200406504 Π) 玖、發明說明 【發明所屬之技術領域】 本發明係有關非電解鍍敷液以及使用其非電解鍍敷液 及非電解鍍敷處理之物件者。 【先前技術】 氟樹脂對於化學藥品其耐久性極強，電氣性質亦良好 ，局溫下亦極女疋之具備各特性者，因此’先彳了於機械部品 、電氣、電子部品等表面通常進行氟樹脂之塗層。針對此 塗層氟樹脂之被處理物件爲提昇其密合性，一般預先使被 處理物件表面進行粗化形成處理後，使氟樹脂進行塗層之 方法之外，亦藉由無機或有機粘合劑進行處理後，層厚度 呈100〜20 0 μπι之氟樹脂進行較厚塗層之方法（如··特開 2001-328121號公報、特開2000-328256號公報、特開平4-3 65 8 75號公報、特公平1 -605 84號公報、特開昭6 1 -23 4202 號公報、特開昭5 1 - 1 1 1 2 3 4 8號公報）。 惟，該先行技術之被處理物件表面經粗化形成處理後 ’於粗化面進行氟樹脂塗層之方法中，其凹凸形狀出現如 下之不適狀況。亦即，形成凹部份與凸部份高低差爲1 μ之 不太大凹凸形狀的粗面化時，藉由氟樹脂其鍍敷層埋入凹 部後幾乎無凹凸之高度，氟樹脂之密合性明顯降低，產生 剝離等問題點。 又，氟樹脂較爲昂貴，因此，爲降低成本，故使氟樹 脂層厚度變薄，減少氟樹脂之使用量以因應市場需求。惟 (2) (2)200406504 ，僅針對氟樹脂塗層變薄’將造成降低氟樹脂與氟樹脂塗 層物相互之磨擦係數，導致密合性極差，且，於被膜極易 產生穿孔，因此，根本不可能形成層厚度爲薄之氟樹脂塗 層被膜之問題點存在之。 【發明內容】 本發明目的係爲提供一種具有與被處理物件之密合性 極佳之氟樹脂被膜之非電解鍍敷被處理物件及其非電解鍍 敷方法，及其所使用之非電解鍍敷液者。 本發明者爲解決該各項問題，進行精密硏討結果，發 現將被處理物件曝露於至少1種含有選自含有氨水及硫代 硫酸鹽之組成液及硫脲之第1鍍敷液後，形成第1鍍敷層之 後，於該第1鍍敷層表面曝露於含有氟樹脂之第2鍍敷液後 形成第2鍍敷層，形成極具良好密合性之氟樹脂被膜之薄 膜。 亦即，本發明最初之實施形態係提供一種以至少1種 含有選自含有金屬鹽與金屬絡合劑與還原劑及氨水及硫代 硫酸鹽之組成液以及硫脲所成群者爲其特徵之非電解鍍敷 液者。 該本發明之非電解鍍敷液中，其該硫脲濃度可爲 0.1 〜lOOppm 者 〇 該本發明之非電解鍍敷液中，其該金屬絡合劑可爲乳 酸者。 該本發明之非電解鍍敷液中，其該金屬絡合劑濃度可 (3) (3)200406504 爲1〜1 OOg "者。 該本發明之非電解鍍敷液中，其該金屬鹽可爲至少1 種以上選自鎳鹽、鈷鹽、鉻鹽、鈦鹽、及次亞磷酸鹽所成 群者。 本發明第2實施形態係提供一種以含有形成第丨鍍敷層 之曝露被處理物件於至少1種含有選自含有金屬鹽與金屬 糸各合劑及還原劑及氨水與硫代硫酸鹽之組成液以及硫脲所 成群之第1非電解鍍敷液後形成於該被處理物件表面之步 驟’與形成第2鍍敷層之更曝露該被處理物件於含有氟樹 脂、金屬鹽、金屬絡合劑、還原劑、及界面活性劑之第2 #電解鍍敷液後形成於該第1鍍敷層之步驟者爲其特徵之 非電解鍍敷方法。 該本發明非電解鍍敷方法中，該硫脲濃度可爲 〇 ·]〜1 0 0 ρ ρ ηι 者。 該本發明非電解鍍敷方法中，該金屬絡合劑可爲乳酸 該本發明非電解鍍敷方法中，該金屬絡合劑濃度可爲 1 〜1 ο 〇 g "者。 該本發明非電解鍍敷方法中，該金屬鹽可爲至少1種 以上選自鎳鹽、鈷鹽、鉻鹽、鈦鹽、及次亞磷酸鹽所成群 者。 該本發明非電解鍍敷方法中，含於該第2非電解鍍敷 液之該金屬鹽可爲至少1種以上選自鎳鹽、鈷鹽、鉻鹽、 欽鹽及次亞磷酸鹽所成群者。 (4) 200406504 該本發明非電解鍍敷方法中，該含於第2非電解鍍敷 液之該界面活性劑可爲至少1種選自陽離子界面活性劑及非 離子界面活性劑所成群者。 該本發明非電解鍍敷方法中，該含於第2非電解鍍敷 液之氟樹脂濃度可爲20〜60g / <者。 本發明第3實施形態係提供一種藉由該非電解鍍敷方法 所取得者爲其特徵之鍍敷被處理物件。 該本發明之鍍敷被處理物件中，其鍍敷硬度可爲 400HV以上 該本發明之鍍敷被處理物件中，鍍敷密合強度可爲 3 5 0kgf /cm以上者。 【實施方式】 [發明實施之最佳形態] 以下針對本發明之非電解鍍敷液，及使用其非電解鍍 敷方法及非電解鍍敷被處理物件之理想形態進行詳細說明 〇 本申請發明之非電解鍍敷液（第1非電解鍍敷液）係 含有至少1種選自含有金屬鹽與金屬絡合劑及還原劑及氨 水與硫代硫酸鹽之組成液及硫脲所成群者。本發明非電解 鍍敷方法更含有曝露被處理物件於該非電解鍍敷液（第i 非電解鍍敷液）後，於該被處理物件表面形成第1鍍敷層 之步驟與曝露該被處理物件於含氟樹脂、金屬鹽、金屬絡 合劑、及界面活性劑之第2非電解鍍敷液後，於該第1鍍敷 - 8 - Λ' ^ ' ϋ' (5) (5)200406504 層形成第2鍍敷層之步驟者。另外，第1圖係代表於鍍敷被 處理物件形成第1鍍敷層狀態所示之槪念截面圖者。第2圖 係代表於鍍敷被處理物件形成第1鍍敷層及第2鍍敷層狀態 所示之槪念截面圖者。1代表被處理物件，2代表凸部，3 代表凹部，4代表第1鍍敷層，5代表第2鍍敷層。 該「非電解鍍敷」係指未通電，於被處理物件進行鍍 敷之方法者。 該被處理物件可使用金屬製品、氧化鋁製品、橡膠製 品、合成樹脂等廣泛基材者。又，被處理物件依其各材質 ’預先進行爲提昇與被處理物件之密合性等之前處理爲宜 〇 含於該第1非電解鍍敷之金屬鹽中含有鎳鹽、鈷鹽、 銘鹽、鈦鹽、及次亞憐酸鹽等，可單獨使用或組合使用 之，惟，未受限於此等者。理想者以至少1種以上選自鎳 鹽及鈷鹽所成群者。 含於本發明第1非電解鍍敷液之金屬絡合劑係與金屬 鹽形成絡合體之有機物等者，惟，以於被處理物件上取得 理想凹面者爲較佳者。雖未特別限定，一般做爲金屬絡合 劑者以乳酸爲理想使用者。金屬絡合劑於鍍敷液中被還原 時，於鍍敷溶液中生成金屬絡合劑之粉末微粒子，而，當 生成約2〜3 μηι之大金屬絡合劑粉末微粒子時，於液中將呈 不安定者，促使液分解，因此，不宜取得凹面。乳酸中， 其微粒子粉末爲1 μ m以下’因此’液分解小，宜取得凹面 。另外，含於第2非電解鍍敷液之金屬絡合劑可使用甘胺 -9 - (6) (6)200406504 酸等慣用者。 含於該第1非電解鍍敷液之金屬絡合劑濃度以1〜l〇〇g 者宜，更佳者爲10〜2 〇g /< 。當增加鍍敷液中之金屬絡 合劑濃度則使鍍敷層粗化，鍍敷層表面之凹凸（高低差） 變大，可取得與氟樹脂塗層相互密合性良好者。金屬絡合 劑濃度於該範圍時，可取得適於氟塗層之凹凸高低差，且 ，無液分解，可取得與氟樹脂塗層之密合性特別良好者。 含於該第1非電解鍍敷液之氨水及硫代硫酸鹽所含組 成液及硫脲可用於均勻形成於鍍敷層表面凹凸之凸部高低 度者，藉此可取得與氟樹脂塗層具極良好密合性之被處理 物件。以下，進行更詳細說明。如上述，以含低濃度金屬 絡合劑之非電解鍍敷液（第1非電解鍍敷液）進行鍍敷被 處理物件時，其鍍敷層表面幾乎無凹凸，於此凹凸（高低 差）極小之表面鍍敷層上即使以氟樹脂進行塗層仍無法取 得良好之氟樹脂塗層。另外，鍍敷液中金屬絡合劑濃度之 增加，鍍敷層呈粗化，於鍍敷層表面凹凸（高低差）變大 ’惟’凸部之局低度不均形成不定化之鍍敷層。如此表面 凸部高低不均之鍍敷層上即使進行氟樹脂塗層，仍未能取 得良好密合性之氟樹脂塗層。本發明者於形成於被處理物 件表面之第1鍍敷層形成時，於第1非電解鍍敷液中含有該 組成液或硫脲或此等混合物後，使第1鍍敷層表面凸部之 高低均勻化，亦即，被形成於鍍敷層平坦表面形成凹部之 第1鍍敷層，此第1鍍敷層以含氟樹脂之第2非電解鍍敷液 進行氟樹脂塗層後’出現與被處理物件相互密合性極佳之 (7) (7)200406504 氟樹脂塗層，進而完成本發明。又，使用該組成液、硫脲 後，表面凸部之高低呈一定化，於平坦部形成凹部之鍍敷 層被形成之機序仍未明朗，惟，可考量該組成液、硫脲以 任意形態下抑制凹凸之析出。 做爲含於含有該氨水及硫代硫酸鹽組成液之硫代硫酸 鹽者可以硫代硫酸鹽等使用之。含於該第1非電解鍍敷液 之含氨水及硫代硫酸鹽組成液中可更含有氯等。 含於該第1非電解鍍敷液之該組成液含量由可取得具 良好密合性氟樹脂塗層面視之，以1〜4 0g /<者宜，又以 10〜30g Μ爲更佳者。 含於非電解鍍敷液之硫脲含量由可取得具良好密合性 氟樹脂塗層面視之，其含於第1非電解鍍敷液中硫脲濃度 以0.1〜lOOppm者宜，更佳者爲50〜lOOppm。另外，大量使 用硫脲後，其毒性作用變強，與氟樹脂反應後，樹脂分解 ’導致不易生成氟樹脂之被膜，而，只要於該濃度範圍內 即可取得理想之氟樹脂塗層。 含於該第1非電解鍍敷液及第2非電解鍍敷液之還原劑 可使用慣用者，如：氫化硼鈉等。 該第1非電解鍍敷液及第2非電解鍍敷液之pH只要含 於此等鍍敷液之金屬鹽可以金屬析出之pH即可。鍍敷液 中之金屬鹽與乳酸形成安定之可溶性絡合物，而伴隨pH之 上昇，游離金屬離子濃度下降，平衡電位往負方向移動， 因此’ pH太高則不易析出金屬，反之，pH太低則被膜將 再熔解，不易析出金屬。本發明鍍敷處理中爲進行良好之 -11 - (8) (8)200406504 金屬析出，該第1非電解鍍敷液及第2非電解鍍敷液之p Η以 4.1〜6.0爲更理想者。 含於該第2非電解鍍敷液之氟樹脂係含氟基之樹脂者 ，可使用四氟乙烯（PTFE )等氟樹脂者。第2非電解鍍敷 液中氟樹脂之含有濃度可依其用途進行任意選取之，一般 以2 0〜60g Μ者宜，未受限於此。 含於該第2非電解鍍敷液之界面活性劑可防止複合化 物質之沈澱，於第1非電解鍍敷液之凹部使氟樹脂之分散 侵入呈良好者，可做爲氟樹脂分散劑之機能充份發揮。此 界面活性劑中，以至少1種選自陽離子系界面活性劑及非 離子界面活性劑所成群者使用爲宜。陽離子系界面活性劑 中，可使用第4銨鹽、第2胺類、第3胺類、咪唑啉類含有 者，非離子界面活性劑中可使用聚環氧乙烷系、聚乙烯系 、羧酸系磺酸系之非離子界面活性者，惟，並未特別限定 於此者。又，亦可使用分子內具有碳元素、氟原子鍵之氟 界面活性劑者。第2非電解鍍敷液中之界面活性劑含量以 0·1〜lg / <者宜，又以〇·1〜〇.5g Μ爲更佳者。該範圍內含 金屬鹽之氟樹脂可於第1鍍敷層之凹部呈良好之分散侵入 者，另外，第2鍍敷層表面粗度降低，可呈適度潤滑表面 者。又，第2非電解鍍敷液中，於第1鍍敷層凹部爲更呈良 好之氟樹脂分散侵入，因此以含有分散補助劑爲宜者。此 分散補助劑一般爲含有氧化鈽、碳化矽者，惟，並未特別 限定於此。 該本發明非電解鍍敷處理步驟可與鍍敷業界常用之非 -12- (9) (9)200406504 電解鍍敷方法相同方法進行之。以下進行說明鍍敷處理步 驟之示例’惟’並未受限於此。首先，將被處理物於液溫 約6 0〜7 0 °C之該第1非電解鍍敷液中浸漬5〜30分鐘後取出 ，水洗後，於常溫約2 5 °C之環境下進行放置、乾燥之， 以§亥弟1非電解鍍敷液藉由鍍敷處理後取得之鍍敷層其凸 部高低呈均勻化者。接著，將第1鍍敷液所處理之被處理 物件於液溫約60〜70 °C之第2非電解鍍敷液中浸漬6〜120 份鐘後，取出、水洗之後，於常溫約2 5 °C環境下，進行 放置，乾燥之。第1鍍敷層及第2鍍敷層於表面將被覆形成 之被處理物件配設於維持昇溫約3 00〜5 00 °C之爐內，放置 1 0〜6 0分鐘後，進行烘烤處理之後，於被處理物件表面取 得具有氟樹脂塗層之本發明鍍敷被處理物件。 以下針對該本發明非電解鍍敷方法所鍍敷之鍍敷被處 理物件進行說明。鍍敷被處理物件之第1鍍敷層膜厚爲取 得被處理物件與氟樹脂相互之密合性，以0 · 1〜50 μπι爲宜 ，又以〇 · 1〜1 0 μηι爲更佳者。爲可發揮良好氟樹脂之密合 性之膜厚，鍍敷被處理物件之第2鍍敷層膜厚亦以0 · 1〜5 0 μηι爲宜，〇.1〜3〇 μηι爲更佳者。 藉由該方法所取得之鍍敷被處理物件其氟樹脂塗層與 被處理物件具有良好之密合性，具有3 5 0kg f /cm，較佳者 爲600kgf /cm以上，75 0kgf /cm以上之密合強度。又，藉 由該方法取得之鍍敷被處理物件爲具有40HV以上之硬度 者，而又以5 00HV以上之硬度爲較佳者，950HV以上爲最 佳者。 -13- (10) (10)200406504 [實施例] 以下代表本發明非電解鍍敷液，使用其非電解鍍敷之 方法，及鍍敷被處理物件之具體例，惟，該實施例爲本發 明實施形態之示例者，並未受限於此等。另外，針對各實 施例所取得之鍍敷被處理物件，依以下測定條件，進行表 面粗細度之測定，鍍敷硬度之測定，鍍敷密合強度之測定 ，耐腐蝕性試驗，以及表面分析。 表面粗細度之測定係利用螢光X線方式進行之。 鍍敷密合強度之測定係依JIS B 772 1所規定之金屬彎 曲方式（亦即，使金屬板進行彎曲，藉由其彎曲力確定表 面處理之剝離方式）進行測定之。 鍍敷硬度測定中，做爲硬度計者，以島津微小硬度計 HNV-2 000 (股份）（島津製作所製）使用之。 