TWI286128B

TWI286128B - Calcinated material and jigs for electronic parts

Info

Publication number: TWI286128B
Application number: TW090101615A
Authority: TW
Inventors: Yasuhisa Izutsu; Kazutomo Hoshino; Noriyuki Takahashi; Toshiya Kunisaki; Tomio Uchida
Original assignee: Mitsui Mining & Smelting Co
Priority date: 2000-01-28
Filing date: 2001-01-29
Publication date: 2007-09-01
Also published as: KR20010078138A; TW200728245A; TWI296267B; KR100549030B1

Abstract

The invention relates a calcinated material for electronic parts, which is characterized in that said electronic parts consist of a partly fused combined-material comprising a zirconia layer made from more than 2 metal oxides such as coarse zirconia with an average diameter of 30 to 500 mum and a fine zirconia with an average diameter of 0.1 to 10 mum coating on a substrate; and a calcinated jigs for electronic parts, which is characterized in that the said electronic parts comprise a substrate, a partly fused combined-material interlayer made from more than 2 metal oxides coating on a substrate and a zirconia layer on said interlayer; and a calcinated jigs for electronic parts, which is characterized in that the said electronic parts comprise a substrate, a partly fused combined-material interlayer made from a metal oxide coating on a substrate and a zirconia alumina yttria layer on said interlayer. The invention provides a calcinated material having a sufficient strength and an excellent contact for electronic parts and being possibly produced in economics.

Description

1286128 A7 B7 五、發明説明（發明領域本發明係關於一種在介電體、積層電容、陶瓷電容、壓電元件、熱敏電阻等電子零件燒成時，所使用的固定器、棚架板、匣缽等電子零件燒成用材料及工模。發明背景做爲電子零件燒成用材料，除了耐熱性或機械強度之必要的性能以外，尙要求其不會與燒成的陶瓷電子零件起反應。介電體等電子零件製品會因與燒成用工模接觸起反應、熔融附著、使得製品組成變動而特性變差等問題產生。通常係使用氧化鋁系材料、氧化鋁莫來石系材料、氧化鋁氧化鎂尖晶石系材料、氧化鋁莫來石蓳青石系材料、或其結合材料來做爲電子零件燒成用材料之基材。又爲了防止製品起反應，則採用在表面層上被覆氧化锆 (氧化锆Zr02)之方法。氧化锆與基材之反應性雖然是很少，但是與基材之熱膨脹係數差異甚大，使得工模在編碼上之反復熱循環之使用環境下，而產生龜裂而剝離之問題更且，氧化錆在〜1100°C附近，會引起其由單斜晶變爲正方晶之相變化。結果，因爲隨著反復熱循環之相變化會使得熱膨脹係數變化，而會有氧化锆之編碼層脫離之問題。又，在使用未安定化氧化鉻之場合下，則會有隨著相變化而發生粉末之問題。在電子零件燒成用材料之基材表面上形成氧化銷層（或氧化銷膜）之方法，係有塗佈法或噴塗法等。此場合下，木紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）請閱讀背之注意事項頁經濟部智慧財產局員工消費合作社印製 1286128 A7 B7 五、發明説明（2 ) 對於負荷由被覆粒徑極其微小的微粒子所成之氧化鉻層時，並且反復熱循環電子零件燒成用材料之使用環境而言，當基材與氧化鍩層間之熱膨脹係數差係不和緩或不能被吸收時，則會有氧化锆層從基材上剝離之情形。又，在使用比較粗的粗粒子所形成之氧化鍩層之場合下，則有不引起氧化鉻膜之緻密化，或形成多氣孔基材等使熱膨脹係數和緩方向作用。但是，會有氧化锆膜與基材之密著性會變差，膜之燒結性變得低下等使得剝離原因。又，電子零件燒成用工模，除了耐熱性或機械強度以外，尙要求其不會與燒成的陶瓷電子零件起反應。介電體等電子零件製品會因與燒成用工模接觸起反應、熔融附著、使得製品組成變動而特性變差等問題產生。通常來說，做爲電子零件燒成用工模之基材，係時常地使用間熱強度高的、熱剝離性良好之氧化鋁•莫來石系基材。但是此氧化鋁•莫來石系基材之電子零件製品係易於起反應，爲了防止此反應，則採用在基材表面上被覆氧化銷之方法。經濟部智慧財產局員工消費合作社印製更且，如前述，氧化锆既發生龜裂又發生剝離，而會有氧化銷之被覆層易於脫離之問題。又且，在使用未安定化氧化銷之場合下，則會有隨著相變化而發生粉末之問題。爲了解決此等問題，建議在電子零件燒成用工模之氧化锆表面層與基材間，有由氧化鉻所成之中間層存在。但是，此電子零件燒成用工模會具有氧化鍩之燒結性不佳，氧本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 1286128 五、發明說明（4) 定化氧化鉻之場合具有同樣的效果；以及使得與基材之密著性向上增加，而可得到：抑制氧化銷層之剝離或粉末化之效果。從而提供了一種具充分強度的、可經濟地製造的、且與基材密著性優異的電子零件燒成用材料。本案之第2發明係爲一種電子零件燒成用工模，其特徵係在於含有基材、在基材表面上被覆2種以上之金屬氧化物所成的部分熔融中間層，及在該中間層上形成氧化鉻表面層。該電子零件燒成用工模，係不同於習用之單一氧化鋁之中間層，由於係使用了 2種以上之金屬氧化物及部分熔融之中間層，則使得液相之熔融氧化物之氧化锆表面層與基材兩者間之密著性向上增加，而賦與了氧化銷表面層良好之耐剝離性。並且，因部分熔融中間層生成時之高溫燒成的部分熔融中間層之燒結性，係向上增加而相對的改善了應力強度。從而，即使在急冷和急熱之反復熱循環之環境下，電子零件燒成用工模仍可使用歷相當長時期。本案之第3發明係爲一種電子零件燒成用工模，其特徵爲含有基材、在基材表面上被覆金屬氧化物所成之中間層，及在該中間層上形成氧化鉻氧化鈣氧化鋁氧化釔表面層〇此電子零件燒成用工模，係不同於習用之單一氧化鋁之中間層，係使用了親和性之中間層或部分熔融，換言之，係使用了氧化鉻氧化鈣氧化鋁氧化釔之表面層。從而，改 1286128 五、發明說明（5) 善了長期耐久性，即使在急冷和急熱之反復熱循環之環境下’電子零件燒成用工模仍可使用歷相當長時期。較佳實施例之說明首先，說明本案之第1發明。本案之第1發明，係在構成由至少使用平均粒徑爲30〜 5 00微米之粗粒氧化鉻之電子零件燒成用材料時，藉由使用微粒子狀之部分熔融結合材料，而防止了粗粒氧化銷之缺點，並且防止剝離性或燒結性變差。由於使用粗粒氧化鉻之氧化锆層因無法完全密·緻化而形成多量的氣孔，使得其與基材之熱膨脹差變爲和緩或被吸收了。更且，藉由使用了微粒子狀之部分熔融結合材料，則該部分熔融結合材料之氧化銷層與基材間之密著性向上增加，而達到了向來不並存之「防止因基材與氧化銷層間之熱膨脹差異所引起之剝離」，並且「使得基材與氧化銷層間之密著性向上增加」。又，第1發明之較佳的實施例，係使用平均粒徑爲30〜 500微米之粗粒氧化鉻和平均粒徑爲0.1〜10微米之微粒氧化鉻，藉由與前述之部分熔融結合材料結合而形成氧化鍩層。依照該實施例，因使用了微粒氧化銷來做爲氧化銷層，而使得其強度向上增加，而達成了如上所述之「防止因基材與氧化銷層間之熱膨脹差異所引起之剝離」，並且「使得基材與氧化銷層間之密著性向上增加」。做爲第1發明之電子零件燒成用材料之氧化鉻之主成分 1286128 A7 B7 經濟部智慧財產局員工消費合作社印製五、發明説明（6 ) ，經由前述，係含有平均粒徑爲30〜500微米之粗粒氧化鍩之必要成分，及平均粒徑爲0.1〜10微米之微粒氧化锆者較佳。粗粒氧化锆之平均粒徑不足30微米時，與基材之熱膨脹差有關之應力和緩效果會變小，而易於產生剝離 ;又平均粒徑超過5 0 0微米，則會使得燒結性變低。微粒氧化锆之平均粒徑不足0 · 1微米時，其與粗粒氧化銷之粒徑差過大，使得粗粒氧化鉻與基材之密著性向上增加之效果變小，又，當超過10微米時，則接近於粗粒氧化鉻，而添加微粒氧化銷之效果變小。在使用粗粒氧化鉻和微粒氧化鉻之場合下，理想上其重量比係自80 : 20到20 : 80 ;在該範圍之外則一方面會使得燒結性惡化，而且熱膨脹差變得不和緩或不被吸收而產生剝離。在僅僅使用粗粒氧化銷之場合下，理想上部分熔融結合材料，仍應維持與微粒氧化锆類似的粒徑範圍。當考量粗粒氧化锆與電子零件之反應性時，理想上係使用未安定化之氧化銷、部分安定化之氧化锆及安定化之氧化鉻、或者是使用其混合物；可在氧化鉻中添加安定化或部分安定化之氧化釔（氧化釔γ2〇3)、氧化鈣（氧化鈣Ca0) 、或氧化鎂（氧化鎂MgO)等來達成。氧化鉻在室溫下係爲單斜晶系，當溫度上昇時，雖然會引起單斜晶系-> (〜117〇。〇正方晶系—（〜237〇。〇立方晶系之相變化，但藉由在氧化鉻上之氧化釔或氧化鎂等之部分熔融結合材料（安定劑）之固溶，而使得高溫相之正本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）1286128 A7 B7 V. FIELD OF THE INVENTION The present invention relates to a fixture, a scaffolding board, and a holder for use in firing electronic components such as dielectrics, laminated capacitors, ceramic capacitors, piezoelectric elements, and thermistors. BACKGROUND OF THE INVENTION As a material for firing electronic parts, in addition to the necessary properties of heat resistance or mechanical strength, it is required to not react with fired ceramic electronic parts. An electronic component such as a dielectric material may be caused by a reaction with a firing mold, a fusion adhesion, a change in product composition, and a deterioration in characteristics. Usually, an alumina-based material or an alumina mullite material is used. An alumina magnesia spinel-based material, an alumina mullite cordierite-based material, or a combination thereof as a substrate for a material for firing an electronic component. Also, in order to prevent the product from reacting, it is used on the surface layer. A method of coating zirconia (zirconia ZrO 2 ). Although the reactivity of zirconia with the substrate is small, the thermal expansion coefficient of the substrate is very different, so that the mold is In the use environment of repeated thermal cycling on the code, the problem of cracking and peeling occurs, and the yttrium oxide is in the vicinity of ~1100 ° C, which causes the phase change from monoclinic crystal to tetragonal crystal. The phase change of the repeated thermal cycle causes the coefficient of thermal expansion to change, and there is a problem that the coded layer of zirconia is detached. Moreover, in the case of using unstabilized chromia, there is a problem of powder accompanying the phase change. A method of forming an oxidized pin layer (or an oxidized pin film) on a surface of a substrate for firing an electronic component, such as a coating method or a spray coating method, etc. In this case, the wood paper scale is applied to the Chinese National Standard (CNS). A4 size (210X297 mm) Please read the notes on the back page of the Ministry of Economic Affairs, Intellectual Property Bureau, Staff and Consumers Co., Ltd. Printed 1286128 A7 B7 V. Description of invention (2) The chrome oxide layer formed by the microparticles with extremely small particle size When the environment of the material for firing the electronic component is repeated, the difference in thermal expansion coefficient between the substrate and the yttrium oxide layer is not moderate or absorbed. In the case where the zirconia layer is peeled off from the substrate, when the ruthenium oxide layer formed by the coarser coarse particles is used, the densification of the chrome oxide film is not caused, or a multi-porous basis is formed. The material has a thermal expansion coefficient and a slow direction. However, the adhesion between the zirconia film and the substrate is deteriorated, and the sinterability of the film is lowered, which causes peeling. In addition to the mechanical or mechanical strength, it is required to not react with the fired ceramic electronic components. The electronic component products such as dielectrics may react with the firing mold, melt and adhere, and the composition of the product may change and the characteristics deteriorate. In general, as a substrate for a mold for firing electronic parts, an alumina-mullite substrate having a high heat-dissipating property and excellent heat-peelability is often used. However, the electronic component product of the alumina mullite substrate is susceptible to reaction, and in order to prevent this reaction, a method of coating an oxidized pin on the surface of the substrate is employed. Printed by the Intellectual Property Office of the Ministry of Economic Affairs, the Consumer Cooperatives. As mentioned above, zirconia is cracked and peeled off, and there is a problem that the coating layer of the oxidized pin is easily detached. Further, in the case where an unstabilized oxidized pin is used, there is a problem that powder occurs as the phase changes. In order to solve such problems, it is recommended that an intermediate layer made of chromium oxide exists between the zirconia surface layer and the substrate of the mold for firing electronic parts. However, this mold for firing electronic parts will have poor sinterability of yttrium oxide. The size of oxygen paper is applicable to China National Standard (CNS) A4 specification (210X297 mm). 1286128 V. Description of invention (4) Qualification of chromium oxide The same effect is obtained in the case; and the adhesion to the substrate is increased upward, and the effect of suppressing peeling or powdering of the oxidation pin layer can be obtained. Thus, there is provided a material for firing an electronic component which is sufficiently strong, economical to manufacture, and excellent in adhesion to a substrate. According to a second aspect of the invention, there is provided a mold for firing an electronic component, comprising: a base material; a partially molten intermediate layer formed by coating two or more kinds of metal oxides on a surface of the base material; and on the intermediate layer A chromium oxide surface layer is formed. The die for firing an electronic component is different from the intermediate layer of a single alumina which is conventionally used. Since two or more metal oxides and a partially melted intermediate layer are used, the zirconia surface of the molten oxide of the liquid phase is obtained. The adhesion between the layer and the substrate is increased upward, and the surface layer of the oxidation pin is imparted with good peeling resistance. Further, the sinterability of the partially molten intermediate layer which is fired at a high temperature when the partially melted intermediate layer is formed is increased upward and the stress strength is relatively improved. Therefore, even in the environment of repeated thermal cycling of quenching and rapid heat, the mold for firing electronic parts can be used for a long period of time. According to a third aspect of the present invention, there is provided a mold for firing an electronic component, comprising: a base material; an intermediate layer formed by coating a metal oxide on a surface of the base material; and a chromium oxide oxidized calcium oxide formed on the intermediate layer. The surface layer of yttrium oxide is a mold for firing electronic parts, which is different from the intermediate layer of a single alumina used in the prior art, and uses an intermediate layer or partial melting of affinity, in other words, chromia oxide, calcium oxide, aluminum oxide ruthenium oxide. The surface layer. Therefore, it is changed to 1286128. 5. Description of the invention (5) The long-term durability is good, and even in the environment of repeated thermal cycling of rapid cooling and rapid heat, the mold for electronic component firing can be used for a long period of time. DESCRIPTION OF THE PREFERRED EMBODIMENTS First, the first invention of the present invention will be described. In the first invention of the present invention, when a material for firing an electronic component using at least a coarse-grained chromium oxide having an average particle diameter of 30 to 500 μm is used, the particulate material is partially melted and the binder is prevented from being coarse. The particle oxidation pin has the disadvantage of preventing peeling property or sinterability from being deteriorated. Since the zirconia layer using the coarse-grained chromia is formed into a large amount of pores due to incomplete densification, the difference in thermal expansion from the substrate becomes slow and absorbed. Moreover, by using a particulate-like partially melted bonding material, the adhesion between the oxidized pin layer of the partially melted bonding material and the substrate is increased upward, thereby achieving the prevention of the substrate and oxidation. The peeling caused by the difference in thermal expansion between the pin layers" and "increasing the adhesion between the substrate and the oxidized pin layer." Further, in a preferred embodiment of the first invention, coarse-grained chromium oxide having an average particle diameter of 30 to 500 μm and fine particle chromium oxide having an average particle diameter of 0.1 to 10 μm are used, and a part of the bonded material is melted by the foregoing. The yttrium oxide layer is formed by bonding. According to this embodiment, since the fine particle of the oxidized pin is used as the oxidized pin layer, the strength thereof is increased upward, and the "preventing the peeling due to the difference in thermal expansion between the substrate and the oxidized pin layer" as described above is achieved. And "the adhesion between the substrate and the oxidized pin layer is increased upwards". The main component of chromium oxide which is the material for firing electronic parts of the first invention is 1286128 A7 B7 Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperatives, Printing 5, Invention Description (6), through the above, contains an average particle size of 30~ The essential component of the 500 μm coarse cerium oxide and the fine particle zirconia having an average particle diameter of 0.1 to 10 μm are preferred. When the average particle diameter of the coarse-grained zirconia is less than 30 μm, the stress and relaxation effect related to the difference in thermal expansion of the substrate become small, and peeling is liable to occur; and the average particle diameter exceeds 500 μm, which causes the sinterability to be low. . When the average particle diameter of the fine particles of zirconia is less than 0 · 1 μm, the difference in particle diameter from the coarse-grained oxide pin is too large, so that the effect of increasing the adhesion of the coarse-grained chromium oxide to the substrate is small, and when it exceeds 10 In the case of micron, it is close to coarse-grained chromium oxide, and the effect of adding the particulate oxidation pin becomes small. In the case of using coarse-grained chromium oxide and particulate chromia, it is desirable that the weight ratio is from 80:20 to 20:80; outside this range, the sinterability is deteriorated on the one hand, and the difference in thermal expansion becomes unsatisfactory. Or peeling without being absorbed. In the case where only coarse-grained oxide pins are used, it is desirable to partially melt the bonding material while still maintaining a similar particle size range as the particulate zirconia. When considering the reactivity of coarse-grained zirconia with electronic parts, it is desirable to use an unstabilized oxidized pin, partially stabilized zirconia and stabilized chrome oxide, or a mixture thereof; The stabilized or partially stabilized cerium oxide (cerium oxide γ2〇3), calcium oxide (calcium oxide Ca0), or magnesium oxide (magnesium oxide MgO) is obtained. Chromium oxide is monoclinic at room temperature, and when the temperature rises, it causes monoclinic system-> (~117〇. 〇正方晶系-(~237〇. However, the solid paper of the high temperature phase is applied to the Chinese National Standard (CNS) A4 specification (210X297 mm) by solid solution of a part of the molten bonding material (stabilizer) such as cerium oxide or magnesium oxide on the chromium oxide.

