range is 1 / 1 〇 or more and 5 / 1 or less. When the mixing ratio (A) / (B) is less than 1 / 50, the obtained surface treated film When the hardness is lowered, it is difficult to obtain sufficient processing adhesion, and when the mixing ratio (A)/(B) exceeds 2 〇/1, it is difficult to obtain adhesion to the metal surface of the base metal, and the surface treatment film is interposed. The adhesion of the laminated film is deteriorated. (Zr compound and Ti compound)

Zr化合物（C1)與Ti化合物（C2)具有使所得之表面處 -19- 201132801 理皮膜提商金屬材料的耐蝕性之作用。於本發明的表面處 理劑中，以此Zr化合物（ci)與Ti化合物（C2)當作必要成 分，以其配合比（C1)/(C2)以重量比表示爲1/1〇以上且未 達2/1之範圍者當作必要的構成。於本發明中，藉由以zr 化合物（Cl)與Ti化合物（C2)當作必要成分，與僅含有任 一方的情況相比，可提高與表面處理皮膜上所層合的樹脂 薄膜或壓出層合樹脂對密接性，更且提高金屬表面的耐蝕 性。 作爲Zr化合物（C1)及Ti化合物（C2)，可使用Zr或 Ti的碳酸鹽、氧化物、氫氧化物、硝酸鹽、硫酸鹽、磷 酸鹽、氟化物、氟酸（鹽）、有機酸鹽、有機錯化合物等， 其中較佳爲兼任後述含氟的無機化合物（D)之氟化物、氟 酸（鹽）。具體地，鹼式碳酸銷、碳酸氧銷、碳酸鉻銨、碳 酸氧锆銨（NH4)2[Zr(C03)2(0H)2]、氧化锆（IV)(zirc〇nia)、 氧化鈦（IV)(titania)、硝酸銷、硝酸氧銷Zr0(N03)2、硝酸 鈦、硫酸銷（IV)、硫酸氧锆、硫酸鈦（III)、硫酸鈦（IV)、 硫酸氧鈦Ti0S04、磷酸氧锆、焦磷酸銷、磷酸二氫氧 锆、氟化鉻' 氟化鈦（III)、氟化鈦（IV)、六氟鍩酸 H2ZrF6、六氟鉻酸銨[(NH4)2ZrF6]、六氟鈦酸H2TiF6、六 氟鈦酸銨[(NH4)2TiF6]、醋酸氧鉻、月桂酸鈦、乙醯丙酮 鉻 Zr(OC( = CH2)CH2COCH3)4、二異丙氧基鈦雙丙酮 (C5H702)2Ti[0CH(CH3)2]2 、 乙 醯 丙 酮 鈦The Zr compound (C1) and the Ti compound (C2) have a function of imparting corrosion resistance to the surface of the obtained metal material at -19-201132801. In the surface treatment agent of the present invention, the Zr compound (ci) and the Ti compound (C2) are used as essential components, and the compounding ratio (C1)/(C2) thereof is represented by a weight ratio of 1/1 〇 or more and not A range of up to 2/1 is considered as a necessary component. In the present invention, by using the zr compound (Cl) and the Ti compound (C2) as essential components, the resin film laminated on the surface treated film can be improved or extruded as compared with the case where only one of them is contained. The laminated resin has good adhesion and improves the corrosion resistance of the metal surface. As the Zr compound (C1) and the Ti compound (C2), a carbonate, an oxide, a hydroxide, a nitrate, a sulfate, a phosphate, a fluoride, a hydrofluoric acid, or an organic acid salt of Zr or Ti can be used. The organic compound or the like is preferably a fluoride or a hydrofluoric acid (salt) which is a fluorine-containing inorganic compound (D) to be described later. Specifically, a basic carbonic acid pin, an oxycarbonate pin, an ammonium hydrogen carbonate, an ammonium zirconium carbonate (NH 4 ) 2 [Zr(C03) 2 (0H) 2 ], a zirconium oxide (IV) (zirc〇nia), a titanium oxide ( IV) (titania), nitric acid pin, nitric oxide pin Zr0 (N03) 2, titanium nitrate, sulfuric acid pin (IV), zirconyl sulfate, titanium (III) sulfate, titanium (IV) sulfate, titanyl sulfate Ti0S04, phosphoric acid oxygen Zirconium, pyrophosphoric acid, zirconium dihydrogen phosphate, chromium fluoride 'titanium (III) fluoride, titanium (IV) fluoride, hexafluoroantimonic acid H2ZrF6, ammonium hexafluorochromate [(NH4)2ZrF6], hexafluoro Titanic acid H2TiF6, ammonium hexafluorotitanate [(NH4)2TiF6], chromium oxyacetate, titanium laurate, acetonitrile acetone chromium Zr(OC(=CH2)CH2COCH3)4, diisopropoxy titanium diacetone (C5H702) 2Ti[0CH(CH3)2]2, titanium acetonate

Ti(OC( = CH2)CH2COCH3)3等。此等亦可爲酐或水合物。Zr 化合物及Ti化合物各自的化合物係可單獨使用’也可組 -20- 201132801 合2種以上使用。Ti(OC(=CH2)CH2COCH3)3 and the like. These may also be anhydrides or hydrates. The compound of each of the Zr compound and the Ti compound may be used singly or in combination of two or more kinds of -20-201132801.

Zr化合物（C1)與Ti化合物（C2)的合計配合量 (C = C1+C2)’對於陽離子性胺甲酸乙酯樹脂（B)而言，配合 比（C)/(B)以重量比表示必須爲00以上丨/2以下，較佳 爲1 /5 0以上1 /4以下’更佳爲丨/2 〇以上1 /1 〇以下。配合 比（C)/(B)未達1/100時，耐蝕性不充分，配合比（C)/(B)超 過1/2時’層合薄膜的密接性或表面處理劑的儲存安定性 有降低的傾向。 又’ Z r化合物（C 1)與 T i化合物（C 2 )係配合比 (C1)/(C2)以重量比表示必須爲1/10以上且未達2/1的範 圍。藉由使zr化合物（C1)與Ti化合物（C2)在此範圍內共 存，可提高所得之表面處理皮膜與所層合的樹脂薄膜或壓 出層合樹脂之密接性，更且可提高金屬表面的耐蝕性。再 者，於Zr化合物（C1)與Ti化合物（C2)不在此範圍內共存 時，無法得到作爲層合金屬材料用的基底皮膜之充分特性 (密接性與耐蝕性）。具體地，配合比（C1)/(C2)未達1/10 時，發生密接性的降低或外觀不良，配合比（C1)/(C2)爲 2/ 1以上時，耐蝕性有降低的傾向。 因此，本發明由如後述的實施例及比較例之結果亦可 明知，發現藉由使Zr化合物（C1)與Ti化合物（C2)共存， 而且著眼於兩者的含有比，使在前述特定的範圍內，則可 解決得到高的密接性（包含加工密接性）及高的耐蝕性（尤 其耐強酸性及耐強鹼性）之開頭的問題。 -21 - 201132801 (含氟的無機化合物） 含氟的無機化合物（D)係在液中放出游離氟化物離子 或錯合氟化物離子’達成作爲對於表面處理皮膜的形成對 象之金屬表面的蝕刻劑之任務。含氟的無機化合物（D)係 沒有特別的限定’例如作爲放出游離氟化物離子者，可舉 出氫氟酸、氟化銨、氟化鈉等。又’作爲錯合氟化物，可 舉出六氟矽酸、六氟矽酸鋅、六氟矽酸錳、六氟矽酸鎂、 六氟矽酸鎳、六氟鈦酸、六氟錯酸等。上述化合物係可單 獨1種類使用’也可混合2種類以上使用。 含氟的無機化合物（D)係可作爲單獨的化合物配合， 也可爲上述Zr化合物（C1)或Ti化合物（C2)。於Zr化合物 (C1)或Ti化合物（C2)含有氟時，含有氟的zr化合物（C1) 或Ti化合物（C2)係成爲此處所言之含氟的無機化合物 (D)。再者，此時’ Zr化合物（C1)或Ti化合物（C2)係可與 其以外之含氟的無機化合物同時被含有。 含氟的無機化合物（D)係氟原子對陽離子性胺甲酸乙 酯樹脂（B)的配合量（氟原子）/(B)以重量比表示必須爲 1/1000以上2/1以下’較佳爲1/500以上1/1，更佳爲 1/250以上1/2以下。氟原子/(B)未達1/1000時，密接性 不充分’氟原子/ (B)超過2/1時，水系表面處理劑的安定 性降低。再者，氟原子係原子換算質量。 (其任意成分） 於本發明的表面處理劑中，可更配合作爲任意成分的 -22- 201132801 由V化合物、Μ 〇化合物、W化合物、C 0化合物、A1化 合物、Zn化合物' Ni化合物、Μη化合物、Ce化合物、 Nb化合物、Sn化合物、Mg化合物及Cr化合物所選出的 至少1種之金屬化合物（E)。此等金屬化合物（E)係特別具 有使耐蝕性升高的功效。作爲金屬化合物（E)，可舉出上 述金屬的碳酸鹽、氧化物、氫氧化物、硝酸鹽、硫酸鹽、 磷酸鹽、氟化錯化合物、有機酸鹽、有機錯化合物等。 作爲V化合物' Mo化合物、W化合物' Co化合物、 A1化合物、Zn化合物，具體地可舉出五氧化二釩、偏釩 酸HV〇3、偏釩酸銨、三氯氧化釩VOCl3、三氧化二釩 V203、二氧化釩、硫酸氧釩 V0S04、乙醯丙酮氧釩 VO(OC( = CH2)CH2COCH3)3、三氯化銳 VC13，磷釩鉬酸 Hi5-x[PVi2-xMo〇4。] · nH2〇(6< X< 12，n< 30)、氧化鉬、 鉬酸H2Mo04、鉬酸銨 '偏鉬酸銨、鉬酸鈉、鉬磷酸化合 物（例如鉬磷酸銨（NH4)3[P04Mo12〇36] . 3H20、鉬磷酸鈉 Na3[P04Mo12〇36] · ηΗ20 等）；偏鎢酸 Η 6 [ H 2 W , 2 Ο 4 〇 ]、偏 鎢酸錢（NH4)6[H2W12〇4Q]、 偏鎢酸鈉、仲鎢酸 H〗0[W12O46H1()]、仲鎢酸銨、仲鎢酸鈉，氯化鈷、氯五胺 合鈷氯化物[c〇ci(nh3)5]ci 、六胺合鈷氯化物 [C 〇 (Ν Η 3) 6 ] C i 2、鉻酸鈷、硫酸鈷、硫酸銨鈷、硝酸鈷、氧 化鈷2鋁CoO · Al2〇3、氫氧化鈷、磷酸鈷，硝酸鎳、硫 酸鎳、碳酸鎳、乙醯丙酮鎳Ni(0C( = CH2)CH2C0CH3)3、 氯化鎳、六胺合鎳氯化物[Ni(NH3.)6]C12、氧化鎳、氫氧化 鎳；硝酸鋁、硫酸鋁 '硫酸鉀鋁、硫酸鈉鋁、硫酸銨鋁、 -23- 201132801 磷酸鋁、碳酸鋁' 氧化鋁、氫氧化鋁、碘化鋁；硫酸鋅、 碳酸鋅、氯化鋅、碘化鋅、乙醯丙酮鋅 Zn(OC( = CH2)CH2COCH3)2、磷酸二氫鋅等。 作爲Μη化合物、Ce化合物、Nb化合物、Sn化合 物、Mg化合物及 Cr化合物，具體地可舉出過錳酸 ΗΜη04 、過錳酸鉀、過錳酸鈉、磷酸二氫錳 Μη(Η2Ρ04)2、硝酸錳 Μη(Ν03)2 ' 硫酸錳（II)、（III)或 (IV)、氟化錳（11)或（ΠΙ)、碳酸猛、醋酸鑑（11)或（111)、硫 酸銨錳、乙醯丙酮錳 Mn(OC( = CH2)CH2COCH3)3、碘化 錳、氧化錳、氫氧化錳；氧化铈、醋酸铈Ce(CH3C02)3、 硝酸姉（III)或（IV)、硝酸鈽銨、硫酸铈、氯化鈽，五氧化 二鈮（Nb205)、鈮酸鈉（NaNb〇3)、氟化鈮（NbF5)、六氟鈮 酸銨（NH4)NbF6，氧化錫（IV)、錫酸鈉Na2Sn03、氯化錫 (Π)、氯化錫（IV)、硝酸錫（π)、硝酸錫（IV)、六氟錫酸銨 (NH4)SnF6 ’硝酸鎂、硫酸鎂、碳酸鎂、氫氧化鎂、氟化 鎂、磷酸銨鎂、磷酸氫鎂、氧化鎂，醋酸鉻、硫酸鉻、硝 酸鉻、氟化鉻、磷酸鉻、乙醯丙酮鉻（Cr(C5H702)3)等。 金屬化合物（E)係對於陽離子性胺甲酸乙酯樹脂（B)而 言’配合比（E)/(B)之重量比適當爲1/10〇〇以上1/2以 下’更佳爲1/100以上1/4以下，尤更佳爲1/5〇以上W8 以下。金屬化合物（E)與陽離子性胺甲酸乙酯樹脂（B)的配 合比（E)/(B)以重量比表示未達1/1〇〇〇時，沒有密接性提 商等的效果’另一方面’超過1/2時，藥劑的儲存安定性 顯著降低》再者，配合比（E)/(B)的r (E)」係金屬化合物 -24- 201132801 (E)的原子換算質量。 又’於本發明的表面處理劑中，視需要亦可含有矽石 成分。例如，作爲矽石成分，可使用氣相矽石、膠態矽 石、疏水性矽石等。藉由使含有矽石成分，可作爲表面處 理劑的消泡劑而作用’同時可造成能提高與層合板的密接 性之較佳效果。 如此的矽石對於陽離子性胺甲酸乙酯樹脂（B)而言， 配合比（矽石）/(B)的重量比適當爲1/100以上1/5以下， 更佳爲1/50以上1/10以下。矽石與陽離子性胺甲酸乙酯 樹脂（B)的配合比（矽石）/(B)以重量比表示未達1/100時， 在密接性等沒有效果，另一方面，超過1/5時，皮膜變.脆 而密接性顯著降低。再者，配合比（矽石）/(B)的「（矽 石）」係氧化矽的原子換算質量。 於本發明的表面處理劑中，在不損害水系表面處理劑 的液安定性及皮膜性能之範圍，亦可更配合用於在被塗面 上得到均勻的皮膜之稱爲潤濕性改良劑之界面活性劑或增 黏劑等當作任意成分。 (其它構成） 本發明的表面處理劑所用的介質通常爲水，以改善所 得之表面處理皮膜的乾燥性等爲目的，亦可倂用少量（例 如水性介質全體的1 0容量％以下）的醇、酮、溶纖劑系的 水溶性有機溶劑。 本發明的表面處理劑之p Η係沒有特別的限制，較佳 -25- 201132801 爲3〜12的範圍，更佳爲4〜8的範圍。以鋁或其合金當 作對象材料時，pH低於3時，蝕刻變過多，無法充分發 揮作爲表面處理劑的機能，而且液安定性亦有降低的傾 向。PH超過12時，鋁或其合金的溶解速度增加，而且對 矽烷偶合劑（A)的儲存安定性亦出現不利影響的傾向。於 必須調整pH時，亦可添加氨、二甲胺及三乙胺等的鹼成 分、或醋酸及磷酸等的酸性成分。 關於本發明的表面處理劑中的合計固體成分濃度之下 限’只要能達成本發明的效果，則沒有特別的限制，從液 安定性的觀點來看，上限係受限制。本發明的表面處理劑 之合計固體成分濃度較佳爲調整至 0.1〜40質量％的範 圍，更佳爲調整至1〜30質量％的範圍，尤更佳爲調整至 5〜25質量％的範圍。 本發明的表面處理劑係藉由將矽烷偶合劑（A)、陽離 子性胺甲酸乙酯樹脂（B)、Zr化合物（Cl)、Ti化合物 (C2)、含氟的無機化合物（D)及視情況的金屬化合物（E)加 到分散介質的水中’攪拌而製造。其添加順序係沒有特別 的限制。 [表面處理方法] 其次，說明採用本發明的表面處理劑之表面處理方 法。作爲可採用本發明的表面處理劑之金屬材料，可舉出 以鋁箔、鋁合金箔、不銹鋼箔等當作合適的材料。如此的 金屬材料之厚度係沒有特別的限定，對於稱爲箔、薄片、 -26- 201132801 板者雖然可適用，但於本發明中，由於在以表面處理劑形 成表面處理皮膜後，進行層合加工，然後進行深拉加工、 減薄拉延加工或張拉加工等，而加工成鋰離子蓄電池的外 裝材等，故使用於如此用途的厚者爲較佳。例如，較佳可 採用厚度0.01〜2 mm左右的箔當作金屬材料。 於使用表面處理劑的表面處理方法中，先前的前處理 步驟係沒有特別的限制，通常在進行正式處理之前，爲了 去掉金屬材料上所附著的油分或污垢，用鹼脫脂劑或酸性 脫脂劑來洗淨，或進行熱水洗、溶劑洗淨等。然後，按照 需要，進行酸或鹼等所致的表面調整。於進行此等處理 後，較佳爲進行水洗，以使得洗淨劑儘可能不殘留在金屬 材料的表面。 於表面處理劑對金屬材料的塗佈中，可以採用以往塗 佈方法，例如輥塗、簾幕塗覆、空氣噴灑、無空氣噴灑、 浸漬、硬塗、刷毛塗抹等的通常塗佈方法。表面處理劑的 溫度係沒有特別的限制，本處理劑的溶劑由於是水爲主體 的水系處理劑，其溫度較佳爲 〇〜60°c，更佳爲 5〜 4 0。。。 於以表面處理劑處理而形成表面處理皮膜後的乾燥步 驟中，不需要促進陽離子性胺甲酸乙酯樹脂（B)的硬化而 僅進行附著水的去除時，未必需要熱，可僅藉由風乾或吹 氣等來去除水。然而，爲了促進陽離子性胺甲酸乙酯樹脂 (B)的硬化，或爲了使所形成的表面處理皮膜進行熱軟化 而提高在基底金屬材料上的均勻被覆效果，較佳'爲進行加 -27- 201132801 熱處理。該加熱處理溫度較佳爲50〜250°C，更佳爲60〜 22 0°C » [表面處理皮膜] 以上述表面處理方法所形成的表面處理皮膜，係其附 著量以乾燥皮膜重量表示較佳爲0.01〜lg/m2的範圍。附 著量的更佳範圍爲0.01〜0.5 g/m2的範圍，尤佳爲〇.〇3〜 0.25g/m2。附著量未達0.005g/m2時，由於皮膜量少，耐 蝕性變不充分。又，附著量超過1 g/m2時，反而密接性變 差，同時在成本面亦不利。表面處理皮膜亦可按照目的對 金屬材料表面的單面進行處理。 [層合金屬材料的製造方法] 其次，說明本發明的層合金屬材料之製造方法。層合 金屬材料係藉由在金屬材料的表面上，使用本發明的表面 處理劑，以上述表面處理方法形成表面處理皮膜，更且於 該表面處理皮膜上層合樹脂薄膜（亦稱爲層合薄膜）或壓出 層,合樹脂而製造。樹脂薄膜係按照目的可僅形成在表面處 理金屬材料的單面，也可形成在兩面。 樹脂薄膜的層合係大致區分爲以下兩種：（i)於基底皮 膜的表面處理皮膜之形成後，直接層合樹脂薄膜之方法， (ii)於基底皮膜的表面處理皮膜之形成後，塗佈形成稱爲 底漆的黏著改良劑（聚酯系接著劑、聚醚系接著劑等），然 後將樹脂薄膜層合之方法。可依照所要求的品質和成本來 -28- 201132801 選擇任一者。再者，於層合中，亦可使用將樹脂薄膜層合 之方法與將熔融狀態的樹脂層合之方法（一般稱爲「壓出 層合」，將該樹脂稱爲「壓出層合樹脂」）的任一方法。 所層合的樹脂薄膜或壓出層合樹脂之樹脂材料係沒有特別 的限制，較佳可舉出聚酯系樹脂、聚乙烯系樹脂、聚丙烯 系樹脂或此等的改性樹脂。 於本發明的層合金屬材料之製造方法中，採用上述本 發明的表面處理劑。該表面處理劑係與層合薄膜的密接性 (包含加工密接性）及耐蝕性（尤其耐強酸性、耐強鹼性）優 異，用於製作層合金屬材料、層合金屬容器或層合金屬包 裝材的特佳表面處理劑。再者，該表面處理劑係不含有六 價鉻，也考慮近年之環境問題的完全無鉻，亦具有環境負 荷少的優點。根據以上，本發明的層合金屬材料之製造方 法’係達成可提供密接性、耐蝕性優異的金屬容器或包裝 材當作層合金屬材料之優異效果。 實施例 以下，舉出實施例與比較例來更具體說明本發明。本 發明係不受以下的實施例所限定。再者，以下的「份」係 重量份（與質量份同義）。 [實施例1〜3 0、比較例1〜2 1 ] (供試材及前處理）Total amount of Zr compound (C1) and Ti compound (C2) (C = C1 + C2)' For cationic urethane resin (B), the mixing ratio (C) / (B) is expressed by weight ratio It must be 00 or more 丨/2 or less, preferably 1 /5 0 or more and 1 / 4 or less 'better 丨/2 〇 or more 1 /1 〇 or less. When the mixing ratio (C)/(B) is less than 1/100, the corrosion resistance is insufficient, and when the mixing ratio (C)/(B) exceeds 1/2, the adhesion of the laminated film or the storage stability of the surface treatment agent is satisfied. There is a tendency to decrease. Further, the compounding ratio (C1)/(C2) of the compound of the Zr compound (C1) and the compound (C2) of the formula (C2) must be in the range of 1/10 or more and less than 2/1 by weight. By allowing the zr compound (C1) and the Ti compound (C2) to coexist in this range, the adhesion between the obtained surface treated film and the laminated resin film or the extruded laminate resin can be improved, and the metal surface can be improved. Corrosion resistance. Further, when the Zr compound (C1) and the Ti compound (C2) do not coexist in this range, sufficient characteristics (adhesiveness and corrosion resistance) of the base film for a laminated metal material cannot be obtained. Specifically, when the blend ratio (C1)/(C2) is less than 1/10, the adhesion is lowered or the appearance is poor, and when the blend ratio (C1)/(C2) is 2/1 or more, the corrosion resistance tends to decrease. . Therefore, the present invention is also known from the results of the examples and comparative examples described later, and it has been found that by coexisting the Zr compound (C1) with the Ti compound (C2), and focusing on the content ratio of the two, the specific In the range, the problem of obtaining high adhesion (including processing adhesion) and high corrosion resistance (especially resistance to strong acidity and strong alkali resistance) can be solved. -21 - 201132801 (Fluorinated inorganic compound) The fluorine-containing inorganic compound (D) releases free fluoride ions or mis-fluoride ions in the liquid to achieve an etchant as a metal surface for forming a surface-treated film. The task. The fluorine-containing inorganic compound (D) is not particularly limited. For example, as the release of the free fluoride ion, hydrofluoric acid, ammonium fluoride, sodium fluoride or the like can be mentioned. Further, examples of the mis-fluoride include hexafluoroantimonic acid, zinc hexafluoroantimonate, manganese hexafluoroantimonate, magnesium hexafluoroantimonate, nickel hexafluoroantimonate, hexafluorotitanate, and hexafluoroanthoic acid. . The above compounds may be used singly or in combination of two or more kinds. The fluorine-containing inorganic compound (D) may be compounded as a single compound, or may be the above-mentioned Zr compound (C1) or Ti compound (C2). When the Zr compound (C1) or the Ti compound (C2) contains fluorine, the fluorine-containing zr compound (C1) or the Ti compound (C2) is a fluorine-containing inorganic compound (D) as described herein. Further, at this time, the 'Zr compound (C1) or the Ti compound (C2) may be contained together with the fluorine-containing inorganic compound other than the above. The amount of the fluorine-containing inorganic compound (D)-based fluorine atom to the cationic urethane resin (B) (fluorine atom) / (B) is preferably 1/1000 or more and 2/1 or less by weight. It is 1/500 or more and 1/1, more preferably 1/250 or more and 1/2 or less. When the fluorine atom/(B) is less than 1/1000, the adhesion is insufficient. When the fluorine atom/(B) exceeds 2/1, the stability of the aqueous surface treatment agent is lowered. Further, the fluorine atom is an atom converted mass. (Optional component thereof) In the surface treatment agent of the present invention, it can be further blended as an optional component -22-201132801 from a V compound, an anthraquinone compound, a W compound, a C 0 compound, an A1 compound, a Zn compound 'Ni compound, Μη At least one metal compound (E) selected from the compound, the Ce compound, the Nb compound, the Sn compound, the Mg compound, and the Cr compound. These metal compounds (E) particularly have an effect of increasing corrosion resistance. The metal compound (E) may, for example, be a carbonate, an oxide, a hydroxide, a nitrate, a sulfate, a phosphate, a fluorinated compound, an organic acid salt or an organic compound of the above metal. Specific examples of the V compound 'Mo compound, W compound 'Co compound, A1 compound, and Zn compound include vanadium pentoxide, metavanadic acid HV〇3, ammonium metavanadate, vanadium oxychloride VOCl3, and trioxide. Vanadium V203, vanadium dioxide, vanadyl sulfate V0S04, acetonitrile acetone vanadium VO (OC(=CH2)CH2COCH3)3, trichloropurine VC13, phosphorus vanadium molybdate Hi5-x [PVi2-xMo〇4. nH2〇(6<X<12,n< 30), molybdenum oxide, molybdate H2Mo04, ammonium molybdate' ammonium metamolybdate, sodium molybdate, molybdenum phosphate compound (eg ammonium molybdate (NH4) 3 [P04Mo12] 〇36] . 