200927701 九、發明說明： 【發明所屬之技術領域】 本發明係關⑥一種以陶究基板為主的陶曼成形體之製造 方法，詳細而δ，係關於一種在被燒成體上配設有拘束 層，且經過一面抑制被燒成體於平面方向之收縮一面進行 鍛燒之所謂拘束锻燒之步驟而製造的陶竟基板等之陶竟成 形體之製造方法。 【先前技術】 ® 於陶瓷電子零件中’對於要求較高的平面尺寸精度之陶 究基板等，锻燒步驟中的平面方向之锻燒收縮及該收縮之 不均等會對產品之品質造成較大影響。 因此#為一面抑制上述煅燒步驟中之收縮一面煅燒陶 究成形體之方法，提出有如下的锻燒方法：例如，如圖4 所不在陶究成形體51之兩主面上，在形成有以陶究成形 體w之锻燒溫度下實質上不燒結的氧化銘等之難燒結性材 Ο ;為要成刀的層（拘束層）52a、5213之狀態下進行般燒（拘 束烺燒）藉此，實質上能夠以不產生平面方向之煅燒收 縮之方式進行煅燒（參照專利文獻丨）。 ‘ ι &上述先前之锻燒方法中’為提高拘束層所發揮 拘束力’必須使難燒結性材料之粒徑較小。然而，在使 2徑較小後，由於基材層與拘束層被？固地黏接，故锻燒 2難以去除拘束層，從而具有對基材層表面及電極造成損 1題{列如’在製造已謀求陶瓷層或電極層之薄層 、多層化之多層陶究基板時，於拘束層之去除步驟中， 134679.doc 200927701 具有於基板上產生破裂或者電極剝離之問題。 [專利文獻1]日本專利特開平4 243978號公報 【發明内容】 [發明所欲解決之問題] • 本發明係解決上述問題者’其目的在於提供-種陶瓷成 ㈣之製造方法’於炮燒步驟結束後，可容易去除拘束 層’因此不會在去除拘束層之步驟中對被燒成體造成損 ϋ彳確實且面效地製造尺寸精度高的陶究成形體。 ^ [解決問題之技術手段] 為解決上述問題，本t請案請求項以㈣成形體之製 造方法的特徵在於包括：積層體製作步驟，其係製作未燒 成積層體者，該未燒成積層體具備基材層及拘束層，上述 基材層含有陶究粉末與玻璃射斗，上述拘束層I有：在低 氧環境下進行锻燒後不會燒失、但在使氧分壓相較上述低 氧環境變高而進行烺燒後會燒失的燒失材料，以及在上述 e 基材層之燒結溫度下不燒結的陶瓷粉末；且該拘束層係配 置成與上述基材層之至少一方之主面相接觸； 煅燒步驟，將上述未燒成積層體進行炮燒以使上述基材 層燒結；以及 去除上述拘束層之步驟； 上述锻燒步驟包括： 第1鍛燒步驟’在上述低氧環境下，在具備上述拘束層 之狀態下進行锻燒以使上述基材層燒結；及 第2鍛燒步驟，在使氧分壓比上述第！锻燒步驟高的條件 134679.doc 200927701 下進行緞燒，以使構成上述拘束層之上述燒失材料燒失。 又，請求項2之陶瓷成形體之製造方法中，上述陶瓷成 形體為陶瓷基板。 又，請求項3之陶瓷成形體之製造方法中，於上述第1煅 • 燒步驟中，以讓上述基材層中所含有之上述玻璃材料浸透 到上述拘束層之方式進行煅燒。 又，請求項4之陶瓷成形體之製造方法中，上述燒失材 ❹ 料之粒徑比上述拘束層中含有的陶瓷粉末之粒徑大。 又，請求項5之陶瓷成形體之製造方法中，上述燒失材 料為碳粉末。 又，請求項6之陶瓷成形體之製造方法中，上述拘束層 中所含有之陶瓷粉末係與上述基材層中所含有之陶瓷粉末 為相同材質。 又，請求項7之陶瓷成形體之製造方法包括脫黏合劑步 驟，其係於上述煅燒步驟中的上述第Ϊ煅燒步驟之前，將 Φ 上述基材層中含有之上述黏合劑去除；上述脫黏合劑步驟 二在3氧％境中、且上述燒失材料不會燒失之溫度下實 施。 °月求項8之陶瓷成形體之製造方法中，於上述積層 製作步驟中，上述拘束層係藉由以成使含有上述燒失材 料及上述陶-吏粉末之片材與上述基材層之至少一方之主面 相接觸之方式配置而形成。 吻求項9之陶瓷成形體之製造方法中，於上述積層 體製作步驗4^ 节’上述拘束層係藉由將含有上述燒失材料及 134679.doc 200927701 上述陶瓷粉末之膏塗布於上述基材層之至少一方之主面上 而形成。 又，請求項ίο之陶瓷成形體之製造方法中，上述基材層 具有複數層構造’該複數層構造具備複數個含有上述陶竟 粉末與上述玻璃材料之層。 又，請求項11之陶瓷成形體之製造方法中，上述基材層 於至少一方之主面上具備配線圖案。 又’請求項12之陶瓷成形體之製造方法進一步包括於經 上述鍛燒步輝鍛燒後之基材層之外表面上安裝電子零件之 步驟。 [發明之效果] 本申請案請求項1之陶瓷成形體之製造方法中，作為拘 束層，使用的是含有以下成分之拘束層，即，在低氧環境 下進行烺燒後不會燒失、但在氧分壓相較該低氧環境變高 而進打煅燒後會燒失的燒失材料；以及在基材層之燒結溫 ❿ 度下不燒結之陶瓷粉末，故於第1煅燒步驟中，在燒失材 料不會燒失之低氧環境下進行拘束煅燒，且在使基材層不 會於平面方向收縮而進行燒結後，於第2緞燒步驟中在 氧刀壓比第1煅燒步驟高的條件下進行煅燒，使構成拘束 層之燒失材料燒失，藉此可在拘束層中之燒失材料已燒失 的部分產生微孔，從而成為容易去除拘束層之狀態。其結 果為，可使用對被燒成體造成破裂或缺損等損害之虞較少 的穩定的方法’來有效地去除拘束層。 據本發明，無需複雜的製造步驟即能夠以較佳 134679.doc 200927701 的良率製造尺寸精度高的陶瓷成形體。 再者，於本發明之陶瓷成形體之製造方法中，於第1 燒步驟（拘束锻燒步驟）中，拘束層對基材層發揮抑制其於 平面方向（與主面平行的方向）之收縮之拘束力。而且，於 • 豸拘束力之作用下’基材層於平面方向上的燒結收縮受以 _ :被燒成體實質上僅於厚度方向上燒結收縮，從而可 確實製造平面方向之尺寸精度高的陶竟成形體。 ❹ 又，於本發明中，所謂低氧環境，係指與大氣等相比氧 分f相當低的環境，具體而言，例示於常壓下氧分壓為 10 atm程度以下（即，環境中之氧濃度為1 vol%程度以下） 之環境β A ’ 作為該低氧環境之更佳的條件，例示有例如於常壓下氧 分壓為1〇.3〜1〇-6 atm(氧濃度為0〗〜〇 0001 v〇l⑹之條件。 又，第2煅燒步驟中之所謂氧分壓比第〗煅燒步驟高的條 件，係指可使上述燒失材料燃燒且燒失的氧分壓之環境， 參具體而言，例示於常壓下氧分壓為1〇·, atm以上（即，環境 中之乳濃度為1 0 vol%以上）之環境。 又，如請求項2,本發明在陶瓷成形體中，尤其在應用 於期望平面方向之尺寸精度及形狀精度較高的陶瓷基板之 製造方法時，為較佳的發明，使用本發明可有效地製造尺 寸精度高的陶瓷基板。 又’對於請求項3之陶瓷成形體之製造方法，於第1烺燒 步驟中，基材層中含有之玻璃材料會浸透到拘束層而形成 浸透層。然後，經由該浸透層將拘束層與基材層牢固地接 134679.doc 200927701 合’且於該浸透層之作用 中的基材層於平面方向之收缩實抑制、防止第1鍛燒步驟 :者，為更確實地獲得拘束力’較理想的是基材層之 =材料確實浸透到拘束層中。並且，因此較理想的是， 拘束層以密著於基材層之方式而配設。 ❹ =如請求項4之《成形體之製造方法，使燒失材料 粒徑比拘束層中所含有的陶究粉末之粒徑大，藉此，在 Z拘束層與僅由陶究粉末及黏合劑所構成的先前之情況相 ^可減少拘束層中含有的有機黏合劑之量，從而容易進 行脫黏合劑。 又，於請求項5之陶竟成形體之製造方法中，用作燒失 材料之碳粉末在第！鍛燒步驟中，於低氧分壓環境下進行 =燒後並不燃燒，且亦不收縮’故充分發揮對基材層之锻 燒收縮之抑制功能’又，在第2煅燒步驟中，於氧分壓較 兩的條件下進行烺燒後’燃燒且燒失，故可在以殘留之陶 竞作為主成分的拘束層中形成微孔，從而使拘束層易崩潰 而成為谷易去除之狀態。又’藉由適切地選擇碳粉末之粒 僅，在使拘束層㈣錄末之粒徑較小時，亦可抑制 層之構成材料全體的平均比表面積之增大，從而可減少所 使用的有機黏合劑之量。 再者，作為碳粉末，較理想的是使用粒徑為丨〜5 之範 圍者。此原因在於’當粒徑超過5㈣時，拘束力不充分， 即’當粒徑在5 μιη以下時’可獲得較大之拘束力，又，藉 由使粒徑為1 pm以上，可防止於第！煅燒步驟中燒失，另 134679.doc 200927701 一方面’可確保第2锻燒步驟中之燒失容易度。 又，如請求項6，作為 與基材層中含有之陶:粉末使用 材層向拘束層容易、,^ _者，藉此玻璃從基 易浸透，從而可使拘束力提高。 步請求項7之陶究成形體之製造方法中，於第遣燒 :=;脫!合劑步驟係在含氧環境中，且上述燒失材 所人 之槪度下實施，因此可順利地實施將基材層中 二有之黏合劑確實去除、其後進行拘束烺燒之第i锻燒 ’以及使構成拘束層之燒失材料燒失之第2烺燒步 0 再者’所謂進行脫黏合劑步驟時之含氧環境，例示有大 氣環k、於惰性氣體中導入有大氣之環境等。通常，在大 氣袁境之類的氧分壓高的條件下實施時，可有效地進行脫 黏合劑。 又於本發a月巾，作為形成拘束層之方法，列舉如下方 © ^如請求項8,預先製作含有燒失材料及㈣粉末之片 材’並二與基材層之至少―方之主面相接觸之方式而配 置，如請求項9,將含有燒失材料及陶瓷粉末之膏塗布於 基材層之至少一方之主面上等。藉由使用該等方法，可於 基材層之至少一方之主面上有效地配設拘束層。 、 再者，為確實獲得拘束力，如上所述較理想的是，以使 基材層之玻璃材料確實浸透到拘束層而形成浸透層之方 式，將拘束層密著於基材層。並且，因此較理想的是例 如，在將複數片的拘束層用片材積層而形成拘束層時使 134679.doc 11 200927701 複數片的拘束層用片材於基材層上一面壓接一面積層而形 成拘束層，或者在塗布拘束層用资而形成拘束層時，施加 固定之壓力以使拘束層用膏一面密著於基材層上一面進行 塗布。 又，如請求項ίο之陶瓷成形體之製造方法，將基材層設 為複數層構造，藉此可有效地製造以平面形狀精度優異之 陶究基板為主的各種陶竞成形體。 又，於請求項11之陶瓷成形體之製造方法中，於基材層 之至少-方之主面上形成有配線圖案，故藉由使用以該方 法所製造之陶瓷成形體，如請求項12，可將電子零件安裝 於經煅燒步驟緞燒後之基材層上，從而可有效地製造以具 有於外表面上搭載有電子零件之構造之陶究基板為主的陶 瓷成形體。 【實施方式】200927701 IX. Description of the Invention: [Technical Field] The present invention relates to a method for manufacturing a Tauman shaped body mainly based on a ceramic substrate, and in detail, δ, relating to a method of being disposed on a fired body A method for producing a ceramic molded body such as a ceramic substrate which is produced by a step of restraining the calcination while suppressing the shrinkage of the fired body in the planar direction. [Prior Art] ® In ceramic electronic parts 'For ceramic substrates requiring high dimensional accuracy, the calcination shrinkage in the plane direction during the calcining step and the unevenness of the shrinkage will cause a large deterioration in the quality of the product. influences. Therefore, # is a method of calcining a ceramic molded body while suppressing the shrinkage in the calcination step, and the following calcining method is proposed: for example, as shown in Fig. 4, the two main faces of the ceramic molded body 51 are not formed, In the state of the ceramics (the restraint layer) 52a, 5213, the sinter is not sintered, and the sinter is not sintered. Therefore, it is possible to perform calcination in such a manner that it does not cause calcination shrinkage in the planar direction (see Patent Document). In the above-mentioned prior calcining method, the binding force of the restraint layer is required to make the particle size of the hardly sinterable material small. However, after making the 2 diameter smaller, is the substrate layer and the restraint layer? Solid-bonding, so calcination 2 is difficult to remove the restraint layer, thus causing damage to the surface of the substrate layer and the electrode 1 column [column] in the manufacture of a ceramic layer or electrode layer thin layer, multi-layered multilayer ceramics In the case of the substrate, in the removal step of the restraint layer, 134679.doc 200927701 has a problem of cracking or electrode peeling on the substrate. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 4 243 978. [Invention] [The problem to be solved by the invention] The present invention is directed to solving the above problems, and the object of the invention is to provide a method for producing ceramics (four) After the completion of the step, the restraint layer can be easily removed. Therefore, in the step of removing the restraint layer, the cast body is not damaged, and the ceramic molded article having high dimensional accuracy is produced. [Technical means for solving the problem] In order to solve the above problem, the method for producing a molded article of the present invention is characterized in that the method for producing a molded body includes a step of producing a laminated body, which is an unfired laminate, which is not fired. The laminate includes a base layer and a restraint layer, and the base layer contains a ceramic powder and a glass jet, and the restraint layer I does not burn out after calcination in a low oxygen atmosphere, but the oxygen partial pressure phase a burn-in material that is burned out after being calcined, and a ceramic powder that is not sintered at a sintering temperature of the e-substrate layer; and the restraint layer is disposed to be in contact with the substrate layer At least one of the main faces is in contact with each other; a calcination step of calcining the unfired laminate to sinter the substrate layer; and removing the restraining layer; the calcining step comprising: the first calcining step In a low-oxygen environment, calcination is performed in a state in which the above-mentioned restraint layer is provided to sinter the base material layer; and in the second calcination step, the oxygen partial pressure is made to be higher than the above-mentioned first! The condition of high calcination step 134679.doc 200927701 Satin burning is performed to burn out the above-mentioned loss-generating material constituting the above-mentioned restraint layer. Further, in the method of producing a ceramic formed body according to claim 2, the ceramic formed body is a ceramic substrate. Further, in the method of producing a ceramic formed body according to claim 3, in the first calcining step, the glass material contained in the base material layer is impregnated into the restraint layer. Further, in the method for producing a ceramic formed body according to claim 4, the particle size of the burn-in material is larger than the particle diameter of the ceramic powder contained in the restraint layer. Further, in the method of producing a ceramic formed body according to claim 5, the burn-in material is carbon powder. Further, in the method of producing a ceramic formed body according to claim 6, the ceramic powder contained in the restraint layer is made of the same material as the ceramic powder contained in the base material layer. Further, the method for producing a ceramic formed body according to claim 7 includes a debonding step of removing the above-mentioned binder contained in the base material layer before the second calcination step in the calcination step; the debonding described above The second step of the agent is carried out at a temperature of 3% oxygen and at a temperature at which the burn-in material does not burn out. In the method for producing a ceramic molded body according to the item 8, in the step of fabricating the layer, the restraining layer is formed by forming a sheet containing the burn-in material and the ceramic-ceramic powder and the substrate layer. At least one of the main faces is arranged to be in contact with each other. In the method for producing a ceramic molded body of the above-mentioned item 9, in the above-mentioned laminated body production step 4, the above-mentioned restraint layer is applied to the base by applying a paste containing the above-mentioned burn-in material and 134679.doc 200927701 It is formed on the main surface of at least one of the material layers. Further, in the method of producing a ceramic molded body of the invention, the base material layer has a plurality of layers. The plurality of layers have a plurality of layers containing the ceramic powder and the glass material. Further, in the method of producing a ceramic molded body according to claim 11, the base material layer has a wiring pattern on at least one of the main surfaces. Further, the method of producing a ceramic formed body of claim 12, further comprising the step of mounting an electronic component on the outer surface of the base material layer after the calcining step. [Effect of the Invention] In the method for producing a ceramic formed article according to the first aspect of the present invention, the restraining layer is a restraining layer containing a component which does not burn out after being calcined in a low-oxygen environment. However, in the first calcination step, the gas-burning material which is higher in oxygen partial pressure than in the low-oxygen environment and burned out after calcination; and the ceramic powder which is not sintered at the sintering temperature of the substrate layer, After the sintering is performed in a low-oxygen environment in which the loss-loss material does not burn out, and the base material layer is not shrunk in the planar direction and sintered, the second soda burning step is performed at the oxygen knife pressure ratio to the first calcination. The calcination is carried out under the high-step conditions, and the loss-generating material constituting the restraint layer is burned out, whereby micropores can be generated in the portion where the loss-loss material in the restraint layer has been burnt, and the restraint layer can be easily removed. As a result, it is possible to effectively remove the restraint layer by using a stable method which causes less damage such as cracks or defects in the fired body. According to the present invention, a ceramic molded body having high dimensional accuracy can be produced at a yield of preferably 134679.doc 200927701 without complicated manufacturing steps. Further, in the method for producing a ceramic molded body of the present invention, in the first firing step (constrained calcination step), the restraining layer exhibits shrinkage of the base material layer in the planar direction (direction parallel to the main surface). Binding power. Moreover, under the action of the restraint force, the sintering shrinkage of the base material layer in the plane direction is _: the fired body is substantially sintered and shrunk only in the thickness direction, so that the dimensional accuracy of the plane direction can be surely produced. Pottery formed a body. In the present invention, the hypoxic environment refers to an environment in which the oxygen fraction f is relatively low compared with the atmosphere, and specifically, the oxygen partial pressure is less than or equal to 10 atm under normal pressure (that is, in the environment). The environment β A ' is preferably a condition of the oxygen concentration of 1 vol% or less. For example, the oxygen partial pressure at normal pressure is 1 〇.3 〜1 〇 -6 atm (oxygen concentration). The condition of 0 to 〇0001 v〇l (6). The condition that the so-called oxygen partial pressure in the second calcination step is higher than the first calcination step means the partial pressure of oxygen which can burn and lose the above-mentioned loss-generating material. The environment, as exemplified, is an environment in which the partial pressure of oxygen is 1 〇·, atm or more (that is, the concentration of milk in the environment is 10 vol% or more) under normal pressure. Further, as in the claim 2, the present invention In the ceramic molded body, in particular, when it is applied to a method of manufacturing a ceramic substrate having a desired dimensional accuracy and shape accuracy in a planar direction, it is preferable to use the present invention to efficiently produce a ceramic substrate having high dimensional accuracy. For the method of manufacturing the ceramic formed body of claim 