1286128 A7 B7 經濟部智慧財產局員工消費合作社印製五、發明説明（7 ) 方晶系或立方晶系可在室溫下安定化。雖然，未安定化氧化銷會因單斜晶系^正方晶系之相變狀態而產生了體積變化’但部分丨谷融結合材料之經固丨谷的安定化氧化銷並不會發生相變化。所添加的部分熔融結合材料，係含有自氧化釔（氧化釔 Y2〇3)、氧化鈣（氧化鈣CaO)、氧化鎂（氧化鎂Mg0)及氧化緦（氧化鎂SrO)中所選出之至少1種以上之金屬氧化物，較宜是由含有2種以上之金屬氧化物與氧化鋁（Al2〇3)所組成。氧化鋁以外之金屬氧化物，宜是具有透過燒成時之液相與未安定化氧化鉻表面之氧化鍩粒子起反應，而使得一部分之氧化錯安定化之機能。又，氧化銘宜是與基材與氧化鉻層配合良好者。相對於氧化锆與部分熔融結合材料之總量，理想上，部分熔融結合材料之比例係在3〜2 5重量％左右。當添加不足3重量％時則不完全具有添加之效果；又，當超過2 5重量％時，與經浸透部分熔融結合材料之基材，則在本身係獨立之部分熔融結合材料之氧化鉻層以外形成熔融層時，其密著性恐怕會變差。彼等具有金屬氧化物之部分熔融結合材料，係會使得由同樣的粗粒氧化鉻、或結合粗粒氧化鉻與微粒氧化鉻之氧化銷層之強度’在燒成時係會向上增加。依據氧化銷燒結之觀點來看，該部分熔融結合材料理想上係使用從粢微米 (請先閱讀背面之注意事項再辦寫本頁) •i衣· 與舄本1286128 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 5, invention description (7) The cubic system or cubic system can be stabilized at room temperature. Although the unstabilized oxidized pin will have a volume change due to the phase transition state of the monoclinic system or the tetragonal system, the stability of the oxidized pin of the glutinous glutinous composite material will not change. . The partially melted bonding material added contains at least 1 selected from the group consisting of cerium oxide (yttrium oxide Y2〇3), calcium oxide (calcium oxide CaO), magnesium oxide (magnesium oxide MgO) and cerium oxide (magnesium oxide SrO). The above metal oxide is preferably composed of two or more kinds of metal oxides and alumina (Al2〇3). The metal oxide other than alumina is preferably a function of reacting the liquid phase during firing with the cerium oxide particles on the surface of the unstabilized chromia to cause a part of the oxidation to be unstable. Further, the oxidation is preferably a combination with the substrate and the chromium oxide layer. The ratio of the partially melted bonding material is desirably about 3 to 25 wt%, relative to the total amount of the zirconia and the partially melted bonding material. When the addition is less than 3% by weight, the effect of the addition is not completely obtained; further, when it exceeds 25% by weight, the oxidized chromium layer of the bonded material is melted in a part of the substrate which is partially fused with the partially fused portion. When a molten layer is formed outside, the adhesion may be deteriorated. These portions of the molten bonding material having a metal oxide cause the strength of the oxidized pin layer of the same coarse chrome oxide or combined with the coarse chromia oxide and the particulate chromia to increase upward during firing. According to the viewpoint of oxidation pin sintering, the partially melted bonding material is ideally used from 粢 micron (please read the back of the note before writing this page) • i clothing · and 舄

