201229254 六、發明說明： 【發明所屬之技術領域】 本發明係關於電磁開關、斷路器、繼電器等電磁開閉器所 使用的電接點材料。 【先前技術】 習知銀-氧化物系電接點材料為求耐熔接性、耐消耗性、 溫度特性的提升，係利用内部氧化條件的變更、或添加第3 元素、第4元素，而逐次克服性能的問題。例如在Ag中添 加Sn、In、Sb、Bi等並施行内部氧化處理的材料(例如參照 專利文獻1)。 再者，已提案有：將具有依mass(質量)％計，含有：Sn : 4〜11%、In : 1 〜5%、Te : 0.05〜3%、Cd : 0.05〜3%，視需要 進一步含有Fe、Ni、Co中之1種以上：0.01〜1%，其餘為 Ag與不可避免的雜質所構成之組織的Ag合金，施行内部 氧化處理者(例如參照專利文獻2)。 [先行技術文獻] [專利文獻] [專利文獻1]曰本專利特開2002-363665號公報 [專利文獻2]日本專利特開平5-86426號公報 【發明内容】 (發明所欲解決之問題） 然而，上述習知技術中，銀-氧化物系電接點材料係藉由 100126295 3 201229254 重複進行電性開閉，而在接點表層堆積氧化物，因為此原因 而會有接點表面的接觸電阻提高、引發溫度上升的問題。 為解決此種溫度上升的問題，雖有減少所添加氧化物量的 方法，但若減少所添加氧化物的量，便會有耐溶接性、财消 耗性下降的問題。 獲得安定的接觸電阻，且實現優異的溫度特性，恰與圖謀 熔接性、耐消耗性的提升相違背，在接點材料的選擇時通常 會構成問題。 本發明的課題便在於解決此種問題。 (解決問題之手段） 緣是，本發明係在銀-氧化物系電接點材料的接點面，將 1 〜99mass%Ag-W、1 〜99mass%Ag-WC、WC 或 W 中之 1 種 以上施行厚度0.1 μιη〜1 ΟΟΟμπι的塗佈’藉此便可降低接點的 電阻值，且不會有異常的溫度上升，且達耐熔接性、耐消耗 性的大幅提升，即便使用於高負荷用電接點材料的情況，仍 可作為長壽命的接點。 舉例而言，圖18係顯示在91.7Ag-5.5SnO2-2.5In2O3-0.3NiO的接 點材料塗佈W的接點之組織照片。 再者，在電接點材料與 1〜99mass%Ag-W、 1〜99mass%Ag-WC、WC或W的塗佈層之間’施行pt、Au、 Ag、Ni、Cu中之至少1種的盡佈，藉此便可降低接點的電 阻值，且具有防止異常溫度上升之效果，且達耐熔接性、耐 100126295 4 201229254 消耗性的大幅提升，即便使用於高負荷用電接點材料的情 況，仍可作為長壽命的接點。 另外，塗佈方法係利用電漿熔射、氣體熔射、高速火焰熔 射等熔射施行的塗佈，或在諸如圖1與圖2所示氣中或液中 利用間歇式放電、脈衝等放電施行的塗佈，或PVD、CVD 等蒸鍍法等等實施。 上述中’將塗佈層的1層厚度設為〇·1μιη〜l〇〇〇Mm範圍之 理由為：若1層的厚度未滿〇.lMm，便沒有塗佈的效果。又， 若1層的厚度超過ΙΟΟΟμπι，就從技術及生產成本的層面觀 之，較難施行塗佈的緣故所致。 再者，1〜99mass%Ag-W、1〜99mass%Ag-WC 中，若 Ag 成为未滿lmass%、及超過99mass%，便喪失Ag合金的意 義。 (發明效果） 依此構成的本發明係藉由在銀_氧化物系的電接點材料施 行上述構成的塗佈，便可降低接點的電阻值，提升耐熔接 性、耐消耗性，俾可達長壽命化。 再者，藉由在電接點材料與塗佈層之間，施行pt、Au、 g Cu中之至少1種的塗佈，便可更加降低接點的電 阻值，防止異常的溫度上升，大巾I提升翁接性、耐消耗性， 即便使用於尚負相電接點材料的情況’仍可達長壽命化。 【實施方式】 100126295 201229254 以下’參照圖式，針對本發明的實施例進行說明。 首先’製作板厚L2mm、3.5mm見方尺寸、經依氧分壓 0.5MPa、内部氧化溫度7〇〇ΐ施行48小時内部氧化，且由 91.7mass%Ag - 5.5mass%Sn - 2.5mass%In - 0.3mass%Ni 構 成的接點材料。 [實施例1] 對上述接點材料利用氣中放電（參照圖1)施行 lmaSS%Ag-W的塗佈而形成8〇〇μιη層厚。 氣中放電的條件係陽極連接著由lmass%Ag-W構成的接 點材料’而陰極連接著由9i.7mass%Ag - 5.5mass%Sn -2‘5mass%In - a3mass%Ni構成的接點材料，在大氣中，依 電流1〜3A、電壓60V、放電距離lmm、300〜400Hz產生振 動，藉由間歇式放電而施加如圖3所示塗佈層4。 另外’圖1中’ 1係電極，2係接點。 再者’上述係依氣中放電實施，但亦可為液中放電，如圖 2所示’將接點2放入磷酸三鈣溶液或5%檸檬酸水溶液等 一般的電解液3中，並在與電極丨之間施行放電。 [實施例2] 對上述接點材料利用氣中放電（參照圖丨）施行 lmaSS%Ag-WC的塗佈而形成1〇〇μηι層厚。 氣中放電的條件係陽極連接著lmass%Ag-WC的接點材 料，而陰極連接著 91.7mass%Ag - 5.5mass%Sn - 2.5mass0/〇In 100126295 6 201229254 -0.3mass%Ni的接點材料，在大氣中，依電流、電壓 60V、放電距離lmm、3〇〇〜4〇〇Hz產生振動藉由間歇式放 電而施加如圖4所示部分塗佈層4。 [實施例3] 對上述接點材料表面施行噴擊處理後，利用電漿喷流熔射 施行塗佈。 上述電漿噴流熔射的條件係在電漿噴流環境中，將粒度 5〜125μηι的Ag粉末、與w粉末，依成為5〇 : i的方式混 入，並在大氣中，依噴射電流5〇〇〜8〇〇A、熔射距離1〇〇mm、 電漿氣體使用氬（流量3〇1/min)，使熔射槍依·mm/sec進 行往復移動而施加塗佈層4的厚度為〇.1μιη、且塗佈層4的 組成為50mass%Ag-W的塗佈層。 [實施例4] 利用與上述實施例3同樣的電漿熔射，施加塗佈層4的厚 度為20μιη、塗佈層4的組成為5〇mass%Ag WC的塗佈層4。 [實施例5] 利用與上述實施例3同樣的電漿熔射，施加塗佈層4的厚 度為500μιη、塗佈層4的組成為99mass%Ag-W的塗佈層4。 [實施例6] 利用與上述實施例3同樣的電漿熔射，施加塗佈層4的厚 度為ΙΟΟΟμπι、塗佈層4的組成為99mass%Ag-WC的塗佈層 4 〇 100126295 7 201229254 [實施例7] 利用與上述實施例3同樣的電漿熔射，施加塗佈層4的厚 度為300μηι、塗佈層4的組成為w的塗佈層4。 [實施例8] 利用與上述實施例3同樣的電漿熔射，施加塗佈層4的厚 度為600μηι、塗佈層4的組成為WC的塗佈層4。 [實施例9] 利用與上述實施例3同樣的電漿熔射，施加塗佈層的i 層厚度為50μηι ’塗佈層的組成如圖5所示，從下方起設為 由lmass%Ag_W與lmass°/〇Ag-WC呈交錯形成8層的塗佈 層4。 [實施例10] 利用與上述實施例3同樣的電聚炫射，施加塗佈層的1 層厚度為50μηι，塗佈層的組成如圖6所示，從下方起設為 由50mass%Ag-W與50mass%Ag-WC呈交錯形成6層的塗 佈層4。 [實施例11] 利用與上述實施例3同樣的電漿熔射，施加塗佈層的1 層厚度為50μιη，塗佈層的組成如圖7所示’從下方起設為 由99mass%Ag-W與99mass%Ag-WC呈交錯形成4層的玄 佈層4。 [實施例12] 100126295 8 201229254 利用與上述實施例3同樣的電漿熔射，施加塗佈層的1 層厚度為50μιη ’塗佈層的組成如圖8所示，從下方起設為 由W與WC形成2層的塗佈層4。 [實施例13] 對板厚1.2mm、3.5mm見方尺寸、經依氧分壓〇.5MPa、 内部氧化溫度700 C施行48小時内部氧化，且由 91.7mass%Ag - 5.5mass%Sn - 2.5mass%In - 0.3mass%Ni 構 成的接點材料表面施行噴擊處理後，利用電漿喷流熔射施加 塗佈層。 電漿喷流熔射的條件係依與上述實施例3同樣的條件實 施，在電漿噴流環境中將粒度5〜125μιη的Ag粉末與W粉 末依成為99 : 1的方式混入，逐漸增加w粉末的量而使組 成呈階段性變化’並施加塗佈層的1層厚度為ΙΟΟμιη、塗佈 層的組成如圖9所示，從下方起設為99mass%Ag-W、 75massAg-W 、50mass%Ag-W、25mass%Ag-W 、及 lmass%Ag-W的塗佈層4。 [實施例14] 與實施例13同樣地操作，施加塗佈層的1層厚度為 ΙΟΟμιη，塗佈層的組成如圖10所示，從下方起為 99mass%Ag-WC、75mass%Ag-WC、50mass%Ag-WC、 25mass%Ag-WC、及 lmass%Ag-WC 的塗佈層 4。 [實施例15] 100126295 9 201229254 對板厚1.2mm、3.5mm見方尺寸、經依氧分壓〇.5MPa、 内部氧化溫度700¾施行48小時内部氧化，且由 91.7mass%Ag · 5.5mass%Sn - 2.5mass%In - 0.；3mass%Ni 構 成的接點材料表面施行噴擊處理後，利用電漿喷流熔射施加 塗佈層。 電激喷流熔射的條件係依照與上述實施例3同樣的條件 施行’施加塗佈層的1層厚度為5〇μιη ’塗佈層的組成如圖 11所不’從下方起由lmass%Ag-W與Au呈交錯形成5層 的塗佈層4。 [實施例16] 與上述實施例15同樣地操作，施加塗佈層的1層厚度為 40μιη ’塗佈層的組成如圖丄2所示，從下方起為 lmass%Ag-W、Au及Pt呈交錯形成7層的塗佈層4。 [實施例17] 與上述實施例15同樣地操作，施加塗佈層的1層厚度為 50μιη ’塗佈層的組成如圖13所示，從下方起為 50mass%Ag-W與Au呈交錯形成5層的塗佈層4。 [實施例18] 與上述實施例15同樣地操作，施加塗佈層的1層厚度為 40μιη ’塗佈層的組成如圖14所示，從下方起為 50mass%Ag_W ' Au及pt呈交錯形成7層的塗佈層4。 [實施例19] 100126295 10 201229254 與上述實施例15同樣地操作，施加塗佈層的1層厚度為 20μηι，塗佈層的扭成如圖15所示，從下方起為 99mass°/〇Ag-W與Au呈交錯形成9層的塗佈層4。 [實施例20] 與上述實施例15同樣地操作，施加塗佈層的1層厚度為 20μιη，塗佈層的組成如圖16所示，從下方起為 99mass%Ag-WC、Au及Pt呈交錯形成10層的塗佈層4。 [實施例21] 與上述實施例15同樣地操作，施加塗佈層的1層厚度為 ΙΟμιη，塗佈層的組成如圖17所示，從下方起為 99mass%Ag-WC、Ni、Ag及Cu呈交錯形成9層的塗佈層4。 [比較例1] 製作板厚1.2mm、3.5mm見方尺寸、經依氧分壓0.5MPa、 内部氧化溫度700°C施行48小時内部氧化，且由 91.7mass%Ag - 5.5mass%Sn - 2.5mass%In - 0.3mass%Ni 構 成的接點。 [比較例2] 製作板厚1.2mm、3.5mm見方尺寸、經依氧分壓0.5MPa、 内部氧化溫度700°C施行48小時内部氧化，且由 92.3mass%Ag - 5mass%Sn - 2.5mass%In - 0.2mass%Ni 的接點。 [比較例3] 100126295 11 201229254 製作板厚1.2mm、3.5mm見方尺寸、經依氧分壓0.5MPa、 内部氧化溫度700°C施行48小時内部氧化，且由 91.9mass%Ag - 7mass%Sn - lmass%In - 0.1mass%Ni 構成的 接點。 針對上述各實施例與比較例施行接點試驗。接點試驗係施 行接觸電阻的測定與熔接試驗(60A定格用），以及利用市售 接觸器進行的消耗量測定(AC200V 20A)，並對電氣特性進 行評估。 100126295 12 201229254 【Id 接觸電阻(πιΏ) 10萬次開閉後 0.43 0.52 0.58 0.51 0.47 0.41 0.48 0.45 0.45 0.49 0.64 0.53 0.51 0.53 0.56 0.57 0.58 0.55 0.54 0.58 0.63 0.64 0.75 0.67 使用前 0.23 0.28 0.27 0.32 0.22 0.21 0.25 0.24 0.23 0.26 0.26 0.24 0.23 !_〇·25 0.25 0.26 0.27 0.31 0.22 0.24 0.28 0.33 0.35 0.30 溶接次數(次) 條件60Α 10萬次開閉 CN 寸 卜 (N 寸 cn ro 寸 m ro 寸 Ο 寸 Ο 00 寸 消耗量(g) 10萬次開閉 0.54 0.66 0.73 0.69 0.63 0.52 0.65 1 0.59 0.60 0.61 0.66 0.67 0.56 0.53 0.55 0.57 0.58 0.61 0.66 0.68 0.72 0.82 0.78 0.85 S 1—Η 00 VO 寸 (N 卜 卜 〇\ Ο Os \ \ I 孝 800 〇 〇 500 1000 300 600 400 300 200 100 500 500 250 280 250 280 180 200 \ \ \ (母材 佈材） 91.7%Ag-5.5%Sn-2.5%In-0.3°/〇Ni/l%Ag-W 91.7%Ag-5.5%Sn-2.5%In-0.3%Ni/l%Ag-WC 91.7%Ag-5.5%Sn-2.5%In-0.3%Ni/50%Ag-W 91.7%Ag-5.5%Sn-2.5%In-0.3%Ni/50%Ag-WC 91.7%Ag-5.5%Sn-2.5%In-0.3%Ni/99%Ag-W 91.7%Ag-5.5%Sn-2.5%In-0.3%Ni/99°/〇Ag-WC 91.7%Ag-5.5%Sn-2.5%In-0.3%NiAV 91.7%Ag-5.5%Sn-2.5%In-0.3%NiAVC 91.7%Ag-5.5%Sn-2.5%In-0.3%Ni/l%Ag-W,l%Ag-WC 91.7%Ag-5.5%Sn-2.5%In-0.3%Ni/50%Ag-W,50%Ag-WC 91.7%Ag-5.5%Sn-2.5%In-0.3%Ni/99%Ag-W,99%Ag-WC 91.7%Ag-5.5%Sn-2.5°/〇In-0.3%Ni/W,WC 91.7%Ag-5.5%Sn-2.5%In-0.3%Ni/l%Ag-W~99%Ag-W o 窆 όο < S? σί ό S s m d> a 客 ό CN Os 91.7%Ag-5.5%Sn-2.5%In-0.3%Ni/l%Ag-W,Au | 91.7%Ag-5.5%Sn-2.5%In-0.3%Ni/l%Ag-W,Pt,Au 91.7%Ag-5.5%Sn-2.5%In-0.3%Ni/50%Ag-W,Au 91.7%Ag-5.5%Sn-2.5%In-0.3%Ni/50%Ag-W,Pt,Au 91.7%Ag-5.5%Sn-2.5°/〇In-0.3%Ni/99%Ag-W,Au 91.7%Ag-5.5%Sn-2.5%In-0.3%Ni/99%Ag-WC,Pt,Au 91,7%Ag-5.5%Sn-2.5%In-0.4%Ni/99%Ag-WC,Ni, Ag,Cu 91.7%Ag-5.5%Sn-2.5%In-0.3%Ni 92.3%Ag-5%Sn-2.5%In-0.2%Ni 91.9%Ag-7°/〇Sn-1 %Ιη-0.1 %Νΐ 實施例1 實施例2 實施例3 實施例4 1實施例5 1 |實施例61 |實施例7 |實施例8| |實施例9| 丨實施例io |實施例ii| |實施例 |實施例13| |實施例14| |實施例15| 實施例16! |實施例17| |實施例18| 1實施例19| 1實施例2〇| 1 實施例2l| Ρ比較例ι| 1比較例2| 1比較例3 1 s ει-39-001 201229254 【圖式簡單說明】 圖1係依氣中放電施行塗佈的概略說明圖。 