3, in the first calcining step The glass material contained in the substrate layer is impregnated into the restraining layer to form a permeation layer. Then, the restraining layer and the substrate layer are firmly adhered through the impregnating layer, and in the function of the impregnating layer. The shrinkage of the base material layer in the planar direction is suppressed, and the first calcination step is prevented. In order to obtain the restraining force more reliably, it is preferable that the material of the base material layer is surely impregnated into the restraint layer. The restraining layer is disposed in such a manner as to adhere to the substrate layer. ❹ = The method for producing a molded body according to claim 4, wherein the particle size of the loss-generating material is larger than that of the ceramic powder contained in the restraining layer. By making the diameter large, it is possible to reduce the amount of the organic binder contained in the restraining layer in the Z-constrained layer and the previous case consisting only of the ceramic powder and the binder, thereby facilitating the debonding agent. In the method for producing a ceramic molded body according to claim 5, the carbon powder used as the loss-generating material is subjected to a low-oxygen partial pressure environment in the first calcining step, and does not burn after burning, and does not shrink. Therefore, give full play to the calcination shrinkage of the substrate layer In the second calcination step, in the second calcination step, after the calcination is carried out under two conditions of oxygen partial pressure, the mixture is burned and burned out, so that micropores can be formed in the restraint layer containing the residual pottery as a main component. Therefore, the restraint layer is easily collapsed and becomes the state of removal of the valley. In addition, by appropriately selecting the particles of the carbon powder, only when the particle size of the binding layer (4) is small, the constituent materials of the layer can be suppressed. The average specific surface area is increased to reduce the amount of the organic binder used. Further, as the carbon powder, it is preferred to use a particle size of 丨~5. When it exceeds 5 (four), the binding force is insufficient, that is, 'when the particle size is 5 μm or less', a large binding force can be obtained, and by making the particle size 1 pm or more, it can be prevented! In the calcination step, the loss of burning, the other 134679.doc 200927701 on the one side can ensure the ease of burning loss in the second calcination step. Further, in the case of the request item 6, it is easy to adhere to the barrier layer in the ceramic material layer to be contained in the base material layer, whereby the glass is easily impregnated from the base, and the restraining force can be improved. In the method for producing a ceramic molded body according to the seventh aspect of the invention, the step of removing the mixture is carried out in an oxygen-containing environment, and the burnt-loss material is carried out under the enthalpy of the above, so that the method can be smoothly carried out. The second layer of the binder in the substrate layer is removed, and then the i-th calcination of the constrained simmering is performed, and the second smoldering step 0 which burns out the loss-generating material constituting the restraint layer is further described as "de-bonding" The oxygen-containing environment at the time of the agent step is exemplified by an atmosphere ring k, an atmosphere in which an atmosphere is introduced into an inert gas, or the like. In general, when it is carried out under conditions of high partial pressure of oxygen such as atmospheric conditions, the debonding agent can be effectively carried out. Further, in the present invention, as a method of forming a restraint layer, the following method is given: ^. As claimed in claim 8, a sheet containing a burn-in material and (4) a powder is prepared in advance, and at least a part of the substrate layer is formed. In the case where the surface is in contact with each other, as in the case of claim 9, a paste containing a loss-generating material and a ceramic powder is applied onto at least one of the main surfaces of the base material layer. By using these methods, the restraining layer can be effectively disposed on at least one of the main surfaces of the base material layer. Further, in order to obtain binding force as desired, it is preferable to adhere the barrier layer to the base material layer so that the glass material of the base material layer is surely impregnated into the restraining layer to form the impregnation layer. Further, it is preferable that, for example, when a plurality of layers of the restraint layer are laminated to form a restraint layer, the sheet for the restraint layer of the plurality of sheets of 134679.doc 11 200927701 is pressed against the substrate layer by one surface layer. When a restraint layer is formed or a restraint layer is formed by applying a restraint layer, a pressure is applied to apply the paste layer to the base material layer while adhering to the base layer. Further, in the method for producing a ceramic molded body of the present invention, the base material layer has a plurality of layers, whereby various ceramic bodies mainly composed of ceramic substrates excellent in planar shape accuracy can be efficiently produced. Further, in the method for producing a ceramic formed body according to claim 11, the wiring pattern is formed on at least the main surface of the base material layer, and therefore, the ceramic molded body produced by the method is used, as in claim 12 The electronic component can be mounted on the base material layer after the satin burning in the calcination step, whereby the ceramic molded body mainly composed of the ceramic substrate having the structure on which the electronic component is mounted on the outer surface can be efficiently manufactured. [Embodiment]
以下，顯示本發明之實施例 更詳細的說明。 對本發明之特徵部分進行 (1)含有陶瓷粉末及玻璃材料之基材層之製作 為形成作為構成陶瓷基板之主要部分的基材層首先， 向由陶瓷粉末及玻璃材料混合後之混合粉末中，分別、商 添加黏合劑、分散劑、可塑劑及有機溶劑等，並將該=、、 合，由此製作陶瓷漿料。 展 但作為較好的材料之一 亦可係於锻燒步驟中析 作為陶究粉末，可使用各種者， 例’列舉氧化鋁（ai2o3)粉末。 玻璃材料最初可含有玻璃粉末， 134679.doc 12 200927701 出玻璃質者。又’上述玻璃材料亦可係於煅燒步驟之至少 最終階段使結晶質析出並藉此結晶化者。作為玻璃材料， 例如’可用利地使用使得矽酸鎂石、鎂黃長石或透輝石之 類的介電損失小的結晶質析出而獲得之硼矽酸玻璃系之玻 璃粉末。 其次，將該陶瓷漿料以刮刀成形法等之方法而成形為薄 片狀，製作基材層用之胚片（基板用陶瓷胚片）la(圖3)。再 者’更具體而言，將作為玻璃粉末的以Ca〇 : 1〇〜55 Wt%、Si02 : 45〜70 wt%、Al2〇3 : 〇〜30 wt%、雜質：〇〜1〇 wt%、B2〇3: 5〜20 wt%之比例所含有之組成之玻璃粉末（平 均粒徑為15 μ„〇50〜64 wt%，與作為陶究粉末的Ai2〇3粉末 (平均粒徑為1.0 μηι)35〜5〇 wt%進行混合，並使該混合物分 散到由有機溶劑、可塑劑等所組成之有機媒劑中，以調製 漿料。然後將該漿料以刮刀成形法或堯轉法而成形為片材 參 狀’由此製作基板用陶究胚片。再者，作為陶究粉末之 Α1ζ〇3粉末，亦可係含有〇〜1〇 wt%之雜質者。 :，基板(基材層)通常係藉由將複數塊陶究胚片積層而 較好的Γ亦可由一塊陶究胚片構成。x，基板用陶竟胚片 較好的疋以上W材成形法所形成之料 ::膜印刷法所形成之未燒結之厚膜印刷層心= 二L述絕緣邀材料之外，還可使用鐵氧體等之磁= 材科、鈦酸鋇等之電介質材料。 又，作為基板用陶瓷胚片，較妊 之溫卢谁純4 較好的是使用以1050t以下 又進仃燒口之低溫燒結陶瓷胚片。 並且，因此較理想 134679.doc -33- 200927701 的是’上述玻璃粉末使用具有750°C以下之軟化點者為。 (2)拘束層 於本發明之陶瓷成形體之製造方法中，拘束層必須具備 如下2個性質： U)在直至構成基材層之低溫燒結陶瓷材料燒結為止之期 間，即，於低氧環境下進行煅燒之第丨煅燒步驟中，發揮 對抑制基材層之收縮的拘束層本來之功能； ❹ ❹ (b)於其後之氧分壓比第丨緞燒步驟高的條件下進行煅燒 之第2煅燒步驟中燒失。 