3H20, sodium molybdate phosphate Na3 [P04Mo12〇36] · ηΗ20, etc.; bismuth metatungstate 6 [ H 2 W , 2 Ο 4 〇], tungstic acid (NH4) 6 [H2W12 〇 4Q], Sodium metatungstate, paratungstic acid H 0 [W12O46H1 ()], ammonium paratungstate, sodium paratungstate, cobalt chloride, chloropentamine cobalt chloride [c〇ci (nh3) 5] ci, hexamine cobalt Chloride [C 〇(Ν Η 3) 6 ] C i 2, cobalt chromate, cobalt sulfate, cobalt ammonium sulfate, cobalt nitrate, cobalt oxide 2 aluminum CoO · Al2〇3, cobalt hydroxide, cobalt phosphate, nickel nitrate, Nickel sulfate, nickel carbonate, acetonitrile acetone nickel Ni(0C(=CH2)CH2C0CH3)3, nickel chloride, hexamine nickel chloride [Ni(NH3.)6]C12, nickel oxide, nickel hydroxide; aluminum nitrate , aluminum sulfate 'potassium aluminum sulfate, aluminum sulfate aluminum, aluminum ammonium sulfate, -23- 201132801 aluminum phosphate, aluminum carbonate 'alumina, aluminum hydroxide, aluminum iodide; zinc sulfate, zinc carbonate, zinc chloride, zinc iodide , acetonitrile zinc Zn (OC (= CH2) CH2COCH3) 2, phosphoric acid Hydrogen zinc. Specific examples of the Μη compound, the Ce compound, the Nb compound, the Sn compound, the Mg compound, and the Cr compound include permanganic acid ΗΜη04, potassium permanganate, sodium permanganate, manganese dihydrogen phosphate Η(Η2Ρ04) 2, and nitric acid. Manganese Μη(Ν03)2 'Manganese (II), (III) or (IV), manganese fluoride (11) or (ΠΙ), carbonic acid, acetic acid (11) or (111), ammonium manganese sulfate, B醯Acetone manganese Mn(OC(=CH2)CH2COCH3)3, manganese iodide, manganese oxide, manganese hydroxide; cerium oxide, cerium acetate Ce(CH3C02)3, cerium (III) nitrate or (IV), ammonium cerium nitrate, Barium sulphate, barium chloride, bismuth pentoxide (Nb205), sodium citrate (NaNb〇3), cesium fluoride (NbF5), ammonium hexafluoroantimonate (NH4) NbF6, tin (IV) oxide, sodium stannate Na2Sn03, tin chloride (antimony), tin (IV) chloride, tin (π) nitrate, tin (IV) nitrate, ammonium hexafluorostannate (NH4)SnF6 'magnesium nitrate, magnesium sulfate, magnesium carbonate, magnesium hydroxide , magnesium fluoride, magnesium ammonium phosphate, magnesium hydrogen phosphate, magnesium oxide, chromium acetate, chromium sulfate, chromium nitrate, chromium fluoride, chromium phosphate, chromium acetonitrile (Cr (C5H702) 3). The metal compound (E) is preferably a weight ratio of the compounding ratio (E)/(B) to the cationic urethane resin (B) of 1/10 Å or more and 1/2 or less. More than 100 1/4 or less, and more preferably 1/5 〇 or more and W8 or less. When the compounding ratio (E)/(B) of the metal compound (E) and the cationic urethane resin (B) is less than 1/1 Torr by weight ratio, there is no effect of adhesion and the like. On the one hand, when the amount exceeds 1/2, the storage stability of the drug is remarkably lowered. Further, the atomic conversion mass of the metal compound-24-201132801 (E) of the ratio (E)/(B) is mixed. Further, in the surface treatment agent of the present invention, a vermiculite component may be contained as needed. For example, as the vermiculite component, gas phase vermiculite, colloidal vermiculite, hydrophobic vermiculite or the like can be used. By containing the vermiculite component, it acts as a defoaming agent for the surface treatment agent, and at the same time, it can produce a better effect of improving the adhesion to the laminate. In the case of the cationic urethane resin (B), the weight ratio of the blend ratio (meteorite)/(B) is suitably 1/100 or more and 1/5 or less, more preferably 1/50 or more. /10 or less. When the ratio of the vermiculite to the cationic urethane resin (B) (the vermiculite) / (B) is less than 1/100 by weight ratio, there is no effect on the adhesion, and the like, on the other hand, more than 1/5. At the time, the film becomes brittle and the adhesion is remarkably lowered. In addition, the "(矽石)" of the mixing ratio (矽石) / (B) is the atomic conversion mass of cerium oxide. In the surface treatment agent of the present invention, the range of the liquid stability and the film properties of the aqueous surface treatment agent is not impaired, and the wettability improver may be further blended to obtain a uniform film on the coated surface. A surfactant or a tackifier is used as an optional component. (Other configuration) The medium used for the surface treatment agent of the present invention is usually water, and for the purpose of improving the drying property of the obtained surface treatment film, etc., a small amount (for example, 10% by volume or less of the entire aqueous medium) may be used. , a ketone, a cellosolve-based water-soluble organic solvent. The p-type system of the surface treating agent of the present invention is not particularly limited, and preferably -25 to 201132801 is in the range of 3 to 12, more preferably in the range of 4 to 8. When aluminum or an alloy thereof is used as a target material, when the pH is less than 3, the etching becomes excessive, the function as a surface treatment agent is not sufficiently exhibited, and the liquid stability is also lowered. When the pH exceeds 12, the dissolution rate of aluminum or its alloy increases, and the storage stability of the decane coupling agent (A) tends to be adversely affected. When it is necessary to adjust the pH, an alkali component such as ammonia, dimethylamine or triethylamine or an acidic component such as acetic acid or phosphoric acid may be added. The lower limit of the total solid content concentration in the surface treatment agent of the present invention is not particularly limited as long as the effect of the present invention can be attained, and the upper limit is limited from the viewpoint of liquid stability. The total solid content concentration of the surface treatment agent of the present invention is preferably adjusted to a range of 0.1 to 40% by mass, more preferably 1 to 30% by mass, even more preferably 5 to 25% by mass. . The surface treatment agent of the present