耐腐蝕性試驗係藉（A )於1 0 0 °C之鹽酸液（濃度 3 6 · 4 7 % )中滲透6 0分鐘後，由液中取出，水洗後，常溫下 進行放置，乾燥之，（B )於1 〇〇 °C之氫氧化鈉液（濃度 5 0 % )中滲透8 0分鐘後，由液中取出，常溫下放置，乾燥 之，（C )於100 °C三氯乙烯液（濃度50% )(氟酸液、 鹽酸液、硫酸液均爲濃度20% )、溫度25 t下，滲透24 小時後，由液中取出，分別利用電子顯微鏡（Scanning E 1 e c t r ο η M i c r 〇 s c 〇 )將純水洗淨後常溫乾燥者擴大表面呈 5 00 00倍後，觀察檢測之。 表面分析係檢測是否出現粒子脫落、穿孔產生者。將 -14- (11) (11)200406504 被處理物件表面藉由電子顯微鏡擴大爲50〇〇〇倍後進行觀 察檢測之。 [實施例1] 於含有40g Μ硫酸鎳、25g Μ醋酸鈷、0.5g Μ次亞 磷酸鈉，做爲金屬絡合劑爲l〇g / <乳酸及40g / <之40重 量％氨水，與5 0重量％硫代硫酸鹽與1 0重量％氯所成之組 成液，液之p Η爲5.8，液溫維持於8 0 °C之第1非電解鍍敷 液中浸漬不銹鋼板（JIS規格SUS 3 04 ) 3 0分鐘後，將此不 銹鋼板由第1非電解鍍敷液中取出，水洗後常溫環境下放 置、乾燥之。不銹鋼板之表面粗細度爲0.18 μπι者。不銹 鋼板表面於平坦面具有溝道深度約4 μιη之凹部的層厚5 μπι 之第1鍍敷層被形成之。 更使該具有第1鍍敷層之不銹鋼板浸漬於維持70 °C 之第1非電解鍍敷液中20分鐘後，將此不銹鋼板由第2非電 解鍍敷液取出，水洗後常溫環境下進行放置、乾燥之。該 第2非電解鍍敷中含有30g Μ硫酸鎳、20g Μ醋酸鈷、 〇 · 5 g Μ次亞磷酸鈉，0.5 g Μ做爲金屬絡合劑之甘胺酸， 1 5 g /<做爲分散補助劑之氧化鈽，6 0 g Μ做爲氟樹脂之 四氟乙烯（PTEF > ，10g / <做爲表面安定效果之氧化磷 ，陽離子界面活性劑之Megafac F-150(大日本油墨工業 (股份））、及非離子界面活性劑之Tritomnx-100 (石津 製藥（股份）），做成液pH爲3.5。該不銹鋼板之第1鍍敷 層中具有古銅色，形成層厚7 μιτι之第2鍍敷層。此第2鍍敷 •15- (12) (12)200406504 層之表面藉由PTFE做成平坦面。 將被覆第1及第2鍍敷層於表面所形成之不銹鋼板配置 於維持昇溫至3 8 0 t之爐內後，放置3 0分鐘後進行烘烤處 理，藉由非電解鍍敷取得表面形成薄膜最終製品之鍍敷被 處理物件。 該最終被鍍敷被處理物件之表面粗細度爲〇 . 8 1 μηι。 如上述，該第1鍍敷層表面粗細度及不銹鋼板表面粗細度 分別爲0.35 μιη，及0.18 μηι者，此證明最終被鍍敷被處理 物件（第2鍍敷層）之表面粗細度爲極滑順者。 又，如上述取得之薄膜鍍敷硬度爲4 8 0HV之極高値者 。另外，最終被鍍敷被處理物件之鍍敷密合度爲7 5 0 kgf /cm者。做爲耐腐蝕性試驗由該（A )進行至（C )者，結 果均未出現粒子脫落、穿孔產生之異狀，無任何變化。 [實施例2] 於含有3 0 g / <硫酸鎳、2 0 g / <醋酸銘、0 · 5 g Μ次亞 磷酸鈉，做爲金屬絡合劑之1 · 5 g Μ乳酸，及1 5 g Μ由4 0 重量％氨水，50重量％硫代硫酸鹽，1()重量％氯所成之組成 液’使液之ρ Η爲5 · 3 ’維持液溫於7 0 °C之第1非電解鍍敷 液中浸漬不銹鋼板（JIS規格SUS 3〇4 ) 20分鐘後，由第1 非電解鍍敷液取出此不銹鋼板後，水洗後常溫下進行放置 、乾燥之。不銹鋼板之表面粗細度爲1 μπι。不銹鋼板之表 面於平坦面形成具有溝道涂度約3 μ m凹部之層厚1 〇 μ m的 第1鍍敷層。 - 16- (13) (13)200406504 更將具有該第1鍍敷層之不銹鋼板浸漬於保持70 °C 之第1非電解鍍敷液後，由第2非電解鍍敷液取出此不銹鋼 板，水洗後，於常溫下進行放置乾燥之。該第2非電解鍍 敷液中含有40g / <硫酸鎳、20g Μ醋酸鈷、0.5g Μ次亞 磷酸鈉，做爲金屬絡合劑之〇.5g 甘胺酸，做爲分散補 助劑之1 . 5 g /<氧化鈽，做爲氟樹脂之4 0 g /<聚四氟乙烯 (PTEF )，做爲還原劑之1.5g Μ氧化鈦，陽離子系界面 活性劑之Megafac F-150 (大日本油墨工業（股份））、 及非離子界面活性劑之Tritomnx-100 (石津製藥（股份） )，液之p Η爲5 · 3者。該不銹鋼板之第1鍍敷層上形成具有 古銅色之層厚1〇 μπα之第2鍍敷層。該第2鍍敷層表面藉由 T E F呈平坦面。 第1及第2鍍敷層於表面被覆形成之不銹鋼板配設於保 持昇溫至70 t之爐內，放置20分鐘後進行烘烤處理，藉 由非電解鍍敷取得表面形成薄膜之最終製品被處理物件。 該最終被鍍敷被處理物件之表面粗細度爲5 μηι者。如 上述，第1鍍敷層之表面粗細度及不銹鋼板之表面粗細度 分別爲3 μηι及4 μΐΒ者，此證明最終被鍍敷被處理物件（第 2鍍敷層）之表面粗細度爲極滑順者。 又，如上述取得之薄膜鍍敷硬度爲9 8 0HV之極高値者 。且，最終被鍍敷被處理物件之鍍敷密合度爲7 5 0k gf /cm 者。做爲耐腐蝕性試驗者由該（A )進行至（C )，而， 結果均未出現粒子脫落、穿孔產生之異狀現象，無任何變 化者。 •17- (14) (14)200406504 [實施例3] 於含有40g / <硫酸鎳、40g Μ醋酸鈷、0.5g "次亞 磷酸鈉，1.5g / Μ故爲金屬絡合劑之乳酸，及1 .5g Μ由40 重量％氨水，50重量％硫代硫酸鹽，10重量％氯所成之組成 液，液pH做成6.0，保持液溫於70 °C之第1非電解鍍敷液 中浸漬不銹鋼板（JIS規格SUS 3 04 ) 3 0分鐘後，由第1非 電解鍍敷液中取出此不銹鋼板後，水洗後常溫下進行放置 、乾燥之。不銹鋼板之表面粗細度爲3 μιη。不銹鋼板之表 面於平坦面形成具有溝道深度約3 μπι之凹部的層厚度1 0 μηι之第1鍍敷層。 更使具有第丨鍍敷層之不銹鋼板浸漬於保持7 0 °C之 第Γ非電解鍍敷液中2 0分鐘後，由第2非電解鍍敷液取出此 不銹鋼板，於水洗後，常溫下進行放置、乾燥之。該第2 非電解鍍敷中做成含有2 0 g Μ硫酸鎳、1 5 g /<醋酸鈷、 0 · 5 g / Γ次亞磷酸鈉，做爲金屬絡合劑之〇 . 5 g / <甘胺酸， 做爲分散補助劑之0 · 5 g /<氧化鈽，做爲氟樹脂之4 5 g / < 聚四氟乙烯（PTEF )，做爲還原劑之l〇g Μ氧化鈦，陽 離子性界面活性劑之Megafac F-150 (大日本油墨工業（ 股份））、及非離子界面活性劑之Tritomnx-100 (石津製 藥（股份）），液之pH爲5 · 8者。該不銹鋼板之第1鍍敷層 中形成具有古銅色之層厚10 μιη的第2鍍敷層。此第2鍍敷 層表面藉由TEF呈平坦面。 第1及第2鍍敷層被覆形成於表面之不銹鋼板配設於維 -18- (15) (15)200406504 持昇溫至7 0 °C之爐內，放置2 0分鐘後，進行烘烤處理， 藉由非電解鍍敷取得薄膜形成於表面之最終製品被鍍敷被 處理物件者。 該最終被鍍敷被處理物件之表面粗細度爲2 μιη者。如 上述，第1鍍敷層之表面粗細度及不銹鋼板之表面粗細度 分別爲1 μιη及2 μπι者，此證明最終被鍍敷處理物件（第2 鍍敷層）之表面粗細度爲極滑順者。 又，上述取得之薄膜鍍敷硬度爲48 0HV之極高値者。 且，最終被鍍敷被處理物件之鍍敷密合度爲7 5 0kgf /cm者 。做爲耐腐触性試驗者由該（A )進行至（C )者，而， 結果均未出現粒子脫落、穿孔等異常現象，無任何變化。 [實施例4 ] 於含有30g Μ硫酸鎳、l〇g Μ醋酸鈷、〇.5g / <次亞 磷酸鈉，做爲金屬絡合劑之1 5 g Μ乳酸，及15 g Μ由4 0 重量％氨水’ 50重量％硫代硫酸鹽，1〇重量％氯所成之組成 液，液ρ Η爲5 . 3，維持液溫於7 0 °C之第1非電解鍍敷液中 浸漬不銹鋼板（JIS規格SUS 3〇4 ) 20分鐘後，由第1非電 解鍍敷液取出此不銹鋼板後，水洗後常溫下進行放置、乾 燥之。再與該實施例1相同使用第2非電解鍍敷液後同法進 行鍍敷處理，同條件下進行烘烤處理後，取得鍍敷被處理 物件。 不銹鋼板表面於平坦面形成具有溝道深度約2 μηι凹部 之層厚2 μπι之第1鍍敷層。該第〗鍍敷層形成具古銅色之層 (16) (16)200406504 厚1 5 μηι之第2鍍敷層。 該最終被鍍敷被處理物件之表面粗細度爲2 μηι者。第 1鍍敷層表面粗細度及不銹鋼板表面粗細度分別爲2 μιη及5 μΐΏ者，此證明最終被鍍敷被處理物件（第2鍍敷層）之表 面粗細度爲極滑順者。 又，該取得薄膜之鍍敷硬度爲4 8 0HV之極高値者。且 ，最終被鍍敷被處理物件之鍍敷密合度爲7 8 0k gf /cm。耐 腐蝕性試驗係由該（A )進行至（C )，結果均未出現粒 子脫落、穿孔之異常現象，無任何變化。 [實施例5] 於含有40g / <硫酸鎳、5g Μ醋酸鈷、20g "次亞磷 酸鈉，做爲金屬絡合劑之15g Μ乳酸，〇.5ppm硫脲，液pH 爲5，維持液溫於60 °C之第1非電解鍍敷液中浸漬不銹鋼 板（JIS規格SUS 3 04 ) 20分鐘後，由第1非電解鍍敷液取 出此不銹鋼板，水洗後常溫下進行放置、乾燥之。再與該 實施例1相同使用第2非電解鍍敷液同法進行鍍敷處理，同 條件下，進行烘烤處理後取得鍍敷被處理物件。不銹鋼板 表面於平坦面形成溝道深度具約2 μηι凹部之層厚3 μϊη之第 1鍍敷層。該第〗鍍敷層上形成具古銅色之層厚1 0 μιτι之第2 鍍敷層。 該最終被鍍敷被處理物件表面粗細度爲4 μιη者。第1 鍍敷層表面粗細度及不銹鋼板表面粗細度分別爲2 >m及3 μηι者，此證明最終被鍍敷被處理物件（第2鍍敷層）之表 -20- (17) (17)200406504 面粗細度爲極滑順者。 又，該取得薄膜之鍍敷硬度爲4 8 0HV之極高値者。且 ，最終被鍍敷被處理物件之鍍敷密合度爲7 8 0kgf /cm者。 耐腐蝕性試驗係由該（A )進行至（C )，結果均未出現 粒子脫落、穿孔之異常現象，無任何變化。 【圖式簡單說明】 第1圖代表形成第1鍍敷層於鍍敷被處理物件之狀態所 顯示之截面圖者。 第2圖代表形成第！鍍敷層與第2鍍敷層於鍍敷被處理 物件中之狀態所顯示之截面圖者。 主要元件對照表 3 凹部 2 凸部 4第1鍍敷層 1被處理物件 5第2鍍敷層200406504 Π) 发明. Description of the invention [Technical field to which the invention belongs] The present invention relates to an electroless plating solution and objects using the electroless plating solution and electroless plating treatment. [Previous technology] Fluororesins are extremely durable for chemicals, and have good electrical properties. They are also very good for women who have various characteristics at local temperatures. Therefore, they are usually used on the surfaces of mechanical parts, electrical and electronic parts. Coating of fluororesin. In order to improve the adhesion of the treated object coated with fluororesin, the surface of the processed object is generally roughened in advance, and the method of coating the fluororesin is also performed by inorganic or organic bonding. After the agent is processed, a method for performing a thick coating on a fluororesin having a layer thickness of 100 to 20 μm (eg, JP 2001-328121, JP 2000-328256, JP 4-3 65 8 No. 75, JP 1-605, No. 84, JP 6 1 -23 4202, JP 5 1-1 1 1 2 3 4 8). However, in the prior art method of roughening the surface of the object to be processed, the method of applying a