JPH0625033B2 - Method for producing black mullite sintered body - Google Patents
Method for producing black mullite sintered bodyInfo
- Publication number
- JPH0625033B2 JPH0625033B2 JP60204470A JP20447085A JPH0625033B2 JP H0625033 B2 JPH0625033 B2 JP H0625033B2 JP 60204470 A JP60204470 A JP 60204470A JP 20447085 A JP20447085 A JP 20447085A JP H0625033 B2 JPH0625033 B2 JP H0625033B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- mullite
- sintered body
- black
- less
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
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- Compositions Of Oxide Ceramics (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は、Ｓｉチップをマウントする回路基板およびセ
ラミックパッケージとして用いる黒色ムライト焼結体の
製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a black mullite sintered body used as a circuit board for mounting a Si chip and a ceramic package.
従来の技術 従来からシリコンチップを搭載するＩＣパッケージの材
質としてはアルミナが使用されてきた。その理由はアル
ミナは電気絶縁性が良く、比較的高い熱伝導率と高い機
械的強度さらに熱や酸アルカリに対する耐久性がすぐれ
ているといった総合的な信頼性が高いためである。2. Description of the Related Art Conventionally, alumina has been used as a material for an IC package on which a silicon chip is mounted. The reason for this is that alumina has good electrical insulation properties, and has a high overall reliability such as relatively high thermal conductivity, high mechanical strength, and excellent durability against heat and acid / alkali.
しかしながら、アルミナの熱膨脹係数は７〜８×10-6で
シリコンの約４×10-6と大きく違うため、接着による歪
が問題となってきている。However, the coefficient of thermal expansion of alumina is 7 to 8 × 10 −6, which is greatly different from about 4 × 10 −6 of silicon, so that distortion due to adhesion has become a problem.
そこで熱伝導率が低いという問題はあるけれども、シリ
コンの熱膨脹に近く、アルミナに次ぐ安定性を有する黒
色ムライトが現在注目されてきている。Therefore, although there is a problem of low thermal conductivity, black mullite, which has a stability close to that of silicon and is second only to alumina, is currently attracting attention.
前記従来の黒色ムライトの製造は、ムライトかまたはカ
オリンとアルミナに焼結助剤と、黒色化剤を数重量％か
ら10数重量％添加したものを焼成していた。In the production of the conventional black mullite, mullite or kaolin and alumina containing a sintering aid and a blackening agent of several wt% to several tens wt% were fired.
焼結助剤としては、アルカリ金属酸化物（Ｌｉ２Ｏ、Ｎ
ａ２Ｏ、Ｋ２Ｏ）、アルカリ土類酸化物（ＭｇＯ、Ｃａ
Ｏ、ＳｒＯ、ＢａＯ）さらにこれらのアルミナシリケー
トである各種長石その他にＢ２Ｏ３、ガラスフリットが
知られており、数種類の助剤を組合せて、焼結体の緻密
化を促進している。As a sintering aid, an alkali metal oxide (Li 2 O, N
a 2 O, K 2 O), alkaline earth oxides (MgO, Ca
O, SrO, BaO) further various feldspar Other B 2 O 3 is these alumina silicate, are known glass frit, a combination of several kinds of auxiliaries, it promotes the densification of the sintered body.
一方、黒色化剤としては一般の陶磁器に用いる黒色顔料
が使用され、その組成はよく知られているが、その配合
の一例を示すと、ＭｎＯ２60.2％、Ｃｒ２Ｏ３21.4％、
Ｆｅ２Ｏ３17.6％、ＣｏＯ 0.9％よりなるものが挙げら
れる。On the other hand, a black pigment used in general ceramics is used as a blackening agent, and its composition is well known. An example of its composition is as follows: MnO 2 60.2%, Cr 2 O 3 21.4%,
One of which is Fe 2 O 3 17.6% and CoO 0.9%.