圖2係依液中放電施行塗佈的概略說明圖。 圖3係1層塗佈的概略說明圖。 圖4係部分塗佈的概略說明圖。 圖5係實施例9的概略說明圖。 圖6係貫施例10的概略說明圖。 圖7係貫施例11的概略說明圖。 圖8係實施例12的概略說明圖。 圖9係實施例13的概略說明圖。 圖10係實施例14的概略說明圖。 圖11係實施例15的概略說明圖。 圖12係實施例16的概略說明圖。 圖13係實施例17的概略說明圖。 圖14係實施例18的概略說明圖。 圖15係實施例19的概略說明圖。 圖16係實施例20的概略說明圖。 圖17係實施例21的概略說明圖。 圖18係經施行塗佈的接點之截面組織照片。 【主要元件符號說明】 1 電極 2 接點 100126295 14 201229254 3 電解液 4 塗佈層 100126295 15201229254 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to electrical contact materials used in electromagnetic switches such as electromagnetic switches, circuit breakers, and relays. [Prior Art] Conventional silver-oxide-based electrical contact materials are designed to improve weld resistance, wear resistance, and temperature characteristics, and to overcome performance by changing internal oxidation conditions or adding third and fourth elements. The problem. For example, a material in which Sn, In, Sb, Bi, or the like is added to Ag and subjected to internal oxidation treatment (for example, refer to Patent Document 1). Furthermore, it has been proposed to have: according to mass%, containing: Sn: 4 to 11%, In: 1 to 5%, Te: 0.05 to 3%, Cd: 0.05 to 3%, if necessary further An Ag alloy containing one or more of Fe, Ni, and Co: 0.01 to 1%, and a structure of Ag and an unavoidable impurity, is subjected to internal oxidation treatment (for example, see Patent Document 2). [PRIOR ART DOCUMENT] [Patent Document 1] [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. However, in the above-mentioned prior art, the silver-oxide-based electrical contact material is repeatedly electrically opened and closed by 100126295 3 201229254, and oxide is deposited on the contact surface layer, because of this, there is contact resistance of the contact surface. Raise and raise the issue of temperature rise. In order to solve such a problem of temperature rise, although there is a method of reducing the amount of added oxide, if the amount of the added oxide is reduced, there is a problem that the resistance to fusion and the loss of the consumables are lowered. Obtaining a stable contact resistance and achieving excellent temperature characteristics are contrary to the improvement in weldability and wear resistance, and often pose a problem in the selection of the contact material. The problem of the present invention is to solve such a problem. (Means for Solving the Problem) The reason is that the present invention is one of 1 to 99 mass% Ag-W, 1 to 99 mass% Ag-WC, WC or W on the joint surface of the silver-oxide-based electrical contact material. By applying a coating having a thickness of 0.1 μm to 1 ΟΟΟμπι, the resistance value of the contact can be lowered, and an abnormal temperature rise is not caused, and the weld resistance and