丄以1556 九、發明說明： 【發明所屬之技術領域】 本發明係有關一種電子零件用燒成治具。 【先前技術】 以往，在燒成陶瓷電容器、熱敏電阻、肥粒鐵系等由陶瓷構成的電子 零件時，例如採用在氧化鋁質的燒成用治具（例如匣缽、板等）上面载置 _電子零件而進行燒成的方法。但是，爲了防止對電子零件（被燒成物）的 特性産生不良影響的成分（例如二氧化石夕⑽2)等）飛散上述的燒成治 具需要盡可能地提高氧化銘（·3)含量，但如果提高氧化紹（Ai2〇3)含 ϊ ’熱膨麟數就會增大’耐熱衝擊崎低，壽命縮短。 爲了解決上述問題，人們採用在陶究材料（基材）的表面形成氧化錯 (Zr〇2)塗層的燒成用治具，或者在陶究材料（基材）和氧化錯⑽）塗 層之間熱噴鍍氧化IS (Al2〇3)㈣彡成中間層的燒成用治具。 _ 科’還#、_了在_料（紐）絲面具有由械於未穩定 化氧化錯和$全穩定化氧聽的總量或者部分穩定化氧化錯的總量爲W 質《的氧化朗構成的塗層的燒成用治具（參照專利文獻D，以及，將含 有氧聽_)和氧储（祕）的共晶_熱讀_作塗層或中間 層的燒成治具（參照專利文獻2)。與以往的燒成治具相比，專利文獻！和 專利文獻2的燒成治具可以防止在實際使用時塗層從基材上剝離以及防止 塗層中産生或生長裂紋’因此耐熱衝擊性優異並且壽命長。 但是’近年來由於電子料的多樣化，_f知的燒成治具燒成含有 1321556 各種成分的電子零件的機會增多，在燒成電子零件時，由於對基材具有不 良影響的成分從電子料通過麵（⑽和"層）碰透，贿在使用 次數少’即會發生燒成後電子零件_到燒成治具上，或者發生塗層的剝 離或電子零件的外觀不良等問題。 專利文獻1 :特開平10-1369號公報 專利文獻2 :特開2001-220248號公報 【發明内容】 本發明是上述習知技術中存在的問題而完，本發明的目的在 於’在燒成電子零件時，糊巾間層做從電子零件通過塗層（表層和中 間層）的對基材具有不良f彡響的成分，從而提供在誠後電子零件不會枯 附到燒成/。具上並且可以防止發生塗層剝離或電子零件外觀不良的電子零 件用燒成治具。 爲了實現上述目的’本發明提供以下的電子零件用燒成治具。 ⑴本發明電作制燒絲具，是在喊所構成絲社形成有塗 d /、特徵在於.U亥塗層係、為在基材的表面形成至少一層中間層該中間 層為可吸收被燒成物所產生之通縣層對紐林好影響之成份、及形成 -與被燒成物反應性低而形成在中間層之表_表層者。 (2)上述（1)所述的電子零件用燒成治具，所述中間層中含有未穩 定化Zr〇2。 1321556 所述中間層是未 (3)上述（1)或（2)所述的電子零件用燒成治具， 穩定化Zr〇2和Al2〇3的混合物° (4) 上述（1)或（2)所述的電子零件用燒成治具，所迷+ 通過燒結附著或電漿熱喷鍍而形成。 (5) 上述（1)或（2)所述的電子零件用燒成治具，所 见禾穩定化Zr〇2 的平均粒徑爲卜50/zm。 ⑻上述⑴或⑵所述的電子零件用燒成治具，所述未穩定化祕 的添加量爲5〜80質量％。 (7)上述⑴4⑵所述的電子零件職成治具，所述表層的主成 分由穩定化Zr〇2、ZrCa〇3、Ti〇2中的至少一種構成。 ⑻上述⑴4⑵所述的電子零件職絲具，所述表層的主成 分由ZrCa〇3和穩定化21_〇2的混合物構成。 本發明的電子料峨辦具，燒銳電子零財細_燒成治具 上’可以防止發生塗層剝離或電子零件的外觀不良。 【實施方式】 ▲以下摘本發明的實施方式，但是本發明並碰於以下的實施方式， 應當理賴，在不超__旨的範_，基於本領域技術人員的常 識可以適當地進行方案的變更、改良等。 本發明的電子零件職絲具，在由喊所構成的紐絲面上具有 塗層，所相塗層包括中間層和表層，所述中間層是在所述基材的表面上 形成’並且包含5 + 王夕—層含有吸收從被燒成物通過表層、對所述基材具有 1321556 不良影響的成分的材質的層’所述表層位於所述㈣層的表面，由與被燒 成物的反應性低的材質形成。 在此’本發明的電子零件用燒成治具的主要特徵在於，由既有的中間 層中添加規定量的未穩定化ΖΚ)2，絲成電子零件時，存在於中間層 内的未穩定化叾办吸收從電子零件通過塗層（表層和中間層）之對基材具 有不良影響的成分’而可以防止對基材具有不良影_成分渗透到基材 中。因而’較反復使財發_電子轉用燒絲具，在燒成電子零件 後電子零件也不會飾到燒成治具上，可以長期防止發生塗層讎或電子 零件外觀不良。 另外，本發明的電子零件用燒成治具，由於在中間層中固溶的對基材 具有不良影響的成分因也對未穩定化Zr_作穩定劑的作用，因此可以防 止由於在中間層中添加未穩定化Zr_容易産生的中間層粉化現象，進而 中間層的穩定化可以有助於包含表層和中間層峨層的穩定化。 對基材具有不良影響的成分沒有特別限制，可舉出例如以、此、此等 成分’另夕卜，從基材擴散的對被燒成物具有不良影響的成分也沒有特別限 制’可舉出例如Si等成分。 構成本發明的㈣層的域分較佳絲穩定化ZrQ2和歸的混合物。 這是因爲’舰合物對於使從電子料（概成品）通過麵（表層和中 間層）、對基材具有不良影響的成分與中間層的未狀化⑽固溶，產生被 中間層吸㈣效果是必不可少的，同時在發揮絲制定在基材上用的緩 衝材料的作用方面也是十分重要的。 1321556 另-方面，中間層爲氧化!s (則3)和氧化錐（Zr⑹的共晶體（以— 定的混合比例結晶的晶體）時，由於不存在獨立的未穩統Μ，對基材 具有不良影響的成分（例如Ca、Mn、Ba等成分）不能與未穩定化Μ固溶， 、 祕材具有不良影響的成分（例如Ca、Mn、Ba等成分）會滲透到基材中並 '反應，因而在燒成f子料後，電子零件容絲_燒成治具上，不能防 止發生塗層剝離或電子零件外觀不良。 另外，構成本發明的中間層較佳通過燒結附著或電浆熱喷鍛而形成。 _構成本發明的中間層的厚度較佳爲小於等於1〇〇〇_，更較佳爲 50 500"m進步較佳爲⑽〜細卵，從施加中間層時防止産生應力以及 減輕治具的重量的角度考慮，這樣的厚度範圍是理想的。 此時，構成本發明的中間層的未穩定化Μ的平均粒獲在卜50/zm較 爲L 這疋因肖上述未穩疋化Zr〇2的平均粒徑不足1以肌時，通寞初期 的中間層的強度降低較大，存在剝離的危險；反之，上述未穩定化Zr〇2的 平均粒徑超過心m時’未穩定化祕的粒子變得粗大，對紐具有不良 鲁影響的成分（例如Ca、Mn、Ba等成分：）*能有效地進行固溶化。 另外，構成本發明的中間層的未穩定化Μ的添加量爲5〜8〇質量％以 下’更較佳爲20〜70質量％，進一步較佳爲.6〇質量％。這是因爲，上述 未穩定化Zr〇2的添加量不足5 f量％時，不能防止對基材具有不良影響的成 • 刀（例如以此、Ba等成分）向基材中滲透；反之，上述未穩定化zr〇2 的添加量超過80質量％時，未穩定化Zr〇2的添加量過多，不能保持中間層 的強度。 1321556 另外’構成本發明的表層的主成分較佳由穩定化Zr〇2、ZrCa〇3、τ瓜 中的至少-種構成。在此’本發财制的表層必須是與作爲電子零件材 料的被燒成物反應性⑽材質，該材·據被燒成物_類而不同。 構成本發明的表層的厚度較佳爲小於等於10〇〇wm，更較佳爲 30〜300_，進一步較佳爲50~150卵，從儘量減少與被燒成物反應而産生 的殘留膨脹等的應力的角度考慮，是較佳的。 另外’本發明中使用的穩定化Zr〇2沒有特別限制，可以適當選擇使用 Y2〇3穩定化Zr〇2、Y2〇3部分穩定化Zr〇2、Ca〇穩定化Zr〇2、Ca〇部分穩定化 Zr〇2中的1種、2種或2種以上。 進而，構成本發明的基材的主成分較佳的是，選自由耐碎裂性和耐彎丄 1556 IX. Invention: [Technical Field to Be Invented by the Invention] The present invention relates to a firing fixture for electronic parts. [Prior Art] Conventionally, when firing an electronic component made of ceramic such as a ceramic capacitor, a thermistor, or a ferrite-based iron, for example, it is used on a fixture for baking alumina (for example, a crucible or a plate). A method of firing by mounting an electronic component. However, it is necessary to increase the content of the oxidation (·3) as much as possible in order to prevent the components that adversely affect the characteristics of the electronic component (the burned material) (for example, the oxidized stone (10) 2). However, if the oxidized sulphur (Ai2〇3) is contained, the 'hot expansion number will increase', the heat shock resistance is low, and the life is shortened. In