201009277 六、發明說明： 【發明所屬之技術領域】 本發明係有關於一種煅燒用載置器。 【先前技術】 、作為電子部件煅燒用載置器，除了要求耐熱性或機械強度以外，亦要 求不與锻燒的陶瓷電子部件發生反應。習知作為具有這類特性的載置器可 使用，在氧化鋁、莫來石（mullite)系的基材表面形成由氧化鋁所構成的中 間層，且進一步在其表面被覆氧化錘（hrcoj^a)的載置器（專利文獻1)。 ❹ ❷ 近年來，党到各企業減少二氧化碳排出量方針的影響，於陶瓷電容器 (C〇ndenSer)等陶瓷電子部件製作中，也在進行低溫下具有可煅燒組成物 的部件的·。在低溫下具有可職域物的料，其特點為含有 BaO、MnO、CaO、SrO、NiO等低熔點金屬氧化物。 這類低嫁點金屬氧化物雖可進行部件的低溫锻燒，然而在煅燒部件時 其等會擴散到載置H的表層或巾間層，而在此絲引發由化學反應所產生 之載置器的變質之新問題的主要因素。 具體而言，作為上述3層構造載置器的中間層’ -般所使用之Al2〇3 雖具有稱為=剛玉魏構」的晶體結構，但祕與祕（alkali)成 份的反應性高’而與例如上述的Bao反應產生BaAlc>4或B為^。該化 子反使具有習知剛玉^{晶體結構之巾間層的晶體結構向尖晶石型晶體結 構轉變。在由剛玉型的晶體結構向尖晶石型晶體結構轉變的晶體部份中、， 晶轴延伸的結果致使中間層膨脹·此處產生應力4該應力所引起 置器的弯曲或載置器表層的剝離等現象，會造成載置器壽命變短的問題。 【專利文獻1】日本特開2007_15882號公報 【發明内容】 【發明所欲解決之課題】 本發月的目的係/^了解決上述問題’並提供—種在 化物之部件馳燒時，不舍^㈣mum ’祕點金屬氧 不會產生《 —f曲或載置器表層_離等問題 201009277 的煅燒載置器。 【用於解決課題之方式】 為解決上述問題而於本發明中所製成的锻燒用載置器，是—種由基材 和塗層所構成的煅燒用載置器，其特徵在於，該塗 央晶石型晶體結 構。 申请專利範圍第2項所述之發明為如申請專利範圍第i項所述之锻燒 用載置器’其中’上述基材由氧化銘或/和莫來石所構成上述塗層由形成 於基材表面的中間層和形成於中間層表面的表層所構成，且該表層由與自 對象锻燒物而來之化學物質反應性低的材質所構成。 義 ^專圍第3項所述之發明為如t請專機圍第2獅述之锻燒 ® 載置器’其中，中間層以氧化銘為主要成份、且由含有Na、K、Mg、Ca、 Sr、Ba中至少一種之尖晶石型晶體結構的晶體所構成。 此處，尖晶;5型晶體結構是^XMgAl2〇4為代表的晶體結構。 申请專利細第4項所述之發明為如中請專職圍第3項所述之锻燒 用載置器’其中，中間層含有0.1〜6〇重量0/〇之Na、K、Mg、Ca、Sr、Ba 中的至少一種元素。 申請專利額第5摘狀發，如中請專利第4橋述之缎燒 用載置器’其中，中間層由含有0.1〜25重量％之灿、{：、(：3、分、抱中 的至少一種元素的β氧化銘型晶體結構的晶體所構成。 ❹ 此處’ β氧化銘型晶體結構是指含有Α1成份、Ο成份和Na、Κ、Ca、201009277 VI. Description of the Invention: [Technical Field to Which the Invention Is Along] The present invention relates to a carrier for calcination. [Prior Art] As a mount for electronic component firing, in addition to heat resistance and mechanical strength, it is also required to react with the calcined ceramic electronic component. Conventionally, as a carrier having such characteristics, an intermediate layer made of alumina is formed on the surface of an alumina, mullite-based substrate, and the surface is further coated with an oxidized hammer (hrcoj^ A carrier of a) (Patent Document 1). ❹ ❷ In recent years, the influence of the party-to-business reduction of the carbon dioxide emission policy has been carried out in the production of ceramic electronic components such as ceramic capacitors (C〇ndenSer), as well as components having a calcinable composition at low temperatures. A material having a workable substance at a low temperature, which is characterized by containing a low melting point metal oxide such as BaO, MnO, CaO, SrO or NiO. Such a low-margin point metal oxide can perform low-temperature calcination of the component, but when the component is calcined, it will diffuse to the surface layer or the inter-sheet layer on which H is placed, and the filament is caused to be placed by the chemical reaction. The main factor in the new problem of deterioration. Specifically, Al2〇3, which is used as the intermediate layer of the above-described three-layer structure mount, has a crystal structure called = corundum structure, but has high reactivity with the alkal component. However, it is reacted with, for example, Bao described above to produce BaAlc > 4 or B. This chemistry reverses the crystal structure of the interlining layer having the conventional corundum structure to the spinel crystal structure. In the crystal portion transformed from the corundum crystal structure to the spinel crystal structure, the result of the crystal axis extension causes the intermediate layer to expand. Here, the stress 4 is generated, which causes the bend of the holder or the surface of the carrier. The phenomenon of peeling or the like causes a problem that the life of the carrier is shortened. [Patent Document 1] JP-A-2007-15882 SUMMARY OF INVENTION [Problems to be Solved by the Invention] The purpose of this month is to solve the above problem and provide a kind of problem in which the components of the compound are burned. ^ (d) mum 