the wear resistance are greatly improved, even if it is used for high In the case of load electrical contact materials, it can still be used as a long-life contact. For example, Fig. 18 is a photograph showing the structure of a joint coated with a contact material of 91.7Ag-5.5SnO2-2.5In2O3-0.3NiO. Further, at least one of pt, Au, Ag, Ni, and Cu is applied between the electrical contact material and the coating layer of 1 to 99 mass% Ag-W, 1 to 99 mass% Ag-WC, WC or W. By the end of the cloth, the resistance value of the contact can be lowered, and the effect of preventing abnormal temperature rise can be achieved, and the welding resistance and the resistance of 100126295 4 201229254 can be greatly improved, even when used for high-load electric contact materials. The situation can still be used as a long-life contact. In addition, the coating method is coating by spraying such as plasma spraying, gas spraying, high-speed flame spraying, or intermittent discharge, pulse, or the like in a gas or a liquid such as shown in FIGS. 1 and 2. Coating by discharge, or vapor deposition by PVD, CVD, or the like. In the above, the reason why the thickness of one layer of the coating layer is in the range of 〇·1 μm to l〇〇〇Mm is that if the thickness of one layer is less than 0.1 Mm, there is no coating effect. Further, if the thickness of one layer exceeds ΙΟΟΟμπι, it is difficult to apply the coating from the viewpoint of technical and production cost. Further, in the case of 1 to 99 mass% Ag-W and 1 to 99 mass% Ag-WC, if Ag is less than lmass% and more than 99 mass%, the meaning of the Ag alloy is lost. (Effect of the Invention) According to the present invention, the coating of the above-described configuration is applied to the silver-oxide-based electrical contact material, whereby the resistance value of the contact can be lowered, and the weld resistance and the wear resistance can be improved. Long life. Further, by applying at least one of pt, Au, and g Cu between the electrical contact material and the coating layer, the resistance value of the contact can be further reduced, and an abnormal temperature rise can be prevented. The towel I improves the interminability and wear resistance, and even when used in the case of a negative phase electrical contact material, it can still have a long life. [Embodiment] 100126295 201229254 Hereinafter, an embodiment of the present invention will be described with reference to the drawings. Firstly, the thickness of L2mm, 3.5mm square, oxygen partial pressure 0.5MPa, internal oxidation temperature 7〇〇ΐ, internal oxidation for 48 hours, and 91.7mass% Ag - 5.5mass%Sn - 2.5mass%In - A joint material composed of 0.3 mass% Ni. [Example 1] The contact material was applied by gas discharge (see Fig. 1) by lmaSS%Ag-W to form a layer thickness of 8 μm. The condition of gas discharge is that the anode is connected to the joint material composed of lmass%Ag-W and the cathode is connected to the joint composed of 9i.7mass%Ag - 5.5mass%Sn -2'5mass%In - a3mass%Ni The material was vibrated in the atmosphere at a current of 1 to 3 A, a voltage of 60 V, a discharge distance of 1 mm, and 300 to 