order to solve the above problems, a jig for forming a oxidized (Zr〇2) coating on the surface of a ceramic material (substrate), or a ceramic (substrate) and oxidized (10) coating is used. Thermal spraying of IS (Al2〇3) (4) into a middle layer of the fixture for firing. _ 科'还#, _ _ _ material (new) silk surface has a total amount of mechanically unstabilized oxidative error and fully stabilized oxygen or partially stabilized oxidative error a jig for firing of a coating composed of a lang (refer to Patent Document D, and a eutectic _ heat-reading/oxygen _ _ _ _ _ _ _ _ _ _ _ _ _ Refer to Patent Document 2). Compared with the previous firing fixtures, the patent literature! The firing jig of Patent Document 2 can prevent the coating from peeling off from the substrate in actual use and prevent cracks from occurring or growing in the coating layer. Therefore, it is excellent in thermal shock resistance and long in life. However, in recent years, due to the diversification of electronic materials, there has been an increase in the number of electronic components containing 1321556 various components in the firing fixtures, and the components that have adverse effects on the substrate are burned into electronic components. By touching the surface ((10) and "layers), the bribe is used less frequently, that is, the electronic parts _ to the firing fixture after firing, or the peeling of the coating or the poor appearance of the electronic parts. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. 2001-220248. SUMMARY OF THE INVENTION The present invention has been made in the above-mentioned prior art, and the object of the present invention is to "fire in electronics". In the case of the parts, the inter-paste layer is made of an electronic component that passes through the coating (the surface layer and the intermediate layer) and has a bad squeaking effect on the substrate, thereby providing the electronic parts in the after-sales without being attached to the firing/. A firing fixture for electronic parts that can be used to prevent peeling of coatings or poor appearance of electronic parts. In order to achieve the above object, the present invention provides the following firing fixture for electronic parts. (1) The electroforming machine of the present invention is formed by coating a silk fabric with a coating d/, characterized by an .U-coating system, for forming at least one intermediate layer on the surface of the substrate, the intermediate layer being absorbable The components of the Tongxian layer produced by the burnt material have a good influence on Newlin, and the formation-lower reactivity with the burned material is formed in the surface layer of the intermediate layer. (2) The firing fixture for an electronic component according to the above (1), wherein the intermediate layer contains unstabilized Zr〇2. 1321556 The intermediate layer is not a mixture of the above-mentioned (1) or (2), and the mixture of Zr〇2 and Al2〇3 is stabilized. (4) The above (1) or 2) The above-mentioned electronic component firing fixture is formed by sintering adhesion or plasma thermal spraying. (5) The firing fixture for an electronic component according to the above (1) or (2), wherein the stabilized Zr〇2 has an average particle diameter of 50/zm. (8) The firing fixture for an electronic component according to the above (1) or (2), wherein the amount of the unstabilized secret is 5 to 80% by mass. (7) The electronic component assembly tool according to (1), wherein the main component of the surface layer is composed of at least one of stabilized Zr〇2, ZrCa〇3, and Ti〇2. (8) The electronic component yarn according to the above (1), wherein the main component of the surface layer is composed of a mixture of ZrCa〇3 and stabilized 21_〇2. The electronic material preparation device of the present invention can prevent the peeling of the coating layer or the appearance of the electronic component from being caused by the burning of the electrons. [Embodiment] ▲ The