、1T, 1T

本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 1286128 Α7 Β7 五、發明説明（8 ) 到1 0微米在右之微粒。因此，第1發明中所使用之部分熔融結合材料，由於係氧化锆安定化化合物、與從Y2〇3、CaO、MgO及SrO中所選出之2種以上的金屬氧化物、基材以及含有使其相稱性增加之化合物之氧化鋁之故，而使得粗粒氧化锆及/或微粒氧化锆之結合強度向上增加；於是，在祇由粗粒氧化鉻構成之氧化锆層時，會與該粗粒氧化錆本身係做爲微細結合材強固地結合；在使用未安定化氧化鉻之場合下，該氧化鉻之至少一部分也會安定化；從而，在可經濟地、有利地使用未安定化氧化锆之場合下，同樣的也可在使用安定化氧化銷之場合下，得到同等的效果；以及所謂的和基材之密著性向上增加的氧化锆層之剝離或粉末化也受到控制了等3種效果。在基材表面上之氧化鉻層（氧化锆膜）之形成法，是使用習用的塗布或熱分解氧化鉻化合物液之方法、噴塗氧化銷粉末之方法、及使基材浸漬於氧化鍩化合物溶液後再以上述熱分解前之化合物來更換氧化錯之方法來進行較宜。所使用的基材較宜是與習用的相同，例如是使用前述之氧化經濟部智慧財產局員工消費合作社印製錦系材料、氧化鋁-莫來石系材料、氧化鋁-氧化鎂系尖晶石材料、氧化鋁_莫來石_蓳青石系材料、或組合其他材料〇虽所使用形成如此之氧化锆層之燒成溫度，係爲比實際上電子零件之燒成溫度更筒之溫度.時，則在燒成第1發明 -10- 本紙張尺度適用中國國家標準（CNS ) M規格（2Η)'χ297公釐- 1286128 A7 ____B7 五、發明説明（9 ) 之電子零件燒成用材料時，將可望是不會劣化的。從而電子零件之燒成溫度通常宜爲12〇〇〜1 400°C，而氧化銷層之燒成溫度則係在1 300〜1 600°C左右較宜。其次，說明本案之第2發明。本案之第2發明係爲一種電子零件燒成用工模，其特徵係爲··在基材與氧化鉻表面層間，具有2種以上之金屬氧化物所成的部分熔融中間層（以下，在本發明說明書中，在燒成前之層簡稱爲「中間層」，在燒成後之層簡稱爲「部分溶融中間層」）。第2發明之電子零件燒成用工模之基材材質，宜是與習用的相同，例如是使用氧化鋁系材料、氧化鋁-莫來石系材料、氧化鋁-氧化鎂系尖晶石材料、氧化鋁-莫來石-蓳青石系材料、或組合其他材料。經濟部智慧財產局員工消費合作社印製在此種基材上所形成的部分熔融中間層，係可使用2種以上之金屬氧化物經高溫燒成而得。構成該部分熔融中間層之金屬氧化物，係可自氧化鋁（氧化鋁A 12〇3 )、氧化鍩（氧化銷Zr 203 )、氧化釔（氧化釔Y2〇3)、氧化鈣（氧化鈣Ca〇) 、氧化鎂（氧化鎂MgO )、氧化總（氧化總S rO )、及氧化金呂 •氧化鎂尖晶石複合氧化物（Al2〇3 · MgO，以下稱爲「尖晶石氧化物」）中所選出之2種以上來做成。具體來說，理想上係爲氧化鋁與其他的金屬氧化物組合而成，例如氧化鋁-尖晶石氧化物-氧化鎂-氧化鈣-氧化釔所組合的具有優異特性之部分熔融中間層。 -11- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 1286128 A7 B7 五、發明説明（10) 金屬氧化物之混合比例並沒特別的限淛，較宜是使用1 種金屬氧化物之含有量係超過9 0重量％者時，使用2種以上金屬氧化物之混合物，其效果至少並沒有比較好。構成部分熔融中間層的金屬氧化物之粒徑並沒特別的限制，以無規粒徑之金屬氧化物來構成部分熔融中間層或中間層也可以。可以用粗粒子和微粒子混合而成，例如，含有平均粒徑爲30〜500微米之粗粒子和平均粒徑爲0.1〜1〇微米之微粒子，藉由氣孔率大的粗粒子之金屬氧化物，而在部分熔融中間層上形成空隙，則會使得氧化锆表面層與部分熔融中間層間、以及部分熔融中間層與基材間之熱膨脹係數之差，被吸收而和緩，也可在急熱急冷之反復熱循環之環境下使用，即使用使用比較長的時期亦不剝離。但是，以對應於部分熔融中間層之總量計，該粗粒子之量係在90重量％以下。超出90重量％時則得不到部分熔融之效果，或者產生膜面密緻化不符合之事。經濟部智慧財產局員工消費合作社印製前述中間層係可藉由塗布-熱分解法、噴塗法及浸漬塗覆法，而形成在基材表面上。對於塗布-熱分解法，係將塗布在基材表面上之金屬硝酸鹽之金屬鹽溶液，藉由熱分解而將所對應的金屬氧化物被覆在基材表面上之方法。噴塗法係將有預定粒徑之金屬氧化物粒子懸浮之溶媒，將溶媒噴射在基材表面上，使飛散的金屬氧化物被覆於基材表面上之方法。又，浸漬塗布法，係將基材浸漬於含有溶解或懸浮金屬氧化物粒子之溶液中，使含有金屬氧化物之液 -12- 本紙張尺度適用中國國家標準（CNS ) A4規格（21〇Χ297公釐） 1286128 A7 _____B7_ 五、發明説明（11 ) 層形成在基材表面上，使之乾燥除去溶媒而形成金屬氧化物層之方法。以塗布-熱分解法及浸漬塗覆法來生成的金屬氧化物粒子之粒徑並不易調節，理想上所期望的金屬氧化物之粒徑分布，係例如在以直接噴霧之噴塗法來形成由前述之粗粒子與微粒子所組成之金屬氧化物中間層時之預定的金屬氧化物粒徑。部分熔融中間層之厚度並沒特別的限制，僅由金屬氧化物微粒子來形成之場合，以10〜200微米較宜，其係依各製造方法中，在基材上之金屬或金屬.化合物之噴霧量，或者是金屬或金屬化合物溶液之被覆量，以及所除去的溶媒量來考慮，而任意地來調節所形成的中間層之厚度。經濟部智慧財產局員工消費合作社印製因此所形成的中間層係藉由高溫燒成而變換爲部分熔融中間層。當第2發明之電子零件燒成用工模之燒成溫度，係使用實際上高於電子零件之燒成溫度時，則可望其不會劣化。通常，由於電子零件之燒成溫度係爲1 200〜1400 °C，則中間層之燒成溫度較宜是在1 300〜1 600 °C左右。又，中間層係可在氧化銷表面層形成後燒成，而更宜是與該氧化銷表面層之燒成同時進行，因而可減少此燒成工程之次數。在這樣所形成的部分熔融中間層（或中間層）上，使形成氧化銷表面層。該製法係與前述中間層相同，均可爲塗布 -熱分解法、噴塗法及浸漬塗覆法等。 -13- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 1286128 A7 B7 五、發明説明（12 ) 雖然也可以用無規粒徑之氧化锆來燒成而形成氧化鉻層，但是與前述之中間層同樣是以粗粒子和微粒子混合時，例如，存在並混合有平均粒徑爲30〜500微米之粗粒子和平均粒徑爲0.1〜10微米之微粒子時，藉由氣孔率大的氧化锆粗粒子而在表面層上形成空隙，則會使得能夠藉由在部分熔融中間層形成空隙，加上能夠藉形成空隙，則會使得氧化鍩表面層與部分熔融中間層間之熱膨脹係數之差被吸收而和緩。以對應於氧化锆表面層之總量計，理想上，該粗粒子之量係在90重量％以下。經濟部智慧財產局員工消費合作社印製又，該氧化锆表面層之材質，雖然可使用具體地未安定化之氧化锆、部分地安定化之氧化锆或安定化之氧化鉻，但由於氧化锆層係直接與電子零件接觸，爲使不賦與電子零件不良的影響，從而理想上係使用經氧化釔、·氧化鈣及氧化鎂等而部分安定化之氧化鍩、或安定化之氧化錯或者其混合物。氧化銷在室溫下係爲單斜晶系，當溫度上昇時，雖然會引起單斜晶系—（〜1170 °C )—正方晶系—（〜 23 70 °C )—立方晶系之相變化，但藉由在氧化銷上之氧化釔或氧化鎂等之部分熔融結合材料（安定劑）之固溶，而使得高溫相之正方晶系或立方晶系可在室溫下安定化。因此而製得之第2發明之電子零件燒成用工模，其以2 種以上金屬氧化物所構成之中間層，在加熱燒成時，其中有一部分會熔融而成爲部分熔融中間層，部分熔融所形成之液相則會與氧化锆表面層和及基材兩者反應，因此顯著 -14- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 1286128 A7 B7 五、發明説明（13) 地改善了各層與基材間之密著力。換句話說’氧化锆表面層變得不會從基材剝離。又，當液相量過多時，因爲在液相固化之際收縮的膜或基材會變形，則理想上加熱條件應適切地設定。更且，由於部分熔融中間層係使用2種以上的金屬氧化物做成的，故藉由其他的金屬氧化物而補足了 1種金屬氧化物差的燒結性，使得全體之燒結性向上而改善了部分熔融中間層之強度。又，由於使用2種金屬氧化物，其熔點係會比單一金屬氧化物（例如氧化鋁之熔點爲約2000°C )之場合來得低，故宜使用1 300〜1 600°C之燒成溫度而變得容易燒成了。從而，達成了該向來僅僅有1種金屬氧化物所形成的中間層之電子零件燒成用工模，實質上所達不到之由於減少了基材與氧化銷表面層間之熱膨脹係數差異而防止其剝離，以及使部分熔融中間層之強度向上增加。以下，茲說明本案之第3發明。本案之第3發明之電子零件燒成用工模，係由基材、中間層及表面層所形成；其係使用向來所使用的氧化锆氧化鈣氧化鋁氧化釔，或者是經氧化釔安定化氧化鉻。該中間層並無特別之限制，可使用氧化鋁單一層、或進行燒成之氧化鉻氧化鈣氧化鋁氧化釔之部分熔融中間層，或者含有之氧化鋁氧化鈣氧化鎂之部分熔融中間層。第3發明之電子零件燒成用工模之基材之材質，與習用 -15- 本紙張尺度適用中國國家標準（CNS ) A4規格（21〇X：297公釐） (請先閱讀背面之注意事項本頁) 、τThis paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) 1286128 Α7 Β7 V. Invention description (8) to 10 micron particles on the right. Therefore, the partially melt-bonded material used in the first invention is a zirconia-stabilizing compound, and two or more kinds of metal oxides, base materials, and inclusions selected from Y2〇3, CaO, MgO, and SrO. The alumina of the compound having an increased proportionality causes the bonding strength of the coarse-grained zirconia and/or the particulate zirconia to increase upward; thus, when the zirconia layer composed only of coarse-grained chromia is used, The cerium oxide itself is strongly bonded as a fine bonding material; in the case of using unstabilized chromic oxide, at least a part of the chromium oxide is also stabilized; thus, economically and advantageously using unstabilized oxidation In the case of zirconium, the same effect can be obtained in the case of using a stabilized oxidized pin, and the peeling or pulverization of the zirconia layer which is increased in adhesion to the substrate is also controlled. 3 effects. The chromium oxide layer (zirconia film) formed on the surface of the substrate is a conventional method of coating or thermally decomposing a chromium oxide compound liquid, a method of spraying an oxidation pin powder, and immersing a substrate in a cerium oxide compound solution. It is preferred to carry out the method of replacing the oxidative error with the above compound before thermal decomposition. The substrate to be used is preferably the same as conventional ones, for example, using the aforementioned Ministry of Oxidation and Economy, Intellectual Property Bureau, Staff Consumer Cooperative, printed with a brocade material, alumina-mullite material, alumina-magnesia-based spinel. The stone material, the alumina_mullite_cordierite-based material, or a combination of other materials, although the firing temperature for forming such a zirconium oxide layer is a temperature that is more than the firing temperature of the actual electronic component. In the case of firing the first invention - the paper size applies to the Chinese National Standard (CNS) M specification (2 Η) 'χ297 mm - 1286128 A7 ____B7 5. Inventive Note (9) It will be expected to not deteriorate. Therefore, the firing temperature of the electronic component is usually from 12 〇〇 to 1 400 ° C, and the firing temperature of the oxidized pin layer is preferably from about 1,300 to 1,600 °C. Next, the second invention of the present invention will be described. The second invention of the present invention is a mold for firing an electronic component, characterized in that it has a partially melted intermediate layer formed of two or more kinds of metal oxides between a base material and a surface layer of chromium oxide (hereinafter, In the specification of the invention, the layer before firing is simply referred to as "intermediate layer", and the layer after firing is simply referred to as "partially melted intermediate layer"). The base material of the mold for firing an electronic component according to the second aspect of the invention is preferably the same as that of the conventional one, and for example, an alumina-based material, an alumina-mullite material, an alumina-magnesia-based spinel material, or the like is used. Alumina-mullite-cordierite-based materials, or combinations of other materials. Printed by the Intellectual Property Office of the Ministry of Economic Affairs, the Consumers' Cooperatives. The partially melted intermediate layer formed on such a substrate can be obtained by firing at a high temperature using two or more kinds of metal oxides. The metal oxide constituting the partially melted intermediate layer may be derived from alumina (alumina A 12〇3 ), cerium oxide (oxidized pin Zr 203 ), cerium oxide (yttrium oxide Y 2 〇 3 ), calcium oxide (calcium oxide Ca 〇), magnesium oxide (magnesium oxide MgO), total oxidation (oxidation total S rO ), and oxidized gold lan-magnesia spinel composite oxide (Al2〇3 · MgO, hereinafter referred to as "spinel oxide" Two or more of the selected ones are made. Specifically, it is desirable to combine alumina with other metal oxides, such as a partially melted intermediate layer having excellent characteristics in combination of aluminum oxide-spinel oxide-magnesium oxide-calcium oxide-yttria. -11- This paper scale is applicable to China National Standard (CNS) A4 specification (210X297 mm) 1286128 A7 B7 V. Description of invention (10) The mixing ratio of metal oxide is not limited to Zhejiang, and it is better to use one metal. When the content of the oxide is more than 90% by weight, a mixture of two or more kinds of metal oxides is used, and the effect is at least not preferable. The particle diameter of the metal oxide constituting the partially melted intermediate layer is not particularly limited, and a partially melted intermediate layer or an intermediate layer may be formed by a metal oxide having a random particle diameter. The coarse particles and the fine particles may be mixed, for example, a coarse particle having an average particle diameter of 30 to 500 μm and a fine particle having an average particle diameter of 0.1 to 1 μm, and a metal oxide of a coarse particle having a large porosity. When a void is formed in the partially melted intermediate layer, the difference between the thermal expansion coefficient between the zirconia surface layer and the partially molten intermediate layer and between the partially melted intermediate layer and the substrate is absorbed and moderated, and may be quenched and quenched. It is used in the environment of repeated thermal cycling, that is, it does not peel off when it is used for a long period of time. However, the amount of the coarse particles is 90% by weight or less based on the total amount of the partially melted intermediate layer. When it exceeds 90% by weight, the effect of partial melting is not obtained, or the film surface densification does not conform. Printed by the Intellectual Property Office of the Ministry of Economic Affairs, the Consumers' Cooperatives. The intermediate layer can be formed on the surface of the substrate by coating-thermal decomposition, spray coating and dip coating. For the coating-thermal decomposition method, a metal salt solution of a metal nitrate coated on the surface of a substrate is coated with a corresponding metal oxide on the surface of the substrate by thermal decomposition. The spray coating method is a method in which a metal oxide particle having a predetermined particle diameter is suspended, and a solvent is sprayed on the surface of the substrate to cover the surface of the substrate with the scattered metal oxide. Further, the dip coating method is to immerse the substrate in a solution containing dissolved or suspended metal oxide particles, so that the metal oxide-containing liquid-12-this paper scale is applicable to the Chinese National Standard (CNS) A4 specification (21〇Χ297 1286128 A7 _____B7_ V. DESCRIPTION OF THE INVENTION (11) A method in which a layer is formed on a surface of a substrate and dried to remove a solvent to form a metal oxide layer. The particle diameter of the metal oxide particles produced by the coating-thermal decomposition method and the dip coating method is not easily adjusted, and the particle size distribution of the desired metal oxide is desirably formed, for example, by a direct spray coating method. The predetermined metal oxide particle size in the case of the aforementioned metal oxide intermediate layer composed of the coarse particles and the fine particles. The thickness of the partially melted intermediate layer is not particularly limited, and is preferably formed by metal oxide fine particles, preferably 10 to 200 μm, depending on the metal or metal compound on the substrate in each manufacturing method. The amount of spray, either the amount of coating of the metal or metal compound solution, and the amount of solvent removed, is arbitrarily adjusted to the thickness of the intermediate layer formed. Printed by the Ministry of Economic Affairs, the Intellectual Property Office, and the Consumer Cooperatives. The intermediate layer thus formed is converted into a partially melted intermediate layer by high-temperature firing. When the firing temperature of the mold for firing an electronic component according to the second aspect of the invention is actually higher than the firing temperature of the electronic component, it is expected that it will not deteriorate. Usually, since the firing temperature of the electronic component is 1 200 to 1400 ° C, the firing temperature of the intermediate layer is preferably about 1,300 to 1,600 °C. Further, the intermediate layer can be fired after the surface layer of the oxidized pin is formed, and is preferably carried out simultaneously with the firing of the surface layer of the oxidized pin, so that the number of times of the firing process can be reduced. On the partially melted intermediate layer (or intermediate layer) thus formed, an oxidation pin surface layer is formed. This method is the same as the above intermediate layer, and may be a coating-thermal decomposition method, a spray coating method, a dip coating method, or the like. -13- This paper scale applies to China National Standard (CNS) A4 specification (210X 297 mm) 1286128 A7 B7 V. Description of invention (12) Although it is also possible to use a random particle size of zirconia to form a chromium oxide layer. However, when the coarse particles and the fine particles are mixed in the same manner as the intermediate layer described above, for example, when coarse particles having an average particle diameter of 30 to 500 μm and fine particles having an average particle diameter of 0.1 to 10 μm are present and mixed, the pores are obtained by the pores. The large zirconia coarse particles form voids on the surface layer, which enables thermal expansion between the yttrium oxide surface layer and the partially molten intermediate layer by forming voids in the partially melted intermediate layer, and by forming voids. The difference between the coefficients is absorbed and gentle. The amount of the coarse particles is desirably 90% by weight or less based on the total amount of the surface layer corresponding to zirconia. Printed by the Intellectual Property Office of the Ministry of Economic Affairs, the consumer cooperatives, the material of the zirconia surface layer, although specifically unsteady zirconia, partially stabilized zirconia or stabilized chromia, but due to zirconia The layer is directly in contact with the electronic component, and in order to prevent the adverse effect of the electronic component, it is preferable to use a cerium oxide partially stabilized by cerium oxide, calcium oxide, magnesium oxide, or the like, or an oxidative error of stabilization or Its mixture. The oxidation pin is monoclinic at room temperature. When the temperature rises, it will cause monoclinic system - (~1170 °C) - tetragonal system - (~ 23 70 °C) - cubic phase The change is, but the solid solution of the high-temperature phase or the cubic system can be stabilized at room temperature by solid solution of a part of the fusion bonding material (stabilizer) of cerium oxide or magnesium oxide on the oxidation pin. Therefore, in the mold for firing an electronic component according to the second aspect of the invention, when the intermediate layer composed of two or more kinds of metal oxides is heated and fired, a part of the intermediate layer is melted to become a partially melted intermediate layer, and partially melted. The formed liquid phase will react with both the zirconia surface layer and the substrate, so it is significant - 14 - This paper scale applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) 1286128 A7 B7 V. Description of the invention ( 13) The adhesion between the layers and the substrate is improved. In other words, the zirconia surface layer does not peel off from the substrate. Further, when the amount of the liquid phase is too large, since the film or the substrate which shrinks when the liquid phase is solidified is deformed, the ideal heating condition should be appropriately set. In addition, since the partially melted intermediate layer is made of two or more kinds of metal oxides, the sinterability of one type of metal oxide is complemented by other metal oxides, and the overall sinterability is improved. The strength of the partially melted intermediate layer. Further, since two kinds of metal oxides are used, the melting point thereof is lower than that of a single metal oxide (for example, the melting point of alumina is about 2000 ° C), so the firing temperature of 1 300 to 1 600 ° C is preferably used. And it becomes easy to burn. Therefore, the mold for firing an electronic component in which the intermediate layer formed of only one type of metal oxide has been obtained is substantially prevented, and the difference in thermal expansion coefficient between the substrate and the surface layer of the oxidized pin is prevented from being substantially prevented. Peeling, and increasing the strength of the partially molten intermediate layer. Hereinafter, the third invention of the present invention will be described. The mold for firing an electronic component according to the third invention of the present invention is formed of a base material, an intermediate layer, and a surface layer; the zirconia-calcium oxide alumina cerium oxide used in the past is used, or the cerium oxide is stabilized and oxidized by cerium oxide. chromium. The intermediate layer is not particularly limited, and a single layer of alumina or a partially melted intermediate layer of calcined chromia-calcium oxide alumina cerium oxide or a partially molten intermediate layer containing alumina oxidized calcium oxide may be used. The material of the base material of the mold for firing electronic parts according to the third invention, and the conventional -15- This paper scale applies the Chinese National Standard (CNS) A4 specification (21〇X: 297 mm) (Please read the notes on the back first) This page), τ