作為具備上述性質之拘束層，本發明中使用的是含有於 絲環境下進行㈣後不會燒失、但在使氧分壓相較該低 氧環境變高而進行緞燒後會燒失的燒失材料、以及在基材 層之燒結溫度下不燒結之陶瓷粉末作為主要成分者。 作為該拘束層之-較佳例，例示如下：含有碳粉末來作 述燒失材料、且含有氧化鋁粉末來作為於基材層之燒 結溫度下不燒結之陶究粉末者。具體而言，使於上述基板 用陶竟胚片之炮燒溫度下實質上不燒結之氧化銘粉末等之 瓷粕末及碳粉末之混合粉末，分散到由有機黏合劑、有 機冷劑T塑劑等所組成之有機媒劑令來調製聚料，並將 所獲得之襞料成形為片材狀，以製作拘束層用陶究胚片， 再根據需要將此積層而形成拘束層。 氧化紹粉末係容易€得性狀及特性穩定之粉末，於基材 層之燒結溫度下不燒結，具備作為發揮拘束力之陶竟^末 之理想的條件。再者，使用有氧化㈣末及碳粉末之拘束 134679.doc 14 200927701 層用陶瓷胚片之燒結溫度為"〇〇〜16〇〇。。，於基板用陶瓷 胚片之燒結溫度下實質上不燒結。另外，該拘束層亦可由 上述的一塊拘束層用陶究胜片而構成，還可藉由將複數塊 拘束層用陶瓷胚片積層而構成。 作為陶究粉末，較好的是使用平均粒徑為(Μ〜5·〇 μηι 者m粉末之平均粒縣滿o.i㈣，料與作為基材 層之陶兗層之表層近傍所含有的玻璃在烺燒中進行激烈反 ❹應’並在煅燒後陶瓷層與拘東層密著，從而煅燒後無法去 除拘束層，或者因為小粒徑而導致片材中之黏合劑等之有 機成分於锻燒步驟中難以分解飛散，從而有時會於基材層 中產生分層（de—)。另—方面，若陶兗粉末之平均 粒徑超過5·0 μηι ’則锻燒收縮之抑制力下降，從而基材層 容易多餘地進行於平面方向(xy方向)之收縮或者弯曲。 再者，構成拘束層d是粉末可為在基材層之锻燒步驟 =實質上不燒結之陶聽末，且除氧化銘以外亦可使用 〇 &化錯或氧化鎮等各種陶究粉末。其中，因為基材層之表 層區域上存在有較多的玻璃，故基材層與拘束層具有某種 程度之親和性’在基材層之表層與拘束層相接觸之邊境 i ’較理想的是基材層表層之玻璃適度地漢濕拘束層。並 且目此較好的是，使用與構成基材層之陶究粉末同類之 陶竟粉末來作為構成拘束層之陶曼粉末。 又’作為燒失材料之碳粉末即便於A氣中其燃燒速度亦 緩慢，且不會在氧分壓之作用下於基材層之锻燒溫度域中 消失，故可用作無收縮煅燒用之拘束層材料。因此，碳粉 134679.doc 15 200927701 末在烺燒步驟中直至基材層收縮結束之時刻為止（即，直 至第！烺燒步驟結束為止）的期間不會燒失，而是維持拘束 功能，在收縮結束後可燃燒、消失。而且，藉由使碳粉末 燃燒且消失，可在以殘留之陶曼為主要成分之拘束層中產 生微孔’從而使拘束層易崩潰而成為容易去除之狀態。 & ’藉由適當地選擇碳粉末之粒徑’從而即便使拘束層用 之陶瓷粉末之粒徑較小時’亦可抑制平均比表面積之择 λ，由此可㈣作為拘束層之構成㈣全體的平均比^ ^ 積之增大。 並且，因此碳粉末使用相較拘束層中所使用之氧化銘等 之陶竟粉末之粒徑更大者，且較好的是使用粒徑為2〜2〇 μπι之範圍者。當碳粉末之粒徑比μ粉末之粒徑小、且 在未滿2㈣時，與僅由㈣粉末及黏合劑而構成拘束層之 先前之情況（未含有碳粉末之情況）相比，所使用的有機黏 合劑之量變多，脫黏合劑步驟所需之時間變長，且碳粉末 ❹ <比表面積變大’於基材層收縮結束之前燃燒、消失，由 此導致拘束力下降而不佳。又，當碳粉末之粒徑超過20 μπι時’拘束層之表面平滑性變差，其凹凸被轉印到基材 層(基板)之表面’故不佳。又，拘束層中之碳粉末之比例 較好的是設為10〜50 νο1%之範圍。此原因在於，若碳粉末 之比例少於10 νο1%，則容易去除拘束層之效果較小若 碳粉末之比例多於50 νο1%，則煅燒步驟中之拘束力 降。 即，拘束層之基本的拘束力係藉由粒徑較小的氧化銘粉 134679.doc 16- 200927701 末等之陶£粉末而確保’另—方面’碳粉末在直至基材層 收縮、纟》束為止之期間係作為無機材料而存在於拘束層中， 直至收縮結束時，拘束層被細敏地保持，因而不存在拘束 力之下降而且’藉由收縮結束後使碳燒失，從而於拘束 層中產生有微孔，因此在陶聽末使用粒徑較小者之情況 下，炮燒後之拘束層亦成為多孔而容易去除。又，藉由使 用粒徑比㈣粉末大的碳粉末，使得平均比表面積變小， 故即便在使用粒徑較小之H粉末時，亦可減小所使用的 有機黏合劑之1 2 ’從而使得脫黏合劑步驟快速結束。 — 拘束層之厚度較好的是25〜500 μιη。此原因在於， 若厚度未滿25 μηΐ，則煅燒收縮之抑制力變小，基板會於 平面方向㈣方向)發生必要以上之收縮或者弯曲，又，若 厚又超過500 μιη ’則基板用陶兗胚片中之黏合劑等之有機 成分難以在煅燒中分解、飛散，從而會出現於基板中產生 分層等之問題。 ❹ •17· 1 關於形成於基材層上之導體及使用於其之導電材料 於基材層上，在未燒成之階段形成有通料體、通孔導 、作為外料體及㈣㈣之導體圖㈣， =之導電材料，較好的是使用以低電阻難氧化性材料之 亦：：料(例如，Ag)為主成分者。但是，作為導電材料， 。用其他材料，例如，亦可使用Ag-Pd、Au、Pt等。 2 又’當與陶瓷之接合強度成為必要時 中添—之添加物1種以上。而且，向上：主= (導電材料)中，以特定之比例添加有機媒劑，並攪拌二 I34679.doc 200927701 練’由此製作導體性膏，使用該導體性膏可形成通孔導 體、通孔導體、作為外部導體及内部導體之導體圖案等。 其中，構成導電性膏之主成分、添加成分、有機媒劑等之 種類及調配比例並無特別限制。 又’有機媒劑係混合黏合劑樹脂與溶劑者，作為黏合劑 樹脂，可使用例如乙基纖維素、丙烯酸樹脂、聚乙烯醇縮 丁酿、甲基丙稀酸樹脂等。又，作為溶劑’可使用例如松 /由醇一虱权油醇、二氫松油醇醋酸醋（dihydroterpineol acetate)、丁基卡必醇、丁基卡必醇醋酸酯、醇類等。進 而，根據需要，亦可添加各種分散劑、可塑劑、活性劑 等。 又’考慮到印刷性’導體性膏之黏度較理想的是設為 50〜700 Pa 進而，於基材層表面之導體圖案上，亦包 3用以將上下層間之導體圖案彼此連接之通孔導體及通孔 導體等之貫通導體於表面所露出之部分。該等貫通導體可 由以下方法而形成，即，將上述膏經印刷而埋入到以沖 孔加工等方法形成於破璃陶究胚片上之貫通孔中。 (4)脫黏合劑步驟 脫^劑步驟通常係藉由於大氣中從室溫升溫至黏合劑 分解或燃燒溫度為纟，並保㈣料間而實施。例如j 大氣中1室溫升溫至赠，並保持 進 行脫黏合劑。 ^此了進 再者’於本發明之陶究成形體之製造 步驟係在大氣中等之4〜s T脫黏合劑 氧刀壓㈣環境中進行，其在取得高 I34679.doc 200927701 效率方面較理想，但是，亦 逸耔朌私人 隹乳刀壓比大軋低的條件下 =仃脫黏合劑，而且根據情況，還可在氧分壓相較 常低的低氧環境下進行。 (5)煅燒條件 (a)第1煅燒步驟係藉由在脫黏合劑步驟後導入氮，使美 材層之燒結溫度例如從4〇〇°c升溫至95〇〇c而進行。 於本發明中，所謂第1緞燒步驟中的低氧環境 分壓比大氣低的環境，但特別當使氧分壓為1〇-3 時，拘束層中之碳粉末等之燒失材料不會燒失， 束基材層，故較佳。 Ο ❹ ’係指氧 atm 可確實拘 (b)第2煅燒步驟係在氧分壓比第i煅燒步驟高的條件下 實施’使拘束層中之燒失材料燒m提高其後的拘束 層之去除性。 例如，在第丨煅燒步驟結束後，導入大氣，並於常壓 下，在氧分壓為0.21 atm、95CTC之條件下保持1〇分鐘以 使拘束層中之碳燒失。 再者，第1煅燒步驟與第2煅燒步驟可在如上所述相同之 煅燒溫度下實施，但亦可使第1煅燒步驟與第2煅燒步驟中 之溫度不同。又，第1煅燒步驟與第2煅燒步驟可連續進 行’另外，亦可在第丨椴燒步驟進行之後，暫時從爐中取 出’然後再次放入爐中並進行第2煅燒步驟。 以下顯示本發明之實施例’對本發明之特徵部分進行更 詳細的說明。 [實施例1] 134679.doc •19- 200927701 圖1係表示藉由本發明實施例（實施例1)之陶瓷基板之製 造方法所製造的陶瓷基板（多層陶瓷基板）之示圖，圖2係表 示於圖1之陶瓷基板上搭載有安裝零件之狀態之示圖，圖3 係表示於製造圖1及圖2之陶瓷基板之步驟中所製作的具備 拘束層之未燒成積層體之示圖。 圖1所不之陶瓷基板A具備：將含有陶瓷粉末及玻璃材料 之低/ΙΕ·燒結陶究原料組合物锻燒而成之絕緣性陶瓷層1、 ❹ 以及配設於該絕緣性陶瓷層1上之導體部2 ^再者，該實施 例1之陶瓷基板A成為具有積層有複數層絕緣性陶瓷層1之 複數層構造之多層基板。 作為構成絕緣性陶瓷層1之低溫燒結陶瓷組合物，使用 的疋將氧化鋁系之陶瓷粉末及硼矽酸玻璃系之玻璃粉末調 配而成之低溫燒結陶瓷組合物。 又，導體部2係由以下部分構成：位於陶瓷基板a之表面 上的表面導體（外部導體）21 ;配設於相互接合之複數個絕 Φ 緣性陶瓷層1、1之間的層間導體（内部導體）22、以及將層 間導體22彼此或者表面導體21與層間導體22加以連接的通 孔導體23。 表面導體2 1、層間導體22係藉由將以印刷的方式形成有 導電性膏(例如，銀系導電性膏)之外部導體膜及内部導體 膜進行炮燒而形成。又，通孔導體23例如係藉由向貫通孔 中填充導電性膏及導體粉末並進行锻燒而形成。 /又’搭载有圖2之電子零件的陶瓷基板(多層陶瓷基板译 係藉由於圖1之陶兗基板（多層陶兗基板）A上酉己設半導體元 134679.doc •20- 200927701 件及晶片電容器等之安裝電子零件3a、3b而形成。 其次，對該多層陶瓷基板A及B之製造方法加以說明。 以下’一面參照圖1至圖3 —面進行說明。 Ο )首先，向由陶瓷粉末及玻璃材料混合後之混合粉末 中’分別適量添加黏合劑、分散劑、可塑劑及有機溶劑 等，並將該等混合’由此製作陶瓷聚料。 ❹Hereinafter, a more detailed description of an embodiment of the present invention will be shown. In the characteristic part of the present invention, (1) the base material layer containing the ceramic powder and the glass material is formed into a base material layer which is a main part constituting the ceramic substrate, firstly, in a mixed powder obtained by mixing ceramic powder and glass material, A binder, a dispersant, a plasticizer, an organic solvent, and the like are separately added, and the ceramic slurry is prepared by combining the =, and the combination. However, it may be one of the preferred materials. It may be used as a ceramic powder in the calcination step, and various types of alumina powder (ai2o3) powder may be used. The glass material may initially contain glass powder, 134679.doc 12 200927701 out of the glass. Further, the above glass material may be formed by crystallizing and crystallizing at least in the final stage of the calcination step. As the glass material, for example, a glass borosilicate glass-based glass powder obtained by precipitating a crystal having a small dielectric loss such as bismuth silicate, magnesite or diopside can be used. Then, the ceramic slurry is formed into a sheet shape by a doctor blade method or the like to form a green sheet (base ceramic sheet) la (Fig. 3) for a base material layer. Further, 'more specifically, it will be Ca 〇 as a glass powder: 1 〇 to 55 Wt%, SiO 2 : 45 to 70 wt%, Al 2 〇 3 : 〇 〜 30 wt%, impurities: 〇 〜1 〇 wt% , B2〇3: a glass powder of a composition containing 5 to 20% by weight (average particle size of 15 μ 〇 50 to 64 wt%, and Ai2 〇 3 powder as a ceramic powder (average particle size is 1.0) Ηηι) 35~5〇wt% is mixed, and the mixture is dispersed in an organic vehicle composed of an organic solvent, a plasticizer, or the like to prepare a slurry, and then the slurry is subjected to a doctor blade forming method or a twisting method. Further, it is formed into a sheet-like shape to prepare a ceramic sheet for a substrate. Further, as a ceramic powder, a powder of ζ〇1ζ〇3 may be contained in a 〇~1〇wt% impurity. The material layer is usually formed by laminating a plurality of ceramic slabs, or it may be composed of a ceramic slab. x, the substrate is made of ceramic slabs, and the material formed by the W material forming method is better. ::Unsintered thick film printing layer core formed by film printing method = In addition to the insulating material, it is also possible to use ferrite or other materials such as magnets, barium titanate, etc. As a dielectric material for ceramics, it is better to use a ceramic slab for the substrate. It is better to use a low temperature sintered ceramic slab with a temperature of 1050 t or less and a sinter sinter. Therefore, it is preferable to 134679.doc -33 - 200927701 is: 'The glass powder used has a softening point of 750 ° C or less. (2) Constraining layer In the manufacturing method of the ceramic formed body of the present invention, the restraining layer