'secret point metal oxygen will not produce the "f-curve or the surface of the loader_offering problem 201009277 calcination loader. [Means for Solving the Problem] The calcining mount which is produced by the present invention in order to solve the above problems is a calcining mount comprising a base material and a coating layer, and is characterized in that The coated naphthalene type crystal structure. The invention described in claim 2, wherein the above-mentioned substrate is formed of oxidized or/and mullite, wherein the above-mentioned substrate is formed of the above-mentioned substrate. The intermediate layer on the surface of the substrate and the surface layer formed on the surface of the intermediate layer are composed of a material having low reactivity with a chemical substance derived from the object calcined product. The invention described in Item 3 of the Yigong Special Zone is a special machine for the second lion's calcination® carrier. The middle layer is mainly composed of oxidized crystal and contains Na, K, Mg, Ca. A crystal of a spinel crystal structure of at least one of Sr and Ba. Here, the spinel; the crystal structure of the type 5 is a crystal structure represented by ^XMgAl2〇4. The invention described in the fourth application of the patent application is the calcining carrier described in item 3 of the full-time division, wherein the intermediate layer contains 0.1 to 6 〇 of 0/〇 of Na, K, Mg, Ca. At least one element of Sr, Ba. Patent application No. 5, the satin burning carrier of the fourth section of the patent, wherein the intermediate layer contains 0.1 to 25% by weight of the can, {:, (: 3, minute, hug The at least one element is composed of a crystal of a β-oxidized crystal structure. ❹ Here, the β-oxidized crystal structure refers to a composition containing Α1, Ο and Na, Κ, Ca,
Sr、Ba成份中的任何一種，在晶體結構中具有單純的六方晶，且空間群為 P63/mm (194)的晶體結構。 申請專利範園第6項所述之發明為如中請專利細第2項至第5項令 任一項所述之锻燒用載置器，其中’中間層的厚度為2〇〜5〇〇μιη。 申請專利範園第7項所述之發明為如中請專利範圍第2項至第6項中 任-項所述之缎燒用載置器，其中’表層的主成份為安定化（stabiHzed)氧 化锆或锆酸鹽。 申請專利範圍第8項所述之發明為如中請專利範圍第2項至第7項中 任-項所述之锻燒践置器’其巾’表層的厚度為20〜500μιη。 【發明之效果】 201009277 。發明械讀燒㈣置財，在由基材轉顧構叙峨用載置 器中’透過預先使塗層具有尖晶石型晶體結構，在烺燒含有低熔點金屬氧 化物的部件時，可以解決由習知剛玉型晶體結構之塗層所產生的問題（因 化學反應而使中間層由剛玉型晶體結構轉縣尖晶石型晶體結構 ，且由此 產生的應力’會導致載置㈣料或載置器表層賴離等現象產生，而使 載置器的壽命變短的間題）。 【實施方式】 【用於實施發明之最佳型態】 』 本發明之烺燒用載置器係在由基材和塗層構成的锻燒用載置器中，塗 〇層具有尖晶石型晶體結構。圖！係表示本發明的一種實施方式。以下，如 圖！所示，說明本發明相關的實施方式，其中，基材3由氧她或/和莫來 石構成上述塗層由中間層2和表層j構成，該令間層2形成在基材$表 面’且該表層1由與自對綠祕而來德學物f反雜賴㈣所構成。 構成本發賴t闕2以A1成份為主要成份，贿减他成份雌佳 3 〇、Na、K、Mg、Ca、Sr、Ba中的至少一種元素，但是只要是具有尖 晶石型晶體結構的物質即可，不特別限定於這類物質。本發明的中間層2 的晶體結構’從形成中間層2時起即具有尖晶石型構造。因此，電子部件 锻燒時，自部件而來的Ba0、_、Ca〇、Sr〇、腦等的低雜金屬氧化 ❹=使擴散到塗佈（coating)層（表層j或中間層2)時，由這類低熔點金 屬氧化物和氧化_所纽聽學反應，衫會使㈣層2的晶體結構從 剛玉型晶體結構轉變成尖晶石型晶體結構，可有效防止由晶體結構的變化 而引起的應力產生’或由於伴隨應力產生而引起之載置器的弯曲或塗層 剝離所導致之载置器的短壽命化。 另外，構成本發明之中間層2較佳以燒結或電漿火焰喷塗（科戰 spray)所形成。構成本發明的中間層2的厚度較佳為2〇〜5〇〇晔，若亦考 量治具輕量財面，败佳為·〜3⑻陴。這是㈣巾縣2的厚度在 2_以下時’會被認為有引起部件變質的傾向，且此係自基材而來的二 化石夕成份不被_在中_中，而是透過中間層到達表層表面之故。而另 方面’中間層的厚度為5〇0μπι以上時，則會變得難以形成中間層2本身。 201009277 ^ ^發層2較佳具有尖晶石㈣體結構1含有q卜的重 量/〇之Na、K、Mg、Ca、Sr、Ba，更佳具有p氧 α!〜25 娜之Na、K、Mg、Ca、Sr、Ba4Na、K、t:^ = 的含量不到0.1質量％，則中間層的晶體社構I g β 、-構…、去侍到尖晶石型晶體結構或 β氧化銘型阳體結構，僅為剛玉型晶體結構。剛玉 與部件成份反應而引起晶舰構變化，因此 t構lB日體由於 層剝離，另一方面，Na、K、Mg、Ca :B=，A«™ χτ ^ λ/Γ ^ Mg La Sr Ba的含量超過60質量％時， ❹ 層本身。因此’長時間使用載置器時，會變得 ♦易產生a K、Ca、Sr、Ba成份的變動，有對部件 因此’從巾W自細綱糊侧本 發明的中間層2較佳作成上述結構。特別是透過作成含〇】〜25重°量=彻 的β氧德㈣構’即餘高溫使祕件下，也極少會有成份的變動 及結晶形_變化’可製成能長時間使㈣锻燒用載置器。 ㈣再^構ίΓΓ表層1的域份，她由安定錄錄或錯酸鹽 靡朗絲層1必狄與電子部件㈣的碰燒體反 應之反應性低賴質’可啸據觀燒體的種類而改變其材質。 另外，構成本發明之表層i的厚度較佳為2〇〜5〇〇师。從儘量減少與 被锻燒體反應而產生之餘留膨脹等應力的觀點而言，厚度更佳為5〇〜 150μηι。 ”” 更進步構成本發明之基材3的主成份，較佳具有耐剝落性和对寶 曲性優異的氧化鋁或莫來石。 而後’本發明的锻燒用治具的製作方法為首先用燒結或電浆火焰喷塗 在基材3上而形成中間層2後，在製成之中間層2的上方經由喷塗燒結或 電漿火焰喷塗形成表層1，而在基材上形成塗層。 於此’火财塗是指透珊金屬__細婦末加熱（以下，稱為 火焰喷塗材料）成熔融狀態’再吹到對象物的表面上而形成喷塗被膜的方 法。雖鱗在有以加狀綠錢義敎焰軌社焰喷塗以及使用 電弧的電弧倾等各法，但本發雜佳為透過側絲倾（ρΐ_ jet)的電漿火焰噴塗以形成中間層2的火焰噴塗被膜。 