fluororesin coating on the roughened surface showed the following uncomfortable shape. That is, when a rough surface with a small unevenness with a height difference of 1 μ between the concave portion and the convex portion is formed, there is almost no unevenness in the concave portion after the plating layer is buried in the fluororesin, and the density of the fluororesin is dense. The adhesiveness is significantly reduced, and problems such as peeling occur. In addition, fluororesins are expensive. Therefore, in order to reduce costs, the thickness of the fluororesin layer is reduced, and the amount of fluororesins used is reduced to meet market demand. However, (2) (2) 200406504, only for the thinning of the fluororesin coating will cause a reduction in the friction coefficient between the fluororesin and the fluororesin coating, resulting in extremely poor adhesion, and it is easy to produce perforations in the coating. Therefore, there is a problem that it is impossible to form a fluororesin coating film having a thin layer thickness. [Summary of the Invention] The object of the present invention is to provide a non-electrolytic plating object to be treated having a fluororesin film with excellent adhesion to the object to be processed, a method for electroless plating thereof, and a method for electroless plating used therefor. Apply liquid. In order to solve these problems, the present inventors conducted precise investigations and found that the object to be treated was exposed to at least one first plating solution containing a composition liquid selected from the group consisting of ammonia and thiosulfate and thiourea. After the first plating layer is formed, the second plating layer is formed after the surface of the first plating layer is exposed to a second plating solution containing a fluororesin to form a thin film of a fluororesin film having excellent adhesion. That is, the first embodiment of the present invention is characterized by providing at least one group containing a composition liquid selected from the group consisting of a metal salt and a metal complexing agent and a reducing agent, ammonia water and a thiosulfate, and thiourea. Non-electrolytic plating solution. In the non-electrolytic plating solution of the present invention, the thiourea concentration may be 0.1 to 100 ppm. In the non-electrolytic plating solution of the present invention, the metal complexing agent may be lactic acid. In the non-electrolytic plating solution of the present invention, the concentration of the metal complexing agent may be (3) (3) 200406504 is 1 to 100 g ". In the electroless plating solution of the present invention, the metal salt may be at least one selected from the group consisting of nickel salt, cobalt salt, chromium salt, titanium salt, and hypophosphite. A second embodiment of the present invention provides a composition liquid containing at least one object to be exposed which forms a first plating layer, and a composition liquid selected from the group consisting of a metal salt and a metal compound, a reducing agent, and ammonia and a thiosulfate. And the step of forming the first non-electrolytic plating solution in the group of thiourea on the surface of the object to be treated, and forming the second plating layer, further exposing the object to be treated to a fluorine-containing resin, a metal salt, and a metal complexing agent A step of forming the first plating layer after the second #electrolytic plating solution of a reducing agent, a surfactant, and a surfactant is a non-electrolytic plating method characterized by the steps. In the non-electrolytic plating method of the present invention, the thiourea concentration may be in the range of 0 to 10 0 ρ ρ ηι. In the non-electrolytic plating method of the present invention, the metal complexing agent may be lactic acid. In the non-electrolytic plating method of the present invention, the concentration of the metal complexing agent may be 1 to 1 g. In the non-electrolytic plating method of the present invention, the metal salt may be at least one selected from the group consisting of nickel salt, cobalt salt, chromium salt, titanium salt, and hypophosphite. In the non-electrolytic plating method of the present invention, the metal salt contained in the second non-electrolytic plating solution may be at least one selected from the group consisting of a nickel salt, a cobalt salt, a chromium salt, a phosphonium salt, and a hypophosphite. Group of people. (4) 200406504 In the non-electrolytic plating method of the present invention, the surfactant contained in the second non-electrolytic plating solution may be at least one member selected from the group consisting of a cationic surfactant and a non-ionic surfactant. . In the non-electrolytic plating method of the present invention, the concentration of the fluororesin contained in the second non-electrolytic plating solution may be 20 to 60 g / lt; A third embodiment of the present invention provides a plated object to be treated whose characteristics are obtained by the electroless plating method. In the plated object of the present invention, the plating hardness may be 400 HV or more. In the plated object of the present invention, the plating adhesion strength may be 350 kgf / cm or more. [Embodiment] [The best form of the invention implementation] The non-electrolytic plating solution of the present invention, and the ideal form using the non-electrolytic plating method and the non-electrolytic plating object to be processed