201125660 六、發明說明： 【發明所屬之技術領域】 本發明係關於爲控制熔鋼流量之滑動噴嘴裝置（以下 稱爲「SN裝置」。）所使用之板磚的滑動噴嘴板（以下稱 爲「 SN板」。）。 【先前技術】 在鋼的製造中，爲了控制從澆桶或餵槽等熔融金屬容 器排出的熔鋼流量，係使用SN裝置。此SN裝置使用2枚或 3枚具有耐火物製成之噴嘴孔的SN板。此SN板在受到拘束 的條件下，以疊合並更施加表面壓力的狀態來進行滑動， 透過調整噴嘴孔的開度來調整熔鋼的流量。 因此，係要求S N板具有可承受在拘束條件下使用時的 機械強度，對鑄造時之熱應力的抗剝落性，對熔鋼中的成 分和熔渣等的耐蝕性、耐氧化性，以及對於作爲操作面之 滑動面受到損耗之「表面粗糙」的「耐表面粗糙性」等特 性。 SN板通常使用氧化鋁碳質耐火物，例如，爲了提高抗 剝落性，係使用低熱膨脹率的氧化锆/富鋁紅柱石或氧化 鋁/氧化锆等耐火原料。此外，爲了提高耐蝕性，係使用 不容易與熔渣反應的電熔氧化鋁等高純度緻密原料，並硏 究碳的種類和適當的碳含量。爲了提高滑動的耐磨耗性， 藉由使所用的原料具有適當的粒度組成，使組織緻密化以 達到高強度化’並且執行提高滑動面之硏磨精度等手法。 -5- 201125660 此外’使用抗氧化用的碳化矽、碳化硼、氮化鋁等抗氧化 劑’及矽或鋁等金屬作爲燒結材料。 另一方面’專利文獻1係以提高氧化鋁碳質耐火物的 耐氧化性、耐蝕性及抗剝落性爲目的，提出以3〜40質量％ 的碳質原料和0 · 5〜1 5質量％的碳氧化鋁進行配製》此外， 專利文獻2係揭示以氧化鋁-碳氧化鋁作爲主要成分，並且 以碳含量爲0.5〜3.0質量％之電熔耐火骨材進行配製的耐 火物。 然而’ SN板所要求的要素，除了上述的耐氧化性、耐 蝕性及抗剝落性以外，還有能表現出抗滑動面磨損，亦即 抗所謂「表面粗糙」的「耐表面粗糙性」。由於專利文獻 1、2並未考慮到「耐表面粗糙性」，因此根據該等文獻之 記載’要得到「耐表面粗糙性」優異的SN板有其困難。 [先前技術文獻] [專利文獻] [專利文獻1]特開平9 一 295 8 5 7號公報 [專利文獻2]特開昭55 - 60067號公報 【發明內容】 本發明欲解決之問題在於提供一種耐氧化性、耐蝕性 及抗剝落性，加上「耐表面粗糙性j優異的SN板。 本發明之SN板的特徵是含有5〜95質量％之作爲礦物 相的 A1404C。 201125660 如上所述，本發明之S N板係含有特定量的碳氧化銘 AI404C。除了 A1404C之外，已知Al2OC也是碳氧化鋁，但 本發明特別指定是碳氧化鋁之中的A1404C。其係由於相對 於AhOC，Al404c可在工業上製造品質穩定的產品，並穩 定提升SN板特性的效果良好。 亦即，如式（1 )所示，Al404c與FeO等使耐火物中的 碳氧化所產生的CO氣體進行反應，析出氧化鋁和碳，由於 能使組織緻密化，因此已知具有抑制磚氧化的效果。再者 ’如式（2 )所示，由於A1404C與耐火物中的碳反應生成 鋁氣體，該鋁氣體如式（3)所示，同樣會與CO氣體反應 ’析出氧化鋁和碳，因此具有使組織緻密化的效果。此外 ，由於在操作面上，如式（4)所示，鋁氣體與鋼中的FeO 反應，析出氧化鋁，因此同樣可以得到耐氧化性的效果。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sliding nozzle plate for a tile used in a sliding nozzle device (hereinafter referred to as "SN device" for controlling the flow rate of molten steel (hereinafter referred to as " SN board".). [Prior Art] In the manufacture of steel, in order to control the flow rate of molten steel discharged from a molten metal container such as a ladle or a feed tank, an SN device is used. This SN device uses two or three SN plates with nozzle holes made of refractory. The SN plate is slid in a state in which the surface pressure is applied in a state where the SN plate is restrained, and the flow rate of the molten steel is adjusted by adjusting the opening degree of the nozzle hole. Therefore, the SN plate is required to have mechanical strength at the time of use under restraint conditions, peeling resistance against thermal stress during casting, corrosion resistance and oxidation resistance to components and molten slag in the molten steel, and The sliding surface of the operation surface is subjected to characteristics such as "surface roughness" and "surface roughness resistance". The SN plate usually uses an alumina carbonaceous refractory. For example, in order to improve the peeling resistance, a refractory raw material such as zirconia/mullite or alumina/zirconia having a low thermal expansion coefficient is used. Further, in order to improve the corrosion resistance, a high-purity dense raw material such as fused alumina which is not easily reacted with the slag is used, and the kind of carbon and an appropriate carbon content are examined. In order to improve the wear resistance of the sliding, by making the raw material used have an appropriate particle size composition, the structure is densified to achieve high strength and the honing precision of the sliding surface is improved. -5- 201125660 In addition, an anti-oxidant such as antimony carbide, niobium carbide, or aluminum nitride, and a metal such as tantalum or aluminum are used as the sintered material. On the other hand, Patent Document 1 proposes a carbonaceous material of 3 to 40% by mass and 0. 