following describes an embodiment of the present invention. However, the present invention is not limited to the following embodiments, and it should be understood that the scheme can be appropriately performed based on the common knowledge of those skilled in the art without exceeding the scope of the present invention. Change, improvement, etc. The electronic component wire of the present invention has a coating on a yarn surface composed of a shout, and the phase coating includes an intermediate layer and a skin layer, and the intermediate layer is formed on the surface of the substrate and includes 5 + The layer containing a material that absorbs a component that has a bad influence on the substrate from the surface of the fired material and has a bad influence on the substrate; the surface layer is located on the surface of the (four) layer, and is formed by the burned material. A material with low reactivity is formed. Here, the main feature of the firing fixture for an electronic component according to the present invention is that a predetermined amount of unstabilized crucible 2 is added to an existing intermediate layer, and when it is an electronic component, it is not stabilized in the intermediate layer. The chemical absorption from the electronic component through the coating (the surface layer and the intermediate layer) which has an adverse effect on the substrate can prevent the substrate from having a poor image-infiltration into the substrate. Therefore, the electronic components are switched to the burn-in tool, and the electronic components are not attached to the firing fixture after firing the electronic components, so that the coating defects or the appearance of the electronic components can be prevented from occurring for a long period of time. Further, in the firing fixture for an electronic component of the present invention, since the component which has a solid effect on the substrate which is solid-solved in the intermediate layer also acts as a stabilizer for the unstabilized Zr_, it can be prevented from being in the intermediate layer. The intermediate layer pulverization phenomenon which is easily generated by the unstabilized Zr_ is added, and further stabilization of the intermediate layer can contribute to stabilization of the surface layer and the intermediate layer ruthenium layer. The component which has an adverse effect on the substrate is not particularly limited, and examples thereof include, for example, these components, and the component which diffuses from the substrate and has an adverse effect on the object to be fired is not particularly limited. A component such as Si is formed. The domains constituting the (four) layer of the present invention are preferably a mixture of stabilized ZrQ2 and ruthenium. This is because the hull compound is used to make the solid layer (10) solid solution in the surface (the surface layer and the intermediate layer) which has an adverse effect on the substrate from the electronic material (the finished product), and the intermediate layer is sucked (4). The effect is indispensable, and it is also important to play the role of the cushioning material used for the silk on the substrate. 1321556 On the other hand, the intermediate layer is oxidized!s (then 3) and the oxidized cone (Zr(6) eutectic (crystals crystallized in a predetermined mixing ratio), since there is no independent unsteady enthalpy, Ingredients that are adversely affected (such as Ca, Mn, Ba, etc.) cannot be dissolved in the unstabilized bismuth, and components with adverse effects (such as Ca, Mn, Ba, etc.) penetrate into the substrate and react Therefore, after firing the f-substrate, the electronic component is required to prevent peeling of the coating or poor appearance of the electronic component. Further, the intermediate layer constituting the present invention preferably passes through sintering adhesion or plasma heat. It is formed by spray forging. The thickness of the intermediate layer constituting