6 201009277 本發明特佳為在電漿火焰喷塗中使用水電漿火焰喷塗（水安定化電裝 火焰喷塗）。這是因為由氣體電漿火焰喷塗而形成的喷塗被膜的最大膜厚為 300μιη左右，然而藉由水（安定化）電漿火焰噴塗則可形成最大膜厚為 ΙΟΟΟμιη左右之厚的被膜。另外，水（安定化）電漿火焰喷塗由於較為多孔 性（porous) ’可形成表面粗棱的被膜，且在由提高與基材3的密合性的觀 點而言亦較佳。 【實施例】 以下，以實施例具體說明本發明，但本發明不受此等實施例的限定。 〈實施例1〜13、比較例1〜5> - 藉由以下所示之方法，分別製作電子部件用煅燒治具的試片（test O Piece)。此處’表1、表2的實施例1〜9及比較例1〜5是用於研討中間層 的材質、施行方法以及厚度的試片，且在所有的試片中，表層由厚度1〇〇μηι 並含有8質量％之Υ2〇3的安定化氧化鍅所構成。另外，實施例1〇〜2〇、比 較例6〜9為用於研討表層的材質、施行方法及厚度的試片，且在所有的試 片中，中間層由具有厚度ΙΟΟμιη之β氧化鋁型晶體結構或尖晶石型晶體結 構的晶體所構成。 〈基材的製作方法〉 將已添加黏土及臨時烺燒氧化鋁且混練後之坯料以油壓推壓，並以 lOOMPa之壓力使長i5〇mm \寬15〇mm X厚5mm之板狀體成型而製得成型 體’以便於最大粒徑為150μιη之電融氧化鋁粒子中，使氧化鋁含量成為85 質量％。然後，將製成的成型體乾燥之，於165〇乞下保持5小時以進行煅 燒’即製成試片（實施例1〜20，比較例1〜9)。 〈中間層的製作方法〉 (1) 燒結施行（比較例1): 在溶劑中用水使燒結氧化鋁漿料（slurry)化。在基材上塗佈製成的漿 料後’於145G°C下保持5小時’分別燒結成厚度為·啤的中間層。 (2) 塗佈施行（實施例！〜4、實施例7、實施例9、實施例u〜13、 實施例15、實施例17〜19、比較例3〜6、比較例9): 在溶劑中用水使氧化鋁粒子和含有表丨所示之成份（Na、K、Mg、Ca、 Sr、Ba中的任何一種）的粒子漿料化。在基材上塗佈製成的漿料後，於145〇e>c 201009277 下保持5小時，使表1所示之成份（Na、κ、Mg、Ca、Sr、Ba中的任何〆 種）含有表1所示之比例（〇丨〜邠重量％)，分別燒結成表1所示之厚度的 中間層。 (3)電漿火焰喷塗施行（實施例5〜6、實施例8、實施例1〇、實施 例14、實施例16、實施例2〇、比較例2、比較例7〜8): 透過使用於β氧化鋁或尖晶石中，使表1所示之成份（Na、K、Mg、 Ca、Sr、Ba中的任何一種）含有表丨所示之比例（〇丨〜仞重量％)的粒子 (平均粒徑為70μηι) ’並在基材上進行電漿火焰喷塗，即形成表1所示之 厚度的中間層。 〈表層的製作方法〉 〇 使用表1之安定化氧化锆或锆酸鹽，在基材上進行電漿火焰喷蜜或塗 層施行’即形成表1所示之厚度的表層。 【表1】 中間層的 研討（實施例1〜9、比勒 i例1〜5) 比較例-1 比較例-2 比較例-3 實施例-1 實施例-2 眚掩制-3 實施例-4 間 層 材質 成份 含量％ AI2O3 7 βΑΐ2〇3 Ba 1 尖晶石 Mg 17 βΑ12〇3 Ca 6 βΑ1203 Ba 18 尖晶石 Ba 54 βΑ12〇3 Κ 6 施行方法 塗佈 火焰喷 塗 塗佈 塗佈 塗佈 塗佈 塗佈 厚度（jun) 100 10 15 25 50 120 100 表 層 材質 8Υ-Ζγ07 8Y-ZrO? 8Y-ZrO, 8Y-Zr〇2 8Y-ZK), 8Υ-Ζγ〇2 8Υ-Ζγ02 施行方法 塗佈 塗佈 塗佈 火焰喷 塗 塗佈 塗佈 火焰喷 塗 厚度（nm) 100 100 100 100 100 100 100 實施例-5 實施例-6 P實施例-7 實施例-8 實施例-9 卜|·，輕例-4 fcb妨你1-5 間 層 材質 成份 含量％ 尖晶石 Sr 43 βΑ1203 Sr 12 尖晶石 Ca 25 βΑ1203 Na 4 βΑ1203 Ba 22 βΑ1203 Ca 6 βΑ1203 Sr 12 施行方法 火焰喷 塗 火焰喷 塗 塗係 火焰喷 塗 塗佈 塗佈 塗佈 厚度（Min) 200 150 ~~200 300 500 600 1ΠΛΛ 表 層 材質 8Υ-Ζγ〇2 8Y-Zr02 8Y-Zr02 8Y-Zr02 8Y-ZrO, 8Y-Zr〇2 i WU 8Y-7rO 施行方法 厚度（μιη) 火焰喷 塗 100 火焰喷 塗 100 火焰喷 塗 100 塗佈 100 火焰喷 塗 100 火焰喷 塗 100 塗佈 100 8 201009277 表層的研討（實施例10〜20、比較例6〜9) 比較例_6 比較例-7 實施例 -10 實施例 -11 實施例 12 實施例 -13 實施例 -14 中 間 層 材質 成份 含量％ βΑ12〇3 Na 尖晶石 Mg 17 βΑ1203 Ba 12 βΑ1203 Ba 17 尖晶石 Ca 10 βΑ1203 Ca 6 尖晶石 Ba 36 施行方法 塗佈 火焰喷塗 火焰喷塗 塗佈 塗佈 塗佈 火焰噴塗 厚度（Mm) 100 100 100 100 100 100 100 表 層 材質 8Y-Zr〇2 8Y-Zr07 8Y-Zr02 8Y-ZrO, CaZr〇3 4C-Zr02 4C-Zr02 施行方法 塗佈 塗佈 塗佈 塗饰 火焰喷塗 火焰喷塗 塗佈 厚度（μιη) 10 15 50 100 150 150 200 實施例 -15 實施例 -16 實施例 •17 實施例 -18 實施例 -19 實施例 -20 比較例-8 中 間 層 材質 成份 含量％ βΑ1203 Ba 6 尖晶石 Sr 28 βΑ1203 Sr 8 βΑ1203 Ba 18 βΑ1203 Na 2 βΑ1203 Κ 6 βΑ1203 Ba 12 施行方法 塗佈 火焰喷會 塗稀 塗佈 塗佈 火焰唆塗 火焰 厚度（um) 100 100 100 100 100 100 100 表 層 材質 SrZr02 BaZrO? Mr-Zt02 BaZrO^ Μβ2ΖΤ5〇12 8Υ-Ζγ〇2 8Y-Zr〇9 施行方法 火焰喷塗 火焰喷士 火焰喷塗 火焰喷塗 塗佈 火焰喰i 火焰喷塗 厚度（μη〇 300 150 200 100 250 500 600 比較例-9 中 間 層 材質 成份 含量％ 尖晶石 Mg 17 • 施行方法 塗佈 厚度（um) 100 表 層 材質 BaZrOn 施行方法 火焰喷塗 厚度（μχη) 1000 以下述方法對以上述製作方法所製成的試片進行評價，其結果示於表 2。另外，作為確認用上述製作方法所形成之中間層的晶體結構，以χ光繞 射儀（XRD)測定實施例2所述之中間層表面的結果，可確認為主要產生 BaAbOw，而實施例2的中間層則確認為帶有p氧化鋁型構造的結晶相。 V 〈試片的評價方法1:至產生表層剝離為止之炮燒次數〉 製成於70重量％的水中分散2重量％的BaC〇3、2重量％的尬⑽及 26重量％之BaTi〇3液體，而後在試片（尺寸：15〇mmx2〇mmx4mm)的表 面塗佈該液體（O.Sg)後，反復進行於⑽叱下保持】小時的锻燒，並評 價至產生表層剝離為止的緞燒次數。 〈試片的評償方法2 :伴隨表層剝離之剝離面的弯曲量〉 用上述評價方法在產生表層剝離的同時，以從表面起的最大距離測定 試片整體的彎曲，來評價彎曲量。 ◎:彎曲量為〇.5mm以下 〇：彎曲量為〇 5mm〜1.0mm以下 201009277 △ 零曲重為l.Ornni以上 〈試片的評價方法3 :輿都杜、 製成由以BaT n 1件（燒）之應性（部件反應度）〉 1〇3為主成份的材料而形成的板狀（尺寸： 持ΓΙ時部件。在試片上載置製成的部件’進行於i4〇o°c下保 、 70後，以外觀之觀察來評價部件的變質狀態。 ◎:未確認出部件的變質 〇:已碟認出部件的一部份變f (整面的大約50%以下） △.已確5忍出部件的大部份變質（整面的大約5〇%以 【表2】 中間 (實施例1〜9 、比較例1〜5) 評 剝離性 比較例 -1 9 比較例 -2 比較例 -3 實施例 -1 實施例 .2 實施例 -3 實施例 -4 價 彎曲評價（◎〇△) 彎曲"ί： (mm) △ 2.0 5 △ 1.6 4 Δ 1.5 15 ◎ 0.5 35 ◎ 0.4 20 〇 0.9 35 ◎ 0.2 與部件之反應性 _〇 △ Δ 〇 ◎ 〇 ◎ 實施例 貪施例 實施例 實施例 實施例 比較例 比較例 -5 -6 -7 -8 -9 -4 -5 評 剝離性 30 40 30 35 35 15 10 價 彎曲評價（◎〇△) 卜◎ 〇 ◎ ◎ 〇 Δ 彎曲去（mm) 0.9 0.4 1.0 0.3 0.5 0.9 1.2 與部件之反應性 〇 ◎ 〇 ◎ ◎ Δ △Any of the Sr and Ba components has a simple hexagonal crystal structure in the crystal structure, and the space group has a crystal structure of P63/mm (194). The invention described in the sixth aspect of the present invention, wherein the thickness of the intermediate layer is 2〇~5〇. 