5 to 15% by mass for the purpose of improving the oxidation resistance, corrosion resistance and peeling resistance of the alumina carbonaceous refractory. In addition, Patent Document 2 discloses a refractory which is prepared by using alumina-alumina as a main component and fused refractory aggregate having a carbon content of 0.5 to 3.0% by mass. However, in addition to the above-mentioned oxidation resistance, corrosion resistance and peeling resistance, the elements required for the SN plate can exhibit wear resistance against sliding surfaces, that is, "surface roughness resistance" which is resistant to so-called "surface roughness". Since Patent Documents 1 and 2 do not consider "surface roughness resistance", it is difficult to obtain an SN plate excellent in "surface roughness resistance" according to the description of these documents. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. Oxidation resistance, corrosion resistance, and flaking resistance, and an "SN plate excellent in surface roughness resistance j. The SN plate of the present invention is characterized by containing 5 to 95% by mass of A1404C as a mineral phase. 201125660 As described above, The SN plate of the present invention contains a specific amount of carbon oxide AI 404C. In addition to A1404C, it is known that Al2OC is also carbon alumina, but the present invention is specifically designated as A1404C among aluminum oxides, which is due to Al404c relative to AhOC. It is possible to produce a stable quality product in the industry and to improve the characteristics of the SN plate stably. That is, as shown in the formula (1), Al404c reacts with COO such as carbon oxide generated by carbon oxidation in the refractory. The precipitation of alumina and carbon is known to have the effect of inhibiting the oxidation of bricks by densifying the structure. Further, as shown in the formula (2), since A1404C reacts with carbon in the refractory to form aluminum gas, the aluminum gas As shown in the formula (3), it also reacts with the CO gas to precipitate aluminum oxide and carbon, and therefore has an effect of densifying the structure. Further, since it is on the operation surface, as shown in the formula (4), aluminum gas and steel The FeO reaction precipitates alumina, so that the oxidation resistance effect can be obtained in the same manner.
Al 404c (s) +2CO (g) =2Al2〇3 (s) +3C (s) ··· (1) A 1 4〇4C (s) +3C (s) =4A 1 (g) + 4CO (g) ··· (2) 2 A 1 (g) + 3 C〇（g) =A 1 203 (s) + 3C (s) - (3) 2 A 1 (g) + 3 F e〇（1) =A 1 2〇3 (s) + Fe (s) ... (4) 因此，如式（1 )及式（3 ) 、 （ 4 )所示，可得知 A1404C並不會像金屬鋁那樣地形成所謂的空洞，而會析出 氧化鋁和碳使組織緻密化。 本案發明人使用特開2009 — 204594號公報中記載的（ 耐氧化性）評估方法來嘗試評估SN板之重要特性的「耐表 面粗糙性」。亦即，對於使用圖1所示的感應電爐，其熔 鋼與作爲樣品之耐火物反應所產生之鋼浴部脫碳層厚度的 指數化値（以基底材質當作1 00 )，與該等耐火物在實際 設備使用時，受到滑動面磨損之「表面粗糙」的關係進行 201125660 調査。 圖2表示鋼浴部脫碳層厚度指數與作爲「耐表面粗糙 性」指標之衝擊消化速度的關係。衝擊消化速度是藉由滑 動面的損傷、「表面粗糙」的損耗速度來表示SN板之「耐 表面粗糙性」的指標。換言之，衝擊消化速度越小，「耐 表面粗糙性」越良好。如圖2所示，鋼浴部脫碳層厚度與 「耐表面粗糙性」有良好的相關性，可確認鋼浴部脫碳層 厚度指數越小，衝擊消化速度也越小，「耐表面粗糙性」 越良好。由此可知，以圖1所示的評估方法作爲「耐表面 粗糙性」的評估方法是有效的。 因此，藉由此評估方法來評估應用A1404C之耐火物的 「耐表面粗縫性J 。其結果確認應用Al4〇4C的耐火物只有 在鐵浴部的操作表面上形成作爲薄脫碳層的緻密氧化鋁層 ，由此推定應用Al404c作爲提高「耐表面粗糙性」的手段 是有效的。 雖然如先前所報告者，根據式（1)及式（3) 、（4 )，在作爲操作面的滑動面上，會析出氧化鋁和碳而賦予 耐氧化性，不過在此同時所形成之作爲薄脫碳層的緻密氧 化鋁層，也能賦予對滑動的耐滑動磨耗性，而得到「耐表 面粗糙性」的效果。此外，由於在操作面內部僅保持很小 的AI4O4C反應，因此能維持低熱膨脹率的特徵，而且也能 持續抗剝落性的效果。 