經濟部智慧財產局員工消費合作社印製 1286128 五、發明說明（14 ) 的同樣地’宜是使用例如氧化鋁系材料、氧化鋁莫來石系材料 '氧化鋁氧化鎂尖晶石系材料、氧化鋁莫來石蓳青石系材料、或其組合材料來做成。在此種基材上所形成的中間層或部分熔融中間層，係可以結合劑使1種或2種以上之金屬氧化物相互結合經高溫燒成而得。構成該中間層或部分熔融中間層之金屬氧化物，係爲氧化鋁（氧化鋁Al2〇3)、氧化銷（氧化鉻Zr2Ch)、氧化1乙（氧化銘Y2O3)、氧化鈣（氧化錦CaO )、氧化鎂（氧化鎂 MgO)、氧化緦（氧化緦S !：0)、及氧化鋁•氧化鎂尖晶石複合氧化物（Al2〇3 · MgO，以下稱爲「尖晶石氧化物」）。也可以從其中選出1或2種以上來做成。具體來說，理想上係爲氧化鋁單獨，或是氧化鋁與其他的金屬氧化物組合而成，例如氧化鉻氧化鈣氧化鋁氧化釔、氧化鋁-尖晶石氧化物、或氧化鋁-氧化鈣-氧化釔所組合的具有優異特性之中間層或部分熔融中間層；更且在單獨爲氧化鋁之場合下，則當與後述之表面層組合時可發現優異的特性。在使用一種以上之金屬氧化物之場合下，雖然並沒有特別限定其比例，使用1種金屬氧化物之含有量係超過90 重量％者時，使用2種以上金屬氧化物之混合物，其效果至少並沒有比較好。構成中間層或部分熔融中間層的金屬氧化物之粒徑並沒特別的限制，雖然以無規粒徑之金屬氧化物來構成中間層或部分熔融中間層較佳，但可以用粗粒子和微粒子混合而 -16- 1286128 A7 B7 五、發明説明（15 ) 成，例如，含有平均粒徑爲30〜500微米之粗粒子和平均粒徑爲0 . 1〜1 0微米之微粒子，藉由氣孔率大的粗粒子之金屬氧化物，而在中間層或部分熔融中間層上形成空隙，則會使得表面層與中間層或部分熔融中間層間、以及中間層或部分熔融中間層與基材間之熱膨脹係數之差，被吸收而和緩，也可在急熱急冷之反復熱循環之環境下使用，即使用使用比較長的時期亦不剝離。但是，以對應於中間層或部分熔融中間層之總量計，該粗粒子之量係在90重量％以下。經濟部智慧財產局員工消費合作社印製前述中間層係可藉由塗布-熱分解法、噴塗法及浸漬塗覆法，而形成在基材表面上。對於塗布-熱分解法，係將塗布在基材表面上之金屬硝酸鹽之金屬鹽溶液，藉由熱分解而將所對應的金屬氧化物被覆在基材表面上之方法。噴塗法係將有預定粒徑之金屬氧化物粒子懸浮之溶媒，將溶媒噴射在基材表面上，使飛散的金屬氧化物被覆於基材表面上之方法。又，浸漬塗布法，係將基材浸漬於含有溶解或懸浮金屬氧化物粒子之溶液中，使含有金屬氧化物之液層形成在基材表面上，使之乾燥除去溶媒而形成金屬氧化物層之方法。以塗布-熱分解法及浸漬塗覆法來生成的金屬氧化物粒子之粒徑並不易調節，理想上所期望的金屬氧化物之粒徑分布，係例如在以直接暖霧之噴塗法來形成由前述之粗粒子與微粒子所組成之金屬氧化物中間層時之預定的金屬氧 -17- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 1286128 A7 ___B7 五、發明説明（16 ) 化物粒徑。中間層或部分熔融中間層之厚度並沒特別的限制，僅由金屬氧化物微粒子來形成之場合，以10〜200微米較宜，其係依各製造方法中，在基材上之金屬或金屬化合物之噴霧量，或者是金屬或金屬化合物溶液之被覆量，以及所除去的溶媒量來考慮，而任意地來調節所形成的中間層或部分熔融中間層之厚度。當第3發明之電子零件燒成用工模之燒成溫度，係使用實際上高於電子零件之燒成溫度時，則可望其不會劣化。通常，由於電子零件之燒成溫度係爲1 200〜1 400°C，則中間層之燒成溫度較宜是在1 3 00〜1 600°C左右。又，中間層係可在氧化銷表面層形成後燒成，而更宜是與該氧化銷表面層之燒成同時進行，因而可減少此燒成工程之次數。在如此所形成的中間層或部分熔融中間層上，形成氧化锆表面層。該氧化锆表面層之構成物質，係可使用具氧化鉻氧化鈣氧化鋁氧化釔之複合氧化物，或者是氧化釔安定化之氧化銷。經濟部智慧財產局員工消費合作社印製由於表面層係直接與電子零件接觸，爲使不賦與電子零件不良的影響，從而理想上係使用經氧化釔、氧化鈣及氧化鎂等而部分安定化之氧化锆、或含有氧化锆之複合氧化物。氧化鉻在室溫下係爲單斜晶系，當溫度上昇時，雖然會引起單斜晶系—（〜117(TC )—正方晶系—（〜2370°C )— 立方晶系之相變化，但藉由在氧化鍩上之氧化釔或氧化鎂 -18- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 1286128 A7 _________B7___ 五、發明説明（17 ) 等之部分熔融結合材料（安定劑）之固溶，而使得高溫相之正方晶系或立方晶系可在室溫下安定化。前述表面層之製法，係爲與前述中間層同樣之塗布-熱分解法、噴塗法及浸漬塗覆法。在該表面層內之中間層爲氧化銷氧化鈣氧化鋁氧化釔之複合氧化物之場合下，雖然同樣地可以例如之塗布-熱分解法、噴塗法及浸漬塗覆法等來製造，但是也可以使用其他的方法。例如，以塗布-熱分解法，來製造時，較宜是將硝酸鉻硝酸鈣硝酸鋁硝酸釔溶解在水中而調製成金屬氧化物水溶液，將塗布&在基材表面上之水溶液，藉由熱分解而將所對應的金屬氧化物被覆而形成在基材表面上。氧化鉻氧化鈣氧化錦~氧化釔之混合比例，依其與電子零件反應性考量，氧化鉻理想上是在50%以上，而所含有的其他各種氧化物係在1〜50重量％較理想。經濟部智慧財產局員工消費合作社印製又，氧化釔安定化氧化銷之場合下，雖然是以無規粒徑之添加有少量的氧化釔之氧化鉻燒成形成來較佳，但可以用與前中間層同樣的粗粒子和微粒子混合而成，例如，共同存在有平均粒徑爲30〜500微米之粗粒子和平均粒徑爲 0 · 1〜1 0微米之微粒子，藉由氣孔率大的氧化锆粗粒子，而在表面層上形成空隙，則會使得與中間層或部分熔融中間層間、以及中間層或部分熔融中間層與基材間之熱膨脹係數之差，被吸收而和緩，也可在急熱急冷之反復熱循環之環境下使用，即使用使用比較長的時期亦不剝離。又在 -19- 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） 1286128 A7 B7 五、發明説明（18 ) 此場合下，該粗粒子之量係在總量之90重量％以下。如此所製造的第3發明之電子零件燒成用工模，由於係使用了具有與中間層或部分熔融從來都沒有的高密性之成分來做爲表面層’而使得其在剝離上具有強的而優良的長 •期耐久性。金屬氧化物所構成之中間層，在加熱燒成時，其中有一部分會熔融而成爲部分熔融中間層，部分熔融所形成之液相則會與氧化銷表面層和及基材兩者反應，因此顯著地改善了各層與基材間之密著力。換句話說，氧化銷表面層變得不會從基材剝離。又，當液相量過多時，因爲在液相固化之際收縮的膜或基材會變形，則理想上加熱條件應適切地設定。更且，由於部分熔融中間層係使用2種以上的金屬氧化物做成的，故藉由其他的金屬氧化物而補足了 1·種金屬氧化物差的燒結性，使得全體之燒結性向上而改善了部分熔融中間層之強度。又，由於使用2種金屬氧化物，其熔點係會比單一金屬氧化物（例如氧化鋁之熔點爲約2000°C )之場合來得低，故宜使用1 300〜1 600°C之燒成溫度而變得容易燒成了。經濟部智慧財產局員工消費合作社印製· 從而，達成了該向來僅僅有1種金屬氧化物所形成的中間層之電子零件燒成用工模，實質上所達不到之由於減少了基材與氧化銷表面層間之熱膨脹係數差異而防止其剝離。第3發明也包括僅由1種金屬氧化物所形成的中間層。在第3發明中所使用來做爲中間層的安定化氧化鉻，特 -20- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 1286128 A7 B7 五、發明説明（19 ) (請先閲讀背面之注意事項別是氧化釔安定化氧化鉻，向來係不單獨的使用親和力弱之其他金屬成分來做爲中間層成分，並意識到氧化鋁之強親和力之氧化鋁中間層、安定化氧化銷之表面層，而改善了電子零件燒成用工模之長期耐久性。更且，第3發明之實施例態樣之一，係爲部分熔融中 y間層及表面層β卩氧化锆氧化鈣氧化鋁氧化釔所成之一種電 ί i子零件燒成用工模，會使得部分熔融中間層及表面層組成 |爲同樣的兩層之親和性增加，密著性也增加，更且，在兩 j層間之兩層成分並不擴散而生成混合層，因而兩層間之密 \著性會增加。實施例、11 關於製造本發明之此電子零件燒成用材料或工模之實施例，雖然是如下之記載，但該實施例並不是用來限定本發明。實施例1Ministry of Economic Affairs, Intellectual Property Bureau, Staff and Consumer Cooperatives, Printing 1286128 V. Inventive Note (14) Similarly, it is preferable to use, for example, an alumina-based material, an alumina mullite-based material, an alumina magnesia spinel-based material, and oxidation. Made of aluminum mullite cordierite material or a combination thereof. The intermediate layer or the partially melted intermediate layer formed on such a substrate can be obtained by bonding one or two or more kinds of metal oxides to each other at a high temperature by a binder. The metal oxide constituting the intermediate layer or the partially melted intermediate layer is alumina (alumina Al2〇3), oxidation pin (chromium oxide Zr2Ch), oxidation 1 B (oxidized Y2O3), calcium oxide (oxidized bromine CaO) , magnesium oxide (magnesium oxide MgO), cerium oxide (cerium oxide S!: 0), and alumina/magnesia spinel composite oxide (Al2〇3 · MgO, hereinafter referred to as "spinel oxide") . It is also possible to select one or more of them. Specifically, it is desirably alumina alone or a combination of alumina and other metal oxides, such as chromia oxide, calcium oxide, aluminum oxide ruthenium oxide, alumina-spinel oxide, or aluminum oxide-oxidation. An intermediate layer or a partially molten intermediate layer having excellent characteristics in combination of calcium and cerium oxide; and in the case of alumina alone, excellent characteristics can be found when combined with a surface layer described later. When one or more kinds of metal oxides are used, the ratio is not particularly limited, and when the content of one type of metal oxide is more than 90% by weight, a mixture of two or more kinds of metal oxides is used, and the effect is at least Not quite good. The particle diameter of the metal oxide constituting the intermediate layer or the partially melted intermediate layer is not particularly limited, and although the intermediate layer or the partially melted intermediate layer is preferably composed of a metal oxide having a random particle diameter, coarse particles and fine particles may be used. Mixing and -16 - 1286128 A7 B7 5. Invention Description (15) For example, a coarse particle having an average particle diameter of 30 to 500 μm and a fine particle having an average particle diameter of 0.1 to 1 μm, by porosity Large metal oxide of coarse particles, and voids formed on the intermediate layer or partially molten intermediate layer, which causes thermal expansion between the surface layer and the intermediate layer or partially molten intermediate layer, and between the intermediate layer or a portion of the molten intermediate layer and the substrate. The difference between the coefficients is absorbed and gentle, and it can also be used in the environment of repeated thermal cycling of rapid heat and cold, that is, it is not peeled off during a relatively long period of use. However, the amount of the coarse particles is 90% by weight or less based on the total amount of the intermediate layer or the partially melted intermediate layer. Printed by the Intellectual Property Office of the Ministry of Economic Affairs, the Consumers' Cooperatives. The intermediate layer can be formed on the surface of the substrate by coating-thermal decomposition, spray coating and dip coating. For the coating-thermal decomposition method, a metal salt solution of a metal nitrate coated on the surface of a substrate is coated with a corresponding metal oxide on the surface of the substrate by thermal decomposition. The spray coating method is a method in which a metal oxide particle having a predetermined particle diameter is suspended, and a solvent is sprayed on the surface of the substrate to cover the surface of the substrate with the scattered metal oxide. Further, in the dip coating method, a substrate is immersed in a solution containing dissolved or suspended metal oxide particles, a liquid layer containing a metal oxide is formed on the surface of the substrate, and dried to remove a solvent to form a metal oxide layer. The method. The particle diameter of the metal oxide particles produced by the coating-thermal decomposition method and the dip coating method is not easily adjusted, and the particle size distribution of the desired metal oxide is desirably formed, for example, by a direct warm mist spraying method. The predetermined metal oxygen in the case of the metal oxide intermediate layer composed of the above-mentioned coarse particles and fine particles is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 1286128 A7 ___B7 V. Invention Description (16 The particle size of the compound. The thickness of the intermediate layer or the partially melted intermediate layer is not particularly limited, and is preferably formed by metal oxide fine particles, preferably 10 to 200 μm, depending on the metal or metal on the substrate in each manufacturing method. The thickness of the formed intermediate layer or partially molten intermediate layer is arbitrarily adjusted in consideration of the amount of the compound sprayed, or the amount of the metal or metal compound solution to be coated, and the amount of the solvent to be removed. When the firing temperature of the mold for firing an electronic component according to the third aspect of the invention is actually higher than the firing temperature of the electronic component, it is expected that the firing temperature is not deteriorated. Usually, since the firing temperature of the electronic component is 1 200 to 1 400 ° C, the firing temperature of the intermediate layer is preferably about 1 300 to 1 600 °C. Further, the intermediate layer can be fired after the surface layer of the oxidized pin is formed, and is preferably carried out simultaneously with the firing of the surface layer of the oxidized pin, so that the number of times of the firing process can be reduced. On the intermediate layer or partially melted intermediate layer thus formed, a zirconia surface layer is formed. The constituent material of the zirconia surface layer may be a composite oxide of chromia oxide, calcium oxide, aluminum oxide and cerium oxide, or an oxidized pin of cerium oxide. Printed by the Ministry of Economic Affairs, the Intellectual Property Bureau, the employee's consumer cooperative, because the surface layer is directly in contact with the electronic components, so that it is not affected by the adverse effects of the electronic components, so it is ideally stabilized by using yttria, calcium oxide and magnesium oxide. Zirconium oxide or a composite oxide containing zirconia. Chromium oxide is monoclinic at room temperature, and when the temperature rises, it will cause monoclinic system - (~117 (TC) - tetragonal system - (~2370 ° C) - cubic phase change However, by using yttrium oxide or yttrium oxide on yttrium oxide - this paper scale applies Chinese National Standard (CNS) A4 specification (210X297 mm) 1286128 A7 _________B7___ V. Inventive Note (17) The solid solution of the stabilizer (the stabilizer) allows the tetragonal system or the cubic system of the high temperature phase to be stabilized at room temperature. The surface layer is prepared by the same coating-thermal decomposition method and spray method as the intermediate layer. And the dip coating method. When the intermediate layer in the surface layer is a composite oxide of oxidized pin calcium oxide aluminum oxide cerium oxide, it can be similarly coated, for example, by thermal decomposition, spray coating, and dip coating. Other methods may be used. For example, when the coating-thermal decomposition method is used, it is preferred to dissolve the chromium nitrate calcium nitrate aluminum nitrate nitrate in water to prepare an aqueous metal oxide solution. And an aqueous solution on the surface of the substrate is formed by coating the corresponding metal oxide on the surface of the substrate by thermal decomposition. The mixing ratio of the oxidized chromium oxide to the oxidized cerium to cerium oxide is reacted with the electronic component. For the sake of consideration, the chromium oxide is ideally 50% or more, and the other various oxides contained in the system are preferably 1 to 50% by weight. The Ministry of Economic Affairs, the Intellectual Property Bureau, the employee consumption cooperative, and the oxidized yttrium In this case, it is preferable to form a chrome oxide having a small amount of cerium oxide added with a random particle diameter, but it may be formed by mixing coarse particles and fine particles similar to those of the front intermediate layer, for example, an average exists in common. The coarse particles having a particle diameter of 30 to 500 μm and the fine particles having an average particle diameter of 0·1 to 10 μm, and the coarse particles of zirconia having a large porosity, and voids formed on the surface layer, make the intermediate layer Or the difference between the thermal expansion coefficients of the partially melted intermediate layer and the intermediate layer or the partially melted intermediate layer and the substrate is absorbed and gentle, and can also be used in the environment of repeated thermal cycling of rapid heat and rapid cooling. That is, it will not be peeled off when it is used for a long period of time. It is also applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) at the -19- paper scale. 1286128 A7 B7 V. Invention Description (18) In this case, The amount of the coarse particles is 90% by weight or less based on the total amount. The mold for firing an electronic component according to the third aspect of the invention is manufactured by using a component having high density which is never in the middle layer or partially melted. It is a surface layer' which has strong and excellent long-term durability on the peeling. The intermediate layer composed of metal oxides, when heated and fired, some of them melt to become a partially melted intermediate layer, part of The liquid phase formed by the melting reacts with both the surface layer of the oxidation pin and the substrate, thereby significantly improving the adhesion between the layers and the substrate. In other words, the surface layer of the oxidized pin does not peel off from the substrate. Further, when the amount of the liquid phase is too large, since the film or the substrate which shrinks when the liquid phase is solidified is deformed, it is desirable that the heating condition should be appropriately set. Further, since the partially melted intermediate layer is made of two or more kinds of metal oxides, the sinterability of the one type of metal oxide is made up by the other metal oxides, so that the entire sinterability is upward. The strength of the partially molten intermediate layer is improved. Further, since two kinds of metal oxides are used, the melting point thereof is lower than that of a single metal oxide (for example, the melting point of alumina is about 2000 ° C), so the firing temperature of 1 300 to 1 600 ° C is preferably used. And it becomes easy to burn. Printed by the Ministry of Economic Affairs, the Intellectual Property Office, and the Consumer Cooperatives. In this way, the mold for the firing of electronic components, which has always been formed of only one type of metal oxide, has been achieved, which is substantially impossible to achieve due to the reduction of the substrate and The difference in thermal expansion coefficient between the surface layers of the oxidized pin prevents the peeling. The third invention also includes an intermediate layer formed of only one type of metal oxide. The stabilized chrome oxide used as the intermediate layer in the third invention, the special -20- paper scale applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) 1286128 A7 B7 V. Invention Description (19) ( Please read the note on the back first. Do not use yttrium oxide to stabilize the chrome oxide. It has always used other metal components with weak affinity as the intermediate layer component, and realized the strong affinity of alumina. The surface layer of the oxidized pin is used to improve the long-term durability of the mold for firing an electronic component. Further, one of the embodiments of the third invention is a partially melted y inter-layer and a surface layer of β-yttrium zirconia. Calcium oxide, aluminum oxide and yttrium oxide, which are used to form a part of the molten intermediate layer and the surface layer. The affinity of the same two layers is increased, and the adhesion is also increased. The two layers between the two layers do not diffuse to form a mixed layer, so that the adhesion between the two layers increases. Examples and 11 Examples of the material or mold for manufacturing the electronic component of the present invention Although the following is described, this embodiment is not intended to limit the invention.