400 Hz, and the coating layer 4 shown in Fig. 3 was applied by intermittent discharge. Further, in Fig. 1, the 1 series electrode and the 2 series contact. In addition, the above-mentioned system is performed in accordance with the discharge in the gas, but it may also be a liquid discharge, as shown in FIG. 2, 'the contact 2 is placed in a general electrolyte 3 such as a tricalcium phosphate solution or a 5% citric acid aqueous solution, and Discharge is performed between the electrode and the electrode. [Example 2] The above-mentioned contact material was coated with lmaSS%Ag-WC by gas discharge (see Fig. 丨) to form a layer thickness of 1 μm. The condition of gas discharge is that the anode is connected to the joint material of lmass%Ag-WC, and the cathode is connected with the joint material of 91.7 mass% Ag - 5.5 mass% Sn - 2.5 mass 0 / 〇 In 100126295 6 201229254 - 0.3 mass % Ni In the atmosphere, a vibration is generated by a current, a voltage of 60 V, a discharge distance of 1 mm, and a frequency of 3 〇〇 to 4 Hz. The partial coating layer 4 shown in Fig. 4 is applied by intermittent discharge. [Example 3] After the surface of the above-mentioned contact material was subjected to a blast treatment, it was applied by a plasma jet spray. The above-mentioned plasma jet flow is carried out in a plasma jet flow environment, and Ag powder having a particle size of 5 to 125 μm is mixed with w powder in a manner of 5 〇: i, and in the atmosphere, according to a jet current of 5 〇〇. ~8〇〇A, the melting distance is 1〇〇mm, and the plasma gas is argon (flow rate 3〇1/min), and the thickness of the coating layer 4 is applied by reciprocating the spray gun in mm/sec. .1 μηη, and the coating layer 4 has a composition of 50 mass% Ag-W. [Example 4] Using the same plasma spray as in the above-described Example 3, the coating layer 4 having a thickness of the coating layer 4 of 20 μm and a coating layer 4 of 5 〇 mass% Ag WC was applied. [Example 5] Using the same plasma spray as in the above-described Example 3, the coating layer 4 having a thickness of the coating layer 4 of 500 μm and a composition of the coating layer 4 of 99 mass% Ag-W was applied. [Example 6] Using the same plasma spray as in the above-described Example 3, the coating layer 4 having a thickness of the coating layer 4 of ΙΟΟΟμπι and the coating layer 4 having a composition of 99 mass% Ag-WC was applied. 〇100126295 7 201229254 [ Example 7] Using the same plasma spray as in the above-described Example 3, the coating layer 4 having a coating layer 4 of 300 μm and a coating layer 4 of w was applied. [Example 8] Using the same plasma spray as in the above-described Example 3, the coating layer 4 having a coating layer 4 having a thickness of 600 μm and the coating layer 4 having a composition of WC was applied. [Example 9] Using the same plasma spray as in the above-described Example 3, the thickness of the i-layer to which the coating layer was applied was 50 μm. The composition of the coating layer was as shown in Fig. 5, and was set from the bottom to be mmass% Ag_W and Lmass ° / 〇 Ag - WC are interlaced to form an 8-layer coating layer 4 . [Example 10] Using