雖然對金屬鋁也可以期待同樣的效果，但是在金屬鋁 的情況下，反應後除了形成空洞以外，由於熔點低所以在 -8 - 201125660 滑動面內部也會進行反應，生成碳化鋁或經由碳化鋁生成 氧化鋁。因此，與A1404C相比，其抗氧化效果持續貧乏， 而且經過燒結後組織過度緻密化會使抗剝落性降低。 由上可知，如果應用Al4〇4C，不僅能緩和被認爲係「 表面粗糙」的主要成因之一之熱衝擊所引起的組織鬆散， 而且還能得到高度「耐表面粗糙性」的效果。 同樣地’雖然碳氧化鋁Al2OC也可以期待同樣的效果 ，然而如圖3的Al2〇3 — Al4c3系相圖所示，Al2OC只有在高 溫區才是穩定的，常溫下係以順穩定相存在。因此，尤其 是藉由使用電爐之溶融法來穩定製造Al2OC組成物有其困 難，且控制ai2oc的特性和品質亦有其困難。相較於此， 由於A1404C在常溫下係以穩定相存在，因此在工業上可製 造品質穩定的原料。 根據本發明，可以得到耐氧化性 '耐蝕性及抗剝落性 ’且加上耐表面粗糙性優異的SN板。 【實施方式】 本發明使用的A14 〇4 c可藉由利用燒成爐熱處理含碳原 料和氧化鋁原料的燒結法，或是利用電弧爐進行熔融的熔 融法來製造。尤其是如本案申請人於特願2009 - 82729所 提出者，均勻混合50篩目以下之含碳原料和100篩目以下 之含氧化鋁原料所構成的組成物，使其成爲c成分的偏差 在± 1 0%以內者，利用電弧爐使該混合物熔融’可製造高純 度的 A1404C。 201125660 此A1404C和其他耐火原料按預定比例混合成 行燒成，得到本發明的S N板。必要時，可在燒成 青浸漬。 本發明之SN板含有5〜95質量％之作爲租 A1404C。Al4〇4C含量未達5質量％時，無法得到: 耐表面粗糙性」及抗剝落性的效果。另一方面， 量％時’ Al4〇4C的反應所引起的體積變化會產生 ，因此無法製造SN板。A1404C的含量，較佳爲40 %，且更佳爲7 0〜9 5質量％。 此外’本發明之SN板，其熱膨脹係數較佳爲 K以下。熱膨脹係數超過8χ10·6/Κ時，噴嘴孔的 裂、噴嘴孔的邊緣崩裂等，以及熱應力所引起的 大。再者’在鑄造時，噴嘴內孔部的高溫膨脹不 邊緣崩裂’而且空氣從SN板面間進入也會成爲促 氧化和損耗的主要原因。因此熱膨脹係數較佳爲 Κ以下。 此外’本發明之SN板，其常溫抗彎強度較佳 以上60Mpa以下。SN板係安裝於SN裝置上，在受 條件下使用。因此，在對於拘束力沒有充分強度 ’發生異常龜裂會成爲故障的主要原因。此外， 性模數有相互關係，強度越高，彈性模數會有越 。因此’強度過大時，抗剝落性會降低，例如， 等會成爲耐用性降低的主要原因。 形後，進 後進行瀝 廣物相的 充分的^ 超過95質 燒成龜裂 〜95質量 8xlO"6/ 放射狀龜 損耗會變 僅會造成 使滑動面 8xl〇-6/ 爲 lOMPa 到拘束的 的情況下 強度和彈 高的傾向 邊緣崩裂 -10- 201125660 [實施例] 在以AUCUC、氧化鋁骨材原料、氧化鉻系原料、作爲 燒結材料之鋁及/或矽以及碳爲主，並且按預定比例配製 的耐火原料組成物中’按預定比例添加酚樹脂，進行混合 、成形後，在預定條件下燒成，進一步經由瀝青浸漬、塡 隙來製造磚’並評估其特性（表1〜3 )。具體而言，係評 估其抗剝落性、熱膨脹率及「耐表面粗糙性」以及耐蝕性 〇 抗剝落性是根據在1 600 °C的熔鋼中浸漬3分鐘之後的 龜裂狀況來判斷其好壞。表1〜3中，◦表示輕微龜裂，爲 良好者’ △表示產生小龜裂，X表示產生大龜裂，爲不良 者。 熱膨脹係數可有效作爲SN板邊緣崩裂的評估指標。也 就是說，熱膨脹係數較小時，由於熔鋼流的高溫所引起的 噴嘴內孔部膨脹受到抑制，因此熱應力較低，不容易產生 邊緣崩裂。熱膨脹係數是根據n S R 2 2 0 7，由1 5 0 0 °c下測 得的熱膨脹率所算出。 此外’關於S N板之重要特性的「耐表面粗糙性」，係 於使用圖1所示之感應電爐的液相氧化試驗中，以作爲基 底材質之比較例1的厚度當作1 00，將熔鋼與耐火物（樣品 )反應所產生的鋼浴部脫碳層厚度進行指數化來加以評估 。鋼浴部脫碳層厚度的指數越小，其「耐表面粗糙性」越 好。 此外，關於耐蝕性，係於感應電爐中使用熔鐵與氧化 -11 - 201125660 鐵粉，在1 6 0 0 °C下進行2小時的熔損試驗，評估其熔損量 。表1〜3中，以比較例1的熔損量當作1 〇 〇進行指數化，指 數越小，耐蝕性越優異。 化學成分係藉由X射線繞射及JIS R2212、2216中規定 的耐火物分析法進行化學分析。具體而言，先根據內部標 準法，由X射線繞射結果將AI4O4C定量，再由JIS R2212、 2216規定的分析結果，扣除相當於定量後之A1404C量的 Al2〇3量及C量，計算出剩餘部分的Zr02、Al2〇3、C含量。 化學成分合計不到1 00%者，其剩餘部分中包含鋁和矽等金 屬，或爲這些金屬之反應物的碳化物、氧氮化物、氮化物 ，並且包含碳化物、硼化物等抗氧化劑的成分。 表1表示A14 0 4 C含量變化的情形。表1中，實施例1〜4 的Al4〇4C含量在本發明的範圍內，其「耐表面粗糙性」及 抗剝落性優異。A1404C含量越多，熱膨脹率會有降低的傾 向。相較於此，比較例1和2的A1404C含量少於本發明的範 圍，其「耐表面粗糙性」及抗剝落性不佳。其熱膨脹率比 實施例高，因此改善邊緣崩裂的效果小。此外，由於比較 例3的A1404C含量亦多於本發明的範圍，因此燒成時 A1404C的體積變化會造成龜裂。 表2表示熱膨脹係數變化的情形。熱膨脹係數可藉由 作爲低熱膨脹率骨材原料的氧化鋁/氧化锆或氧化銷/富鋁 紅柱石等氧化锆系原料、富鋁紅柱石或熔融二氧化矽等含 Si02骨材、碳化矽或碳化硼，以及氮化矽、氮化鋁等碳化 物、氮化物的添加量，還有碳添加量、燒成溫度、燒成時 -12- 201125660 間等來進行調整。表2中’在本發明的範圍內調整作爲低 熱膨脹率骨材的A14 Ο 4 C和氧化鋁/氧化锆原料、碳添加量 ’以及燒成溫度來改變熱膨脹係數。雖然每個實施例都能 得到充分的「耐表面粗糙性」的效果’但實施例5的熱膨 脹係數雖高達8 . 1 X 1 (Γ6 / K ’但其抗剝落性的評價卻比熱膨 脹係數爲8.0x10-6/K以下的實施例6〜9差。因此，熱膨脹 係數在8.〇χ1〇·6/κ以上時’會有因熱應力的損耗而造成問 題的情形。 表3表示常溫抗彎強度變化的情形。常溫抗彎強度可 藉由鋁或矽等作爲燒結材料之金屬的添加量、燒成溫度或 燒成時間等燒成條件、混合耐火原料組成物的充塡密度或 粒度組成等來進行調整。表3中，在本發明的範圍內調整 金屬添加量及粒度組成來改變常溫抗彎強度。雖然每個實 施例都能得到充分的「耐表面粗糙性」的效果，但若實施 例10的常溫抗彎強度爲lOMPa以下則由於強度爲低，因此 在實際設備使用時，滑動面有產生異常龜裂的可能。此外 ，實施例14的常溫抗彎強度爲60MPa以上的高強度，但在 抗剝落性試驗中卻比實施例1 1〜1 3差，因此噴嘴孔邊緣缺 損等在實際設備中因熱應力而造成的損耗是令人擔憂的。 實施例1 1〜1 3可以得到充分的抗彎強度，且其「耐表面粗 糙性」也是良好的。 以上說明的實施例及比較例中，對實施例2、實施例5 、實施例1 2及比較例2，製作真實形狀的SN板，進行實際 設備測試。