will be described in detail below. The non-electrolytic plating solution (the first non-electrolytic plating solution) is a group containing at least one selected from the group consisting of a composition liquid containing a metal salt and a metal complexing agent and a reducing agent, ammonia water and a thiosulfate, and thiourea. The non-electrolytic plating method of the present invention further includes the steps of exposing the object to be processed to the non-electrolytic plating solution (i-th non-electrolytic plating solution), forming a first plating layer on the surface of the object to be processed, and exposing the object to be processed After the second non-electrolytic plating solution of fluororesin, metal salt, metal complexing agent, and surfactant, the first plating-8-Λ '^' ϋ '(5) (5) 200406504 layer is formed Steps of the second plating layer. In addition, Fig. 1 is a schematic cross-sectional view showing a state where a first plating layer is formed on an object to be plated. Fig. 2 is a schematic cross-sectional view showing a state where a first plating layer and a second plating layer are formed on an object to be plated. 1 represents an object to be processed, 2 represents a convex portion, 3 represents a concave portion, 4 represents a first plating layer, and 5 represents a second plating layer. The "non-electrolytic plating" refers to a method of plating on an object to be processed without being energized. The object to be processed can be a wide range of substrates such as metal products, alumina products, rubber products, and synthetic resins. In addition, it is preferable that the object to be processed is processed in advance to improve the adhesiveness with the object to be processed, etc. in advance. The metal salt contained in the first non-electrolytic plating contains nickel salt, cobalt salt, and salt salt. , Titanium salt, and hypophosphite can be used alone or in combination, but they are not limited to these. Ideally, at least one or more members are selected from the group consisting of nickel salts and cobalt salts. The metal complexing agent contained in the first non-electrolytic plating solution of the present invention is an organic substance or the like which forms a complex with a metal salt. However, it is preferable to obtain an ideal concave surface on the object to be processed. Although not particularly limited, lactic acid is generally preferred as a metal complexing agent. When the metal complexing agent is reduced in the plating solution, powder particles of the metal complexing agent are generated in the plating solution, and when large metal complexing agent powder particles of about 2 to 3 μm are generated, the solution will be unstable in the liquid. In order to promote the decomposition of the liquid, it is not appropriate to obtain a concave surface. In lactic acid, the fine particle powder is 1 μm or less, so the liquid decomposition is small, and a concave surface is preferable. In addition, as the metal complexing agent contained in the second non-electrolytic plating solution, conventional ones such as glycine-9-(6) (6) 200406504 acid can be used. The concentration of the metal complexing agent contained in the first non-electrolytic plating solution is preferably 1 to 100 g, and more preferably 10 to 20 g / <. When the concentration of the metal complexing agent in the plating solution is increased, the plating layer is roughened, and the unevenness (level difference) on the surface of the plating layer becomes larger, and a good adhesion with the fluororesin coating can be obtained. When the concentration of the metal complexing agent is within this range, the unevenness level suitable for the fluorine coating can be obtained, and no liquid is decomposed, and a particularly good adhesion with the fluorine resin coating can be obtained. The composition solution containing ammonia water and thiosulfate and thiourea contained in the first non-electrolytic plating solution can be used for uniformly forming the convex and concave convex portions on the surface of the plating layer to obtain a coating with fluororesin. Objects with very good adhesion. Hereinafter, it demonstrates in more detail. As described above, when plating an object to be treated with a non-electrolytic plating solution (first non-electrolytic plating solution) containing a low-concentration metal complexing agent, the surface of the plating layer has almost no unevenness, and the unevenness (level difference) is extremely small. Even with a fluororesin coating on the surface plating layer, a good fluororesin coating cannot be obtained. In addition, as the concentration of the metal complexing agent in the plating solution increases, the plating layer becomes rough, and the unevenness (level difference) on the surface of the plating layer becomes larger. However, the unevenness of the localized unevenness of the 'but' convex portion forms an irregular plating layer. . Even if a fluororesin coating is applied to the plating layer with uneven surface protrusions in this manner, a fluororesin coating with good adhesion cannot be obtained. When the present inventors formed the first plating layer formed on the surface of the object to be treated, the first electroless plating solution contained the composition liquid, thiourea, or a mixture thereof, and then raised the convex portion on the surface of the first plating layer. The uniformity of the height, that is, the first plating layer formed on the flat surface of the plating