また、現在生産されている黒ムライトの配合の一例を示
すと下記のとおりである。（単位重量％） ３Ａｌ２Ｏ３・２ＳｉＯ２ 87％ ３ＭｇＯ・４ＳｉＯ２・Ｈ２Ｏ ２％ ＣａＣＯ３ ２％ Ａｌ２Ｏ３ ２％ ＴｉＯ２ ２％ 黒顔料 ５％ 発明が解決しようとする問題点 上記従来の黒色ムライトは、焼結体に膨らみ（ブク）、
色むら（シミ）、異物（ボロ）が多数発生し、歩留りが
極めて低かった。その理由は次のように説明される。An example of the black mullite formulation currently produced is as follows. (Unit weight%) 3Al 2 O 3 · 2SiO 2 87% 3MgO · 4SiO 2 · H 2 O 2% CaCO 3 2% Al 2 O 3 problem 2% TiO 2 2% black pigment 5% Invention is to Solve The above-mentioned conventional black mullite is swelled in a sintered body,
A large number of color spots (stains) and foreign matters (boros) were generated, and the yield was extremely low. The reason is explained as follows.
Ｘ線的にムライトからなる粉末は、平均粒径が約３μｍ
以下の場合、1000Kg／cm２の力で成形された成形体は16
50℃から1700℃で緻密化する。工業的な生産性を上げる
ため1350℃付近まで焼成温度を下げるには、焼結助剤を
添加し、液相による焼結が行なわれる。既に述べた各種
の焼結助剤を状態図で調べると、これらの焼結助剤は12
50℃以下の共融組成はなろうとして反応を開始すること
が判る。ここで重要なことは、黒色顔料が存在するとさ
らに液相のの生成温度が低下すると同時に、ムライト粒
子間で起る反応は一様の速度ではなくなるので、部分的
に液相の組成に違いが生じてくる。このような状態で
は、黒色顔料の溶解度の差のため焼結体に色ムラが発生
したり、液相の蒸気圧が高くなり過ぎた場合は、膨らみ
（ブク）が発生する。X-ray powder consisting of mullite has an average particle size of about 3 μm.
In the following cases, the number of compacts molded with a force of 1000 kg / cm 2 is 16
Densify at 50 ° C to 1700 ° C. In order to lower the firing temperature to around 1350 ° C. in order to increase industrial productivity, a sintering aid is added and liquid phase sintering is performed. Examining the various sintering aids already mentioned in the phase diagram, these sintering aids
It can be seen that the reaction starts as if the eutectic composition below 50 ° C is about to disappear. What is important here is that the presence of the black pigment further lowers the temperature at which the liquid phase is formed, and at the same time, the reaction that occurs between the mullite particles is not uniform, so there is a partial difference in the composition of the liquid phase. Will occur. In such a state, color unevenness occurs in the sintered body due to the difference in solubility of the black pigment, or bulging occurs when the vapor pressure of the liquid phase becomes too high.
さらにムライトを焼結させるための敷台も、ムライトを
含む高アルミナ質の材質なので、粘性の低い液相は、敷
台や敷台に付着した耐火性粉末とも反応し、異物（ボ
ロ）が接着するという不具合が生ずることになる。Furthermore, the bed for sintering mullite is also a high-alumina material containing mullite, so the liquid phase with low viscosity reacts with the bed and the refractory powder adhering to the bed, and foreign matter (boro) adheres. This will cause a problem.
問題点を解決するための手段 本発明は上記問題点に鑑み、各酸化物とムライトの反応
性を研究した結果、従来必要と考えられていた焼結助剤
は全く不用で、さらに黒色顔料の中でも酸化鉄と酸化マ
ンガンとさらに望ましくは酸化チタニウムをムライトに
添加することにより、従来の欠点が解決できるという知
見を得て本発明に到達した。Means for Solving the Problems In view of the above problems, the present invention has studied the reactivity of each oxide with mullite, and as a result, a sintering aid that was conventionally considered necessary is completely unnecessary, and further, a black pigment Among others, the present invention has been achieved by finding that conventional defects can be solved by adding iron oxide, manganese oxide, and more preferably titanium oxide to mullite.