the same electropolymerization as in the above Example 3, the thickness of one layer of the applied coating layer was 50 μm, and the composition of the coating layer was as shown in Fig. 6 and was set to 50 mass% Ag-from the bottom. W is interlaced with 50 mass% Ag-WC to form a coating layer 4 of 6 layers. [Example 11] Using the same plasma spray as in the above Example 3, the thickness of one layer of the applied coating layer was 50 μm, and the composition of the coating layer was as shown in Fig. 7 'from the bottom to be 99 mass% Ag- W and 99mass%Ag-WC are interlaced to form a 4-layer quilt layer 4. [Example 12] 100126295 8 201229254 Using the same plasma spray as in the above Example 3, the thickness of one layer of the applied coating layer was 50 μm. The composition of the coating layer was as shown in Fig. 8 and was set from W to the bottom. A coating layer 4 of two layers is formed with WC. [Example 13] Internal oxidation was carried out for a plate thickness of 1.2 mm, a thickness of 3.5 mm, an oxygen partial pressure of 55 MPa, an internal oxidation temperature of 700 C, and an internal oxidation temperature of 48 1.7 % Ag - 5.5 mass % Sn - 2.5 mass After the surface of the contact material composed of %In - 0.3mass%Ni was subjected to a blast treatment, the coating layer was applied by a plasma jet spray. The conditions of the plasma jet spraying were carried out under the same conditions as in the above-mentioned Example 3, and Ag powder having a particle size of 5 to 125 μm was mixed with W powder in a manner of 99:1 in a plasma jet flow environment, and w powder was gradually increased. The amount of the composition is changed stepwise, and the thickness of one layer to which the coating layer is applied is ΙΟΟμιη, and the composition of the coating layer is as shown in Fig. 9, and is set to 99 mass% Ag-W, 75 mass Ag-W, 50 mass% from the bottom. Coating layer 4 of Ag-W, 25 mass% Ag-W, and lmass% Ag-W. [Example 14] In the same manner as in Example 13, the thickness of one layer of the applied coating layer was ΙΟΟμιη, and the composition of the coating layer was as shown in Fig. 10, and 99 mass% Ag-WC, 75 mass% Ag-WC from the bottom. Coating layer 4 of 50 mass% Ag-WC, 25 mass% Ag-WC, and lmass% Ag-WC. [Example 15] 100126295 9 201229254 For internal thickness of 1.2 mm, 3.5 mm square, oxygen partial pressure 〇5 MPa, internal oxidation temperature 7003⁄4, 48 hours internal oxidation, and from 91.7 mass% Ag · 5.5 mass% Sn - 2.5mass%In - 0.; 3mass%Ni The surface of the joint material is sprayed, and then the coating layer is applied by plasma spray. The conditions of the electrospray jet spraying were carried out under the same conditions as in the above-mentioned Example 3, and the thickness of one layer to which the coating layer was applied was 5 μm. The composition of the coating layer was as shown in Fig. 11 from the bottom. Ag-W and Au are interleaved to form a five-layer coating layer 4. [Example 16] In the same manner as in the above-described Example 15, the thickness of one layer of the applied coating layer was 40 μm. The composition of the coating layer is as shown in Fig. 2, and is mmass% Ag-W, Au, and Pt from the bottom. The coating layer 4 of 7 layers is formed in a staggered manner. [Example 17] In the same manner as in Example 15, the thickness of one layer of the applied coating layer was 50 μm. The composition of the coating layer was as shown in Fig. 13, and 50 mass% of Ag-W and Au were interlaced from the bottom. 