經濟部智慧財產局員工消費合作社印製使用矽成分至高約1 〇重量％之氧化鋁莫來石基材來做爲基材。以平均粒徑爲約丨〇〇微米之氧化釔安定化之氧化锆來做爲粗粒氧化銷，以平均粒徑爲約5微米之氧化釔安定化之氧化銷來做爲微粒氧化鉻，以氧化釔（20莫耳％ )、氧化錦（22莫耳％)及氧化鈣（58莫耳％)所成之複合氧化物來做爲部分纟谷融結合材料，分別以製備成8 〇重量％、ί 〇重量 %及1 0重量％之比例。以球形硏磨機而均一混合之，加入含水及黏合劑到聚乙 -21 - 度適用中國國家標準（CNS ) A4規格（21QX297公董）一" '—" - 1286128 A7 B7 五、發明説明（20 ) 烯基醇使成爲漿液。將漿液噴塗在前述之基材表面上。得到厚度約爲100微米之氧化锆層。.在以100°C乾燥經噴塗的基材後，於1 4 0 0〜1 6 0 0 °C下保持2小時，以燒成之氧化鍩來製做電子零件燒成用材料。爲了調查該電子零件燒成用材料之氧化鉻層，對剝離及粉末化之耐性，則將該電子零件燒成用材料，以500°C開始到1 3 0 0 °C爲止急熱3小時，其次以1 3 0 〇 °c開始到5 0 0 °C 爲止急冷3小時之熱循環反復操作，調查一直到生成剝離及粉末化之熱循環次數，經過1 5 0次之熱循環仍不剝離及粉末化。此結果係示於表1中。 ’ (請先閱讀背面之注意事項舄本頁訂Printed by the Ministry of Economic Affairs, the Intellectual Property Office, and the Consumer Cooperatives. Use an alumina mullite substrate with a composition of up to about 1% by weight as the substrate. The zirconia stabilized zirconia having an average particle diameter of about 丨〇〇μm is used as a coarse-grained oxidized pin, and the oxidized pin of cerium oxide having an average particle diameter of about 5 μm is used as the particulate chromia. A composite oxide of cerium oxide (20 mol%), oxidized bromine (22 mol%) and calcium oxide (58 mol%) is used as a partial glutinous glutinous bond material, respectively, to prepare 8 〇 wt% , ί 重量% by weight and 10% by weight. Uniformly mixed with a spherical honing machine, adding water and binder to the polyethylene-21-degree. Applicable to China National Standard (CNS) A4 Specification (21QX297 Gongdong)-"'-" - 1286128 A7 B7 V. Invention Description (20) The alkenyl alcohol is made into a slurry. The slurry is sprayed onto the surface of the aforementioned substrate. A layer of zirconium oxide having a thickness of about 100 microns was obtained. After drying the sprayed substrate at 100 ° C, it was kept at 14,000 to 1 600 ° C for 2 hours to prepare a material for firing electronic parts by firing the ruthenium oxide. In order to investigate the resistance to peeling and pulverization of the chromium oxide layer of the material for firing the electronic component, the material for firing the electronic component is heated at 500 ° C for 1 hour at 1300 ° C. Next, the thermal cycle of quenching and cooling for 3 hours from 1 300 °C to 500 °C was repeated, and the number of thermal cycles of peeling and pulverization was investigated until the thermal cycle of 150 times was not peeled off. Powdered. This result is shown in Table 1. ’ (Please read the notes on the back 舄 this page