〇μιη. The invention described in claim 7 is the satin mount according to any one of items 2 to 6, wherein the main component of the surface layer is stabilized (stabiHzed). Zirconia or zirconate. The invention described in the eighth aspect of the invention is the thickness of the surface layer of the calcining device as described in the second aspect of the invention, which is in the range of from 20 to 500 μm. [Effects of the Invention] 201009277. The invention of the mechanical reading and burning (4) fortune, in the transfer of the substrate from the substrate to the placement device, the coating has a spinel crystal structure in advance, and when the component containing the low melting point metal oxide is burned, Solving the problem caused by the coating of the conventional corundum crystal structure (the intermediate layer is transformed from the corundum crystal structure to the spinel crystal structure due to the chemical reaction, and the resulting stress will cause the (four) material to be placed Or the phenomenon that the surface of the carrier is separated, and the life of the carrier is shortened. [Embodiment] [Best Mode for Carrying Out the Invention] The simmering mount of the present invention is in a calcining mount composed of a substrate and a coating layer, and the enamel layer has a spinel. Type crystal structure. Figure! An embodiment of the invention is shown. Below, as shown! Illustrated, a related embodiment of the present invention is illustrated in which the substrate 3 is composed of oxygen or/and mullite. The above coating layer is composed of an intermediate layer 2 and a surface layer j, and the intervening layer 2 is formed on the surface of the substrate. And the surface layer 1 is composed of the self-study of the scholastic material and the anti-missing (four). The composition of the hairpin t阙2 is based on the A1 component and bribes at least one of the elements of the female, 3, Na, K, Mg, Ca, Sr, Ba, but as long as it has a spinel crystal structure. The substance may be, and is not particularly limited to such a substance. The crystal structure ' of the intermediate layer 2 of the present invention has a spinel type structure from the time of forming the intermediate layer 2. Therefore, when the electronic component is calcined, the low-metal cerium oxide of Ba0, _, Ca 〇, Sr 〇, brain, etc. from the component is caused to diffuse to the coating layer (surface layer j or intermediate layer 2). By the low-melting-point metal oxide and the oxidation reaction, the shirt will transform the crystal structure of the (four) layer 2 from the corundum crystal structure to the spinel crystal structure, which can effectively prevent the crystal structure from being changed. The resulting stress produces 'or short life of the mount due to bending of the carrier or peeling of the coating due to stress generation. Further, the intermediate layer 2 constituting the present invention is preferably formed by sintering or plasma flame spraying. The thickness of the intermediate layer 2 constituting the present invention is preferably 2 Å to 5 Å, and if it is also considered to have a light weight, it is preferably 〜3 (8) 陴. This is because (4) when the thickness of the towel county 2 is 2 Å or less, it is considered to cause a deterioration of the component, and the composition of the bismuth from the substrate is not _ in the middle, but through the intermediate layer. Arrived at the surface of the surface. On the other hand, when the thickness of the intermediate layer is 5 〇 0 μm or more, it becomes difficult to form the intermediate layer 2 itself. 