must have the following two properties: U) until During the sintering of the low-temperature sintered ceramic material constituting the base material layer, that is, in the second calcination step of calcining in a low-oxygen environment, the original function of the restraining layer for suppressing shrinkage of the base material layer is exhibited; ❹ ❹ (b) In the second calcination step in which the subsequent oxygen partial pressure is higher than the second satin burning step, the loss is burned out. As the restraining layer having the above properties, the present invention is used in the silk environment (4). A ceramic powder that does not burn out, but which is burned out after satin burning with a partial pressure of oxygen higher than that in a low-oxygen environment, and a ceramic powder that does not sinter at a sintering temperature of the substrate layer as a main component As The preferred embodiment of the restraining layer is exemplified by a carbon powder containing a loss-generating material and containing alumina powder as a ceramic powder which is not sintered at a sintering temperature of the substrate layer. a mixed powder of porcelain powder and carbon powder, such as an oxidized powder, which is substantially non-sintered at a firing temperature of the ceramic substrate, is dispersed in an organic binder, an organic refrigerant T plasticizer, or the like The organic vehicle is used to prepare a polymer, and the obtained material is formed into a sheet shape to prepare a ceramic layer for the restraint layer, and then laminated as needed to form a restraining layer. The powder having stable properties and characteristics is not sintered at the sintering temperature of the base material layer, and is ideal for the purpose of exerting a restraining force. Furthermore, the use of oxidized (tetra) and carbon powder is limited. 134679.doc 14 200927701 The ceramic slab has a sintering temperature of "〇〇~16〇〇. . It does not substantially sinter at the sintering temperature of the ceramic green sheets for the substrate. Further, the restraining layer may be composed of the above-mentioned one restraining layer, and may be formed by laminating a plurality of restraining layers with ceramic plaques. As the ceramic powder, it is preferred to use an average particle diameter of Μ~5·〇μηι, the average grain of the m powder, o.i (four), and the glass contained in the surface layer of the ceramic layer as the substrate layer. In the simmering process, the violent reaction is carried out, and after the calcination, the ceramic layer is adhered to the detained layer, so that the restraint layer cannot be removed after calcination, or the organic component such as the binder in the sheet is forged due to the small particle size. It is difficult to decompose and scatter in the burning step, and sometimes delamination (de-) occurs in the substrate layer. On the other hand, if the average particle size of the ceramic powder exceeds 5·0 μηι ', the inhibition of calcination shrinkage decreases. Therefore, the base material layer is easily excessively contracted or bent in the plane direction (xy direction). Further, the formation of the restraining layer d is a powder which can be a calcining step in the substrate layer = substantially non-sintered. In addition to the oxidation, various ceramic powders such as 〇& falsification or oxidation town can be used. Among them, since there are more glass on the surface layer of the substrate layer, the substrate layer and the restraining layer have a certain degree. Affinity' is at the surface of the substrate layer and restrained It is preferable that the border of the contact i' is a moderately wet layer of the glass of the surface layer of the base material layer, and it is preferable to use the ceramic powder of the same type as the ceramic powder constituting the base material layer as a constraint. The layer of Taoman powder. Also, the carbon powder as the loss-loss material has a slow burning rate even in the A gas, and does not disappear in the calcination temperature domain of the substrate layer under the action of the oxygen partial pressure. It can be used as a material for the restraint layer for non-shrinkage calcination. Therefore, the toner 134679.doc 15 200927701 is at the end of the calcination step until the end of the shrinkage of the substrate layer (that is, until the end of the first! It does not burn out, but maintains the restraint function, and can burn and disappear after the end of shrinkage. Moreover, by burning and disappearing the carbon powder, micropores can be generated in the restraint layer containing the residual Tauman as a main component. Therefore, the restraint layer is easily collapsed and becomes easily removed. & 'By appropriately selecting the particle diameter of the carbon powder, the average specific surface area can be suppressed even when the particle diameter of the ceramic powder for the restraint layer is small. It λ, whereby (4) the composition of the restraint layer (4) the increase in the average ratio of the whole product. Therefore, the use of the carbon powder is larger than that of the ceramic powder used in the restraint layer. Preferably, the particle size is in the range of 2 to 2 〇μπι. When the particle size of the carbon powder is smaller than the particle size of the μ powder, and less than 2 (four), and only (4) powder and binder In the case of the previous case of the restraint layer (in the case where no carbon powder is contained), the amount of the organic binder used is increased, the time required for the debonding step is lengthened, and the carbon powder ❹ < specific surface area When it becomes larger, it burns and disappears before the end of the shrinkage of the substrate layer, which results in a decrease in the restraining force. Further, when the particle size of the carbon powder exceeds 20 μm, the surface smoothness of the restraint layer is deteriorated, and the unevenness thereof is Transfer to the surface of the substrate layer (substrate) is not preferable. Further, the ratio of the carbon powder in the restraining layer is preferably in the range of 10 to 50 νο1%. The reason for this is that if the proportion of the carbon powder is less than 10 νο1%, the effect of easily removing the restraining layer is small. If the proportion of the carbon powder is more than 50 νο1%, the restraining force in the calcination step is lowered. That is, the basic binding force of the restraint layer is to ensure that the 'other-side' carbon powder shrinks and 纟 in the substrate layer by the oxidized powder 134679.doc 16-200927701 The period until the bundle is in the restraint layer as an inorganic material, and the restraint layer is kept finely sensitive until the end of the contraction, so there is no decrease in restraint force and the carbon is burned out after the end of the shrinkage. Micropores are formed in the restraint layer. Therefore, in the case where the particle size is smaller at the end of the pottery, the restraint layer after the burn is also porous and easily removed. Further, by using a carbon powder having a larger particle diameter than the (four) powder, the average specific surface area is made smaller, so that even when a powder having a small particle size is used, the organic binder used can be reduced by 1 2 '. Thereby the debonding step is quickly terminated. — The thickness of the restraint layer is preferably 25 to 500 μm. The reason is that if the thickness is less than 25 μηΐ, the suppression force of the calcination shrinkage becomes small, and the substrate shrinks or bends more than necessary in the plane direction (four) direction, and if the thickness exceeds 500 μm, the substrate is used for ceramics. The organic component such as the binder in the embryo sheet is difficult to be decomposed and scattered in the calcination, which may cause problems such as delamination in the substrate. 