invention is composed of a decane coupling agent (A), a cationic urethane resin (B), a Zr compound (Cl), a Ti compound (C2), a fluorine-containing inorganic compound (D), and In the case where the metal compound (E) is added to the water of the dispersion medium, it is produced by stirring. The order of addition thereof is not particularly limited. [Surface treatment method] Next, a surface treatment method using the surface treatment agent of the present invention will be described. As the metal material to which the surface treatment agent of the present invention can be used, an aluminum foil, an aluminum alloy foil, a stainless steel foil or the like can be used as a suitable material. The thickness of such a metal material is not particularly limited, and may be applied to a plate called a foil, a sheet, or a -26-201132801 plate. However, in the present invention, since the surface treatment film is formed by a surface treatment agent, lamination is performed. It is processed, and then subjected to deep drawing, thin drawing, or drawing processing, and processed into an exterior material of a lithium ion secondary battery, etc., so that it is preferable to use it for such a thick use. For example, a foil having a thickness of about 0.01 to 2 mm can be preferably used as the metal material. In the surface treatment method using the surface treatment agent, the previous pretreatment step is not particularly limited, and usually, before the formal treatment, in order to remove the oil or dirt adhering to the metal material, an alkali degreasing agent or an acidic degreaser is used. Wash, or wash with hot water, wash with solvents, etc. Then, surface adjustment by acid or alkali is performed as needed. After such treatment, it is preferred to carry out water washing so that the detergent does not remain on the surface of the metal material as much as possible. In the coating of the metal material by the surface treating agent, a conventional coating method such as roll coating, curtain coating, air spraying, airless spraying, dipping, hard coating, brush application, or the like can be employed. The temperature of the surface treatment agent is not particularly limited, and the solvent of the treatment agent is preferably a water-based treatment agent, and the temperature thereof is preferably 〇60 ° C, more preferably 5 to 40 °. . . In the drying step after the surface treatment film is formed by the surface treatment agent, it is not necessary to heat the cationic urethane resin (B) to promote the curing of the cationic urethane resin (B), and heat is not required, and it may be dried only by air drying. Or blow air to remove water. However, in order to promote the hardening of the cationic urethane resin (B), or to improve the uniform coating effect on the base metal material in order to thermally soften the formed surface-treated film, it is preferred to carry out the addition of -27- 201132801 Heat treatment. The heat treatment temperature is preferably from 50 to 250 ° C, more preferably from 60 to 22 ° C » [Surface treatment film] The surface treatment film formed by the above surface treatment method is expressed by the weight of the dry film. Preferably, it is in the range of 0.01 to lg/m2. The attached amount is more preferably in the range of 0.01 to 0.5 g/m2, and particularly preferably 〇.〇3 to 0.25 g/m2. When the amount of adhesion is less than 0.005 g/m2, the amount of the film is small, and the corrosion resistance is insufficient. Further, when the adhesion amount exceeds 1 g/m2, the adhesion is deteriorated, and the cost is also disadvantageous. The surface treatment film can also treat one side of the surface of the metal material according to the purpose. [Method for Producing Laminated Metal Material] Next, a method for producing the laminated metal material of the present invention will be described. The laminated metal material is formed by the surface treatment method on the surface of the metal material by using the surface treatment agent of the present invention, and the surface treatment film is laminated on the surface treatment film (also referred to as a laminate film). Or the extruded layer is made of resin. The resin film may be formed only on one surface of the surface treatment metal material according to the purpose, or may be formed on both sides. The lamination system of the resin film is roughly classified into two types: (i) a method of directly laminating a resin film after formation of a surface treatment film of the base film, and (ii) coating of a surface treatment film of the base film. The cloth is formed by a method of forming an adhesive film (a polyester-based adhesive, a polyether-based adhesive, etc.) called a primer, and then laminating the resin film. Depending on the quality and cost required -28- 201132801 Choose either. Further, in the lamination, a method of laminating a resin film and a method of laminating a resin in a molten state (generally referred to as "extrusion lamination") may be used, and the resin may be referred to as "extrusion lamination resin". Any of the methods. The resin film to be laminated or the resin material from which the laminated resin is extruded is not particularly limited, and preferably a polyester resin, a polyethylene resin, a polypropylene resin or a modified resin thereof. In the method for producing a laminated metal material of the present invention, the above surface treatment agent of the present invention is used. The surface treatment agent is excellent in adhesion to a laminated film (including process adhesion) and corrosion resistance (especially strong acid resistance and strong alkali resistance), and is used for producing a laminated metal material, a laminated metal container or a laminated metal. A special surface treatment for packaging materials. Further, the surface treatment agent does not contain hexavalent chromium, and it is also considered to be completely chromium-free in consideration of environmental problems in recent years, and has an advantage of less environmental load. According to the above, the method for producing a laminated metal material according to the present invention achieves an excellent effect of providing a metal container or a packaging material excellent in adhesion and corrosion resistance as a laminated metal material. EXAMPLES Hereinafter, the present invention will be more specifically described by way of examples and comparative examples. The present invention is not limited by the following examples. In addition, the following "parts" are parts by weight (synonymous with the mass parts). [Examples 1 to 30, Comparative Examples 1 to 2 1] (for test materials and pretreatment)