the present invention is preferably 1 〇〇〇 or less, more preferably 50 500 quot; m is preferably (10) ~ fine egg, and stress is prevented from being applied from the intermediate layer. In view of the weight reduction of the jig, such a thickness range is desirable. At this time, the average particle size of the unstabilized ruthenium constituting the intermediate layer of the present invention is obtained at a ratio of 50/zm to L. The average particle size of the stabilized Zr〇2 is less than 1 to the muscle The strength of the intermediate layer in the initial stage of the overnight sputum is greatly reduced, and there is a risk of peeling off. On the contrary, when the average particle diameter of the unstabilized Zr 〇 2 exceeds the heart m, the particles which are not stabilized become coarse, and the nucleus is defective. The components affected by Lu (for example, components such as Ca, Mn, and Ba: *) can be effectively dissolved. Further, the amount of unstabilized ruthenium constituting the intermediate layer of the present invention is 5 to 8 % by mass or less. It is preferably 20 to 70% by mass, and more preferably 6.6% by mass. This is because when the amount of the unstabilized Zr〇2 added is less than 5 f%, it is not possible to prevent the adverse effect on the substrate. The scalpel (for example, a component such as Ba or the like) permeates into the substrate; on the other hand, when the amount of the unstabilized zr 〇 2 added exceeds 80% by mass, the amount of the unstabilized Zr 〇 2 is excessively increased, and the intermediate layer cannot be maintained. 1321556 Further, the main component constituting the surface layer of the present invention is preferably composed of at least one of stabilized Zr〇2, ZrCa〇3, and tau. Here, the surface layer of the present financial system must be used as an electronic component. Material burnt material reactivity (10) material, the material The thickness of the surface layer constituting the present invention is preferably 10 〇〇wm or less, more preferably 30 to 300 Å, still more preferably 50 to 150 eggs, and is minimized and Further, the stabilized Zr〇2 used in the present invention is not particularly limited, and the Y2〇3 stabilized Zr〇2 can be appropriately selected and used. Y2〇3 partially stabilized Zr〇2, Ca〇 stabilized Zr〇2, and Ca〇 partially stabilized Zr〇2 one, two or more. Further, the main component of the substrate constituting the present invention is more Preferably, it is selected from chipping resistance and bending resistance
Al2〇3-Si〇2 ^ SiC-Si3N4 ^ Al2〇3-Si〇2-Mg〇 . Si-SiC ^ SiC 中的至少一種。 構成本發明的基材的的含量在7〇〜95質量％爲宜。這是因爲，基 材的胤的含量不足m時，基材的熱傳導率低，容易出現燒成治具_ 溫度偏差’導致燒成治具上的被歧品特性變得不均一；反之基材的A1 〇 的含1大於95%時’基材的熱膨脹率增大，由溫度差引起的應力増大，從而 容易産生裂紋。 本發明_絲频製造綠，首先，_燒_縣钱熱喷錢在 基材上形成中間層，然後，通過喷塗燒結畴或魏熱倾在所得到的中 間層上形成表層，從而在基材上形成塗層。 這裏所說的熱噴鍍，是指將金屬或陶躺微粉末（以下稱爲‘‘熱额 法'轨、开4炫融狀態’喷吹到物件物的表面而形成熱喷鍍覆膜的方 0 ......的方財’彳加熱綠使用燃燒焰喊體熱賴、利用電弧 鍍等各種方法’在本發财，較麵過彻電㈣射的電聚熱 噴鍍而形成中間層的熱嗔鍵覆膜。 + :柄β在電賴倾巾制触制水電麵賴（水穩定化 θ裝嗔鍍）&因爲，糊氣體電漿熱魏形搞熱賴細的最大膜 ^爲3叫m左右’而如果採用水（穩定化）電漿熱倾，可以形成最大膜 厚爲麵_左摘厚的舰。糾，•水（穩定化）熱喷鏟可以 形成比較多孔、表面粗糙的覆膜，因此在提高對於紐_著性方面也是 較佳的。 X下通過’ϋ列更具體地s兒明本發明，但本發明並不限於這些實施例 (表 1)〇 實施例卜13、比較例1〜5 採用以下所述的方法，分別製作電子零件用燒成治具的試驗片。 〈基材的製作方法〉 (1) Al2〇3-Si〇2 最大粒徑150，的電熔氧化錄子中添加枯土、很燒氧化銘，使氧化 紹含量達到85質量％，並進行混煉，利用油壓壓力機以誦kg/cra2的壓力 將混煉後的土成形爲長度2GGinmx寬度2GGmmx厚度5mm的錄體，得到成 形體。將得到的成形體乾燥，在1650°C下保持5小時而進行燒成，製成試 驗片（實施例1~7、實施例9〜13、比較例;[〜5)。 (2) SiC-Si3N4 將70質量％的最大粒徑脚m的证粒子、25質侧平均粒 、1C 5貝里/。的金屬Si混合，把混合後的原料製成裝料，利用石膏模具 進仃洗庄成形，得到長度⑽瞧寬度15Gmmx厚度8_的板狀體。將所得到 的板狀體乾燥，在氮氣爐内於·t保持5小時進行燒成，製成試驗片（實 施例8)。 Λ 〈中間層的製作方法〉 ⑴燒結崎加卫A :伽水作爲關，概結附著氧魅（平均粒 徑1，）製成轉。將得到的漿料塗布到基材上，然後在i45(rc保持5小 時，分別燒結附著厚度議⑽的中間層（比較例1和比較例2)。 ⑵燒結畴加n脉作爲溶劑，將添加了表丨所示的平均粒 裡和比例（質量％)的未穩定化Zr〇2的燒結附著氧化銘（平均粒徑製 成漿料。將制的漿料塗布到基材上，然後在145此保持5小時，分別燒 結附著厚度i’m的中間層（實施例卜4、實施例612、比較例3 5)。 (3) 電槳熱噴鍍加工1縣加了表i所示的平均雜和比例（質量 0的未穩疋化Zr〇2的電炫氧化銘（平均粒徑7〇#m)，對紐進行電浆熱喷 鍍’制成厚度100#m的中間層（實施例 ⑷中間層的2層加卫：使用添加了 5G f量％的平均粒徑的未 穩定化Zr〇2加上含有8質量％的秘的穩定化Zr〇2 (平均粒徑7〇簡），對基 材進行電聚熱喷鑛，製作厚度1〇〇_的中間第i層。接著，在中間第】層 上塗布榮料化（溶劑爲水）的燒結附著氧脑（平均粒徑1⑽），然後在 13.21556 1450°C下保持5小時’燒結附著厚度5〇//m的中間第2層（實施例13)。 