5 layers of coating layer 4. [Example 18] In the same manner as in Example 15, the thickness of one layer of the applied coating layer was 40 μm. The composition of the coating layer was as shown in Fig. 14. From the bottom, 50 mass% Ag_W 'Au and pt were interlaced. 7 layers of coating layer 4. [Example 19] 100126295 10 201229254 In the same manner as in the above Example 15, the thickness of one layer of the applied coating layer was 20 μm, and the twist of the coating layer was as shown in Fig. 15, which was 99 mass ° / 〇 Ag from the bottom. W and Au are interleaved to form a coating layer 4 of 9 layers. [Example 20] In the same manner as in Example 15, the thickness of one layer of the applied coating layer was 20 μm, and the composition of the coating layer was as shown in Fig. 16, and 99 mass% of Ag-WC, Au, and Pt were from the bottom. The coating layer 4 of 10 layers is formed in a staggered manner. [Example 21] In the same manner as in Example 15, the thickness of one layer of the applied coating layer was ΙΟμιη, and the composition of the coating layer was as shown in Fig. 17, and 99 mass% Ag-WC, Ni, Ag, and Cu is interlaced to form a coating layer 4 of 9 layers. [Comparative Example 1] A plate thickness of 1.2 mm, a thickness of 3.5 mm square, an oxygen partial pressure of 0.5 MPa, and an internal oxidation temperature of 700 ° C were applied for 48 hours of internal oxidation, and from 91.7 mass% Ag - 5.5 mass% Sn - 2.5 mass The joint formed by %In - 0.3mass%Ni. [Comparative Example 2] A plate thickness of 1.2 mm, a thickness of 3.5 mm square, an oxygen partial pressure of 0.5 MPa, and an internal oxidation temperature of 700 ° C were applied for 48 hours of internal oxidation, and from 92.3 mass% Ag - 5 mass% Sn - 2.5 mass% In - 0.2mass%Ni contact. [Comparative Example 3] 100126295 11 201229254 A plate thickness of 1.2 mm, a thickness of 3.5 mm square, an oxygen partial pressure of 0.5 MPa, an internal oxidation temperature of 700 ° C for 48 hours of internal oxidation, and 91.9 mass% Ag - 7 mass% Sn - Lmass%In - 0.1mass%Ni The joint formed. A joint test was performed for each of the above examples and comparative examples. The contact test was performed by measuring the contact resistance and welding test (for 60A freeze), and measuring the consumption (AC200V 20A) using a commercially available contactor, and evaluating the electrical characteristics. 100126295 12 201229254 [Id contact resistance (πιΏ) after opening and closing 100,000 times 0.43 0.52 0.58 0.51 0.47 0.41 0.48 0.45 0.45 0.49 0.64 0.53 0.51 0.53 0.56 0.57 0.58 0.55 0.54 0.58 0.63 0.64 0.75 0.67 Before use 0.23 0.28 0.27 0.32 0.22 0.21 0.25 0.24 0.23 0.26 0.26 0.24 0.23 !