すなわち、本発明は主原料が主としてムライトからなる
粉末 100重量％に対して、添加剤として酸化鉄15重量％
以下、酸化マンガン15重量％以下の１種又は２種と酸化
チタニウム５重量％以下を総量で４重量％以上添加し、
1300〜1550℃で焼成することを特徴とする黒色ムライト
焼結体の製造方法である。That is, the present invention is based on 100% by weight of a powder mainly composed of mullite, and 15% by weight of iron oxide as an additive.
Below, one or two kinds of manganese oxide of 15% by weight or less and titanium oxide of 5% by weight or less are added in a total amount of 4% by weight or more,
A method for producing a black mullite sintered body, which comprises firing at 1300 to 1550 ° C.
上記添加剤の添加量が総計で４重量％未満の場合は焼成
温度が1550℃を越え、また焼結体の色も茶色となり実用
上意味がなくなる。When the total amount of the above additives is less than 4% by weight, the firing temperature exceeds 1550 ° C. and the color of the sintered body becomes brown, which is meaningless in practical use.
酸化鉄、酸化マンガンは共に15重量％越えると、1400℃
如何で焼成できても、敷台との反応が強く、異物が接着
し、実用上使用できない。If both iron oxide and manganese oxide exceed 15% by weight, 1400 ° C
No matter how it can be fired, it reacts strongly with the bed and foreign matter adheres to it, making it practically unusable.
酸化チタニウムは単味で添加すると白色となるが、酸化
鉄と酸化マンガンとともに添加すると、焼結体の黒色度
を増し、焼結促進効果を有するので、一種の黒色化剤と
考えることができる。その効果は５重量％までで、それ
以上添加しても効果はない。Titanium oxide becomes white when added alone, but when it is added together with iron oxide and manganese oxide, it increases the blackness of the sintered body and has a sintering promoting effect, so it can be considered as a kind of blackening agent. The effect is up to 5% by weight, and adding more than that has no effect.
原料の粒度は特に限定されないが、平均粒径が５μｍ以
下で充分である。当然のことながら、粒径が粉かくなる
と焼成温度は低くなる。The particle size of the raw material is not particularly limited, but an average particle size of 5 μm or less is sufficient. As a matter of course, as the particle size becomes finer, the firing temperature becomes lower.
なお、本発明で用いる主原料のムライトは、通常工業的
に用いられているムライトを意味しており、必ずしも化
学式（３Al2O3・2SiO2）に拘束されるものではない。In addition, the main raw material mullite used in the present invention means mullite which is usually used industrially, and is not necessarily restricted to the chemical formula (3Al 2 O 3 .2SiO 2 ).
実施例 主原料であるムライトはカオリンとアルミナからあらか
じめ合成したものでＸ線回析によればムライトのみの結
晶相であった。このムライトに工業用ベン柄（Ｆｅ２Ｏ
３）、電解マンガンの酸化物（ＭｎＯ２）、アナターゼ
（ＴｉＯ２）を表に示す割合で配合し、平均粒径５μｍ
になるまで粉砕した。この混合物を乾燥後、バインダー
としてＰ．Ｖ．Ａ．を３重量％添加し、1000Kg／cm2で
プレスしたものを電気炉で焼成した。Example The main raw material, mullite, was synthesized in advance from kaolin and alumina. According to X-ray diffraction, mullite was the only crystalline phase. This mullite has an industrial Ben pattern (Fe 2 O
3 ), electrolytic manganese oxide (MnO 2 ), and anatase (TiO 2 ) were mixed in the proportions shown in the table, and the average particle size was 5 μm.
Crushed until. After drying this mixture, P. V. A. Was added in an amount of 3% by weight and pressed at 1000 kg / cm 2 and then fired in an electric furnace.