〈表層的製作方法：除實施例9 (5〇_)外，塗層厚度1〇〇μιη> (1) ®漿熱噴鍍加工A :使用含有8質量％的γ2〇3的穩定化Zr〇2 (平均 粒徑7〇βπι)(實施例卜4、實施例6〜8、實施例13、比較例卜比較例3〜5)。 (2) 電裝熱嗔鍍加工Β:使用添加了 5〇質量％的平均粒徑2〇_的未 穩定化Zr〇2加上含有8質量％的m的穩定化Zr〇2 (平均粒徑鄭⑹（比較 例2)。 ® (3)電漿熱嘴鍍加工c :使用Ti〇2 (平均粒徑2〇_)(實施例9)。 (4) 電梁熱噴鍍加工D:使用ZrCa〇3 (平均粒徑7〇//m)(實施例1〇)。 (5) 電漿熱噴鍍加工£ :使用平均粒徑的含有8質量％的γ必 的穩疋化Zr〇2 (50質量％) +平均粒徑7〇_的ZrCa〇3 (5〇質量(實施 例 11)〇 (6) 電聚熱噴鍍加工F :使用平均粒徑7〇_的含有8質量％的γ必 的穩疋化Zr〇2 (70質量％) +平均粒徑加卵的⑽（3〇質量％)(實施例 镰 12)。 (Ό燒結附著加工：使用含有8質量％的γ2〇3的穩定化Zr〇2 (平均粒徑 5em)(實施例5)。 表1 ZZ3F： ~ί 出明爵fni ·结1麻、ΓΟΊ ·销〇 甘++ 材質 禾德定 化 Zr〇2(質 M%) 塗 布 法 塗層厚 度 (μπι) 材質 未穩定 化 Zr02(質 量％) 1泪 卜1 · 平均粒 徑 (μηι) 5Rr ^ 塗 布 法 曾J 塗層厚 度 (μηι) 材質 實施 例1 管施 穩定化 Zr02 描―化 0 熱 噴 鍍 100 Al2〇3 + 未穩定化 Zr02 5 20 燒 結 附 著 100 Al2〇3 + Si02 貝/ΠΒ 例2 橋疋化 Zr〇? 0 熱 嗜 100 Al2〇3 + 未穩定化 50 燒 結 100 Al2〇3 + Si02 13 1321556 鍍 Zr〇2 附 著 實施 例3 穩定化 Zr02 0 熱 噴 鍍 100 A1203 + 未穩定化 Zr02 50 5 燒 結 附 著 100 Al2〇3 + S1O2 實施 例4 穩定化 Zr02 0 熱 噴 鍍 100 AI2O3 + 未穩定化 Zr02 50 20 燒 結 附 著 100 Al203 + Si〇2 實施 例5 穩定化 Zr02 0 燒 結 附 著 100 AI2O3 + 未穩定化 Zr02 50 20 熱 噴 鍍 100 Al2〇3 + Si〇2 實施 例6 穩定化 Zr02 0 熱 噴 鍍 100 AI2O3 + 未穩定化 Zr02 50 50 燒 結 附 著 100 Al2〇3 + Si〇2 實施 例7 穩定化 Zr02 0 熱 噴 鏟 100 AI2O3 + 未彘定化 Zr〇2 80 20 燒 結 附 著 100 A1203 + S1O2 實施 例8 穩定化 Zr02 0 熱 噴 鍍 100 A1203 + 未_定化 Zr02 50 20 燒 結 附 著 100 SiC + S13N4 實施 例9 Ti02 0 熱 噴 鍍 50 AI2O3 + 未穩定化 Zr〇2 50 20 燒 結 附 著 100 Al203 + Si〇2 實施 例10 ZrCa〇3 0 熱 噴 鍍 100 A1203 + 未穩定化 Zr02 50 20 燒 結 附 著 100 Al203 + Si02 實施 例11 穩定化 Zr〇2 + ZrCa03 0 熱 噴 鍍 100 AI2O3 + 未穩疋化 Zr02 50 20 燒 結 附 著 100 AI2O3 + Si02 實施 例12 穩定化 Zr02 + Ti02 0 熱 噴 鍍 100 AI2O3 + 未禱定化 Zr02 50 20 燒 結 附 著 100 ai2o3 + Si02 實施 例13 穩定化 Zr〇2 0 熱 噴 鑛 100 [1]穩定化 Zr02 +未 穩定化 Zr〇2 [2]Α12〇3 50 20 [1] 熱 噴 鍍 [2] 燒 結 附 著 [1]100 [2]50 ai2o3 + Si02 比較 例1 穩定化 Zr02 0 熱 噴 鍍 100 AI2O3 0 — 燒 結 附 著 100 ai2〇3 + Si02 比較 例2 穩定化 Zr〇2 + 未穩定 化 Zr07 50 熱 噴 鍍 100 ai2o3 0 — 燒 結 附 著 100 AI2O3 + Si02 比較 例3 穩定化 Zr02 0 熱 噴 鍍 100 Al2〇3 + 未穩定化 Zr〇2 3 20 燒 結 附 著 100 ai2〇3 + Si02 比較 穩定化 0 熱 100 Ab〇3 + 50 100 燒 100 AI2O3 14 1321556 例4 ------— Zr02 镀 3穩定化 Zr02 比較 例5 --— 穩定化 Zr02 0 熱 噴 鍍 100 AI2O3 + 未穩定化 ΖγΌ2 採用下述方法來評價按上述製作方法所得到的試片 中 結附著Al2〇3-Si〇2 ^ SiC-Si3N4 ^ Al2〇3-Si〇2-Mg〇 . At least one of Si-SiC ^ SiC. The content of the substrate constituting the present invention is preferably from 7 Å to 95% by mass. This is because when the content of the ruthenium of the substrate is less than m, the thermal conductivity of the substrate is low, and the firing fixture _ temperature deviation is likely to cause the ambiguous properties on the firing fixture to become non-uniform; When the content of A1 〇 is more than 95%, the thermal expansion coefficient of the substrate increases, and the stress caused by the temperature difference is large, so that cracks are likely to occur. The invention _ silk frequency to produce green, firstly, _ burning _ county money thermal spray money on the substrate to form an intermediate layer, and then by spraying the sintered domain or Wei heat tilt on the resulting intermediate layer to form a surface layer, thereby A coating is formed on the material. The term "thermal spraying" as used herein refers to the spraying of a metal or a ceramic powder (hereinafter referred to as a ''heating method' rail, a 4th molten state> onto a surface of an object to form a thermal spray coating. Fang 0 ...... Fangcai' 彳 heating green using the burning flame shouting body heat, using arc plating and other methods 'in this fortune, more than the face of electricity (four) shot of electric polythermal spraying The hot layer of the middle layer is covered with a film. + : The handle β is in the electric water-repellent surface of the electric dish (water stabilization θ mounting plate) & The film ^ is 3 m or so 'and if water (stabilized) plasma is used for thermal tilting, a ship with a maximum film thickness of _ left thick can be formed. Correction, • water (stabilized) hot shovel can form a relatively porous The film having a rough surface is also preferable in terms of improving the traits of the ruthenium. The present invention is more specifically described by the ϋ column, but