本發明之所有實施例與比較例2相比，其滑動 -13- 201125660 面損傷的「表面粗糙」都較爲輕微，且其耐用性更爲提高 [表1] 實施例1 實施例2 實施例3 實施例4 比較例1 比較例2 比較例3 化學成分(質量％) Zr02 5 5 5 2 5 5 1 AI2O3 85 50 20 0 90 86 0 AI4O4C 5 40 70 95 0 4 96 C 3 3 3 3 3 3 3 合計 98 98 98 100 98 98 100 評估項目 抗剝落性 〇 〇 〇 〇 X X 燒成 剝落試驗結果 龜裂 常溫抗彎強度 MPa 20 30 35 40 15 18 — 熱膨脹係數 — χ10'6/Κ 7.17 6.00 5.00 4.17 7.33 7.20 耐氧化性(表面粗糙性） 脫碳層厚度指數 85 40 25 10 100 95 — 耐蝕性(熔損指數） 熔融FeO : 1600°Cx2hr 90 85 75 70 100 99 - -14- 201125660 [表2] 實施例5 實施例6 實施例7 實施例8 實施例9 化學成分(質量％) Zr02 0 0 4 2 5 Al2〇3 91 90 87 83 71 AI4O4C 5 6 5 5 20 C 2 2 2 8 2 合計 98 98 98 98 98 評估項目 抗剝落性 Δ 〇 〇 〇 〇 剝落試驗結果 常溫抗彎強度 MPa 20 20 20 15 25 熱膨脹係數 X 10'6/K 8.10 7.90 7.83 7.93 7.27 耐氧化性(表面粗糙性） 脫碳層厚度指數 82 81 82 116 60 耐蝕性(熔損指數） 熔融FeO : 1600°C x2hr 75 75 79 97 76 -15- 201125660 [表3] 實施例10 實施例11 實施例12 實施例13 實施例Η 化學成分(質量％) Zr02 0 0 0 0 0 ai2o3 92 91 90 87 86 AI4O4C 5 5 5 5 5 c 2 2 2 2 2 合計 99 98 97 94 93 評估項目 抗剝落性 〇 〇 〇 〇 △ 剝落試驗結果 常溫抗彎強度 MPa 9 10 20 60 61 熱膨脹係數 X 10'6/K 8.10 8.10 8.10 8.10 8.10 耐氧化性(表面粗糙性） 脫碳層厚度指數 82 82 82 82 82 耐蝕性(熔損指數） 熔融FeO : 1600。。X 2hr 75 75 75 75 75 【圖式簡單說明】 圖1表示用來評估耐表面粗糙性的液相氧化試驗裝置 圖2表示液相氧化試驗之鋼浴部脫碳層厚度與衝擊消 化速度（耐表面粗糙性）的關係。 圖3爲A!2〇3 — AI4C3系相圖。 -16-Al 404c (s) +2CO (g) =2Al2〇3 (s) +3C (s) ··· (1) A 1 4〇4C (s) +3C (s) =4A 1 (g) + 4CO ( g) ··· (2) 2 A 1 (g) + 3 C〇(g) =A 1 203 (s) + 3C (s) - (3) 2 A 1 (g) + 3 F e〇(1 ) =A 1 2〇3 (s) + Fe (s) (4) Therefore, as shown in equation (1) and equations (3) and (4), it can be seen that A1404C does not resemble metal aluminum. In this way, so-called voids are formed, and alumina and carbon are precipitated to densify the structure. The inventors of the present invention attempted to evaluate the "surface roughness resistance" of the important characteristics of the SN plate by using the (oxidation resistance) evaluation method described in JP-A-2009-204594. That is, for the induction electric furnace shown in Fig. 1, the thickness of the decarburization layer of the steel bath portion produced by the reaction between the molten steel and the refractory material as the sample is (the base material is regarded as 100), and When the refractory is used in actual equipment, the relationship between the "surface roughness" of the sliding surface wear is investigated in 201125660. Fig. 2 shows the relationship between the thickness index of the decarburization layer in the steel bath portion and the impact digestion rate as an index of "surface roughness resistance". The impact digestion rate is an index indicating the "surface roughness resistance" of the SN plate by the damage of the sliding surface and the loss rate of "surface roughness". In other words, the smaller the impact digestion rate, the better the "surface roughness resistance". As shown in Fig. 2, the thickness of the decarburized layer in the steel bath has a good correlation with the "surface roughness resistance". It can be confirmed that the smaller the thickness index of the decarburized layer in the steel bath, the smaller the impact digestion rate. The better the sex. From this, it is understood that the evaluation method shown in Fig. 1 is effective as an evaluation method of "surface roughness resistance". Therefore, the "surface roughening resistance J" of the refractory to which A1404C was applied was evaluated by the evaluation method. As a result, it was confirmed that the refractory using Al4〇4C formed only a dense layer as a thin decarburized layer on the operation surface of the iron bath portion. In the aluminum oxide layer, it is estimated that the application of Al404c as a means for improving "surface roughness resistance" is effective. According to the formula (1) and the formulas (3) and (4), alumina and carbon are precipitated on the sliding surface as the operation surface to impart oxidation