經濟部智慧財產局員工消費合作社印製 -22- 本紙張尺度適用中國國家標準（CNS )八4規格（210X297公釐） 1286128 A7 ___B7 五、發明説明（22 ) 實施例2〜1 3 依照表1所示者來變動粗粒氧化錯、微粒氧化锆之安定處理狀態之重量％、結合材料之重量％、及金屬氧化物之莫耳％ ’以和實施例1同樣的條件來製作電子零件燒成用材料。依次以和實施例1同樣的條件之熱循環，來反復操作實施例2〜1 3之各種材料，調查一直到生成剝離及粉末化之熱循環次數。此結果係通通示於表1中。表2 比較例粗粒、微粒之種類及重量％、結合材料之重量％結合材料 (莫耳％) 觀察到剝離粉末化之熱循環次數粗粒微粒結合材料 m AI2O3 CaO SrO Mg 0 1 Υ安定化 90 未安定化 10 0 _ —— — — — 在10次時剝離 2 未安定化 90 未安定化 10 0 _ — — — — 在1次時剝離 3 未安定化 60 未安定化 10 30 18 21 61 — — 在π次時剝離 4 未安定化 10 Υ安定化 10 30 _ 70 28 — 2 k 31次時剝離 5 未安定化 50 未安定化 10 40 — 25 30 45 — 膜熔融 6 未安定化 50 0 50 23 23 54 — 一膜熔融又，以X射線繞射法來觀察在實施例7〜1 0中所得到之電子零件燒成用材料之氧化锆層之結晶構造。在X射線繞射峰値中，觀察氧化锆之正方晶或立方晶所得到的峰値，可分辨出未安定氧化銷（單斜晶）係爲部分地安定化。 -24- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閱讀背面之注意事項\^寫本頁)Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing -22- This paper scale applies China National Standard (CNS) VIII 4 specifications (210X297 mm) 1286128 A7 ___B7 V. Invention description (22) Example 2~1 3 According to Table 1 The electronic component firing was performed under the same conditions as in Example 1 by changing the weight percent of the coarse particle oxidation oxidization, the weighting treatment state of the fine particle zirconia, the weight % of the bonding material, and the molar % of the metal oxide. Use materials. The materials of Examples 2 to 13 were repeatedly operated in the thermal cycle under the same conditions as in Example 1, and the number of thermal cycles until peeling and powdering were generated was investigated. The results are shown in Table 1. Table 2 Comparative examples of coarse particles, types and weight % of the particles, and weight % of the bonding materials. Binding materials (% by mole) The number of thermal cycles of the peeling powder was observed. The coarse particle bonding material m AI2O3 CaO SrO Mg 0 1 Υ 90 Unstabilized 10 0 _ —— — — — Stripping at 10 times 2 Unstabilized 90 Unstabilized 10 0 _ — — — — Stripping at 1 time 3 Unstabilized 60 Unstabilized 10 30 18 21 61 — — peeling at π times 4 unstabilized 10 Υ stability 10 30 _ 70 28 — 2 k 31 times peeling 5 unstabilized 50 unstabilized 10 40 — 25 30 45 — film melting 6 unstabilized 50 0 50 23 23 54 - A film was melted, and the crystal structure of the zirconium oxide layer of the material for firing an electronic component obtained in Examples 7 to 10 was observed by an X-ray diffraction method. In the X-ray diffraction peak, the peak obtained by the tetragonal or cubic crystal of zirconia was observed, and it was found that the unstabilized oxidation pin (monoclinic crystal) was partially stabilized. -24- This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) (Please read the notes on the back first\^Write this page)

、1T, 1T

經濟部智慧財產局員工消費合作社印製 1286128 五、發明說明（23) 比較例1 除了在部分熔融結合材料中不添加的成分，係以氧化|乙安定粗粒氧化銷替代以外，以和實施例1同樣的條件來製作電子零件燒成用材料，以和實施例i同樣的條件之熱循環來反復操作，調查一直到生成剝離及粉末化之熱循環次數。由表2所示，經反復操作1 〇次之熱循環，即可觀察到氧化鍩層之剝離。比較例2〜6 依照表2所示者來變動粗粒氧化銷、微粒氧化鉻之安定處理狀態之重量％、結合材料之重量％、及金屬氧化物之莫耳％，以和比較例1同樣的條件來製作電子零件燒成用材料。依次以和比較例1同樣的條件之熱循環，來反復操作比較例2〜6之各種材料，調查一直到生成剝離及粉末化之熱循環次數。此結果係通通示於表2中。相對於比較例 2〜4分別經反復操作1次、17次及31次之熱循環即剝離 ’在比較例5及6中於氧化鉻層剝前，氧化鉻層（氧化鉻膜）本身即先溶解了。由前述之實施例及比較例，可理解到經添加部分熔融結合材料之電子零件燒成用材料，對於熱循環之耐性會大幅地提高。該部分熔融結合材料之添加量，以部分熔融結合材料之總量計，理想上係爲3〜2 5重量％，在小於0重量％或超過30重量％之場合下，約300次以下之熱循環，即使侍氧化銷層剝離或溶融，可見其耐性不足。 -25- 1286128 A7 ___B7_ 五、發明説明（24 ) 實施例14 使用砍成分至高約1 0重量％之氧化錦莫來石基材來做爲基材。以球形硏磨機將各種微粒狀之氧化鋁（70重量％)、氧化鈣（28重量％)及氧化鎂（3重量％)均一混合，加入含有水及黏合劑之聚乙烯基醇。將漿液噴塗在前述之基材表面上。在以100°C乾燥經噴塗的基材後，得到厚度約爲100 微米之中間層。其次，在該中間層之表面上，噴塗以氧化釔（Y2〇3)安定化之氧化鍩層。在以100 °C乾燥經噴塗的基材後，得到厚度約爲100微米之表面層。於1 400〜1 600°C 下保持2小時，製做成以部分熔融中間層來變換前記之中間層之電子零件燒成用工模。爲了調查該電子零件燒成用工模之氧化鉻表面層、部分熔融中間層及基材之剝離性，則以電氣爐從500°C開始到 1 3 00°C爲止急熱3小時，其次以13 00°C開始到500°C爲止急冷3小時之熱循環反復操作，調查一直到生成剝離及粉末化之熱循環次數，結果，經過150次之熱循環仍不剝離及粉末化。此結果係示於表3中。經濟部智慧財產局員工消費合作社印製 -26- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 1286128 A7 B7 五、發明說明（25 ) 表3 實施例部分熔融中間層組成 (重量％) 氧化锆表面層之材質觀察到表面層/中間層/基材間之剝離前之熱循環次數 Al2〇3 Mg ΑΙΑ Ca〇 Mg 0 Y2〇3 Sr〇 14 70(0) 28 2 丫2〇3安定化Zr〇2 150次以上 15 70(40) 28 2 Y2〇3安定化Zr02 150次以上 16 70(80) 28 2 Y2〇3安定化Ζι·02 + 未安定化ΖιΌ2 150次以上 17 66(0) 30 4 Υ2〇3安定化Zr〇2 118次 18 69(0) 13 18 Y2〇3安定化ΖιΌ2 145次 19 55(0) 15(0) 30 ΥΛ安定化Ζι*〇2 107次 20 55(50) 15(20) 30 Υ2〇3安定化ΖΚ)2 121次 21 24(0) 63(0) 13 Υ2〇3部分安定化 Zr02 125次 22 24(0) 63(50) 13 Υ2〇3安定化ΖΚ)2 + 未安定化Zr02 103次 23 56(0) 23 21 Y2〇3 安定化 Ζι·02 + 未安定化ΖιΌ2 150次以上 24 56(60) 23 21 Υ2〇3安定化Zr02 + 未安定化Zr02 150次以上 25 54(0) 5 41 ΥΛ部分安定化 Ζΐ·〇2 120次 26 47(0) 53 Υ2〇3部分安定化 Zr02 103次 27 29(0) 19 52， Y2〇3安定化Zr〇2 115次 "T— — — — — — II a — — — — — — — — (請先閱讀背面之注意事1填寫本頁)Ministry of Economic Affairs, Intellectual Property Bureau, Staff and Consumers Co., Ltd. Printed 1286128 V. Inventive Note (23) Comparative Example 1 In addition to the component which is not added to the partially melted bonded material, it is replaced by the oxidized | (1) The material for firing electronic parts was produced under the same conditions, and the operation was repeated under the thermal cycle of the same conditions as in Example i, and the number of thermal cycles until peeling and powdering were generated was investigated. As shown in Table 2, the peeling of the ruthenium oxide layer was observed by repeated thermal cycles of 1 〇. Comparative Examples 2 to 6 The weight % of the stability treatment state of the coarse particle oxidation powder and the particulate chromium oxide, the weight % of the bonding material, and the molar % of the metal oxide were changed in the same manner as in Comparative Example 1 in accordance with Table 2 The conditions for the production of electronic parts firing materials. The materials of Comparative Examples 2 to 6 were repeatedly operated in the same thermal cycle as in Comparative Example 1, and the number of thermal cycles until peeling and powdering were generated was investigated. The results are shown in Table 2. The thermal cycle, that is, the peeling was repeated once, 17 times, and 31 times with respect to Comparative Examples 2 to 4, respectively. In Comparative Examples 5 and 6, the chromium oxide layer (chromium oxide film) itself was first before the chromium oxide layer was peeled off. Dissolved. From the foregoing examples and comparative examples, it is understood that the material for firing an electronic component to which a part of the molten composite material is added is greatly improved in resistance to thermal cycling. The amount of the partially melted bonding material added is preferably 3 to 25 wt% based on the total amount of the partially melted bonding material, and less than 0 wt% or more than 30 wt% in the case of less than 0 wt% or more. Cycling, even if the oxidized pin layer is peeled off or melted, it is seen that the resistance is insufficient. -25- 1286128 A7 ___B7_ V. INSTRUCTION DESCRIPTION (24) Example 14 An oxidized nylon mullite substrate having a chopping component up to about 10% by weight was used as a substrate. Various particulate alumina (70% by weight), calcium oxide (28% by weight), and magnesium oxide (3% by weight) were uniformly mixed by a ball honing machine, and polyvinyl alcohol containing water and a binder was added. The slurry is sprayed onto the surface of the aforementioned substrate. After drying the sprayed substrate at 100 ° C, an intermediate layer having a thickness of about 100 μm was obtained. Next, on the surface of the intermediate layer, a cerium oxide layer stabilized with yttrium oxide (Y2 〇 3) was sprayed. After drying the sprayed substrate at 100 ° C, a surface layer having a thickness of about 100 μm was obtained. It was kept at 1 400 to 1 600 ° C for 2 hours to prepare a mold for firing electronic parts in which the intermediate layer was previously melted by partially melting the intermediate layer. In order to investigate the peeling property of the chromium oxide surface layer, the partially melted intermediate layer, and the substrate of the mold for firing the electronic component, the electric furnace was heated from 500 ° C to 1 300 ° C for 3 hours, followed by 13 The heat cycle was started from 00 ° C to 500 ° C for 3 hours, and the heat cycle was repeated until the number of thermal cycles of peeling and powdering was investigated. As a result, the heat cycle was not peeled off and powdered after 150 cycles. This result is shown in Table 3. Printed by the Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperatives -26- This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) 1286128 A7 B7 V. Description of invention (25) Table 3 Example of partially melted intermediate layer composition ( % by weight) The material of the zirconia surface layer was observed before the peeling of the surface layer/intermediate layer/substrate. Al2〇3 Mg ΑΙΑ Ca〇Mg 0 Y2〇3 Sr〇14 70(0) 28 2 丫2 〇3 stabilized Zr〇2 150 times or more 15 70(40) 28 2 Y2〇3 stabilized Zr02 150 times or more 16 70(80) 28 2 Y2〇3 stabilized Ζι·02 + not stabilized ΖιΌ2 150 times or more 17 66(0) 30 4 Υ2〇3 stabilized Zr〇2 118 times 18 69(0) 13 18 Y2〇3 stabilized ΖιΌ2 145 times 19 55(0) 15(0) 30 ΥΛ安定化Ζι*〇2 107 times 20 55(50) 15(20) 30 Υ2〇3 stability ΖΚ) 2 121 times 21 24(0) 63(0) 13 Υ2〇3 part stabilization Zr02 125 times 22 24(0) 63(50) 13 Υ2 〇3 安定化ΖΚ)2 + Unstabilized Zr02 103 times 23 56(0) 23 21 Y2〇3 Stabilized Ζι·02 + Unstabilized ΖιΌ2 150 times or more 24 56(60) 23 21 Υ2〇3 Qualified Zr02 + Unstabilized Zr02 150 times or more 25 54 (0) 5 41 ΥΛ Partially stabilized Ζΐ · 〇 2 120 times 26 47 (0) 53 Υ 2 〇 3 parts stabilized Zr02 103 times 27 29 (0) 19 52 , Y2〇3 安定化Zr〇2 115次"T— — — — — II a — — — — — — — — (Please read the note on the back first)