201009277 ^ ^ Hair layer 2 preferably has a spinel (four) body structure 1 containing the weight of q / Na, K, Mg, Ca, Sr, Ba, more preferably p oxygen α! ~ 25 Na Na, K When the content of Mg, Ca, Sr, Ba4Na, K, and t:^ = is less than 0.1% by mass, the crystal structure of the intermediate layer is I g β , - structure, and the spinel crystal structure or β oxidation The type of the male body structure is only a corundum crystal structure. Corundum reacts with the components of the component to cause a change in the crystal structure. Therefore, the t-structure of the lB is due to layer peeling. On the other hand, Na, K, Mg, Ca: B =, A «TM χτ ^ λ / Γ ^ Mg La Sr Ba When the content exceeds 60% by mass, the ruthenium layer itself. Therefore, when the carrier is used for a long period of time, it is easy to cause a change in the components of a K, Ca, Sr, and Ba, and the pair of members is preferably made from the intermediate layer 2 of the present invention from the side of the towel W. The above structure. In particular, it can be made for a long time by making a 〇 〇 〜 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 Mounting device for calcination. (4) Reconstructing the domain of the surface layer 1, she is recorded by the stable or the acid salt of the sapphire layer 1 and the reaction of the electronic component (4). Change the material of the type. Further, the thickness of the surface layer i constituting the present invention is preferably 2 Å to 5 Å. From the viewpoint of minimizing stress such as residual expansion generated by the reaction with the calcined body, the thickness is more preferably 5 Å to 150 μm. Further, the main component constituting the substrate 3 of the present invention is more preferably alumina or mullite excellent in peeling resistance and excellent in flexibility. Then, the method for producing the calcining tool of the present invention is first formed by sintering or plasma flame spraying on the substrate 3 to form the intermediate layer 2, and then sintered or electrically sprayed on the upper portion of the intermediate layer 2 which is formed. The slurry flame spray forms the skin layer 1 and forms a coating on the substrate. Here, the "fire coating" refers to a method in which a fine coating of a fine metal (hereinafter referred to as a flame spraying material) is melted and then blown onto the surface of an object to form a spray coating. Although the scales are in various ways, such as the addition of the green money, the flame spraying, and the arcing of the arc, the present invention is a plasma flame spraying through the side wire (ρΐ_jet) to form an intermediate layer. 2 flame sprayed the film. 6 201009277 The invention is particularly useful for the use of water plasma flame spraying (water stabilization electric flame spraying) in plasma flame spraying. This is because the maximum film thickness of the sprayed coating formed by gas plasma flame spraying is about 300 μm, whereas by water (stabilized) plasma flame spraying, a film having a maximum thickness of about ΙΟΟΟμηη can be formed. Further, water (stabilized) plasma flame spraying is preferable because it is porous, and a film having a rough surface can be formed, and it is preferable from the viewpoint of improving the adhesion to the substrate 3. EXAMPLES Hereinafter, the present invention will be specifically described by examples, but the present invention is not limited by the examples. <Examples 1 to 13 and Comparative Examples 1 to 5> - A test piece (test O Piece) of a firing fixture for an electronic component was produced by the method described below. Here, Examples 1 to 9 and Comparative Examples 1 to 5 of Tables 1 and 2 are test pieces for investigating the material, the method of execution, and the thickness of the intermediate layer, and in all the test pieces, the thickness of the surface layer is 1〇. 