resistance, but at the same time, The dense alumina layer which is a thin decarburization layer can also impart sliding wear resistance to sliding, and the effect of "surface roughness resistance" can be obtained. Further, since only a small AI4O4C reaction is maintained inside the operation surface, the characteristic of low thermal expansion rate can be maintained, and the anti-flaking effect can be continued. Although the same effect can be expected for metallic aluminum, in the case of metallic aluminum, in addition to the formation of voids after the reaction, since the melting point is low, the reaction is also performed inside the sliding surface of -8 - 201125660 to form aluminum carbide or via aluminum carbide. Alumina is formed. Therefore, compared with A1404C, its antioxidant effect continues to be poor, and excessive densification of the structure after sintering causes a decrease in peeling resistance. As can be seen from the above, when Al4〇4C is applied, not only the looseness of the structure caused by the thermal shock which is considered to be one of the main causes of "surface roughness" but also the effect of high "surface roughness resistance" can be obtained. Similarly, although the same effect can be expected for the alumina alumina Al2OC, as shown in the phase diagram of Al2〇3 - Al4c3 of Fig. 3, Al2OC is stable only in the high temperature region, and exists as a stable phase at normal temperature. Therefore, it is difficult to stably manufacture the Al2OC composition by using the melting method of the electric furnace, and it is difficult to control the characteristics and quality of the ai2oc. In contrast, since A1404C exists as a stable phase at normal temperature, it is industrially possible to produce a raw material of stable quality. According to the present invention, an SN plate excellent in oxidation resistance 'corrosion resistance and peeling resistance' and excellent in surface roughening resistance can be obtained. [Embodiment] The A14 〇 4 c used in the present invention can be produced by a sintering method in which a carbonaceous material and an alumina raw material are heat-treated in a firing furnace, or a melting method in which an electric arc furnace is used for melting. In particular, as proposed by the applicant in Japanese Patent Application No. 2009-82729, the composition of the carbonaceous material below 50 mesh and the alumina-containing raw material below 100 mesh is uniformly mixed, so that the deviation of the component c is Within ±10%, the mixture is melted by an electric arc furnace to produce high purity A1404C. 201125660 This A1404C and other refractory raw materials are mixed and fired in a predetermined ratio to obtain the S N plate of the present invention. If necessary, it can be impregnated in the green. The SN plate of the present invention contains 5 to 95% by mass of the rent A1404C. When the content of Al4〇4C is less than 5% by mass, the effect of surface roughening resistance and peeling resistance cannot be obtained. On the other hand, the volume change caused by the reaction of 'Al4〇4C at the time of % is generated, so that the SN plate cannot be manufactured. The content of A1404C is preferably 40%, and more preferably 70 to 9.5 mass%. Further, the SN plate of the present invention preferably has a thermal expansion coefficient of K or less. When the coefficient of thermal expansion exceeds 8 