その結果を比較例とともに表に示す。ムライト100重量
％に対して、酸化鉄15重量％以下と酸化マンガン15重量
％以下の少なくとも１種を総量で４重量％以上含み、13
00〜1550℃の温度で焼成された本発明例（実施例）の場
合には、黒色度が均一で、ブク、シミ、ホロといった欠
陥も認められず、焼結体の性状が良好であった。さら
に、酸化チタニウムを１〜５重量％添加した本発明例の
場合にも、黒色度および性状ともに良好な焼結体が得ら
れた。The results are shown in the table together with comparative examples. Containing at least 4% by weight or more of at least one of iron oxide 15% by weight and manganese oxide 15% by weight or less based on 100% by weight of mullite, 13
In the case of the present invention example (Example) fired at a temperature of 00 to 1550 ° C., the blackness was uniform, defects such as Buku, stains, and holo were not observed, and the properties of the sintered body were good. . Further, also in the case of the present invention example in which 1 to 5% by weight of titanium oxide was added, a sintered body having good blackness and properties was obtained.
これに対し、添加剤の量が５重量％未満あるいは15重量
％越え、焼成温度が1550℃越えの比較例の場合には、黒
色が得られないことに加えて、ブクの発生があり、焼結
体の性状は不良であった。On the other hand, in the case of the comparative example in which the amount of the additive is less than 5% by weight or more than 15% by weight and the firing temperature is more than 1550 ° C., black is not obtained, and burrs are generated. The properties of the union were poor.
また、本発明で得られる焼結体は、熱膨張係数が４〜５
×10-6とシリコンの膨張係数に近く、ＩＣパッケージ用
材料として満足できるものであった。Further, the sintered body obtained in the present invention has a coefficient of thermal expansion of 4 to 5
It was close to the expansion coefficient of silicon of × 10 -6 and was satisfactory as a material for IC packages.
発明の効果 本発明によればブク、シミ、ボロの発生のない黒色ムラ
イト焼結体が得られるため、歩留りが向上し、ＩＣパッ
ケージとして有用な材質が効率よく得られる。 EFFECTS OF THE INVENTION According to the present invention, a black mullite sintered body that does not generate burrs, stains, and boros is obtained, so that the yield is improved and a material useful as an IC package is efficiently obtained.
Claims (2)
して、添加剤として酸化鉄15重量％以下、酸化マンガン
15重量％以下の１種又は２種を総量で４重量％以上添加
し、1300〜1550℃で焼成することを特徴とする黒色ムラ
イト焼結体の製造方法。1. Iron oxide 15% by weight or less and manganese oxide as an additive with respect to 100% by weight of mullite powder as a main raw material.
A method for producing a black mullite sintered body, which comprises adding 15% by weight or less of one kind or two kinds in a total amount of 4% by weight or more and firing at 1300 to 1550 ° C.
して、添加剤として酸化鉄15重量％以下、酸化マンガン
15重量％以下の１種又は２種と、酸化チタニウム５重量
％以下とを総量で４重量％以上添加し、1300〜1550℃で
焼成することを特徴とする黒色ムライト焼結体の製造方
法。2. Iron oxide 15% by weight or less and manganese oxide as an additive based on 100% by weight of mullite powder as a main raw material.
A method for producing a black mullite sintered body, comprising adding 1 or 2 of 15% by weight or less and 5% by weight or less of titanium oxide in a total amount of 4% by weight or more and firing at 1300 to 1550 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60204470A JPH0625033B2 (en) | 1985-09-18 | 1985-09-18 | Method for producing black mullite sintered body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60204470A JPH0625033B2 (en) | 1985-09-18 | 1985-09-18 | Method for producing black mullite sintered body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6265967A JPS6265967A (en) | 1987-03-25 |
| JPH0625033B2 true JPH0625033B2 (en) | 1994-04-06 |
Family
ID=16491062
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60204470A Expired - Lifetime JPH0625033B2 (en) | 1985-09-18 | 1985-09-18 | Method for producing black mullite sintered body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0625033B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4994092B2 (en) * | 2007-04-10 | 2012-08-08 | 株式会社ニッカトー | Black alumina sintered body and manufacturing method thereof |
| WO2012043658A1 (en) * | 2010-09-28 | 2012-04-05 | 京セラ株式会社 | Mullite sintered object and circuit board using the same, and probe card |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60176966A (en) * | 1984-02-20 | 1985-09-11 | 日本特殊陶業株式会社 | Colored alumina ceramic composition |
-
1985
- 1985-09-18 JP JP60204470A patent/JPH0625033B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6265967A (en) | 1987-03-25 |
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