作爲供試材，使用市售的銘合金板（銘-鑑合金板：JIS -29- 201132801 A 3004，板厚：0.3mm，板尺寸：200mmx300mm)。藉由 對於此鋁合金板，在75°C噴灑市售的酸性洗淨劑（Palclean 500:日本PARKERIZING株式會社製）的8%水溶液20秒 而洗淨，接著水洗而潔淨其表面。另一方面，作爲另一供 試材，使用市售的不銹鋼板（JIS SUS304，板厚：〇.3mm， 板尺寸：200mmx300mm)。藉由對於此不銹鋼板，在60°C 噴灑市售的洗淨劑（Finecleaner 43 28 ： 日本 PARKERIZING株式會社製）的2 %水溶液2 0秒而洗淨，接 著水洗而潔淨其表面。 (表面處理及表面處理劑） 於前處理後的供試材之表面（單面）上，使用以表1中 所示配合而形成的表面處理劑，以輥塗機來塗佈而使得乾 燥皮膜重量（附著量）成爲〇.lg/m2，以熱風乾燥爐進行乾 燥而使得供試材的到達溫度成爲8 0 °C。 表1中，Ν ο · 1〜3 0係本發明的表面處理劑（實施例1 〜30) ’ No.3 1〜47係本發明的範圍外之表面處理劑（比較 例1〜17)。構成No.15的矽烷偶合劑（A)之A1的胺基與 A3的環氧丙基之當量比爲5:1。又，表}中，（A)/(B)係 矽烷偶合劑（A)與陽離子性胺甲酸乙酯樹脂（B)的配合質量 比’（C1)/(C2)係Zr化合物（C1)與Ti化合物（C2)的配合質 量比’（C)/(B)係Zr化合物及Ti化合物的合計與陽離子性 胺甲酸乙酯樹脂（B)之配合質量比，（E)/(B)係構成金屬化 合物的金屬種（E)(原子換算重量）與陽離子性胺甲酸乙酯樹 -30- 201132801 脂（B)之配合質量比，氟/(B)係構成含氟的無機化合物（D) 的氟（原子換算重量）與陽離子性胺甲酸乙酯樹脂（B)之配 合質量比。以下顯示表1中的各成分之內容。 〈矽烷偶合劑（A)&gt; A1 : γ-胺基丙基三乙氧基矽烷 Α2 ·· 2-胺基乙基-3-胺基丙基三甲氧基矽烷 A3: γ-環氧丙氧基丙基三甲氧基矽烷 Α4 : γ-巯基丙基三甲氧基矽烷 &lt;陽離子性水系聚胺甲酸乙酯樹脂（Β) &gt; Β1:陽離子性聚醚系聚胺甲酸乙酯水分散體 Β2:陽離子性聚酯系聚胺甲酸乙酯水分散體 Β3:陽離子性聚碳酸酯系聚胺甲酸乙酯水分散體 Β4: Superflex 410(陰離子性聚碳酸酯系聚胺甲酸乙 酯水分散體，第一工業製藥株式會社製） B5: Primal K-3(聚丙烯酸樹脂，ROHM AND HAAS 公 司製） 上述中’ Bl、B2及B3係藉由以下的手法調整。 『B1:陽離子性聚醚系聚胺甲酸乙酯樹脂（水分散 體）』 將150質量份的聚醚多元醇（合成成分：聚丁二醇及 乙二醇，分子量1 500)、6質量份的三羥甲基丙烷、24質 量份的N-甲基-Ν,Ν-二乙醇胺、94質量份的異佛爾酮二異 氰酸酯基及135質量份的甲基乙基酮分別取入反應容器 中’邊保持在70〜75 °C邊使反應，於所形成的胺甲酸乙酯 •31 - 201132801 預聚物中，添加15質量份的硫酸二甲酯，於50〜60 °C使 反應3 0〜6 0分鐘，而得到陽離子性胺甲酸乙酯預聚物。 再者，將576質量份的水加到前述陽離子性胺甲酸乙酯預 聚物中，使均勻乳化後，回收甲基乙基酮，而得到陽離子 性的水溶性聚胺甲酸乙酯樹脂（B 1)。 『B2:陽離子性聚酯系聚胺甲酸乙酯樹脂（水分散 體）』 將135質量份的聚酯多元醇（合成成分：間苯二甲 酸、己二酸及1,6-己二醇、乙二醇、分子量170 0)、5質 量份的三羥甲基丙烷、22質量份的N-甲基-N，N-二乙醇 胺、86質量份的異佛爾酮二異氰酸酯及120質量份的甲 基乙基酮分別取入反應容器中，邊保持在70〜75 °C邊使反 應，於所形成的胺甲酸乙酯預聚物中，添加1 7質量份的 硫酸二甲酯，於50〜60°C使反應30〜60分鐘，而得到陽 離子性胺甲酸乙酯預聚物。再者，將615質量份的水加到 前述陽離子性胺甲酸乙酯預聚物中，使均勻乳化後，回收 甲基乙基酮，而得到陽離子性的水溶性聚胺甲酸乙酯樹脂 (B2)。 『B3:陽離子性聚碳酸酯系聚胺甲酸乙酯樹脂（水分 散體）』 將130質量份的聚碳酸酯多元醇（合成成分：1，6-己烷 碳酸酯二醇、乙二醇、分子量2000)、4質量份的三羥甲 基丙烷、21質量份的N-甲基-N，N-二乙醇胺、75質量份 的異佛爾酮二異氰酸酯及115質量份的甲基乙基酮分別取 -32- 201132801 入反應容器中，邊保持在70〜75 °C邊使反應’於所形成的 胺甲酸乙酯預聚物中，添加22質量份的硫酸二甲酯，於 50〜60 °C使反應30〜60分鐘，而得到陽離子性胺甲酸乙 酯預聚物。再者，將6 33質量份的水加到前述陽離子性胺 甲酸乙酯預聚物中，使均勻乳化後，回收甲基乙基酮，而 得到陽離子性的水溶性聚胺甲酸乙酯樹脂（B3)。 &lt; Zr化合物（C1) &gt; C 1 1 :六氟鉻酸 c 1 2 :六氟鉻酸銨 C13 :乙醯丙酮锆 C14 :碳酸鉻銨 C 1 5 :氧化锆溶膠 &lt; Ti化合物（C2)&gt; C 2 1 :乙醯丙酮鈦 C22 :硫酸氧鈦 C23 :六氟鈦酸 C24 :六氟鈦酸銨 C25 :月桂酸鈦 〈含氟的無機化合物（D)&gt; D 1 :氟化銨 D2 :氫氟酸 D3 :六氟矽酸 〈金屬化合物（E)&gt; E1 :乙醯丙酮氧釩 -33- 201132801 E 2 :鉬酸銨 E 3 :偏鶴酸錶 E4 :硝酸鈷 E5 :氫氧化鋁 E6 :硝酸鈽銨 E7 :碳酸鎳 &lt;矽石&gt; 使用膠態矽石（曰產化學工業株式會社製，商品名：As the test material, a commercially available alloy plate (Ming-Ming alloy plate: JIS -29-201132801 A 3004, plate thickness: 0.3 mm, plate size: 200 mm x 300 mm) was used. This aluminum alloy plate was washed with an 8% aqueous solution of a commercially available acidic detergent (Palclean 500: manufactured by Japan PARKERIZING Co., Ltd.) at 75 ° C for 20 seconds, and then washed with water to clean the surface. On the other hand, as another test material, a commercially available stainless steel plate (JIS SUS304, plate thickness: 〇. 3 mm, plate size: 200 mm x 300 mm) was used. This stainless steel plate was washed with a 2% aqueous solution of a commercially available detergent (Finecleaner 43 28: manufactured by Nippon Parker Izing Co., Ltd.) for 20 seconds at 60 ° C, and washed with water to clean the surface. (Surface treatment and surface treatment agent) On the surface (single side) of the test material after the pretreatment, a surface treatment agent formed by blending as shown in Table 1 was used, and coating was performed by a roll coater to dry the film. The weight (adhesion amount) was 〇.lg/m2, and it was dried in a hot air drying oven so that the reaching temperature of the test material became 80 °C. In Table 1, the surface treatment agent of the present invention (Examples 1 to 30) ’ No. 3 1 to 47 is a surface treatment agent outside the scope of the present invention (Comparative Examples 1 to 17). The equivalent ratio of the amine group of A1 of the decane coupling agent (A) constituting No. 15 to the epoxy propyl group of A3 was 5:1. Further, in the table, the mass ratio of the (A)/(B)-based decane coupling agent (A) to the cationic urethane resin (B) is '(C1)/(C2)-based Zr compound (C1) and The compounding mass ratio of the Ti compound (C2) to the total mass ratio of the (C)/(B) Zr compound and the Ti compound to the cationic urethane resin (B), and the composition of (E)/(B) The metal compound (E) (atomic weight) of the metal compound and the cationic urethane tree -30-201132801 lipid (B), the fluorine / (B) constitutes the fluorine-containing inorganic compound (D) The mass ratio of fluorine (atomic weight) to cationic urethane resin (B). The contents of the respective components in Table 1 are shown below. <decane coupling agent (A) &gt; A1 : γ-aminopropyltriethoxydecane Α2 · 2-aminoethyl-3-aminopropyltrimethoxydecane A3: γ-glycidoxy Propyltrimethoxydecane Α4 : γ-mercaptopropyltrimethoxydecane &lt;cationic water-based polyurethane resin (Β) &gt; Β1: cationic polyether-based polyurethane aqueous dispersion Β2 : cationic polyester-based polyurethane aqueous dispersion Β 3 : cationic polycarbonate-based polyurethane aqueous dispersion Β 4 : Superflex 410 (anionic polycarbonate-based polyurethane aqueous dispersion, B1: Primal K-3 (polyacrylic resin, manufactured by ROHM AND HAAS) The above-mentioned 'Bl, B2, and B3 are adjusted by the following methods. "B1: cationic polyether-based polyurethane resin (aqueous dispersion)" 150 parts by mass of a polyether polyol (synthetic component: polytetramethylene glycol and ethylene glycol, molecular weight 1 500), 6 parts by mass Trimethylolpropane, 24 parts by mass of N-methyl-hydrazine, hydrazine-diethanolamine, 94 parts by mass of isophorone diisocyanate group, and 135 parts by mass of methyl ethyl ketone are respectively taken into the reaction vessel. ' While maintaining the reaction at 70 to 75 ° C, 15 parts by mass of dimethyl sulfate was added to the formed urethane ethyl ester 31 - 201132801 prepolymer, and the reaction was carried out at 50 to 60 ° C. ~60 minutes, and a cationic urethane prepolymer is obtained. Further, 576 parts by mass of water was added to the cationic urethane prepolymer to uniformly emulsifie, and then methyl ethyl ketone was recovered to obtain a cationic water-soluble polyurethane resin (B). 