the present invention is not limited to these examples (Table 1). Example 13 and Comparative Examples 1 to 5 Test pieces of a firing fixture for an electronic component were produced by the following methods. (1) Al2〇3-Si〇2 The maximum particle size of 150, the addition of dry soil to the fused oxide record, the oxidation of the sulphur, so that the content of oxidation is 855% by mass, and mixing, using oil pressure The press was formed into a recorded body having a length of 2 GGinmx and a width of 2 GGmmx and a thickness of 5 mm by a pressure of 诵kg/cra2 to obtain a molded body. The obtained molded body was dried and kept at 1650 ° C for 5 hours to be fired. Test pieces were prepared (Examples 1 to 7, Examples 9 to 13, and Comparative Examples; [~5). (2) SiC-Si3N4 70% by mass of the maximum particle size of the foot of the test particle, 25 mass side average The metal Si of the granules and 1C 5 berrys is mixed, and the mixed raw materials are made into a charge, and the gypsum mold is used for rinsing and forming, and a plate-like body having a length (10) 瞧 width of 15 Gmmx and a thickness of 8 Å is obtained. The plate-shaped body was dried and baked in a nitrogen atmosphere for 5 hours to prepare a test piece (Example 8). Λ <Method for producing the intermediate layer> (1) Sintering Saga Guard A: Gamma as a Guan The attached oxygen odor (average particle size 1,) was made into a turn. The obtained slurry was applied to a substrate and then kept at i45 (rc for 5 hours). The intermediate layer (Comparative Example 1 and Comparative Example 2) to which the thickness (10) was attached was respectively sintered. (2) Sintered domains were added with n veins as a solvent, and the average grain size and ratio (% by mass) shown in Table 添加 were added to the unstabilized Zr.烧结2 sintering adhesion oxidation (average particle size is made into a slurry. The slurry is applied to a substrate, and then held at 145 for 5 hours, respectively, to sinter the intermediate layer of thickness i'm (Example 4 Example 612, Comparative Example 3 5) (3) Electric paddle thermal spraying process 1 county added the average impurity ratio shown in Table i (mass 0 of unstabilized Zr〇2 The average particle size is 7〇#m), and the thermal plating of the nucleus is made into an intermediate layer having a thickness of 100#m (Example (4) Two layers of the intermediate layer are reinforced: the average particle diameter of the amount of 5G f added is used. The unstabilized Zr〇2 plus the stabilized Zr〇2 (average particle size 7〇) containing 8 mass% of the secret, electrothermal polycondensation of the substrate, and the middle of the thickness of 1〇〇_ Floor. Next, on the middle layer, a sintered attached oxygen brain (having an average particle diameter of 1 (10)) was applied, and then held at 13.21556 1450 ° C for 5 hours, and the sintered adhesion thickness was 5 〇 / / m in the middle. Layer 2 (Example 13). <Method for producing surface layer: Coating thickness 1 〇〇 μιη except Example 9 (5〇_)> (1) ® Thermal spray processing A: Stabilized Zr〇 containing 8% by mass of γ2〇3 2 (average particle diameter: 7 〇 β πι) (Examples 4, 6 to 8, Examples 13, Comparative Examples, Comparative Examples 3 to 5). (2) Electrothermal 嗔 plating process: using unstabilized Zr〇2 with an average particle size of 2〇% added with 5〇% by weight plus stabilized Zr〇2 containing 8 mass% of m (average particle size) Zheng (6) (Comparative Example 2) ® (3) Plasma hot-mouth plating c: Use Ti〇2 (average particle size 2〇_) (Example 9) (4) Electro-thermal spraying D: Use ZrCa〇3 (average particle size: 7 〇//m) (Example 1〇). (5) Plasma thermal spray processing £: using averaging particle size of γ-containing stable Zr〇2 containing 8% by mass (50% by mass) + ZrCa〇3 having an average particle diameter of 7 〇 (5 〇 mass (Example 11) 〇 (6) Electrothermal thermal spraying process F: 8% by mass of an average particle diameter of 7 〇 γ must be stabilized Zr〇2 (70% by mass) + (10) (3% by mass) of the average particle size of the egg (Example 镰 12) (ΌSintering adhesion processing: γ2〇3 containing 8% by mass) Stabilized Zr〇2 (average particle size 5em) (Example 5). Table 1 ZZ3F: ~ί 明明爵fni ·结1麻,ΓΟΊ ·〇〇甘++ Material 禾德化化Zr〇2 M%) Coating thickness (μπι) Material unstabilized Zr02 (% by mass) 1 Tears 1 · Average particle size (μ Ηι) 5Rr ^ Coating Method J Coating Thickness (μηι) Material Example 1 Tube Stabilization Zr02 Description 0 Thermal Spray 100 Al2〇3 + Unstabilized Zr02 5 20 Sinter Attachment 100 Al2〇3 + Si02 /ΠΒ Example 2 Bridge Zr〇? 0 Hot 100 Al2〇3 + Unstabilized 50 Sintered 100 Al2〇3 + Si02 13 1321556 Zr〇2 adhered Example 3 Stabilized Zr02 0 Thermal Spray 100 A1203 + No Stabilized Zr02 50 5 Sintered Attachment 100 Al2〇3 + S1O2 Example 4 Stabilized Zr02 0 Thermal Spray 100 AI2O3 + Unstabilized Zr02 50 20 Sinter Attachment 100 Al203 + Si〇2 Example 5 Stabilized Zr02 0 Sinter Attachment 100 AI2O3 + unstabilized Zr02 50 20 thermal spray 100 Al2〇3 + Si〇2 Example 6 Stabilization Zr02 0 Thermal Spray 100 AI2O3 + Unstabilized Zr02 50 50 Sinter Attachment 100 Al2〇3 + Si〇2 Example 7 Stabilized Zr02 0 Hot spray shovel 100 AI2O3 + Undensified Zr〇2 80 20 Sinter-attachment 100 A1203 + S1O2 Example 8 Stabilized Zr02 0 Thermal spray 100 A1203 + Not _ _ _ Zr02 50 20 Sintered adhesion 100 SiC + S13N4 Example 9 Ti02 0 Thermal spraying 50 AI2O3 + Unstabilized Zr〇2 50 20 Sintering adhesion 100 Al203 + Si〇2 Example 10 ZrCa〇3 0 Thermal spraying 100 A1203 + Unstabilized Zr02 50 20 Sintering adhesion 100 Al203 + Si02 Example 11 Stabilized Zr〇2 + ZrCa03 0 Thermal Spray 100 AI2O3 + Unstable Zr02 50 20 Sinter Attachment 100 AI2O3 + Si02 Example 12 Stabilized Zr02 + Ti02 0 Thermal Spray 100 AI2O3 + No Prayer Zr02 50 20 Sintering adhesion 100 ai2o3 + Si02 Example 13 Stabilizing Zr〇2 0 Thermal spray 100 [1] Stabilizing Zr02 + Unstabilized Zr〇2 [2] Α12〇3 50 20 [1] Thermal spraying [2] Sintering adhesion [1]100 [2]50 ai2o3 + Si02 Comparative example 1 Stabilized Zr02 0 Thermal spraying 100 AI2O3 0 - Sintering adhesion 100 ai2〇3 + Si02 Comparative example 2 Stabilized Zr〇2 + Unstabilized Zr07 50 Thermal Spray 100 ai2o3 0 — Sinter Attachment 100 AI2O3 + Si02 Comparative Example 3 Stabilized Zr02 0 Thermal Spray 100 Al2〇3 + Unstabilized Zr〇2 3 20 Sinter Adhesion 100 ai2〇3 + Si02 Comparative Stabilization 0 Heat 100 Ab〇3 + 50 100 Burn 100 AI 2O3 14 1321556 Example 4 ------—Zr02 Plating 3 Stabilized Zr02 Comparative Example 5 --- Stabilized Zr02 0 Thermal Spraying 100 AI2O3 + Unstabilized ΖγΌ2 The following method was used to evaluate the following method. Attachment in the test piece
2C ί燒結附董2C 烧结Sintering Dong
·» 2 0310 hr A 其結果示於表2 材時的通寞次數〉 將2質量％的_3、2質量％的MnC〇3、26質量％的BaTi〇3分散在7〇賀 —的水中，製成分散液，將該分散液（〇 8g)塗佈到試片的表面上然毛 反復進仃在135G C保持1小時的燒成。每5次燒成後，用簡觀察試片^ 斷面’根據Ba、Μη成分（物件成分）到達基材時的燒成次數進行評價。 〈试片的評價方法2 :塗層強度〉 按照JIS祕6進行附著力試驗，按以下所述評價塗層強度。 ◎:沒有發現表層從中間層上剝離。 〇.發現部分表層（小於等於整個面的5⑹從中間層上剝離。 △’發現大部分表層（大於整個面的50%)從中間層上剝離。 〈试片的評價方法3 :與工件（被燒成物）的反應性（工件反應度）〉 由以BaTl〇3爲主成分的材料製作板狀（尺寸：40mmx40_2mm)的工件。 將得到的件放置在試#上’在刪t下保持5小時進行燒成舰以 外觀觀察評價件的霞狀態。 ◎:沒有發現工件變質。 15 1521556 〇’發現工件的一部分（小於等於整個面的5㈤變質。 △.發現工件的大部分（大於整個面的50%)變質。 表2 實施例1 實施例2 直至物件成分到達基 材的通窯次數（次） 塗層強度 工件反應度 --_ 40 —©_ 〇 _〇. 〇 實施例3 40 ◎ 〇 〇 實施例4 45 ◎ 實施例5 45 ◎ 〇 〜 實施例6 30 〇 〇 > 實施例7 70 〇 — 〇 實施例8 — —_ 45 ◎ 〇 〜 實施例9 70 ◎ ◎ ~ 實施例10 50 ◎ ◎ ' 實施例11 50 ◎ ◎ 〜 實施例12 60 ◎ ◎ ' 實施例13 50 〇 〇 ' 比較例1 20 ◎ 〇 〜 比較例2 40 ◎ △ 〜 比較例3 比較例4 20 ◎ 〇 ' 20 〇 〇 〜 比較例5 80 △ 〇 〜 〈考察：實施例1〜13、比較例卜5> 從表2的結果可知，實施例Μ 3由於中間層使用了添加有未穩定化 的氧化鋁，與比較例1~5相比，即使反復使用，在燒成電子零件後電子零 件也不會粘附到燒成治具上，可以長期防止發生塗層的剝離或電子零件的 外觀不良。特別是實施例9〜12，此效果十分顯著。 另一方面，比較例1雖然塗層強度良好，工件反應性也沒有問題’但 13.21556 通窯次數不充分。比較例2由增加表層的未穩定化Zr〇2的添加量，可以增 加通寞次數，但工件反應度存在問題，發現工件變質。比較例3由於在中 間層中添加的未穩定化ZrCb過少，在通窯次數、塗層強度和工件反應度方 面不能得到充分的效果（參照比較例1)。比較例4由於在中間層中添加的 未穩定化Zr〇2的平均粒徑過大，在通窯次數、塗層強度和工件反應度方面 不能得到充分的效果。至於比較例5，雖然可以增加通窯次數，但由於在中 間層中添加的未穩定化Zr〇2過多，不能得到充分的塗層強度。 産業上利用的可能性 本發明的電子零件用燒成治具，可以適合用於燒成陶瓷電容器、熱敏 電阻、肥粒鐵系等由陶瓷構成的電子零件。 