〇μηι consists of 8% by mass of 安2〇3 of stabilized cerium oxide. Further, Examples 1 to 2 and Comparative Examples 6 to 9 are test pieces for investigating the material, the method of execution, and the thickness of the surface layer, and in all of the test pieces, the intermediate layer is made of β alumina having a thickness of ΙΟΟμηη. It consists of a crystal structure or a crystal of a spinel crystal structure. <Method for Producing Substrate> The billet which has been added with clay and temporarily calcined alumina and kneaded is pressed by oil pressure, and is made into a plate having a length of i5〇mm, a width of 15〇mm, and a thickness of 5mm by a pressure of 100 MPa. The molded body was molded to obtain an electro-alumina alumina particle having a maximum particle diameter of 150 μm, and the alumina content was 85 mass%. Then, the obtained molded body was dried and kept at 165 Torr for 5 hours to be calcined. Thus, test pieces were prepared (Examples 1 to 20, Comparative Examples 1 to 9). <Method for Producing Intermediate Layer> (1) Sintering (Comparative Example 1): Sintered alumina slurry was slurried with water in a solvent. After the prepared slurry was coated on the substrate, it was sintered at 145 °C for 5 hours to form an intermediate layer having a thickness of beer. (2) Coating application (Examples! to 4, Example 7, Example 9, Example u to 13, Example 15, Example 17 to 19, Comparative Example 3 to 6, Comparative Example 9): in a solvent The alumina particles and the particles containing the components shown in Table ( (any one of Na, K, Mg, Ca, Sr, and Ba) are slurried with water. After coating the prepared slurry on the substrate, it was kept at 145 〇e >c 201009277 for 5 hours to make the components shown in Table 1 (any of Na, κ, Mg, Ca, Sr, Ba). The ratio (〇丨~邠% by weight) shown in Table 1 was contained, and the intermediate layers of the thickness shown in Table 1 were respectively sintered. (3) Plasma flame spraying (Examples 5 to 6, Example 8, Example 1, Example 14, Example 16, Example 2, Comparative Example 2, Comparative Example 7 to 8): Used in β-alumina or spinel, the components shown in Table 1 (any of Na, K, Mg, Ca, Sr, Ba) are contained in the ratio shown in Table 〇丨 (〇丨~仞% by weight) The particles (average particle size of 70 μηι) were subjected to plasma flame spraying on the substrate to form an intermediate layer of the thickness shown in Table 1. <Method for Producing Surface Layer> 〇 Using the stabilized zirconia or zirconate of Table 1, a plasma flame spray or coating was applied to the substrate to form a surface layer having the thickness shown in Table 1. [Table 1] Discussion of the intermediate layer (Examples 1 to 9, Biller i Examples 1 to 5) Comparative Example-1 Comparative Example-2 Comparative Example-3 Example-1 Example-2 眚 Masking-3 Example -4 interlayer material content % AI2O3 7 βΑΐ2〇3 Ba 1 Spinel Mg 17 βΑ12〇3 Ca 6 βΑ1203 Ba 18 Spinel Ba 54 βΑ12〇3 Κ 6 Application method Coating by flame spray coating Cloth coating thickness (jun) 100 10 15 25 50 120 100 Surface material 8Υ-Ζγ07 8Y-ZrO? 8Y-ZrO, 8Y-Zr〇2 8Y-ZK), 8Υ-Ζγ〇2 8Υ-Ζγ02 Application method Cloth coating coating flame spray coating coating flame spraying thickness (nm) 100 100 100 100 100 100 100 Example-5 Example-6 P Example-7 Example-8 Example -9 Bu|· , light example - 4 fcb you 1-5 layer material content % spinel Sr 43 βΑ1203 Sr 12 spinel Ca 25 βΑ1203 Na 4 βΑ1203 Ba 22 βΑ1203 Ca 6 βΑ1203 Sr 12 Implementation method Flame spray flame spraying Coating flame spraying coating coating