1). "B2: cationic polyester-based polyurethane resin (aqueous dispersion)" 135 parts by mass of a polyester polyol (synthetic components: isophthalic acid, adipic acid, and 1,6-hexanediol, Ethylene glycol, molecular weight 170 0), 5 parts by mass of trimethylolpropane, 22 parts by mass of N-methyl-N,N-diethanolamine, 86 parts by mass of isophorone diisocyanate, and 120 parts by mass The methyl ethyl ketone was separately taken into the reaction vessel, and the reaction was carried out while maintaining the temperature at 70 to 75 ° C. In the formed urethane prepolymer, 17 parts by mass of dimethyl sulfate was added thereto at 50 The reaction was allowed to proceed at ~60 ° C for 30 to 60 minutes to obtain a cationic urethane prepolymer. Further, 615 parts by mass of water was added to the cationic urethane prepolymer to uniformly emulsifie, and then methyl ethyl ketone was recovered to obtain a cationic water-soluble polyurethane resin (B2). ). "B3: cationic polycarbonate-based polyurethane resin (aqueous dispersion)" 130 parts by mass of a polycarbonate polyol (synthetic component: 1,6-hexane carbonate diol, ethylene glycol, Molecular weight 2000), 4 parts by mass of trimethylolpropane, 21 parts by mass of N-methyl-N,N-diethanolamine, 75 parts by mass of isophorone diisocyanate, and 115 parts by mass of methyl ethyl ketone Take -32-201132801 into the reaction vessel, and keep the reaction at 70~75 °C to make the reaction into the formed urethane prepolymer, add 22 parts by mass of dimethyl sulfate, 50~60 The reaction was allowed to proceed for 30 to 60 minutes at ° C to obtain a cationic urethane prepolymer. Further, 6 33 parts by mass of water was added to the cationic urethane prepolymer to uniformly emulsifie, and then methyl ethyl ketone was recovered to obtain a cationic water-soluble polyurethane resin ( B3). &lt; Zr compound (C1) &gt; C 1 1 : hexafluorochromic acid c 1 2 : ammonium hexafluorochromate C13 : acetonitrile acetone zirconium C14 : ammonium chromium carbonate C 1 5 : zirconia sol &lt; Ti compound (C2 C 2 1 : Acetylacetone Titanium C22 : Titanyl sulfate Titanium C23 : Hexafluorotitanate C24 : Ammonium hexafluorotitanate C25 : Titanium laurate <Fluorinated inorganic compound (D)> D 1 : Fluorinated Ammonium D2: hydrofluoric acid D3: hexafluoroantimonic acid <metal compound (E)> E1: acetamidineacetone vanadyl-33- 201132801 E 2 : ammonium molybdate E 3 : hexanoic acid E4: cobalt nitrate E5: Aluminum hydroxide E6: Ammonium cerium nitrate E7: Nickel carbonate &lt;vermiculite&gt; Using colloidal vermiculite (manufactured by Seiko Chemical Industry Co., Ltd., trade name:

Snowtex Ο)當作矽石。加有矽石的表面處理劑係表1中的 Νο·6及No.7之表面處理劑。矽石的配合比係記載於表1 中，Νο·6的表面處理劑係在No.5的表面處理劑中以配合 比（矽石）/(B)爲1/50所配合者，Νο·7的表面處理劑係在 No.5的表面處理劑中以配合比（矽石）/(Β)爲1/10所配合 者。 -34- 201132801 muSnowtex Ο) as a meteorite. The surface treatment agent to which the vermiculite was added was the surface treatment agent of Νο.6 and No.7 in Table 1. The mixing ratio of vermiculite is shown in Table 1, and the surface treatment agent of Νο.6 is matched with the mixing ratio (meteorite)/(B) of 1/50 in the surface treatment agent of No. 5, Νο· The surface treatment agent of 7 is blended in the surface treatment agent of No. 5 with a blend ratio (meteorite) / (Β) of 1/10. -34- 201132801 mu

No 矽烷 偶合劑 ㈧ 陽離子 性胺甲 酸乙酯 樹脂(B) (A)/(B) Zr化合物(Cl) 及 Ti化合物(C2) 金屬種(E) 含氟的 無機化合物(D) 麵 (Cl)/ (C2) (C)/(B) 種類 (E)/(B) 種類 氟 /(B) 1 A1 B1 10/1 C11：C21 8/5 2/5 El 1/50 C11 1/2 2 ·Α1 B1 2/1 C14iC21 8/5 1/20 El 1/50 D2 1/5 3 A1 B1 2/1 C11：C24 8/5 1/20 — — C11.C24 1/20 4 A1 B1 2/1 C11：C23 8/5 2/5 — 一 C11 1/2 5 A1 B1 1/1 C11：C23 9/5 1/10 — — C11.C23 1/3 6 A1 B1 1/1 C11IC23 9/5 1/10 註)含有矽 011.C23 1/3 7 A1 B1 Γ/1 C11;C23 9/5 1/10 註)含a C11.C23 1/3 8 A1 B1 1/1 C12;C21 9/5 1/10 E3 1/200 C12.D1 1/5 9 A1 B1 1/1 C11：C23 3/2 1/10 E4 1/50 C11.C23 1/10 10 A1 B1 1/1 C11；C23 3/2 1/10 E5 1/50 C11.C23 1/10 11 A1 Θ1 1/1 C11：C23 7/5 1/10 E6 1/50 C11.C23 1/10 12 A1 B1 1/1 C11：C23 6/5 1/10 E7 1/50 C11.C23 1/10 13 A1 B1 1/2 C11：C22 6/5 1/5 E3 1/50 C11.D1 2/5 14 A1 B1 1/5 C13：C23 r 9/5 1/10 一 .一 C23.D1 2/5 15 A1.A3 B1 1/1 C11：C23 9/5 1/10 — — C11.C23 1/3 16 A1 B2 1/20 C14：C23 9/5 1/25 — — C23.D1 1/10 17 At B2 1/30 C1t：C24 1/1 1/10 E1 2/5 C11.C24 1/1 18 A2 B2 2/1 C11：C25 1/1 1/10 E2 1/25 C11.D2 1/5 19 A2 B2 2/1 C14：C23 1/1 1/10 E2 1/25 C23 1/3 20 A2 B3 1/5 C13；C23 3/5 1/10 — .一 C23.D2 1/2 21 A2 B3 1/20 C13：C24 3/5 1/10 — — C24 1/4 22 A3 B3 2/1 C11：C21 1/2 2/5 — 一 C11 1/2 23 A3 B1 2/1 C1t：C21 1/2 1/30 E1 1/50 C11 1/30 24 A3 B1 1/5 C13'：C23 2/5 1/10 E1 1/25 C23.D2 2/5 25 A3 B2 1/20 C12：C24 2/5 1/20 E1 1/8 C12，C24 1/10 26 A3 B2 2/1 C11；C23 1/5 1/10 一 — C11.C23 2/1 27 A3 B2 2/1 C14：C21 1/5 1/100 E1 1/4 D1 1/200 28 A3 B3 1/5 C1t；C22 1/5 1/10 一 — C11.D3 1/10 29 A4 B3 1/5 C13：C24 1/10 1/5 一 —— C24.D3 2/5 30 A4 B3 1/20 C15：C25 1/10 1/10 — — D3 1/1 31 A1 32 A1 B1 30/1 C11：C24 3/2 1/25 E1 1/50 C11.C24 1/25 33 A1 B1 1/200 C11：C22 3/2 1/25 E1 1/50 C11 1/25 34 A1 B1 2/1 • 1 35 A1 B1 2/1 1 -1 - 一 一 — — D2 1/25 36 A1 B1 2/1 C11：C23 1/1 3/5 — 一 C11.C23 3/1 37 A1 B4 1/5 C14IC21 1/2 1/10 — 一 — — 38 A1 B1 2/1 C11：- - 2/5 — 一 C11 1/2 39 A1 B1 2/1 -：C23 - 2/5 一 — C23 1/2 40 A1 B1 2/1 C11：C24 11/5 1/25 E1 1/50 C11.C24 1/25 41 A1 B1 2/1 C11：C23 3/1 1/25 E1 1/50 C11.C23 1/25 42 A1 B1 2/1 C11IC23 1/20 1/25 E1 1/50 C11.C23 1/25 43 A1 — — C11：C21 2/5 — — — C11 1/2 44 A1 一 — C11：C21 1/10 — E4 - C11.D1 3/5 45 A1 — — 一：一 — 一 一 — D1 1/10 46 A1 B1 1/5 -：— — — — — D1 1/1 47 A1 B5 1/5 C15：C25 8/5 1/3 — — • — — -35- 201132801 (薄膜層合） 於形成有表面處理皮膜的供試料上，在25(TC5秒的 條件下，熱層合熱塑性聚酯薄膜（膜厚30μπι)，而得到層 合金屬材料。熱層合時的面壓係以50kg/cm2進行。 [比較例1 8〜2 1 ] 作爲比較例1 8，於5 0 °C 5秒噴灑處理市售的磷酸鉻酸 鹽處理劑（AM-K702:日本PARKERIZING株式會社製）， 進行水洗而去除未反應的藥劑，於80°C加熱乾燥1分鐘而 得到試驗片（Cr附著量爲20mg/m2)。又，作爲比較例 19，於40°C20秒噴灑處理市售的磷酸锆處理劑（AL-404 : 日本PARKERIZING株式會社製），進行水洗而去除未反 應的藥劑，於8 0°C加熱乾燥1分鐘而得到試驗片（Zr附著 量爲15mg/m2)。又，作爲比較例20、21，亦製作僅脫脂 的試驗片。 [評價試驗] (1次密接性） 將已薄膜層合的前述層合金屬材料衝壓成φ 140mm， 將此衝壓板拉深加工以製作拉深杯。接著，再度拉深此 杯，更且以3片的锻模進行減薄拉延加工，而形成拉深減 薄拉延罐（罐體）。 觀察前述經拉深減薄拉延加工後的罐體之外觀，將發 生斷裂時評價爲「X」，將沒有斷裂但有損傷評價爲 -36- 201132801 「△」，將沒有斷裂也沒有損傷時評價爲「〇」。然後’ 使用被評價爲「〇」的罐體，藉由市售的 Enamel Rater(Pec〇公司製）來測定洩漏電流。使用0.5%食鹽水當 作測定液，測定在6.3 V 4秒後的電流値。電流値低者爲 佳，將未達0.1mA時評價爲「◎」，將0.1mA以上且未 達0.3mA時評價爲「〇」，將0.3mA以上且未達1.0mA 時評價爲「△」，將1.0mA以上時評價爲「X」。 (2次密接性） 將注有5%的氫氧化鈉水溶液的罐體與注有5%的硫酸 水溶液之罐體在25 °C保管2星期。接著，水洗此等的罐 體，洗濯後，與先前同樣地藉由市售的 Enamel Rater(PeC〇公司製）來測定洩漏電流。測定液亦使用與先 前囘樣的0.5 %食鹽水，測定在6.3 V 4秒後的電流値。電 流値係與先前同樣地低者爲佳，將未達0 . 1 m A時評價爲 「◎」，將0.1mA以上且未達0.3mA時評價爲「〇j ， 將0.3mA以上且未達1 ·0πιΑ時評價爲「△」，將1 .0mA 以上時評價爲「X」。耐酸性、耐鹼性差者係此時的電流 値變大。 (儲存安定性） 於40°C的恆溫裝置中將表面處理劑儲存3個月，以肉 眼觀察其後的膠化或沈澱等之狀態，按照以下的基準來評 價儲存安定性。此時，將無變化時評價爲「〇」，將增黏 時評價爲「△」，將膠化或沈澱時評價爲場合「X」。 -37- 201132801 [評價結果] 對於實施例1〜32及比較例1〜21的各試驗片，實施 前述試驗’按照評價基準進行判定。表2中顯示其結果。 如由表2的結果可明知，本發明的表面處理劑係於採用作 爲層合薄膜用的表面處理時，發揮優異的性能。特別地， 可知藉由使Zr化合物（C1)與Ti化合物（C2)共存且使兩者 的含有比成爲1/1〇以上且未達2/1，特別對於強酸及強鹼 的兩方之2次密接性優異。又，可知使用含矽石的表面處 理劑之實施例6及實施例7，係在全部的評價項目中皆優 異。還有，可知成分組成爲更佳形態或範圍的實施例9〜 !2及實施例15,係在全部的評價項目中皆優異。 -38- 201132801 [表2] 1 材料 表面處理劑 (表1) 乾燥皮膜重量 I i次密接件 2次密接件 1 儲存 安定性 g/m2 加工外觀 洩漏電流 酸 鹼 AL No.1 0.1 〇 〇 〇 〇 〇 SEisai AL No.2 0.1 0 〇 〇 〇 〇 AL No.3 0.1 〇 ◎ 〇 〇 〇 tai齒咖· AL No.4 0.1 〇 〇 〇 〇 〇 _AL_j No.5 0.1 〇 ◎ 〇 〇 〇 AL No.6 0.1 〇 ◎ ◎ ◎ 〇 eiB· AL No.7 0.1 〇 ◎ ◎ ◎ 〇 漏功臞 AL No.8 0.1 〇 ◎ 〇 〇 〇 IEEE· AL No.9 0.1 〇 ◎ ◎ ◎ 〇 AL No.10 - 0.1 0 ◎ ◎ ◎ 〇 SUS No.11 0.1 〇 ◎ ◎ ◎ 〇 Κϊ7編 ESI AL No.12 0.1 〇 ◎ ◎ ◎ 〇 Κ^ϋΒ AL No.13 0.1 〇 〇 〇 〇 〇 wmm'.mm AL No.14 0.1 〇 ◎ 〇 〇 〇 EIE3iia AL No.1 5 0.1 〇 ◎ ◎ ◎ 〇 嘱運咖 AL No.1 6 0.1 〇 〇 〇 〇 〇 wWMva AL No.1 7 0.1 〇 〇 〇 〇 〇 AL No.1 8 0.1 〇 ◎ 〇 〇 〇 ίΐϊ^ΰίΙΕ· AL No.1 9 0.1 〇 ◎ 〇 〇 〇 遍講1 AL No.20 0.1 〇 〇 〇 〇 〇 嘱功 AL No.21 0.1 〇 〇 〇 〇 〇 MkiMim AL No.22 0.1 〇 〇 〇 〇 〇 MiiM'sm AL No.23 0.1 〇 〇 〇 〇 〇 ukumsi AL No.24 0.1 〇 ◎ 〇 〇 〇 AL No.25 0.1 〇 〇 〇 〇 〇 Bwi/iiitslHS AL No.26 0.1 〇 〇 〇 〇 〇 mumm AL No.27 0.1 〇 〇 〇 〇 〇 KT刪挪 AL No.28 0.1 〇 〇 〇 〇 〇 nj編咖 AL No.29 0.1 〇 〇 〇 〇 〇 _ίίϋΙϊϋΐ SUS No.30 0.1 〇 〇 〇 1 〇 〇 麵卽II· AL N^5 0.025 〇 〇 〇 〇 〇 Kmmfa AL No.5 0.45 〇 〇 〇 〇 〇 比較例1 AL No.31 0.1 X — — 1 — 〇 比較例2 AL No.3 2 0.1 Δ 一 — — 〇 比較例3 AL No.3 3 0.1 △ — — — 〇 比較例4 AL No.34 0.1 Δ 一· — 一 〇 KSHil AL No.3 5 0.1 △ — — 一 〇 _辑·國· AL No.3 6 0.1 〇 Δ X Δ X _琪1财1·· AL No.3 8 0.1 〇 △ X X X 1比較例8 1 SUS No.39 0.1 〇 Δ X Δ 〇 to逋測· AL No.40 0.1 〇 △ X △ 〇 搞现Μ*】· AL No.41 0.1 〇 Δ X Δ 〇 _辑_11· AL i No.4 2 1 0.1 〇 X X △ 〇 _琪题個· AL No.43 0.1 〇 △ X X ' 〇 1.比較例131 AL No.44 0.1 △ — -— — X _琪鉍_1 AL No.45 ! 0.1 Δ — —, — X 由测明· AL No.46 0.1 △ 、— — — 〇 呀挪财· AL No.47 0.1 Δ 一 — 一 〇 AL No.48 0.1 Δ — — — 〇 璜效邸财· AL ,磷辞錤敌鹽 Cr20mE/m2 〇 A A 厶 一 腿麵· AL Zr15mfi/m2 0 A X X 一 胡鋼财· AL 僅福 — X 一 一 一 — mmmi SUS 僅脫脂 — X 一 — — — -39-No decane coupling agent (8) Cationic urethane ethyl ester resin (B) (A) / (B) Zr compound (Cl) and Ti compound (C2) Metal species (E) Fluorinated inorganic compound (D) Surface (Cl) / (C2) (C)/(B) Type (E)/(B) Type Fluorine/(B) 1 A1 B1 10/1 C11: C21 8/5 2/5 El 1/50 C11 1/2 2 · Α1 B1 2/1 C14iC21 8/5 1/20 El 1/50 D2 1/5 3 A1 B1 2/1 C11:C24 8/5 1/20 — — C11.C24 1/20 4 A1 B1 2/1 C11 :C23 8/5 2/5 — A C11 1/2 5 A1 B1 1/1 C11:C23 9/5 1/10 — — C11.C23 1/3 6 A1 B1 1/1 C11IC23 9/5 1/10 Note) Contains 矽011.C23 1/3 7 A1 B1 Γ/1 C11; C23 9/5 1/10 Note) Contains a C11.C23 1/3 8 A1 B1 1/1 C12; C21 9/5 1/10 E3 1/200 C12.D1 1/5 9 A1 B1 1/1 C11: C23 3/2 1/10 E4 1/50 C11.C23 1/10 10 A1 B1 1/1 C11; C23 3/2 1/10 E5 1/50 C11.C23 1/10 11 A1 Θ1 1/1 C11: C23 7/5 1/10 E6 1/50 C11.C23 1/10 12 A1 B1 1/1 C11: C23 6/5 1/10 E7 1/50 C11.C23 1/10 13 A1 B1 1/2 C11: C22 6/5 1/5 E3 1/50 C11.D1 2/5 14 A1 B1 1/5 C13: C23 r 9/5 1/ 10 One. One C23.D1 2/5 15 A1.A3 B1 1/1 C11: C23 9/5 1/10 — — C11.C23 1/3 16 A1 B2 1/20 C14:C23 9/5 1/25 — — C23.D1 1/10 17 At B2 1/30 C1t:C24 1/1 1/10 E1 2/5 C11.C24 1/1 18 A2 B2 2/ 1 C11:C25 1/1 1/10 E2 1/25 C11.D2 1/5 19 A2 B2 2/1 C14:C23 1/1 1/10 E2 1/25 C23 1/3 20 A2 B3 1/5 C13 ;C23 3/5 1/10 — .—C23.D2 1/2 21 A2 B3 1/20 C13:C24 3/5 1/10 — — C24 1/4 22 A3 B3 2/1 C11:C21 1/2 2/5 — A C11 1/2 23 A3 B1 2/1 C1t: C21 1/2 1/30 E1 1/50 C11 1/30 24 A3 B1 1/5 C13': C23 2/5 1/10 E1 1 /25 C23.D2 2/5 25 A3 B2 1/20 C12:C24 2/5 1/20 E1 1/8 C12,C24 1/10 26 A3 B2 2/1 C11;C23 1/5 1/10 One— C11.C23 2/1 27 A3 B2 2/1 C14: C21 1/5 1/100 E1 1/4 D1 1/200 28 A3 B3 1/5 C1t; C22 1/5 1/10 A — C11.D3 1 /10 29 A4 B3 1/5 C13: C24 1/10 1/5 One - C24.D3 2/5 30 A4 B3 1/20 C15: C25 1/10 1/10 — — D3 1/1 31 A1 32 A1 B1 30/1 C11: C24 3/2 1/25 E1 1/50 C11.C24 1/25 33 A1 B1 1/200 C11: C22 3/2 1/25 E1 1/50 C11 1/25 34 A1 B1 2/1 • 1 35 A1 B1 2/1 1 -1 - One to one — D2 1/25 36 A1 B1 2/1 C11: C23 1/1 3/5 — C11.C23 3/1 37 A1 B4 1/5 C14IC21 1/2 1/10 — One — — 38 A1 B1 2/1 C11:- - 2/5 — One C11 1/2 39 A1 B1 2/1 -: C23 - 2/5 one - C23 1/2 40 A1 B1 2/1 C11: C24 11/5 1/25 E1 1/50 C11.C24 1/25 41 A1 B1 2/1 C11: C23 3/1 1/ 25 E1 1/50 C11.C23 1/25 42 A1 B1 2/1 C11IC23 1/20 1/25 E1 1/50 C11.C23 1/25 43 A1 — — C11:C21 2/5 — — — C11 1/ 2 44 A1 一— C11:C21 1/10 — E4 - C11.D1 3/5 45 A1 — — 一:一—一一—D1 1/10 46 A1 B1 1/5 —: — — — — — D1 1 /1 47 A1 B5 1/5 C15:C25 8/5 1/3 — — • — — —35- 201132801 (Film lamination) On the test specimen formed with the surface treated film, at 25 (TC 5 sec conditions) A thermoplastic polyester film (film thickness: 30 μm) was thermally laminated to obtain a laminated metal material. The surface pressure at the time of thermal lamination was carried out at 50 kg/cm2. [Comparative Example 1 8 to 2 1 ] As Comparative Example 18, a commercially available phosphoric acid chromate treatment agent (AM-K702: manufactured by Japan PARKERIZING Co., Ltd.) was sprayed at 50 ° C for 5 seconds, and washed with water to remove The reaction agent was dried by heating at 80 ° C for 1 minute to obtain a test piece (Cr adhesion amount was 20 mg/m 2 ). Further, as a comparative example 19, a commercially available zirconium phosphate treatment agent (AL-404: manufactured by Japan PARKERIZING Co., Ltd.) was sprayed at 40 ° C for 20 seconds, and the unreacted drug was removed by washing with water, and dried by heating at 80 ° C. A test piece (Zr adhesion amount: 15 mg/m2) was obtained in minutes. Further, as Comparative Examples 20 and 21, a test piece which was only degreased was also produced. [Evaluation Test] (1st Adhesive Property) The laminated metal material laminated with the film was punched into φ 140 mm, and the punched plate was drawn deep to prepare a draw cup. Then, the cup is further deepened, and the three-piece forging die is used for the drawing and drawing process to form a deep drawing and drawing can (can body). Observing the appearance of the can body after the drawing and drawing process, the evaluation was "X" when the fracture occurred, and the damage was not evaluated but the damage was evaluated as -36 - 201132801 "△", and there was no break or damage. The evaluation is "〇". Then, using a can body evaluated as "〇", a leakage current was measured by a commercially available Enamel Rater (manufactured by Pec Co., Ltd.). Using 0.5% saline as a measuring solution, the current 値 after 4 seconds at 6.3 V was measured. It is preferable that the current is low, and it is evaluated as "◎" when it is less than 0.1 mA, and "〇" when it is 0.1 mA or more and less than 0.3 mA, and "△" when it is 0.3 mA or more and less than 1.0 mA. When it is 1.0 mA or more, it is evaluated as "X". (2nd adhesion) A can body filled with a 5% aqueous solution of sodium hydroxide and a can body filled with a 5% aqueous solution of sulfuric acid were stored at 25 ° C for 2 weeks. Then, the cans were washed with water, and after washing, the leakage current was measured by a commercially available Enamel Rater (manufactured by PeC). The measurement solution was also used with a 0.5% saline solution previously injected, and the current 値 after 4.6 V for 4 seconds was measured. The current system is preferably the same as the previous one, and is evaluated as "◎" when it is less than 0.1 m A, and is evaluated as "〇j when it is 0.1 mA or more and less than 0.3 mA, and 0.3 mA or more is not reached. 