經濟部智慧財產局員工消費合作社印製 A 1 203層及Mg A 1 204層中之括弧內之數字係爲粗粒之比例。實施例15〜27 (實施例15)除了以40重量％之粗粒子狀氧化鋁來做爲部分熔融中間層以外均與實施例1 4相同；又（實施例1 6 )除了以80重量％之粗粒子狀氧化鋁來做爲部分熔融中間層’ -27- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1286128 A7 B7 五、發明説明（26) 以及以氧化IS女疋化氧化錯和未安定化氧化銷之混合物來做爲氧化鉻表面層之材質以外均與實施例1相同；又（實施例1 7 )除了氧化鉻、氧化鈣及氧化鎂之重量％、分別是 6 6重量％、30重量％及4重量％以外均與實施例1相同；又 •(實施例1 8 )除了氧化锆、氧化鈣及氧化鎂之重量％、分別是69重量％、1 3重量％及1 8重量％以外均與實施例1相同，而製做出電子零件燒成用工模。經濟部智慧財產局員工消費合作社印製更且，（實施例1 9 )除了使用尖晶石氧化物（a 12〇3 · Mg A 1 204或者是Mg A 1 204 )來代替氧化鎂，氧化鋁、尖晶石氧化物及氧化鈣之重量％、分別是55重量％、15重量％及30 重量％以外均與實施例1相同；又（實施例20)除了氧化鋁及尖晶石氧化物之粗粒子比例分別是50%及20%以外均與實施例1 9相同；又（實施例2 1 )除了氧化鋁、尖晶石氧化物及氧化鈣之重量％、分別是24重量％、63重量％及13重量％，而且以氧化釔部分安定化之氧化銷來做爲氧化鉻表 ..面層之材質外均與實施例1相同；又（實施例22 )除了氧化鋁及尖晶石氧化物之粗粒子比例分別是50%及20%，以及以氧化纟乙安定化氧化锆和未安定化氧化锆之混合物來做爲氧化锆表面層之材質與實施例21相同；而製做出電子零件燒成用工模。 (實施例23)除了除了使用氧化釔來代替尖晶石氧化物，氧化鋁、氧化鈣及氧化鎂之重量％、分別是56重量％、23 重量％及2 1重量％以外，以及以氧化釔安定化氧化鉻和未 -28- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 1286128 A7 B7 五、發明説明（27 ) 安定化氧化鉻之混合物來做爲氧化鍩表面層之材質與實施例1 4相同；又（實施例2 4 )除了部.分熔融中間層之粗粒子狀氧化鋁爲60重量％以外均與實施例23相同；又（實施例 25 )除了氧化鋁、氧化鈣及氧化釔之重量％、分別是54重量％、5重量％及4 1重量％以外均與實施例1 4相同；而製做出電子零件燒成用工模。 (實施例26)除了使用47重量％之氧化鋁及53重量％之氧化緦來做爲部分熔融中間層以外，均與實施例26相同；又（實施例27)除了使用29重量％之氧化鋁、19重量％氧化鈣及52重量％之氧化緦來做爲部分熔融中間層以外，均與實施例1 4相同；而製做出電子零件燒成用工模。使用與實施例1相同之熱循環，來對實施例15〜27所製做之含有部分熔融中間層之電子零件燒成用工模進行。調查各實施例之電子零件燒成用工模一直到生成剝離之熱循環次數。將此結果示於表3中。經濟部智慧財產局員工消費合作社印製由表3中，可理解到在（實施例1 4〜1 8 )部分熔融中間層係由氧化鋁-氧化鈣-莫來石，及（實施例23〜25)氧化鋁-氧化鈣-氧化釔所成之場合下，電子零件燒成用工模之耐剝離慌特別良好，除此以外之其他的組合之場合，其耐熱循環也在100次以上。又可理解到在（實施例19及20) 部分熔融中間層之構成氧化物，其一部分係爲粗粒子狀做成時，耐剝離性下會向上增加。比較例8〜1 2 -29- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 1286128 A7 B7 五、發明説明（28 ) (請先閱讀背面之注意事項 (比較例8 )除了以1 00%之氧化鋁來做爲相當於部分熔融中間層之單一中間層以外均與實施例1 4相同；又（比較例 9 )除了以7 0重量％之粗粒子狀氧化鋁來做成以外均與比較例8相同；又（比較例1 0 )除了以氧化釔安定化之氧化銷和未女疋化之氧化銷之混合物來做爲氧化銷表面層之材質以外均與比較例9相同，而製做出電子零件燒成用工模。調查各比較例中具有中間層之電子零件燒成用工模一直到生成剝離之熱循環次數。將此結果示於表4中。由表4，可理解到在中間層爲單一氧化物或尖晶石氧化物時，耐不住未滿50次之熱循環。表4 比較例中間ϋ (重: ί組成匱％) 氧化锆表面層之材質觀察到表面層/中間層/基材間之剝離前之熱循環次數 A 1 2〇3 Mg Al2〇4 8 100(0) Y2〇3安定化Zr02 16次 9 100(70) Y2〇3安定化Zr02 + 未安定化Ζι·〇2 47次 10 100(70) Υ2〇3安定化Zr〇2 24次 11 100(0) Y2〇3安定化Zr02 5次 12 100(50) Y2〇3安定化Zr02 21次實施例28 訂 .^1. 經濟部智慧財產局員工消費合作社印製使用矽成分至高約1 0重量％之氧化鋁莫來石基材來做爲基材。以球形硏磨機將各種微粒狀之氧化鉻（7重量％)、氧化鈣（25重量％)、氧化鋁（50重量％)及氧化釔（18重量％)混合’加入含有水及黏合劑之聚乙烯基醇使成爲漿液。將漿 -30- 本紙張ϋ適用中國國家標準（CNS ) A4規格（210X297公釐） 1286128 A7 B7 _ 五、發明説明（29 ) 液噴塗在前述之基材表面上。在以1 0 〇 °c乾燥經噴塗的基材後，所得到之中間層厚度約爲1 00微米。其次，在該中間層之表面上，噴塗以球形硏磨機將各種粗粒狀之氧化锆 (70重量％)、微粒狀之氧化銷（15重量％)、氧化鈣（8重量％) 、氧化鋁（4重量％)及氧化釔（3重量％)混合之混合物。在以100°C乾燥經噴塗的基材後，得到厚度約爲100微米之氧化锆氧化鈣氧化鋁氧化釔表面層。將此積層體於 1 400〜1 600°C下保持2小時，製做成以部分熔融中間層來變換前記之中間層之電子零件燒成用工模。爲了調查該電子零件燒成用工模之氧化銷表面層、部分熔融中間層及基材之剝離性，則以電氣爐從500°C開始到 1 300°C爲止急熱3小時，其次以1 300°C開始到500°C爲止急冷3小時之熱循環反復操作，調查一直到生成剝離及粉末化之熱循環次數，結果，經過150次之熱循環仍不剝離及粉末化。此結果係示於表5中。實施例29〜32 經濟部智慧財產局員工消費合作社印製 (實施例29)除了以單一微粒子氧化鋁來做爲中間層以外均與實施例28相同地製做出電子零件燒成用工模；更且（實施例30)除了以微粒子氧化鋁（75重量％)、氧化鈣（23重量％)、氧化鎂（2重量％)之混合物來做爲部分熔融中間層以外均與實施例28相同地製做出電子零件燒成用工模；又（實施例3 1 )除了以單一微粒子狀氧化釔安定化氧化銷來做爲中間層及表面層以外均與實施例28相同地製做出電 -31 - 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 1286128 A7 B7 五、發明説明（3〇 ) 子零件燒成用工模；又（實施例32)除了以氧化鋁（60重量 % )、氧化鈣（5重量％ )、氧化釔（3 5重量％ )之混合物來做爲中間層以外均與實施例28相同地製做出電子零件燒成用工模。中間層或部分熔融中間層之厚度分別爲1 50微米（實施例29)、150微米（實施例30)、50微米（實施例31)及100 微米（實施例3 2 )。爲了調查該電子零件燒成用工模之氧化鉻表面層、部分熔融中間層及基材之剝離性，則與實施例28同樣地，來反復操作急熱及冷，調查一直到生成剝離及粉末化之熱循環次數，結果，經過1 50次之熱循環仍不剝離。此結果係示於表5中。比較例1 3 除了以由氧化鍩氧化鈣氧化鋁氧化釔來代替氧化釔安定化氧化锆而做爲表面層以外，均與實施例2 9相同地製做出電子零件燒成用工模。該中間層及表面層之厚度，分別爲150微米及200微米。爲了調查該電子零件燒成用工模之氧化锆表面層、部分熔融中間層及基材之剝離性，則與實施例28同樣地條件下，來反復操作急熱及冷，調查一直到生成剝離及粉末化之熱循環次數。結果，在經過1 6次熱循環之階段時，會生成剝離。之後則不能使用。此結果係不於表5中。 -32- 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） (請先閱讀背面之注意事項寫本頁) 衣· \^^寫太The figures in the brackets in the A 1 203 and Mg A 1 204 layers are the ratio of coarse particles in the Intellectual Property Office of the Ministry of Economic Affairs. Examples 15 to 27 (Example 15) were the same as Example 14 except that 40% by weight of the coarse particulate alumina was used as the partially melted intermediate layer; again (Example 16) except 80% by weight Coarse particulate alumina as a partially melted intermediate layer' -27- This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1286128 A7 B7 V. Invention description (26) and oxidation IS female The mixture of deuterated oxidized and unstabilized oxidized pins is the same as that of Example 1 except as the material of the chromium oxide surface layer; (Example 17) except for the weight % of chromium oxide, calcium oxide and magnesium oxide, respectively 6 6 wt%, 30 wt%, and 4 wt% are the same as in Example 1; and (Example 18) except for the weight % of zirconia, calcium oxide, and magnesium oxide, respectively, 69 wt%, 13 The molds for firing electronic parts were prepared in the same manner as in Example 1 except for % by weight and 18% by weight. Printed by the Ministry of Economic Affairs, the Intellectual Property Office, and the Consumer Cooperatives. (Example 19) In addition to using spinel oxide (a 12〇3 · Mg A 1 204 or Mg A 1 204 ) instead of magnesium oxide, alumina The weight % of the spinel oxide and the calcium oxide are the same as those of the first embodiment except that they are 55 wt%, 15 wt%, and 30 wt%, respectively; and (Example 20) except alumina and spinel oxide The ratio of the coarse particles was 50% and 20%, respectively, which were the same as those of Example 19; and (Example 2 1) except for the weight % of alumina, spinel oxide and calcium oxide, respectively, 24% by weight, 63% by weight % and 13% by weight, and the oxidized pin which is stabilized by yttrium oxide is used as the oxidized chromium table. The material of the surface layer is the same as that of the first embodiment; and (Example 22) except for the oxidation of alumina and spinel The ratio of the coarse particles of the material is 50% and 20%, respectively, and the mixture of yttrium oxide yttria and unstabilized zirconia is used as the material of the zirconia surface layer as in the case of Example 21; A tool for firing parts. (Example 23) except that cerium oxide was used in place of the spinel oxide, and the weight % of alumina, calcium oxide, and magnesium oxide were 56% by weight, 23% by weight, and 21% by weight, respectively, and cerium oxide. Stabilized chrome oxide and not -28- This paper scale applies to China National Standard (CNS) A4 specification (210X 297 mm) 1286128 A7 B7 V. Description of invention (27) A mixture of stabilized chrome oxide as the yttrium oxide surface layer The material was the same as that of Example 14; and (Example 24) was the same as Example 23 except that the coarse-grained alumina of the portion of the molten intermediate layer was 60% by weight; and (Example 25) except alumina The weight % of calcium oxide and cerium oxide were the same as those of Example 14 except that they were 54% by weight, 5% by weight, and 41% by weight, respectively, and a mold for firing electronic parts was prepared. (Example 26) The same as Example 26 except that 47% by weight of alumina and 53% by weight of cerium oxide were used as the partially melted intermediate layer; (Example 27) except that 29% by weight of alumina was used. 19% by weight of calcium oxide and 52% by weight of cerium oxide were used as the partially melted intermediate layer, and were the same as in Example 14; and a mold for firing electronic parts was prepared. The electronic component firing molds containing the partially melted intermediate layers prepared in Examples 15 to 27 were subjected to the same thermal cycle as in Example 1. The number of thermal cycles for the firing of the electronic parts of the respective examples was investigated until the peeling was performed. The results are shown in Table 3. Printed by the Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperatives from Table 3, it can be understood that in the (Examples 14 to 18) partially melted intermediate layer is composed of alumina-calcium oxide-mullite, and (Example 23~ 25) In the case where alumina-calcium oxide-cerium oxide is formed, the mold for firing an electronic component is particularly excellent in peeling resistance, and in the case of other combinations, the heat-resistant cycle is also 100 or more. Further, it can be understood that when the constituent oxides of the intermediate layer are partially melted in (Examples 19 and 20), a part of them is formed into a coarse particle shape, and the peeling resistance is increased upward. Comparative Example 8~1 2 -29- This paper scale applies to Chinese National Standard (CNS) A4 specification (210X297 mm) 1286128 A7 B7 V. Invention description (28) (Please read the note on the back (Comparative Example 8) except The same as in Example 14 except that 100% of alumina was used as a single intermediate layer corresponding to the partially melted intermediate layer; (Comparative Example 9) was prepared by using 70% by weight of coarse particulate alumina. The same as in Comparative Example 8 except that (Comparative Example 10) was the same as Comparative Example 9 except that the mixture of the oxidized pin which was stabilized by yttrium oxide and the oxidized pin which was not decidated was used as the material of the surface layer of the oxidized pin. A mold for firing an electronic component was prepared. The number of thermal cycles of the electronic component firing mold having the intermediate layer in each comparative example was investigated until the peeling was generated. The results are shown in Table 4. It is understood that when the intermediate layer is a single oxide or spinel oxide, it can not withstand the thermal cycle less than 50 times. Table 4 Comparative Example Intermediate ϋ (heavy: ί composition 匮%) The material of the zirconia surface layer is observed Peeling between surface layer/intermediate layer/substrate The number of thermal cycles A 1 2〇3 Mg Al2〇4 8 100(0) Y2〇3 stabilization Zr02 16 times 9 100(70) Y2〇3 stabilization Zr02 + unsteady Ζι·〇2 47 times 10 100 ( 70) Υ2〇3 安定化Zr〇2 24 times 11 100(0) Y2〇3 安定化Zr02 5 times 12 100(50) Y2〇3 安定化Zr02 21次例28 订.^1. Ministry of Economics intellectual property The Bureau of Employees' Consumer Cooperatives uses an alumina mullite substrate with a composition of up to about 10% by weight as a substrate. Various particulate chromic oxides (7% by weight) and calcium oxide (25 weights) are used in a spherical honing machine. %), Alumina (50% by weight) and cerium oxide (18% by weight) mixed 'Add a polyvinyl alcohol containing water and a binder to make a slurry. Apply -30 - This paper to Chinese National Standard (CNS) A4 size (210X297 mm) 1286128 A7 B7 _ V. INSTRUCTION DESCRIPTION (29) The liquid is sprayed on the surface of the aforementioned substrate. After drying the sprayed substrate at 10 ° C, the thickness of the intermediate layer is about It is 100 μm. Secondly, on the surface of the intermediate layer, various coarse-grained zirconia (70% by weight) is sprayed by a spherical honing machine. a mixture of particulate oxidation pins (15% by weight), calcium oxide (8% by weight), alumina (4% by weight) and cerium oxide (3% by weight). After drying the sprayed substrate at 100 ° C A surface layer of zirconia oxidized calcium oxide yttria having a thickness of about 100 μm is obtained. The laminate is held at 1 400 to 1 600 ° C for 2 hours to form a partially melted intermediate layer to change the intermediate layer of the former The mold for firing electronic parts. In order to investigate the peeling property of the surface of the oxidized pin, the partially melted intermediate layer, and the substrate of the mold for firing the electronic component, the electric furnace was heated from 500 ° C to 1 300 ° C for 3 hours, followed by 1 300. The temperature cycle of the rapid cooling for 3 hours from the start of °C to 500 °C was repeated, and the number of thermal cycles of peeling and powdering was investigated until the peeling and powdering were repeated. As a result, the heat cycle was not peeled off and powdered after 150 cycles. This result is shown in Table 5. Example 29 to 32 Printing by the Ministry of Economic Affairs, Intellectual Property Office, Employees' Consumer Cooperatives (Example 29) A mold for firing electronic parts was produced in the same manner as in Example 28 except that a single fine particle alumina was used as the intermediate layer. Further, (Example 30) was produced in the same manner as in Example 28 except that a mixture of finely divided alumina (75% by weight), calcium oxide (23% by weight), and magnesium oxide (2% by weight) was used as the partially melted intermediate layer. A mold for firing an electronic component was prepared; and (Example 31), except that the single-particulate yttria stabilized oxidation pin was used as the intermediate layer and the surface layer, the same method as in Example 28 was made. This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) 1286128 A7 B7 V. Invention description (3〇) Sub-part firing mold; again (Example 32) except alumina (60% by weight) A mold for firing an electronic component was produced in the same manner as in Example 28 except that a mixture of calcium oxide (5% by weight) and cerium oxide (35 wt%) was used as the intermediate layer. The thickness of the intermediate layer or partially molten intermediate layer was 150 microns (Example 29), 150 microns (Example 30), 50 microns (Example 31) and 100 microns (Example 3 2), respectively. In order to investigate the peeling property of the chromium oxide surface layer, the partially molten intermediate layer, and the substrate of the mold for firing the electronic component, the heat and cold were repeatedly repeated in the same manner as in Example 28, and investigation was carried out until peeling and powdering were performed. The number of thermal cycles, as a result, did not peel off after 150 cycles of thermal cycling. This result is shown in Table 5. Comparative Example 1 3 A mold for firing an electronic component was produced in the same manner as in Example 29 except that the yttrium oxide lanthanum oxide yttrium oxide was used instead of the yttria-stabilized zirconia as the surface layer. The thickness of the intermediate layer and the surface layer are 150 μm and 200 μm, respectively. In order to investigate the peeling property of the zirconia surface layer, the partially melted intermediate layer, and the substrate of the mold for firing the electronic component, the heat and cold were repeatedly operated under the same conditions as in Example 28, and investigation was carried out until peeling occurred. The number of thermal cycles of powdering. As a result, peeling occurs at the stage of 16 thermal cycles. After that, it cannot be used. This result is not in Table 5. -32- This paper size is applicable to China National Standard (CNS) Α4 specification (210Χ297 mm) (Please read the note on the back first to write this page) Clothing · \^^ Write too