χ 10·6 / Κ, the crack of the nozzle hole, the edge of the nozzle hole is cracked, and the like, and the thermal stress is large. Further, at the time of casting, the high-temperature expansion of the inner hole portion of the nozzle does not cause edge cracking, and the entry of air from the surface of the SN plate also becomes a major cause of oxidation and loss. Therefore, the coefficient of thermal expansion is preferably Κ or less. Further, the SN plate of the present invention preferably has a bending strength at room temperature of 60 MPa or less. The SN board is mounted on the SN unit and used under conditions. Therefore, there is no sufficient strength for restraint. 'An abnormal crack occurs as a cause of failure. In addition, the modulus of the relationship has a relationship, and the higher the intensity, the more the modulus of elasticity will be. Therefore, when the strength is too large, the peeling resistance is lowered, and for example, it may become a cause of deterioration in durability. After the shape, the full phase of the leaching phase is more than 95. The quality of the crack is ~95 mass 8xlO"6/ Radial tortoise loss will only cause the sliding surface 8xl〇-6/ to be lOMPa to the restraint In the case of strength and elastic height, the edge is cracked-10-201125660 [Examples] In the case of AUCUC, alumina aggregate raw materials, chromium oxide raw materials, aluminum and/or tantalum as a sintered material, and carbon, and The refractory raw material composition prepared in a predetermined ratio is added with a phenol resin in a predetermined ratio, mixed, formed, and then fired under predetermined conditions, and further subjected to asphalt impregnation and crevice to fabricate bricks and evaluated for characteristics (Tables 1 to 3). ). Specifically, it is evaluated that its peeling resistance, thermal expansion rate, and "surface roughness resistance" as well as corrosion resistance and flaking resistance are judged based on the cracking condition after immersion for 3 minutes in molten steel at 1 600 °C. Bad. In Tables 1 to 3, ◦ indicates a slight crack, and a good one indicates that a small crack occurs, and X indicates that a large crack is generated, which is a bad one. The coefficient of thermal expansion can be effectively used as an evaluation index for edge cracking of the SN plate. That is to say, when the coefficient of thermal expansion is small, since the expansion of the inner hole portion of the nozzle is suppressed due to the high temperature of the molten steel flow, the thermal stress is low, and edge cracking is less likely to occur. The coefficient of thermal expansion is calculated from the coefficient of thermal expansion measured at 150 °C based on n S R 2 2 0 7 . In addition, in the liquid phase oxidation test using the induction furnace shown in Fig. 1, the thickness of Comparative Example 1 as the base material was taken as 1 00, and the melting was performed. The thickness of the decarburization layer of the steel bath produced by the reaction of the steel with the refractory (sample) is evaluated by indexing. The smaller the index of the thickness of the decarburized layer in the steel bath, the better the "surface roughness resistance". In addition, regarding corrosion resistance, molten iron and oxidized -11 - 201125660 iron powder were used in an induction furnace, and a melt loss test was performed at 1 600 ° C for 2 hours to evaluate the amount of melt loss. In Tables 1 to 3, the melt loss amount of Comparative Example 1 was indexed as 1 〇 ,, and the smaller the index, the more excellent the corrosion resistance. The chemical components were chemically analyzed by X-ray diffraction and refractory analysis as specified in JIS R2212 and 2216. Specifically, according to the internal standard method, the AI4O4C is quantified by the X-ray diffraction result, and the amount of Al2〇3 and the amount of C corresponding to the quantitative A1404C amount are deducted from the analysis results specified in JIS R2222 and 2216, and calculated. The remaining part of Zr02, Al2〇3, C content. The chemical composition is less than 100% in total, and the remainder includes metals such as aluminum and bismuth, or carbides, oxynitrides, and nitrides of reactants of these metals, and contains antioxidants such as carbides and borides. ingredient. Table 1 shows the change in the A14 0 4 C content. In Table 1, the Al4〇4C content of Examples 1 to 4 is within the range of the present invention, and it is excellent in "surface roughness resistance" and peeling resistance. The more the A1404C content, the lower the coefficient of thermal expansion. In contrast, the contents of A1404C of Comparative Examples 1 and 2 were less than the range of the present invention, and their "surface roughness resistance" and peeling resistance were not good. The coefficient of thermal expansion is higher than that of the examples, so that the effect of improving edge cracking is small. Further, since the content of A1404C of Comparative Example 3 was also larger than the range of the present invention, the volume change of A1404C at the time of firing caused cracking. Table 2 shows the case where the coefficient of thermal expansion changes. The coefficient of thermal expansion can be obtained by zirconia-based raw materials such as alumina/zirconia or oxidized pin/mullite as a raw material of low thermal expansion rate, SiO2-containing aggregates such as mullite or molten cerium oxide, or tantalum carbide or Boron carbide, and the addition amount of carbides and nitrides such as tantalum nitride and aluminum nitride, and the amount of carbon added, the firing temperature, and the time between firing and -12-201125660 are adjusted. In Table 2, the A14 Ο 4 C and the alumina/zirconia raw material, the carbon addition amount, and the firing temperature, which are low thermal expansion ratio aggregates, were adjusted within the scope of the present invention to change the thermal expansion coefficient. Although each embodiment can obtain a sufficient "surface roughness resistance" effect, the thermal expansion coefficient of Example 5 is as high as 8. 1 X 1 (Γ6 / K ', but its peeling resistance is evaluated as the coefficient of thermal expansion is Examples 6 to 9 which are 8.0x10-6/K or less are inferior. Therefore, when the coefficient of thermal expansion is 8.