layer to form a recess, and the first plating layer is coated with a fluororesin with a second non-electrolytic plating solution containing a fluororesin. (7) (7) 200406504 fluororesin coating with excellent mutual adhesion with the object to be processed appeared, and the present invention was completed. In addition, after using the composition liquid and thiourea, the height of the convex portion on the surface becomes constant, and the sequence of forming the plating layer forming the concave portion on the flat portion is still unclear. However, the composition liquid and thiourea can be considered at random. Suppresses the precipitation of unevenness in morphology. As the thiosulfate contained in the ammonia water and the thiosulfate composition liquid, thiosulfate can be used. The ammonia-containing water and thiosulfate composition liquid contained in the first non-electrolytic plating solution may further contain chlorine and the like. The content of the composition liquid contained in the first non-electrolytic plating liquid is determined from the surface where a fluororesin coating layer with good adhesion can be obtained, and it is preferably 1 to 40 g / <, and 10 to 30 g M is more preferred. Best. The content of thiourea contained in the non-electrolytic plating solution is based on the surface of the fluororesin coating with good adhesion. The thiourea concentration in the first non-electrolytic plating solution is preferably 0.1 to 100 ppm, and more preferably It is 50 ~ 100ppm. In addition, after a large amount of thiourea is used, its toxic effect becomes stronger, and after the reaction with the fluororesin, the resin is decomposed, resulting in the formation of a film of the fluororesin which is not easy. However, an ideal fluororesin coating can be obtained within the concentration range. As the reducing agent contained in the first non-electrolytic plating solution and the second non-electrolytic plating solution, conventional ones such as sodium borohydride can be used. The pH of the first non-electrolytic plating solution and the second non-electrolytic plating solution need only be a pH at which the metal salt contained in these plating solutions can be metal precipitated. The metal salt in the plating solution forms a stable soluble complex with lactic acid. With the increase of pH, the concentration of free metal ions decreases, and the equilibrium potential moves to the negative direction. Therefore, if the pH is too high, it is not easy to precipitate metal. If it is lower, the film will re-melt and it is difficult to precipitate metal. In the plating process of the present invention, -11-(8) (8) 200406504 metal precipitation is performed well. The p of the first non-electrolytic plating solution and the second non-electrolytic plating solution is preferably 4.1 to 6.0. . As the fluororesin-based fluororesin contained in the second non-electrolytic plating solution, a fluororesin such as tetrafluoroethylene (PTFE) can be used. The content of the fluororesin in the second non-electrolytic plating solution can be arbitrarily selected according to its use, and generally it is preferably 20 to 60 gM, and it is not limited thereto. The surfactant contained in the second non-electrolytic plating solution can prevent the precipitation of composite materials, and the fluororesin dispersion and penetration in the recess of the first non-electrolytic plating solution is good, which can be used as a fluororesin dispersant. Full performance. Among the surfactants, at least one selected from the group consisting of a cationic surfactant and a nonionic surfactant is preferably used. Among cationic surfactants, those containing a 4th ammonium salt, a second amine, a third amine, or an imidazoline can be used. Nonionic surfactants can be polyethylene oxide, polyethylene, or carboxylate. Those having an acidic sulfonic acid nonionic interface activity are not particularly limited thereto. Further, a fluorine surfactant having a carbon element and a fluorine atom bond in the molecule may be used. The content of the surfactant in the second non-electrolytic plating solution is preferably from 0.1 to 1 g / lt; and more preferably from 0.1 to 0.5 gM. A fluororesin containing a metal salt within this range can be a good dispersion invader in the concave portion of the first plating layer, and the surface roughness of the second plating layer can be reduced, and the surface can be appropriately lubricated. Further, in the second non-electrolytic plating solution, it is preferable that the fluororesin is dispersed and penetrated into the concave portion of the first plating layer, and therefore it is preferable to contain a dispersion aid. This dispersion aid is generally one containing rhenium oxide and silicon carbide, but it is not particularly limited thereto. The non-electrolytic plating treatment step of the present invention can be performed in the same manner as the non-electrolytic plating method commonly used in the plating industry. An example of the plating process step is described below, but it is not limited thereto. First, the object to be treated is immersed in the first non-electrolytic plating solution at a liquid temperature of about 60 to 70 ° C for 5 to 30 minutes, and then taken out. After being washed with water, it is placed in an environment of about 25 ° C at normal temperature. ， Hydrolyzed, ①Hai Di 1 non-electrolytic plating solution through the plating layer obtained after the plating process, the height of the convex part is