17 17 17 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 Conductor diagram (4), = conductive material, it is better to use a low-resistance non-oxidizable material: material (for example, Ag) as the main component. However, as a conductive material, . Other materials, for example, Ag-Pd, Au, Pt, or the like can also be used. 2 In addition, when the bonding strength with ceramics is necessary, one or more additives are added. Moreover, in the upward: main = (conductive material), the organic medium is added in a specific ratio, and the two I34679.doc 200927701 is stirred to make a conductive paste, and the conductive paste can be used to form a via-hole conductor and a through-hole. a conductor, a conductor pattern as an outer conductor and an inner conductor, and the like. The type and ratio of the main component, the additive component, the organic vehicle, and the like which constitute the conductive paste are not particularly limited. Further, as the binder resin, a solvent may be used as the binder resin, and for example, ethyl cellulose, acrylic resin, polyvinyl alcohol, methyl acrylate resin or the like can be used. Further, as the solvent, for example, pine/diethanol alcohol, dihydroterpineol acetate, butyl carbitol, butyl carbitol acetate, alcohol or the like can be used. Further, various dispersing agents, plasticizers, active agents and the like may be added as needed. Further, it is preferable that the viscosity of the conductive paste is 50 to 700 Pa, and further, on the conductor pattern on the surface of the substrate layer, a through hole for connecting the conductor patterns between the upper and lower layers to each other. A portion of the through conductor through which the conductor and the via conductor are exposed. The through-conductors may be formed by embedding the paste in a through-hole formed in a glazed ceramic sheet by a method such as punching. (4) Debonding step The debonding step is usually carried out by heating from room temperature in the atmosphere until the decomposition of the binder or the combustion temperature is 纟, and (4). For example, j is heated to room temperature at room temperature and kept debonded. ^This is further in the process of manufacturing the ceramic molded body of the present invention in an environment of 4~s T debonding agent oxygen knife pressure (4) in an atmosphere, which is ideal in achieving high I34679.doc 200927701 efficiency. However, it is also possible to use a 隹 仃 黏 耔朌 仃 仃 仃 仃 仃 仃 仃 仃 仃 仃 仃 仃 仃 仃 仃 仃 仃 仃 仃 仃 仃 。 。 。 。 。 。 。 。 。 。 。 。 。 。 (5) Calcination conditions (a) The first calcination step is carried out by introducing nitrogen into the binder removal step and heating the sintering temperature of the art layer, for example, from 4 ° C to 95 ° C. In the present invention, the low-oxygen environment partial pressure in the first satin burning step is lower than that in the atmosphere, but particularly when the partial pressure of oxygen is 1 〇-3, the carbon-burning material in the restraining layer or the like is lost. It is better not to lose heat and to bundle the substrate layer. Ο 系 ' means oxygen atm can be surely restrained (b) the second calcination step is carried out under the condition that the oxygen partial pressure is higher than the i-th calcination step, and the burn-in material in the restraint layer is burned to increase the subsequent restraint layer. Removeability. For example, after the completion of the second calcination step, the atmosphere is introduced, and under normal pressure, the oxygen partial pressure is maintained at 0.21 atm and 95 CTC for 1 minute to burn off the carbon in the restraint layer. Further, the first calcination step and the second calcination step may be carried out at the same calcination temperature as described above, but the temperatures in the first calcination step and the second calcination step may be different. Further, the first calcination step and the second calcination step may be carried out continuously. Alternatively, after the first calcination step, the furnace may be temporarily taken out from the furnace and then placed in the furnace again to carry out the second calcination step. The features of the present invention are described in more detail below with reference to the embodiments of the present invention. [Example 1] 134679.doc • 19-200927701 Fig. 1 is a view showing a ceramic substrate (multilayer ceramic substrate) manufactured by a method for producing a ceramic substrate according to an embodiment (Example 1) of the present invention, and Fig. 2 is a view showing FIG. 3 is a view showing a state in which mounted components are mounted on the ceramic substrate of FIG. 1, and FIG. 3 is a view showing an unfired laminated body having a restraining layer produced in the step of manufacturing the ceramic substrate of FIGS. 1 and 2. The ceramic substrate A shown in Fig. 1 includes an insulating ceramic layer 1 which is obtained by calcining a low/ΙΕ·sintered ceramic raw material composition containing ceramic powder and a glass material, and is disposed on the insulating ceramic layer 1 Further, the ceramic substrate A of the first embodiment is a multilayer substrate having a plurality of layers in which a plurality of insulating ceramic layers 1 are laminated. The low-temperature sintered ceramic composition constituting the insulating ceramic layer 1 is a low-temperature sintered ceramic composition obtained by mixing an alumina-based ceramic powder and a borosilicate glass-based glass powder. Further, the conductor portion 2 is composed of a surface conductor (outer conductor) 21 on the surface of the ceramic substrate a, and an interlayer conductor disposed between the plurality of Φ-bonded ceramic layers 1, 1 joined to each other ( The inner conductor 22, and the via conductor 23 that connects the interlayer conductors 22 or the surface conductors 21 and the interlayer conductors 22 to each other. The surface conductor 21 and the interlayer conductor 22 are formed by firing an outer conductor film and an inner conductor film in which a conductive paste (for example, a silver-based conductive paste) is formed by printing. Further, the via-hole conductor 23 is formed, for example, by filling a through-hole with a conductive paste and a conductor powder and calcining it. / 'The ceramic substrate equipped with the electronic components of Fig. 2 (the multilayer ceramic substrate is translated by the ceramic substrate of the first embodiment (multilayer ceramic substrate) A has a semiconductor element 134679.doc • 20- 200927701 pieces and wafers Next, the manufacturing method of the multilayer ceramic substrates A and B will be described. The following description will be made with reference to Figs. 1 to 3 . In the mixed powder obtained by mixing the glass materials, 'a suitable amount of a binder, a dispersing agent, a plasticizer, an organic solvent, and the like are added, and these are mixed, and a ceramic aggregate is produced. ❹