1 · 0πιΑ is evaluated as "△", and when it is 1.0 mA or more, it is evaluated as "X". In the case of poor acid resistance and alkali resistance, the current enthalpy becomes large. (Storage stability) The surface treatment agent was stored in a thermostat at 40 ° C for 3 months, and the state of gelation or precipitation after the observation was visually observed, and the storage stability was evaluated according to the following criteria. In this case, when there is no change, it is evaluated as "〇", when the viscosity is increased, it is evaluated as "△", and when it is gelled or precipitated, it is evaluated as "X". -37-201132801 [Evaluation Results] For each of the test pieces of Examples 1 to 32 and Comparative Examples 1 to 21, the above test was carried out, and the evaluation was carried out in accordance with the evaluation criteria. The results are shown in Table 2. As is apparent from the results of Table 2, the surface treating agent of the present invention exhibits excellent performance when used as a surface treatment for a laminated film. In particular, it is understood that the Zr compound (C1) and the Ti compound (C2) coexist and the content ratio of the two is 1/1 〇 or more and less than 2/1, particularly for both the strong acid and the strong base. Excellent in sub-adhesion. Further, it is understood that Examples 6 and 7 using a surface treatment agent containing vermiculite are excellent in all evaluation items. Further, it is understood that Examples 9 to 2 and Example 15 in which the component composition is in a better form or range are excellent in all evaluation items. -38- 201132801 [Table 2] 1 Material surface treatment agent (Table 1) Dry film weight I i times contact piece 2 times adhesion piece 1 Storage stability g/m2 Processing appearance Leakage current acid-base AL No.1 0.1 〇〇〇 〇〇SEisai AL No.2 0.1 0 〇〇〇〇AL No.3 0.1 〇◎ 〇〇〇tai tooth coffee · AL No.4 0.1 〇〇〇〇〇_AL_j No.5 0.1 〇◎ 〇〇〇AL No .6 0.1 〇 ◎ ◎ ◎ 〇 eiB· AL No.7 0.1 〇 ◎ ◎ ◎ 〇 臞 臞 No AL No.8 0.1 〇 ◎ 〇〇〇 IEEE· AL No.9 0.1 〇 ◎ ◎ ◎ 〇 AL No.10 - 0.1 0 ◎ ◎ ◎ 〇 SUS No.11 0.1 〇 ◎ ◎ ◎ 〇Κϊ 7 ESI AL No.12 0.1 〇 ◎ ◎ ◎ 〇Κ ^ϋΒ AL No.13 0.1 〇〇〇〇〇wmm'.mm AL No.14 0.1 〇 ◎ 〇〇〇 EIE3iia AL No.1 5 0.1 〇 ◎ ◎ ◎ 〇嘱 咖 AL AL No.1 6 0.1 〇〇〇〇〇wWMva AL No.1 7 0.1 〇〇〇〇〇AL No.1 8 0.1 〇◎ 〇〇〇ίΐϊ^ΰίΙΕ· AL No.1 9 0.1 〇◎ 〇〇〇 讲 1 AL No.20 0.1 〇〇〇〇〇嘱 AL AL No.21 0.1 〇〇 〇〇MkiMim AL No.22 0.1 〇〇〇〇〇MiiM'sm AL No.23 0.1 〇〇〇〇〇ukumsi AL No.24 0.1 〇◎ 〇〇〇AL No.25 0.1 〇〇〇〇〇Bwi/iiitslHS AL No.26 0.1 〇〇〇〇〇mumm AL No.27 0.1 〇〇〇〇〇KT Delete No.28 0.1 〇〇〇〇〇nj Coffee Maker AL No.29 0.1 〇〇〇〇〇_ίίϋΙϊϋΐ SUS No.30 0.1 〇〇〇1 〇〇 卽 II· AL N^5 0.025 〇〇〇〇〇Kmmfa AL No.5 0.45 〇〇〇〇〇Comparative example 1 AL No.31 0.1 X — — 1 — 〇Compare Example 2 AL No. 3 2 0.1 Δ I - 〇 Comparative Example 3 AL No. 3 3 0.1 △ — — — 〇 Comparative Example 4 AL No. 34 0.1 Δ I·—— 一〇KSHil AL No.3 5 0.1 △ — — 一〇_辑·国· AL No.3 6 0.1 〇Δ X Δ X _ Qi 1 1·· AL No.3 8 0.1 〇△ XXX 1 Comparative Example 8 1 SUS No.39 0.1 〇Δ X Δ 〇 To逋测· AL No.40 0.1 〇△ X △ 〇 Μ Μ 】 】 】 】 】 】 】 】 】 】 】 】 】 】 AL AL AL AL X X X X X X X X X X X X X X 辑 辑 辑 辑 辑· AL No.43 0.1 〇△ XX ' 〇1. Comparative Example 131 AL No.44 0.1 △ — — — — X _ 铋 AL AL AL.45 ! 0.1 Δ — —, — X From the measurement · AL No.46 0.1 △ , — — — 〇 挪 挪 · AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL AL M2 0 AXX 一胡钢财· AL only blessing - X one by one - mmmi SUS only skim - X one — — — -39-

Claims (1)

201132801 七、申請專利範圍 1. 一種層合金屬材料用表面處理劑，其特徵爲含有矽 烷偶合劑（A)、陽離子性胺甲酸乙酯樹脂（B)、Zr化合物 (Cl)、Ti化合物（C2)及含氟的無機化合物（D)， 配合比（A)/(B)以重量比表示爲1/50以上20/1以下， 配合比（C)/(B)以重量比表示爲1/100以上1/2以下（惟， (C)的重量係（C1)與（C2)的合計），配合比（氟原子）/(B)以重 量比表示爲1/1 000以上2/1以下，而且配合比（C1)/(C2) 以重量比表示爲1/10以上且未達2/1。 2. 如申請專利範圍第1項之層合金屬材料用表面處理 劑，其中前述陽離子性胺甲酸乙酯樹脂（B)係含有由二級 胺基及三級胺基所選出的胺基性官能基。 3 .如申請專利範圍第1或2項之層合金屬材料用表面 處理劑，其中前述矽烷偶合劑（A)全體的5質量％以上係 具有由一級胺基、二級胺基、三級胺基及四級銨基所選出 的胺基性官能基之矽烷偶合劑。 4. 如申請專利範圍第1〜3項中任一項之層合金屬材 料用表面處理劑，其中前述Zr化合物（C1)及前述Ti化合 物（C2)係氟化物或氟酸或氟酸鹽。 5. —種層合金屬材料的製造方法，其特徵爲在金屬材 料的表面上塗佈乾燥如申請專利範圍第1〜4項中任一項 之層合金屬材料用表面處理劑，以形成0.01〜lg/m2的皮 膜，接著層合聚酯系樹脂、聚乙烯系樹脂、聚丙烯系樹脂 或此等的改性樹脂。 -40- 201132801 6 ·如申請專利範圍第5項之層合金屬材料的製造方 法，其中前述金屬材料係鋁系或不銹鋼系的金屬箔。 -41 - 201132801 四 指定代表圖： (一） 本案指定代表圖為：無 (二） 本代表圖之元件符號簡單說明：無 201132801 五 本案若有化學式時，請揭示最能顯示發明特徵的化學 式：無201132801 VII. Patent application scope 1. A surface treatment agent for laminated metal materials, which is characterized by containing a decane coupling agent (A), a cationic urethane resin (B), a Zr compound (Cl), and a Ti compound (C2). And the fluorine-containing inorganic compound (D), the mixing ratio (A) / (B) is 1/50 or more and 20/1 or less by weight ratio, and the mixing ratio (C) / (B) is 1/by weight ratio. 100 or more and 1/2 or less (except that the weight of (C) is a total of (C1) and (C2)), and the mixing ratio (fluorine atom) / (B) is represented by a weight ratio of 1/1000 or more and 2/1 or less. And the mixing ratio (C1) / (C2) is represented by a weight ratio of 1/10 or more and less than 2/1. 2. The surface treatment agent for laminated metal materials according to claim 1, wherein the cationic urethane resin (B) contains an amine functional group selected from a secondary amino group and a tertiary amine group. base. 3. The surface treatment agent for laminated metal materials according to claim 1 or 2, wherein 5% by mass or more of the entire decane coupling agent (A) has a primary amine group, a secondary amine group, and a tertiary amine a decane coupling agent of an amino-based functional group selected from a quaternary ammonium group. The surface treatment agent for laminated metal materials according to any one of claims 1 to 3, wherein the Zr compound (C1) and the Ti compound (C2) are fluoride or hydrofluoric acid or a hydrofluoride salt. A method for producing a laminated metal material, which is characterized in that a surface treatment agent for a laminated metal material according to any one of claims 1 to 4 is applied to a surface of a metal material to form 0.01. A film of ~ lg/m2 is followed by lamination of a polyester resin, a polyethylene resin, a polypropylene resin or a modified resin thereof. The method for producing a laminated metal material according to claim 5, wherein the metal material is an aluminum-based or stainless steel-based metal foil. -41 - 201132801 The four designated representative maps: (1) The representative representative of the case is: No (2) The symbol of the representative figure is simple: No 201132801 If there is a chemical formula in the case, please disclose the chemical formula that best shows the characteristics of the invention: no
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