uniform. Next, immerse the object to be processed treated by the first plating solution in a second non-electrolytic plating solution at a liquid temperature of about 60 to 70 ° C for 6 to 120 minutes, and then take it out and wash it at room temperature for about 2 5 Store at ° C and dry. The first plated layer and the second plated layer are coated on the surface with the object to be processed formed, and placed in a furnace that maintains a temperature increase of about 300 to 5000 ° C. After being left for 10 to 60 minutes, baking treatment is performed. After that, the plated to-be-processed object of the present invention having a fluororesin coating is obtained on the surface of the to-be-processed object. The article to be plated to be plated by the non-electrolytic plating method of the present invention will be described below. The thickness of the first plating layer of the object to be plated is to obtain the adhesion between the object to be treated and the fluororesin. It is preferably 0. 1 to 50 μm, and more preferably 0. 1 to 10 μm. . In order to make the film thickness of the good adhesion of the fluororesin, the film thickness of the second plating layer of the object to be plated is preferably 0. 1 to 50 μm, and more preferably 0.1 to 30 μm. . The fluorinated resin coating obtained by this method has good adhesion between the fluororesin coating and the processed object, and has 350 kg f / cm, preferably 600 kgf / cm or more, and 75 0 kgf / cm or more. The close strength. In addition, the object to be plated obtained by this method is one having a hardness of 40 HV or more, and a hardness of 500 HV or more is preferable, and 950 HV or more is the most preferable. -13- (10) (10) 200406504 [Examples] The following represents specific examples of the non-electrolytic plating solution of the present invention, the method of using the non-electrolytic plating, and the plating of objects to be processed, but this embodiment is based Examples of the embodiments of the invention are not limited to these. In addition, for the plated object to be obtained in each Example, the surface roughness was measured, the plating hardness was measured, the plating adhesion strength was measured, the corrosion resistance test, and the surface analysis were performed according to the following measurement conditions. The measurement of the surface roughness was performed by a fluorescent X-ray method. The measurement of the plating adhesion strength is performed in accordance with the metal bending method specified in JIS B 772 1 (that is, the metal plate is bent, and the peeling method of the surface treatment is determined by the bending force). In the measurement of plating hardness, the Shimadzu micro hardness tester HNV-2 000 (shares) (manufactured by Shimadzu Corporation) is used as the hardness tester. The corrosion resistance test was performed by (A) immersing in a hydrochloric acid solution (concentration 36.47%) at 100 ° C for 60 minutes, then taking it out of the solution, washing it, placing it at room temperature and drying it. (B) After permeating in 100 ° C sodium hydroxide solution (concentration 50%) for 80 minutes, take it out of the solution, leave it at room temperature, and dry it. (C) Trichloroethylene solution at 100 ° C (Concentration: 50%) (fluoric acid solution, hydrochloric acid solution, and sulfuric acid solution are all 20%). After infiltration at a temperature of 25 t for 24 hours, they are taken out of the solution and used for electron microscopy (Scanning E 1 ectr ο η M icr) 〇sc 〇) After washing with pure water and drying at room temperature, the surface is enlarged by 5000 times, and then observed. Surface analysis is used to detect the occurrence of particle shedding and perforation. -14- (11) (11) 200406504 The surface of the processed object was enlarged to 50000 times by an electron microscope, and then observed and inspected. [Example 1] A metal complexing agent containing 40 g of nickel sulfate, 25 g of cobalt acetate, and 0.5 g of sodium hypophosphite as a metal complexing agent was 10 g / < lactic acid and 40 g / < 40% by weight of ammonia water, and A composition solution of 50% by weight of thiosulfate and 10% by weight of chlorine, the p Η of the solution is 5.8, and the first non-electrolytic plating solution maintained at 80 ° C is immersed in a stainless steel plate (JIS standard) SUS 3 04) After 30 minutes, the stainless steel plate was taken out of the first non-electrolytic plating solution, and after being washed with water, it was left to dry at room temperature. The surface thickness of the stainless steel plate is 0.18 μm. The first plated layer having a thickness of 5 μm on the flat surface of the steel plate having a recessed portion with a channel depth of about 4 μm was formed. After the stainless steel plate having the first plating layer was immersed in the first non-electrolytic plating solution maintained at 70 ° C for 20 minutes, the stainless steel plate was taken out from the second non-electrolytic plating solution and washed at room temperature under water. Place and dry. The second electroless plating contains 30 g of nickel sulfate, 20 g of cobalt acetate, 0.5 g of sodium hypophosphite, 0.5 g of glycine as a metal complexing agent, and 15 g / < as Disperse supplementary osmium oxide, 60 g Μ as tetrafluoroethylene for fluororesin (PTEF >, 10 g / < Phosphorus oxide as surface stabilization effect, Megafac F-150 (Danippon Ink) Industry (stock)), and non-ionic surfactant Tritomnx-100 (Ishizu Pharmaceutical