(2)其次’將該陶瓷漿料以到刀成形法等之方法成形為 片材狀，製作基板用陶瓷胚片la(圖3)。再者，此處，將 (a)作為玻璃粉末的以CaO : 43 wt%、Si02 : 44 wt%、(2) Next, the ceramic slurry is formed into a sheet shape by a method such as a knife forming method to prepare a ceramic green sheet la for a substrate (Fig. 3). Here, (a) as a glass powder, CaO: 43 wt%, SiO 2 : 44 wt%,
Al2〇3 : 7 wt%、B203 : 6 wt%之比例所含有之組成之玻璃粉 末45 wt%，與 (b)作為陶瓷粉末的ai2〇3粉末55 wt〇/〇 進行混合，並使該混合物分散到由有機溶劑、可塑劑等 所組成之有機媒财，以調製㈣。然後將該漿料以刮刀 成形法或祕法而成形為片材狀，由此製作基板用陶究胚 片。再者，該基板用陶兗胚片之燒結溫度為i〇5〇t以下。 (3)接著，於所獲得之基板用陶究胚片^，根據需要， 用以形成通孔導體之貫通孔12(圖3)，並於該貫通孔Η 孔導2填料電性膏或者導體粉末㈣成有未燒結之通 1導體23a(圖3)(再者，於該實施例1中，貫通孔12中填充 有以Ag作為導電成分之導電性膏）。 真充 (4)又’於基板用陶瓷驻片】3上 刷銀系導電性h形成有未燒π如藉由印 體22a(參照圖3)。彳未紅之外部導體21a、内部導 134679.doc 200927701 以形成拘束層之拘束層用 (5)又’按照以下順序製作用 陶瓷胚片。 首先’使於上述基板用陶瓷胚片之烺燒溫度下實質上不 燒結之陶聽末（於該實施例1中為氧化㈣末）及碳粉末之 混合粉末，分散到由有機黏合劑、有機溶劑、可塑劑等所 組成之有機媒劑中，以調製聚料。 然後，將所獲得之漿料成形為片材狀，以製作拘束層用 陶瓷胚片。 ❹Al2〇3: 7 wt%, B203: 6 wt% of the composition of the glass powder of 45 wt%, and (b) ai2〇3 powder as a ceramic powder 55 wt〇 / 〇 mixed, and the mixture Disperse into an organic medium consisting of an organic solvent, a plasticizer, etc., to prepare (4). Then, the slurry was formed into a sheet shape by a doctor blade molding method or a secret method to prepare a ceramic sheet for a substrate. Further, the sintering temperature of the ceramic plaque for the substrate is i 〇 5 〇 t or less. (3) Next, the obtained ceramic substrate is used for forming a through-hole 12 (Fig. 3) of the via-hole conductor, and a via-hole electrical paste or conductor is formed in the through-hole. The powder (4) is formed into an unsintered through-conductor 23a (Fig. 3). (In addition, in the first embodiment, the through hole 12 is filled with a conductive paste containing Ag as a conductive component). The true charge (4) is also applied to the silver-based conductive layer h of the silver-based conductive layer h to form an unburned π such as by the ink 22a (see Fig. 3). The outer conductor 21a and the inner guide 134679.doc 200927701 are used to form the restraint layer of the restraint layer. (5) The ceramic green sheet is produced in the following order. First, the mixture of the ceramics (the end of the oxidation (4) in the first embodiment) and the carbon powder which are substantially not sintered at the calcining temperature of the ceramic green sheet for the substrate is dispersed to the organic binder, An organic solvent composed of an organic solvent, a plasticizer, or the like is used to prepare a polymer. Then, the obtained slurry was formed into a sheet shape to prepare a ceramic green sheet for a restraint layer. ❹
再者，於該實施例1中，將漿料中之碳粉末之比例設為 20 V〇1%。X ’作為陶兗粉末，使用平均粒徑為i叫之氧 化鋁粉末，作為碳粉末，使用平均粒徑為3 之碳粉末。 該拘束層用陶瓷胚片之燒結溫度為14〇〇〜16〇〇t，其係於 基板用陶瓷胚片之燒結溫度下實質上不燒結者。再者，於 該實施例1中，為可確保充分之拘束力，將拘束層陶瓷胚 片之厚度設為300 μηι。 (6)其次，如圖3所示，將複數個基板用陶瓷胚片la以特 定之順序積層，且將拘束層31配置並積層於具有將基板用 陶瓷胚片la積層所形成之複數層構造之基材層（未燒成之 陶瓷基板）A'之兩主面上，利用靜水壓壓製等方法，例如 以5〜200 MPa之壓力進行擠壓並壓接。藉此，於基材層（未 燒成之陶瓷基板）A’之上下兩側，製作出具有配設有拘束 層3 1之構造之未燒成積層體32(參照圖3)。於該實施例1 中，使基材層（未燒成之陶瓷基板）Α·之厚度為300 μηι，且 拘束層31之厚度為300 μηι。 134679.doc -22- 200927701 再者’根據需要’亦可將該未燒成積層體32切斷成適當 之大小。又’於該實施例1中，將複數個基板用陶瓷胚片 la積層’以製作複數層構造之基材層A·，但亦可使基板用 陶究胚片la之塊數為一塊，製作單層構造之基材層，並製 造單板型之陶瓷基板。 又’於該實施例1中，於基材層（未燒成之陶瓷基板）A,之 上下兩側配設有拘束層31，但亦可構成為將拘束層31配設 於基材層（未燒成之陶瓷基板）A'之僅一方之主面上。 ❹ 而且’拘束層31可藉由將複數塊拘束層用陶瓷胚片積層 而形成’另外還可藉由一塊拘束層用陶瓷胚片而形成。 (7) 其次’將該未燒成積層體32於大氣中以低溫之脫脂 溫度（例如’ 400。(：左右之溫度）進行熱處理，去除黏合劑等 之有機物。 其後’基材層（未燒成之陶瓷基板）A，燒結，但構成拘束 層31之陶瓷粉末不燒結，且在構成拘束層31之燒失材料不 Φ 燒失之條件下’即，該實施例1中，在氧濃度為1 vol%以 下之低氧環境中升溫至850〜950°c並進行煅燒，使基材層 (未燒成之陶瓷基板）A，燒結（第1煅燒步驟）。 .此時，構成拘束層3之陶瓷粉末未燒結，且碳粉末亦未 燒失而是殘留，故拘束層31充分發揮抑制基材層A，於平面 方向收縮之功能。 (8) 其後’在氧分壓比第1烺燒步驟高的條件（於該實施例 1中’氧濃度為10 vol%)下進行煅燒（第2锻燒步驟），使作 為構成拘束層31之燒失材料的碳粉末燒失。藉此，於拘束 134679.doc •23· 200927701 層中之碳粉末燒失之部分形成有微孔’故拘束層成為多孔 而容易去除之狀態。 (9)然後，藉由去除多孔狀態之拘束層3丨而獲得具有如 圖1所示之構造的陶瓷基板A。 再者，根據該實施例丨之方法，於煅燒後之複合積層體 中，拘束層實質上未燒結，且煅燒前含有之碳粉末燒失而 成為多孔的狀態，故與先前之使用有由不含有燒失材料 (該實施例1中之碳粉末）的陶瓷粉末及黏合劑所組成之拘束 層的情況相比，例如，可使得使用噴砂法或濕喷砂法時之 吐出壓力變低，且去除拘束層所需之時間變短。其結果可 不知及基板表面及電極表面之平滑性而去除拘束層故能 夠以較佳的良率製造尺寸精度高的陶瓷成形體。 匕 根據上述實施例1可確認，在使用拘束力高的陶瓷粉末 (實施例1中為氧化鋁粉末）而構成收縮抑制用之拘束層時， 亦可藉由調配碳粉末來確保拘束力，且確保煅燒後之拘束 層去除之容易性。 又，作為副效果，可獲得如下效果：藉由將碳粉末混合 而使拘束層用胚片著色，從而容易與基板用陶瓷胚片進行 區別，可防止將兩者取錯之錯誤，以提高製造步驟之可$ 性。再者，it常在對陶絲片著色時，較多情況是使用2 渡金屬元素，向基材層側擴散而使基材著色，但根據本發 明，基材層並未著色，從而外觀品質未劣化。 再者，於上述實施例〗中，以製造陶瓷基板來作為陶瓷 成形體之情況為例進行了說明，但本發明並非限於陶瓷夹 134679.doc •24· 200927701 板，亦可應用於以陶咨 兗電子零件為主μ 、陶£LC複合零件等之陶 、各種陶瓷成形體之製造方法。 進而，於此外其他 例1者，關於構成基材：’本發明並非係限定於上述實施 種類及㈣陶变粉末及玻璃材料之具體的 類及配比例4 稱成拘束層之燒失材料及陶瓷粉末 體的種類、第1及第2椒植止 瓦物禾之具 步驟…μ 中之具體的條件、脫黏合劑 轡 、件等，可於發明之範圍内進行各種應用、 變形。Further, in the first embodiment, the ratio of the carbon powder in the slurry was set to 20 V 〇 1%. X ’ is used as a ceramic powder, and an aluminum oxide powder having an average particle diameter of i is used, and as a carbon powder, a carbon powder having an average particle diameter of 3 is used. The sintering temperature of the ceramic green sheets for the restraint layer is 14 Å to 16 Torr, which is substantially not sintered at the sintering temperature of the ceramic green sheets for the substrate. Further, in the first embodiment, in order to ensure sufficient binding force, the thickness of the ceramic layer of the restraint layer was set to 300 μm. (6) Next, as shown in FIG. 3, a plurality of substrate ceramic sheets 1a are laminated in a specific order, and the restraint layer 31 is disposed and laminated to have a plurality of layers formed by laminating the ceramic green sheets for the substrate. The two main surfaces of the base material layer (unfired ceramic substrate) A' are pressed and pressure-bonded by a method such as hydrostatic pressing, for example, at a pressure of 5 to 200 MPa. Thereby, an unfired laminated body 32 having a structure in which the restraining layer 31 is disposed is formed on both sides of the base material layer (unfired ceramic substrate) A' (see Fig. 3). In the first embodiment, the thickness of the base material layer (unfired ceramic substrate) was 300 μm, and the thickness of the restraint layer 31 was 300 μm. 134679.doc -22- 200927701 Further, the unfired laminate 32 may be cut into an appropriate size as needed. Further, in the first embodiment, a plurality of substrates are laminated with a ceramic green sheet la to form a base layer A of a plurality of layers, but the number of blocks of the ceramic sheet for the substrate may be made one by one. A substrate layer of a single layer structure, and a single-plate type ceramic substrate is produced. Further, in the first embodiment, the restraint layer 31 is disposed on the upper and lower sides of the base material layer (unfired ceramic substrate) A, but the restraint layer 31 may be disposed on the base material layer ( On the main surface of only one of the unfired ceramic substrates) A'. ❹ And the 'constrained layer 31 can be formed by laminating a plurality of restraint layers with ceramic lamellae', and can also be formed by using a ceramic slab with a restraining layer. (7) Next, 'the unfired laminated body 32 is heat-treated at a low temperature (for example, '400: (about) temperature) in the atmosphere to remove organic substances such as binders. Thereafter, the substrate layer (not The fired ceramic substrate A is sintered, but the ceramic powder constituting the restraint layer 31 is not sintered, and the burn-in material constituting the restraint layer 31 is not Φ burned out, that is, in the first embodiment, in the oxygen concentration In a low-oxygen environment of 1 vol% or less, the temperature is raised to 850 to 950 ° C and calcined, and the base material layer (unfired ceramic substrate) A is sintered (first baking step). At this time, the restraint layer is formed. Since the ceramic powder of 3 is not sintered, and the carbon powder remains without being burned out, the restraining layer 31 sufficiently functions to suppress the base layer A and shrink in the planar direction. (8) Thereafter, the oxygen partial pressure ratio is the first. The calcination (second calcination step) was carried out under the condition that the calcination step was high (the oxygen concentration was 10 vol% in the first embodiment), and the carbon powder as the loss-generating material constituting the restraint layer 31 was burned out. In this way, the carbon powder burned out in the layer of 134679.doc •23·200927701 is formed. The micropores are in a state of being porous and easily removed. (9) Then, the ceramic substrate A having the structure shown in Fig. 1 is obtained by removing the porous layer 3 丨. Further, according to the implementation For example, in the composite laminate after calcination, the restraining layer is substantially unsintered, and the carbon powder contained before calcination is burned out and becomes porous, so that it is not contained in the previous use and does not contain the loss-reduction material ( In comparison with the case where the ceramic powder of the carbon powder in the first embodiment is a restraining layer composed of a binder, for example, the discharge pressure at the time of using the sandblasting method or the wet blasting method can be lowered, and the restraining layer can be removed. The time required is shortened. As a result, the smoothness of the surface of the substrate and the surface of the electrode can be eliminated, and the constrained layer can be removed, so that a ceramic molded body having high dimensional accuracy can be produced with good yield. 匕 According to the above-described Example 1, it can be confirmed that When a restraint layer for shrinkage suppression is formed by using a ceramic powder having high binding force (aluminum powder in Example 1), it is also possible to ensure binding force by blending carbon powder and to secure removal of restraint layer after calcination. In addition, as a side effect, it is possible to obtain an effect of coloring the green sheet for the restraint layer by mixing the carbon powder, thereby easily distinguishing it from the ceramic green sheet for the substrate, thereby preventing the error of taking the error between the two. In order to increase the manufacturing process, it is often used to color the ceramic sheet. In many cases, the metal element is used to diffuse to the substrate layer side to color the substrate, but according to the present invention, The substrate layer is not colored, and the appearance quality is not deteriorated. Further, in the above embodiment, the case of manufacturing a ceramic substrate as a ceramic formed body has been described as an example, but the present invention is not limited to the ceramic clip 134679.doc •24·200927701 The board can also be used in the manufacturing methods of ceramics and various ceramic molded bodies, such as ceramics, ceramics, etc. Further, in the other example 1, the constituent substrate: 'The present invention is not limited to the above-mentioned embodiment and (4) specific types and proportions of the ceramic powder and the glass material, and the loss-reducing material and ceramics which are called the restraining layer. The type of the powder, the first and second pepper planting steps, the specific conditions in the μ, the debonding agent, the member, and the like can be variously applied and deformed within the scope of the invention.
[產業上之可利用性] 如上所述’根據本發明，可充分確保燬燒步驟中之收縮 抑制效果，且於燒成步驟結束後容易去除拘束層，從而不 會在去除拘束層之步驟中對㈣成形體造成損害，可確實 且高效地製造尺寸精度高的陶竟成形體。因此，本發明可 廣泛利用於經煅燒步驟而製造的陶瓷成形體之製造領域。 【圖式簡單說明】 圖1係表示藉由本發明實施例（實施例丨）的陶瓷成形體（陶 瓷基板）之製造方法所製造的陶瓷基板（多層陶瓷基板）之示 圖。 圖2係表示圖1之陶瓷基板上搭載有安裝零件之狀態之示 圖。 圖3係表示在製造圖1及圖2之陶瓷基板之步驟中所製作 的具備拘束層之未燒成積層體之示圖。 圖4係表示先前之使用有以難燒結性材料為主要成分的 拘束層來對陶瓷成形體進行拘束煅燒之方法之示圖。 134679.doc -25- 200927701[Industrial Applicability] As described above, according to the present invention, the shrinkage suppressing effect in the destruction step can be sufficiently ensured, and the restraining layer can be easily removed after the completion of the firing step, so that the step of removing the restraining layer is not performed. Damage to the (four) molded body makes it possible to manufacture a ceramic molded body having high dimensional accuracy with high accuracy. Therefore, the present invention can be widely utilized in the field of manufacturing ceramic shaped bodies produced by the calcination step. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing a ceramic substrate (multilayer ceramic substrate) produced by a method for producing a ceramic formed body (ceramic substrate) according to an embodiment (Example 本) of the present invention. Fig. 2 is a view showing a state in which mounted components are mounted on the ceramic substrate of Fig. 1. Fig. 3 is a view showing an unfired laminated body having a restraining layer produced in the step of manufacturing the ceramic substrate of Figs. 1 and 2; Fig. 4 is a view showing a method of restraining and calcining a ceramic formed body using a restraining layer containing a hardly sinterable material as a main component. 134679.doc -25- 200927701
【主要元件符號說明】 1 絕緣性陶瓷層 1 a 基板用陶瓷胚片 2 導體部 3a，3b 安裝電子零件 12 貫通孔 21 表面導體（外部導體） 21a 未燒結之外部導體 22 層間導體（内部導體） 22a 未燒結之内部導體 23 通孔導體 23a 未燒結之通孔導體 31 拘束層 32 未燒成積層體 A 陶瓷基板（多層陶瓷基板） A, 基材層（未燒成之陶瓷基板） B 陶瓷基板（多層陶瓷基板） 134679.doc -26-[Description of main component symbols] 1 Insulating ceramic layer 1 a Ceramic green sheet for substrate 2 Conductor parts 3a, 3b Mounting electronic parts 12 Through-holes 21 Surface conductors (outer conductors) 21a Unsintered external conductors 22 Interlayer conductors (internal conductors) 22a Unsintered inner conductor 23 Through-hole conductor 23a Unsintered via-hole conductor 31 Constrained layer 32 Unfired laminated body A Ceramic substrate (multilayer ceramic substrate) A, Base material layer (unfired ceramic substrate) B Ceramic substrate (Multilayer Ceramic Substrate) 134679.doc -26-