thickness (Min) 200 150 ~~200 300 500 600 1ΠΛΛ Surface material 8Υ-Ζγ〇2 8Y-Zr02 8Y-Zr02 8Y-Zr02 8Y-ZrO, 8Y-Zr〇2 i WU 8Y-7rO Application Method Thickness (μιη) Flame Spraying 100 Flame Spraying 100 Flame Spraying 100 Coating 100 Flame Spraying 100 Flame Spraying Coating 100 Coating 100 8 201009277 Surface layer discussion (Examples 10 to 20, Comparative Examples 6 to 9) Comparative Example _6 Comparative Example -7 Example-10 Example -11 Example 12 Example-13 Example-14 Intermediate layer material content% βΑ12〇3 Na Spinel Mg 17 βΑ1203 Ba 12 βΑ1203 Ba 17 Spinel Ca 10 βΑ1203 Ca 6 Spinel Ba 36 Application Method Flame Spray Flame Spray Coating Coating Flame Spray Thickness (Mm) 100 100 100 100 100 100 100 Surface Material 8Y-Zr〇2 8Y-Zr07 8Y-Zr02 8Y-ZrO, CaZr〇3 4C-Zr02 4C-Zr02 Application Method Coating Coating Coating Flame Spray Flame Spray Coating Thickness (μιη) 10 15 50 100 150 150 200 Example-15 Example-16 Example • 17 Example-18 Example-19 Example-20 Comparative Example-8 Intermediate Layer Material Composition Content % βΑ1203 Ba 6 Spinel Sr 28 βΑ1203 Sr 8 β 1203 Ba 18 βΑ1203 Na 2 βΑ1203 Κ 6 βΑ1203 Ba 12 Application Method Coating Flame Spraying Coating Dilute Coating Coating Flame Coating Flame Thickness (um) 100 100 100 100 100 100 100 Surface Material SrZr02 BaZrO? Mr-Zt02 BaZrO^ Μβ2ΖΤ5〇12 8Υ-Ζγ〇2 8Y-Zr〇9 Application Method Flame Spray Flame Spray Flame Spray Flame Spray Coating Flame 喰i Flame Spray Thickness (μη〇300 150 200 100 250 500 600 Comparative Example-9 Intermediate layer Material content % Spinel Mg 17 • Application method Coating thickness (um) 100 Surface material BaZrOn Application method Flame spray thickness (μχη) 1000 The test piece prepared by the above production method was evaluated by the following method. The results are shown in Table 2. Further, as a result of confirming the crystal structure of the intermediate layer formed by the above-described production method, the surface of the intermediate layer described in Example 2 was measured by a calender diffractometer (XRD), and it was confirmed that BaAbOw was mainly produced, and Example 2 was obtained. The intermediate layer was confirmed to be a crystalline phase having a p-alumina type structure. V <Evaluation method of test piece 1: number of shots until surface peeling occurred> 2% by weight of BaC〇3, 2% by weight of bismuth (10) and 26% by weight of BaTi〇3 were prepared in 70% by weight of water. After the liquid (O.Sg) was applied to the surface of the test piece (size: 15 mm x 2 mm x 4 mm), the calcination was repeated for (10) under the crucible, and the satin was evaluated until the surface peeling occurred. The number of burns. <Method of Evaluation of Test Piece 2: Bending amount of the peeling surface accompanying the surface layer peeling> The amount of warpage was evaluated by measuring the bending of the entire test piece at the maximum distance from the surface while the surface layer was peeled off by the above-described evaluation method. ◎: The bending amount is 〇.5mm or less 〇: The bending amount is 〇5mm~1.0mm or less 201009277 △ The zero-curve weight is l.Ornni or more <Evaluation method of test piece 3: 舆都杜, made of BaT n 1 piece (sintering) (component reactivity) > 1〇3 is a plate-like material composed of the main component (size: the member held on the test piece. The part placed on the test piece is performed at i4〇o°c) After the protection, after 70, the deterioration state of the parts was evaluated by the observation of the appearance. ◎: The deterioration of the parts was not confirmed. 一: A part of the parts recognized by the dish was changed to f (about 50% or less of the entire surface) △. (5) Most of the components were tolerated (about 5% of the whole surface in the middle of [Table 2] (Examples 1 to 9 and Comparative Examples 1 to 5). Peelability Comparative Example-1 9 Comparative Example-2 Comparative Example -3 Example-1 Example. 