【圖式簡單說明】 *»»> 【元件符號說明】 無·» 2 0310 hr A The number of overnight passes when the results are shown in Table 2> Dispersed 2% by mass of _3, 2% by mass of MnC〇3, and 26% by mass of BaTi〇3 in water of 7〇he A dispersion liquid was prepared, and the dispersion liquid (8 g) was applied onto the surface of the test piece, and the hair was repeatedly subjected to firing at 135 G C for 1 hour. After the firing of the test piece, the cross section was evaluated by the number of times of baking when the Ba and Μη components (object components) reached the substrate. <Evaluation Method 2 of Test Piece: Coating Strength> The adhesion test was carried out in accordance with JIS Secret 6, and the coating strength was evaluated as described below. ◎: No peeling of the surface layer from the intermediate layer was observed. 〇. Part of the surface layer (less than or equal to the entire surface of 5 (6) peeled off from the intermediate layer. △ ' found that most of the surface layer (greater than 50% of the entire surface) peeled off from the intermediate layer. <Test piece evaluation method 3: with the workpiece (being Reactivity (workability of the workpiece) > A plate-shaped (size: 40 mm x 40_2 mm) workpiece was prepared from a material containing BaTl〇3 as a main component. The obtained piece was placed on the test # and kept under the t The fired ship was observed in an hour to observe the state of the evaluation piece. ◎: No deterioration of the workpiece was found. 15 1521556 〇 'Part of the workpiece was found (less than or equal to 5 (five) of the entire surface. △. Most of the workpiece was found (greater than the entire surface) 50%) deterioration. Table 2 Example 1 Example 2 Number of kiln times until the component reaches the substrate (times) Coating strength Workability of the workpiece - _ 40 — © _ _ _ 〇 〇 Example 3 40 ◎ 〇 〇 Example 4 45 ◎ Example 5 45 ◎ 〇 ~ Example 6 30 〇〇 > Example 7 70 〇 - 〇 Example 8 - _ 45 ◎ 〇 ~ Example 9 70 ◎ ◎ ~ Example 10 50 ◎ ◎ 'Example 11 50 ◎ ~ Example 12 60 ◎ ◎ 'Example 13 50 〇〇' Comparative Example 1 20 ◎ 〇 ~ Comparative Example 2 40 ◎ △ ~ Comparative Example 3 Comparative Example 4 20 ◎ 〇 ' 20 〇〇 ~ Comparative Example 5 80 △ 〇 ~ <Inspection: Examples 1 to 13 and Comparative Example 5> From the results of Table 2, it is understood that Example Μ 3 has an unstabilized alumina added to the intermediate layer, and even compared with Comparative Examples 1 to 5, Repeated use, the electronic components will not adhere to the firing fixture after firing the electronic components, and the peeling of the coating or the appearance of the electronic components can be prevented for a long period of time. Especially in Examples 9 to 12, this effect is remarkable. On the other hand, in Comparative Example 1, although the coating strength was good, there was no problem in the reactivity of the workpiece. However, the number of times of 13.21556 kiln was insufficient. In Comparative Example 2, the amount of unstabilized Zr〇2 added to the surface layer could be increased. The number of times, but there is a problem with the degree of reaction of the workpiece, and the workpiece is found to be deteriorated. In Comparative Example 3, since the amount of unstabilized ZrCb added to the intermediate layer is too small, sufficient effect cannot be obtained in terms of the number of times of the kiln, the strength of the coating, and the reactivity of the workpiece. (Refer to Comparative Example 1). In Comparative Example 4, since the average particle diameter of the unstabilized Zr〇2 added to the intermediate layer was too large, sufficient effects could not be obtained in terms of the number of passes, the coating strength, and the degree of reaction of the workpiece. In Example 5, although the number of kiln kiln can be increased, the amount of unstabilized Zr 〇 2 added to the intermediate layer is too large, and sufficient coating strength cannot be obtained. INDUSTRIAL APPLICABILITY The firing fixture for electronic parts of the present invention It can be used for firing electronic components such as ceramic capacitors, thermistors, and ferrite-based irons. [Simple description of the diagram] *»»> [Component symbol description]