Co., Ltd.), made with a liquid pH of 3.5. The first plating layer of this stainless steel plate has a bronze color, forming a layer thickness of 7 μιτι The second plating layer. The surface of this second plating • 15- (12) (12) 200406504 layer is made of PTFE. The stainless steel plate formed by coating the first and second plating layers on the surface is arranged. After maintaining the temperature in the furnace to 380 ton, leave it for 30 minutes and bake it, and obtain the plated object to be processed by electroless plating to form the final product with a film on the surface. The final plated object to be processed The surface thickness of the first plating layer is 0.8 1 μηι. As described above, the surface thickness of the first plating layer is The surface thickness of the stainless steel plate is 0.35 μm and 0.18 μm respectively, which proves that the surface thickness of the object to be plated (the second plating layer) is extremely smooth. Also, the film plating obtained as described above Those with a hardness of 4 8 0 HV are extremely high. In addition, the plating adhesion of the object to be plated is 750 kgf / cm. The corrosion resistance test is performed from (A) to (C). The results did not show any abnormalities such as particle shedding and perforation, without any changes. [Example 2] In the case of containing 30 g / < nickel sulfate, 20 g / < acetate acetate, 0.5 g Sodium phosphate, 1.5 g of lactic acid as a metal complexing agent, and 15 g of liquid consisting of 40% by weight ammonia, 50% by weight thiosulfate, and 1 (%) by weight chlorine Ρ Η is 5 · 3 '. The stainless steel plate (JIS standard SUS 30) was immersed in the first non-electrolytic plating solution at a temperature of 70 ° C at 20 ° C, and then taken out from the first non-electrolytic plating solution. After the stainless steel plate is washed and placed at room temperature and dried, the surface thickness of the stainless steel plate is 1 μm. The surface of the stainless steel plate is On the flat surface, a first plating layer with a thickness of 10 μm having a concave portion with a channel coating degree of about 3 μm is formed.-16- (13) (13) 200406504 Further, the stainless steel plate having the first plating layer is dipped After maintaining the first non-electrolytic plating solution at 70 ° C, the stainless steel plate was taken out from the second non-electrolytic plating solution, washed with water, and left to dry at room temperature. This second non-electrolytic plating solution contains 40 g / < nickel sulfate, 20 g Μ cobalt acetate, 0.5 g MN hypophosphite, 0.5 g of glycine as a metal complexing agent, and 1 of a dispersion aid 5 g / < scandium oxide, 40 g / < polytetrafluoroethylene (PTEF) as a fluororesin, 1.5 g of Μ titanium oxide as a reducing agent, Megafac F-150 (a cationic surfactant) ( Dainippon Ink Industry Co., Ltd.), and Tritomnx-100 (Ishizu Pharmaceutical Co., Ltd.), a non-ionic surfactant, whose p p is 5.3. A second plating layer having a bronze-colored layer thickness of 10 μπα was formed on the first plating layer of the stainless steel plate. The surface of the second plating layer is flat by T E F. The stainless steel plate formed by coating the first and second plating layers on the surface is arranged in a furnace maintained at a temperature of 70 t, and it is baked for 20 minutes, and the final product of the surface-forming film is obtained by non-electrolytic plating. Handle objects. The surface thickness of the finally plated object to be processed is 5 μm. As described above, the surface thickness of the first plating layer and the surface thickness of the stainless steel plate are 3 μηι and 4 μΐΒ, respectively. This proves that the surface thickness of the object to be plated (the second plating layer) is extremely fine. Smooth person. In addition, the thin film plating hardness obtained as described above is extremely high at 980 HV. In addition, the plating adhesion of the object to be plated is 750 kgf / cm. As a corrosion resistance tester, proceed from (A) to (C), and the results did not show the phenomenon of particles falling off and perforation, without any change. • 17- (14) (14) 200406504 [Example 3] In lactic acid containing 40g / < nickel sulfate, 40g Μ cobalt acetate, 0.5g " sodium hypophosphite, 1.5g / Μ is a metal complexing agent, And 1.5 g of the first non-electrolytic plating solution composed of 40% by weight ammonia water, 50% by weight thiosulfate, and 10% by weight chlorine, the liquid pH being 6.0, and the liquid temperature maintained at 70 ° C After 30 minutes, the stainless steel plate (JIS standard SUS 3 04) was taken out from the first non-electrolytic plating solution, and the stainless steel plate was left at room temperature and dried after being washed with water. The surface thickness of the stainless steel plate is 3 μm. On the flat surface of the stainless steel plate, a first plating layer having a layer thickness of 10 μm and a recessed portion having a channel depth of about 3 μm was formed on a flat surface. After immersing the stainless steel plate with the first plating layer in the Γ non-electrolytic plating solution maintained at 70 ° C for 20 minutes, the stainless steel plate was taken out from the second non-electrolytic plating solution, and washed with water at room temperature. Place and dry. In the second electroless plating, 20 g of nickel sulfate, 15 g / < cobalt acetate, 0.5 g / Γ sodium hypophosphite were prepared, and 0.5 g / < Glycine, 0.5 g / < osmium oxide as a dispersion