〇χ1〇·6/κ or more, there is a problem that the problem is caused by the loss of thermal stress. Table 3 shows the normal temperature resistance. The case where the bending strength is changed. The room temperature bending strength can be obtained by the addition amount of the metal such as aluminum or bismuth as the sintering material, the firing temperature such as the firing temperature or the firing time, the filling density or the particle size composition of the mixed refractory raw material composition. In the table 3, the metal addition amount and the particle size composition are adjusted within the scope of the present invention to change the normal temperature bending strength. Although each embodiment can obtain a sufficient "surface roughness resistance" effect, In the case where the room temperature bending strength of the embodiment 10 is 10 MPa or less, the strength is low, so that the sliding surface may be abnormally cracked when the actual equipment is used. Further, the room temperature bending strength of Example 14 is 60 MPa or more. However, in the anti-flaking test, it is inferior to the embodiment 1 1 to 13 3, so that the loss of the nozzle hole edge and the like due to thermal stress in the actual equipment is a concern. Embodiment 1 1 to 1 3 can be A sufficient bending strength is obtained, and the "surface roughness resistance" is also good. In the examples and comparative examples described above, the actual shapes were produced for Example 2, Example 5, Example 12, and Comparative Example 2. The SN board was subjected to actual equipment testing. Compared with Comparative Example 2, all the embodiments of the present invention have a slight "surface roughness" of sliding -13-201125660 surface damage, and the durability thereof is further improved [Table 1] Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Chemical composition (% by mass) Zr02 5 5 5 2 5 5 1 AI2O3 85 50 20 0 90 86 0 AI4O4C 5 40 70 95 0 4 96 C 3 3 3 3 3 3 3 Total 98 98 98 100 98 98 100 Evaluation item resistance to spalling 〇〇〇〇 XX Burning spalling test results Cracking normal temperature bending strength MPa 20 30 35 40 15 18 — Thermal expansion coefficient— Χ10'6/Κ 7.17 6.00 5. 00 4.17 7.33 7.20 Oxidation resistance (surface roughness) Decarburization layer thickness index 85 40 25 10 100 95 — Corrosion resistance (melt loss index) Melt FeO : 1600°C x 2hr 90 85 75 70 100 99 - -14- 201125660 [Table 2] Example 5 Example 6 Example 7 Example 8 Example 9 Chemical composition (% by mass) Zr02 0 0 4 2 5 Al2〇3 91 90 87 83 71 AI4O4C 5 6 5 5 20 C 2 2 2 8 2 Total 98 98 98 98 98 Evaluation item flaking resistance Δ 〇〇〇〇 peeling test result Normal temperature bending strength MPa 20 20 20 15 25 Thermal expansion coefficient X 10'6/K 8.10 7.90 7.83 7.93 7.27 Oxidation resistance (surface roughness) Carbon layer thickness index 82 81 82 116 60 Corrosion resistance (melt loss index) Melt FeO : 1600 ° C x 2 hr 75 75 79 97 76 -15- 201125660 [Table 3] Example 10 Example 11 Example 12 Example 13 Example Η Chemical composition (% by mass) Zr02 0 0 0 0 0 ai2o3 92 91 90 87 86 AI4O4C 5 5 5 5 5 c 2 2 2 2 2 Total 99 98 97 94 93 Evaluation item Anti-flaking 〇〇〇〇 △ Peeling test result Normal temperature bending Degree MPa 9 10 20 60 61 thermal expansion coefficient of X 10'6 / K 8.10 8.10 8.10 8.10 8.10 oxidation resistance (surface roughness) of the decarburized layer thickness index 8282828282 Corrosion resistance (melt loss index) molten FeO: 1600. . X 2hr 75 75 75 75 75 [Simple description of the diagram] Figure 1 shows the liquid phase oxidation test apparatus used to evaluate the surface roughness resistance. Figure 2 shows the decarburization layer thickness and impact digestion speed of the steel bath part of the liquid phase oxidation test. Relationship of surface roughness). Figure 3 shows the phase diagram of A!2〇3 - AI4C3. -16-