，1T 經濟部智慧財產局員工消費合作社印製 1286128 經濟部智慧財產局員工消費合作社印製_ A7 B7 五、發明説明（31 ) 表5 實施例比較例中間層或部分熔融中間層表面層觀察到表面層/ 部分熔融中間層 /基材間之剝離前之熱循環次數 28 氧化锆氧化鈣氧化鋁氧化釔氧化锆氧化鈣氧化鋁氧化釔 150次以上 29 氧化鋁氧化锆氧化鈣氧化鋁氧化釔 150次以上 30 氧化鋁氧化鈣氧化鎂氧化锆氧化鈣氧化鋁氧化釔 150次以上 31 氧化紀安定化氧化銘氧化釔安定化氧化鋁 150次以上 32 氧化鋁氧化鈣氧化釔氧化紀安定化氧化鋁 150次以上 13 氧化鋁氧化記安定化氧化鋁 16次 -33- (請先閲讀背面之注意事項寫本頁) 衣. ^^寫太、?τ •辛本紙張尺度適用中國國家標準（CNS ) Α4規格（210><297公釐）, 1T Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 1286128 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing _ A7 B7 V. Invention Description (31) Table 5 Example Comparative Example Intermediate layer or partially molten intermediate layer surface layer observed Number of thermal cycles before surface layer/partially melted intermediate layer/substrate peeling 28 Zirconia Calcium Oxide Alumina Oxide Oxide Zirconia Calcium Oxide Alumina Oxide 150 times or more 29 Alumina Zirconia Calcium Oxide Alumina Oxide 150 More than 30 times, calcium oxide, magnesia, magnesia, zirconia, calcium oxide, alumina, yttrium oxide, 150 times or more, 31, oxidized, oxidized, oxidized, cerium oxide, stabilized alumina, 150 times or more, 32, alumina, calcium oxide, cerium oxide, oxidized, oxidized, alumina, 150 More than 13 times of alumina oxidation stabilized alumina 16 times -33- (please read the note on the back to write this page) Clothing. ^^Write too, ?τ • Xin Ben paper scale applies to China National Standard (CNS) Α 4 Specifications (210 >< 297 mm)

Claims

1286128

Sixth, the scope of application for patents

Patent No. 90101615 "Materials and Dies for Burning Electronic Parts" (Amended on April 9, 2007) VI. Scope of Application: 1. A material for firing electronic parts, characterized by being coated on the surface of a substrate. a chromium oxide layer formed by a combination of partially melted bonding materials formed by a metal oxide of coarse-grained chromium oxide having an average particle diameter of 30 to 500 μm; wherein the partially melted bonding material is composed of auto-ruthenium oxide, calcium oxide, and magnesium oxide. And the metal oxide and the alumina selected from the total of the oxidation total; and the ratio of the partially molten bonded material is 3 to 25 wt% based on the total amount of the chromium oxide and the partially molten bonded material. 2. A material for firing an electronic component, characterized by coating a substrate with a coarse-grained chromium oxide having an average particle diameter of 30 to 500 μm and an average particle diameter of 0 · 1 to 1 0 a chromium oxide layer formed by partially melting a bonding material formed by a metal oxide of a micron particle oxidation pin; wherein the partially melted bonding material is one or more selected from the group consisting of cerium oxide, calcium oxide, magnesium oxide, and cerium oxide. Jinli Oxide and Oxidation Ming; the weight ratio of coarse particle oxidation pin, (particulate chromium oxide and partially melted bonding material) is from 80:20 to 20:80; partial fusion bonding material pair (coarse chromium oxide + particle) The weight ratio of the chromium oxide + partially melted bonding material is 3% by weight or more and 25% by weight or less. (3) A mold for firing an electronic component, characterized by comprising a substrate, a partially melted intermediate layer formed by coating two or more kinds of metal oxides on a surface of a substrate of the patent application: Forming a chromium oxide surface layer on the intermediate layer; the method comprises a coarse particle having an average particle diameter of 30 to 500 μm and a fine particle having an average particle diameter of 0.1 to 1.0 μm; wherein the metal oxide forming the partially melted intermediate layer a metal oxide selected from the group consisting of alumina, chromia, cerium oxide, calcium oxide, magnesium oxide, cerium oxide, and alumina/magnesia spinel composite oxide; The content of the metal oxide is 90% or less; and the amount of the coarse particles is less than 90% by weight relative to the total weight of the partially molten intermediate layer -