aid, 4 5 g / < polytetrafluoroethylene (PTEF) as a fluororesin, 10 g Μ oxidation as a reducing agent Titanium, Megafac F-150 (Danippon Ink Industry (Stock)), a cationic surfactant, and Tritomnx-100 (Ishizu Pharmaceutical (Stock)), a non-ionic surfactant, whose pH is 5 · 8. A second plating layer having a bronze-colored layer thickness of 10 µm was formed in the first plating layer of the stainless steel plate. The surface of this second plating layer is flat by TEF. The first and second plating layers are formed on the surface of the stainless steel plate. The stainless steel plate is placed in a V-18-18 (15) (15) 200406504. The furnace is heated to 70 ° C and left for 20 minutes before baking. The final product formed on the surface by electroless plating is plated with the object to be processed. The surface thickness of the finally plated object to be processed is 2 μm. As described above, the surface thickness of the first plating layer and the surface thickness of the stainless steel plate are 1 μm and 2 μm, respectively. This proves that the surface thickness of the object to be plated (the second plating layer) is extremely smooth. Along the way. In addition, the obtained film plating hardness was extremely high at 48 0 HV. In addition, the plating adhesion degree of the object to be plated and finally treated is 750 kgf / cm. As the tester for corrosion resistance, the test was carried out from (A) to (C), and the results did not show any abnormalities such as particle shedding and perforation, and there was no change. [Example 4] 15 g of lactic acid as a metal complexing agent containing 30 g of nickel sulfate, 10 g of cobalt acetate, 0.5 g / < sodium hypophosphite, and 15 g of MG by 40 weight % Ammonia water '50% by weight thiosulfate, 10% by weight chlorine composition liquid, the liquid ρ Η is 5.3, the first non-electrolytic plating solution maintained at 70 ° C immersed stainless steel plate (JIS standard SUS 304) After 20 minutes, the stainless steel plate was taken out from the first non-electrolytic plating solution, and it was left to stand at room temperature after being washed with water and dried. After using the second non-electrolytic plating solution in the same manner as in Example 1, the plating treatment was performed in the same manner, and the baking treatment was performed under the same conditions to obtain an object to be plated. On the surface of the stainless steel plate, a first plating layer having a channel thickness of about 2 μm and a recess thickness of about 2 μm was formed on the flat surface. The first plating layer forms a layer with a bronze color. (16) (16) 200406504 A second plating layer with a thickness of 15 μm. The surface thickness of the finally plated object to be treated is 2 μm. The surface thickness of the first plating layer and the surface thickness of the stainless steel plate are 2 μm and 5 μΐΏ, respectively. This proves that the surface thickness of the object to be plated (the second plating layer) is extremely smooth. The obtained film had a plating hardness of extremely high 480 HV. In addition, the plating adhesion of the object to be plated and finally treated was 780 kgf / cm. The corrosion resistance test was carried out from (A) to (C). As a result, there was no abnormal phenomenon of particle shedding and perforation, and there was no change. [Example 5] In a solution containing 15 g of lactic acid as a metal complexing agent containing 40 g / < nickel sulfate, 5 g of cobalt acetate, 20 g of sodium hypophosphite, 0.5 ppm of thiourea, the pH of the liquid was 5, and the maintenance liquid The stainless steel plate (JIS standard SUS 3 04) was immersed in the first non-electrolytic plating solution at a temperature of 60 ° C. After 20 minutes, the stainless steel plate was taken out from the first non-electrolytic plating solution. After being washed, it was left to stand at room temperature and dried. . The second non-electrolytic plating solution was used in the same manner as in Example 1 to perform the plating treatment, and under the same conditions, a plated object was obtained after baking treatment. On the surface of the stainless steel plate, a first plating layer having a channel depth of about 2 μηι and a thickness of 3 μϊη was formed on a flat surface. A second plating layer with a bronze-colored layer thickness of 10 μm was formed on the first plating layer. The final thickness of the surface of the object to be plated is 4 μm. The surface thickness of the first plating layer and the surface thickness of the stainless steel plate are 2 > m and 3 μm, respectively. This proves that the final object to be plated (the second plating layer) is -20- (17) ( 17) 200406504 The surface thickness is extremely smooth. The obtained film had a plating hardness of extremely high 480 HV. And, the plating adhesion degree of the object to be plated and finally treated is 780 kgf / cm. The corrosion resistance test was carried out from (A) to (C). As a result, there were no abnormal phenomena such as particle shedding and perforation, and there was no change. [Brief description of the drawings] Fig. 1 represents a cross-sectional view showing the state where the first plating layer is formed on the plated object. Figure 2 represents the formation of the first! A cross-sectional view showing the state of the plating layer and the second plating layer in a plated object. Comparison table of main components 3 Concave part 2 Convex part 4 First plating layer 1 Object to be processed 5 Second plating layer