2 Example-3 Example-4 Valence bending evaluation (◎〇△) Bending"ί: (mm) △ 2.0 5 △ 1.6 4 Δ 1.5 15 ◎ 0.5 35 ◎ 0.4 20 〇 0.9 35 ◎ 0.2 Reactivity with parts 〇 〇 Δ Δ 〇 ◎ ◎ ◎ Examples of greedy examples Examples Examples Comparative examples Comparative examples -5 -6 -7 -8 -9 -4 -5 Evaluation of peeling property 30 40 30 35 35 15 10 Price bending evaluation (◎〇△) Bu ◎ 〇◎ ◎ 〇Δ Bending to (mm) 0.9 0.4 1.0 0.3 0.5 0.9 1.2 Reactivity with parts 〇 ◎ ◎ ◎ Δ △
中間層的研青施制10〜20、比較例6〜9) 比較例 -6 比較例 -7 實施例 -10 賁施例 11 實施例 -12 實施例 -13 實施例 •14 評 剝離性 30 20 35 40 25 35 25 價 彎曲評價（◎〇△) 〇 〇 ◎ ◎ 〇 ◎ 〇 彆曲量（mm) 1 0.9 0.5 0.3 0.8 0.4 0.8 真部件之反應性 △ △ ◎ @ - 〇 ◎ 〇 實施例 實施例 實施例 實施例 實施例 實施例 比較例 15 -16 -17 -18 -19 -20 -〇 評 剝離性 25 20 35 40 25 35 35 價 t曲評價（◎〇△) ◎ 〇 @~ ◎ ◎ 〇 △ 弩曲量（mm) 0.3 1 0.3 0.2 0.4 0.9 1.5 與部件之反應性 ◎ 〇 ◎ ◎ 〇 〇 比較例 -9 評 剝離性 25 價 彎曲評償（◎〇△) △ 彎曲(mm) 2.0 與部件之反應性 〇 10 201009277 以下，基於表2進行探究。 〈研討中間層（實施例1〜9、比較例ι〜5)相關之探究〉 如比較例1所示，在中間層中使用不具有尖晶石結構的氧化銘時，以9 次煅燒已產生塗層的剝離。而相對於此，如實施例】〜9所示，經由設置 〜500μπι的結晶體中間層，其為由以具有尖晶石型晶體結構的β氧化絲或 尖晶石為主要成份，而作為其他成份則為具有Na、K、Mg Ca、 中至少一種的化合物所構成，可反復進行含有低熔點金屬氧化物之部件的 煅燒，並抑制載置器的彎曲或载置器表層剝離等問題的產生。特別是在中 間層為具有β氧化紹型晶體結構之實施例2、4、6、8、9中，其效果甚為 顯著。 、 〆 ❹〈研討表層（實施例10〜20、比較例6〜9)相關之探究〉 在表層的厚度不到20_時（比較例6、7)，會有「和部件的反應性」 的問題。而另一方面，在表層的厚度超過5〇〇μιη時（比較例8、9)，則會 有「彎曲評價」下降的問題。 【圖式簡單說明】 圖1是本發明之煅燒用載置器的剖面說明圖。 【主要元件符號說明】 1表層 參 2中間層 3基材 11Intermediate layer of decocting system 10 to 20, Comparative Examples 6 to 9) Comparative Example -6 Comparative Example -7 Example-10 Example 11 Example -12 Example-13 Example • 14 Evaluation of peelability 30 20 35 40 25 35 25 Price Bend Evaluation (◎〇△) 〇〇◎ ◎ 〇◎ 曲Differential (mm) 1 0.9 0.5 0.3 0.8 0.4 0.8 Reactivity of True Parts △ △ ◎ @ - 〇 ◎ Example of Example EXAMPLES EXAMPLES EXAMPLES Comparative Examples 15 -16 -17 -18 -19 -20 - Evaluation of peelability 25 20 35 40 25 35 35 Price t curve evaluation (◎ 〇 △) ◎ 〇 @~ ◎ ◎ 〇 △ The amount of twist (mm) 0.3 1 0.3 0.2 0.4 0.9 1.5 Reactivity with parts ◎ 〇 ◎ ◎ 〇〇 Comparative Example -9 Evaluation of peelability 25-valent bending evaluation (◎ 〇 △) △ Bending (mm) 2.0 and parts Reactivity 〇10 201009277 The following is based on Table 2. <Exploration of the intermediate layer (Examples 1 to 9 and Comparative Examples 1 to 5)> As shown in Comparative Example 1, when the oxidation layer having no spinel structure was used in the intermediate layer, 9 calcination was produced. Peeling of the coating. On the other hand, as shown in the examples ～9, a crystalline intermediate layer of 〜500 μm is provided, which is composed of a β-oxide or a spinel having a spinel crystal structure as a main component, and as other components. Further, it is composed of a compound having at least one of Na, K, and Mg Ca, and can repeatedly perform calcination of a member containing a low-melting-point metal oxide, and suppress problems such as bending of the mounter or peeling of the surface layer of the mount. Particularly in the examples 2, 4, 6, 8, and 9 in which the intermediate layer has a β-oxidized crystal structure, the effect is remarkable. 〆❹ <Exploration of the surface layer (Examples 10 to 20, Comparative Examples 6 to 9)> When the thickness of the surface layer is less than 20 mm (Comparative Examples 6 and 7), there is "reactivity with the member". problem. On the other hand, when the thickness of the surface layer exceeds 5 μm η (Comparative Examples 8 and 9), there is a problem that the "bending evaluation" is lowered. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional explanatory view of a carrier for firing according to the present invention. [Main component symbol description] 1 surface layer 2 intermediate layer 3 substrate 11