_〇·25 0.25 0.26 0.27 0.31 0.22 0.24 0.28 0.33 0.35 0.30 Number of times of fusion (times) Condition 60Α 100,000 times of opening and closing CN inch (N inch cn ro inch m ro inch inch inch Ο 00 inch consumption ( g) 100,000 opening and closing 0.54 0.66 0.73 0.69 0.63 0.52 0.65 1 0.59 0.60 0.61 0.66 0.67 0.56 0.53 0.55 0.57 0.58 0.61 0.66 0.68 0.72 0.82 0.78 0.85 S 1—Η 00 VO 寸 (N Bu Bu 〇 Ο Os \ \ I filial piety 800 〇〇500 1000 300 600 400 300 200 100 500 500 250 280 250 280 180 200 \ \ \ (base material) 91.7% Ag-5.5%Sn-2.5%In-0.3°/〇Ni/l%Ag- W 91.7% Ag-5.5% Sn-2.5% In-0.3% Ni/l% Ag-WC 91.7% Ag-5.5% Sn-2.5% In-0.3% Ni/50% Ag-W 91.7% Ag-5.5%Sn -2.5% In-0.3% Ni/50% Ag-WC 91.7% Ag-5.5% Sn-2.5% In-0.3% Ni/99% Ag-W 91.7% Ag-5.5% Sn-2.5% In-0.3% Ni /99°/〇Ag-WC 91.7% Ag-5.5%Sn-2 .5% In-0.3% NiAV 91.7% Ag-5.5% Sn-2.5% In-0.3% NiAVC 91.7% Ag-5.5% Sn-2.5% In-0.3% Ni/l% Ag-W, l% Ag-WC 91.7% Ag-5.5%Sn-2.5%In-0.3%Ni/50%Ag-W, 50%Ag-WC 91.7% Ag-5.5%Sn-2.5%In-0.3%Ni/99%Ag-W,99 %Ag-WC 91.7% Ag-5.5%Sn-2.5°/〇In-0.3%Ni/W, WC 91.7% Ag-5.5%Sn-2.5%In-0.3%Ni/l%Ag-W~99%Ag -W o 窆όο < S? σί ό S sm d> a ό CN Os 91.7% Ag-5.5%Sn-2.5%In-0.3%Ni/l%Ag-W,Au | 91.7%Ag-5.5% Sn-2.5% In-0.3% Ni/l% Ag-W, Pt, Au 91.7% Ag-5.5% Sn-2.5% In-0.3% Ni/50% Ag-W, Au 91.7% Ag-5.5% Sn- 2.5% In-0.3% Ni/50% Ag-W, Pt, Au 91.7% Ag-5.5% Sn-2.5°/〇In-0.3% Ni/99% Ag-W, Au 91.7% Ag-5.5% Sn- 2.5% In-0.3% Ni/99% Ag-WC, Pt, Au 91, 7% Ag-5.5% Sn-2.5% In-0.4% Ni/99% Ag-WC, Ni, Ag, Cu 91.7% Ag- 5.5% Sn-2.5% In-0.3% Ni 92.3% Ag-5% Sn-2.5% In-0.2% Ni 91.9% Ag-7°/〇Sn-1 %Ιη-0.1%Νΐ Example 1 Example 2 Implementation Example 3 Example 4 1 Example 5 1 | Example 61 | Example 7 | Example 8 | | Example 9 | Example io | Example ii | Example | Example 13 | Example 15|Example 16! |Example 17| |Example 18|1Example 19|1 Example 2〇| 1 Example 2l| Example iota | Comparative Example 1 2 | 1 Comparative Example 3 1 s ει-39-001 201229254] [Brief Description of the drawings Figure 1 is performed by gas discharge is a schematic explanatory view of a coating. Fig. 2 is a schematic explanatory view of coating by discharge in a liquid. Fig. 3 is a schematic explanatory view of one layer coating. Fig. 4 is a schematic explanatory view of a partial coating. Fig. 5 is a schematic explanatory view of a ninth embodiment. Fig. 6 is a schematic explanatory view showing a tenth embodiment. Fig. 7 is a schematic explanatory view showing a tenth embodiment. Fig. 8 is a schematic explanatory view of a twelfth embodiment. Fig. 9 is a schematic explanatory view of a thirteenth embodiment. Fig. 10 is a schematic explanatory view showing a fourteenth embodiment. Fig. 11 is a schematic explanatory view showing a fifteenth embodiment. Fig. 12 is a schematic explanatory view showing a sixteenth embodiment. Fig. 13 is a schematic explanatory view showing a seventeenth embodiment. Fig. 14 is a schematic explanatory view of the eighteenth embodiment. Fig. 15 is a schematic explanatory view showing a nineteenth embodiment. Fig. 16 is a schematic explanatory view showing a twenty-second embodiment. Fig. 17 is a schematic explanatory view showing a twenty-first embodiment. Figure 18 is a photograph of a cross-sectional structure of a coated joint. [Main component symbol description] 1 Electrode 2 Contact 100126295 14 201229254 3 Electrolyte 4 Coating layer 100126295 15