JPS6159557B2 - - Google Patents
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- Publication number
- JPS6159557B2 JPS6159557B2 JP16678081A JP16678081A JPS6159557B2 JP S6159557 B2 JPS6159557 B2 JP S6159557B2 JP 16678081 A JP16678081 A JP 16678081A JP 16678081 A JP16678081 A JP 16678081A JP S6159557 B2 JPS6159557 B2 JP S6159557B2
- Authority
- JP
- Japan
- Prior art keywords
- mol
- ceramic substrate
- glaze
- less
- substrate
- 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
Links
- 239000000758 substrate Substances 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 15
- 239000000919 ceramic Substances 0.000 claims description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- LTPBRCUWZOMYOC-UHFFFAOYSA-N Beryllium oxide Chemical compound O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 claims description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 238000010304 firing Methods 0.000 claims description 4
- 239000011521 glass Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- 239000010408 film Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000004017 vitrification Methods 0.000 description 2
- 229910018626 Al(OH) Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000004031 devitrification Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005338 heat storage Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Electronic Switches (AREA)
Description
本発明はグレーズ表面の平坦性および耐熱性が
良好で、PbO、アルカリを含有しないにもかかわ
らず、熱伝導率が低く改良された電子部品用のフ
アクシミリグレーズド基板および薄膜グレーズド
基板に関するものである。
最近、めざましい電子工業の発展に伴い各種電
子部品は、高品質、高精密化されてきている。
グレーズドセラミツクス基板はアルミナやベリ
リア基板上にガラス層を形成させたものであり、
薄膜若しくは厚膜抵抗素子用、高精度膜回路を利
用する集積回路用や感熱記録装置のサーマルヘツ
ド用等に利用されている。
このサーマルヘツドとしてのグレーズド基板の
利用に厚膜および薄膜方式があり、その厚膜方式
では配線が６ドツト／mm以上が可能となり蓄熱ガ
ラス層の挿入で印加電圧は半減し、熱効率が高め
られている。また薄膜方式では配線が８ドツト／
mm以上が可能であり、当然グレーズ表面の平坦
性、耐熱性およびアルカリ、PbOフリーの要求が
高まつている。
更にグレーズに要求される項目として、熱伝導
率が低いことであり、その目標としてＫ＝
0.002Cal／cm・sec・℃の性質が必要である。こ
の熱伝導率ではグレーズ層の厚みを薄く形成出来
るために、グレーズの盛り上りや突起等が小さく
表面の平坦なグレーズドセラミツクス基板とな
る。
本発明は以上のような要求される品質と耐熱屈
伏点が700℃以上の高温グレーズの開発を目的と
して成されたものであり、その要旨はSiO256〜
71モル％、BaO15.5〜28モル％、Al2O36〜16モル
％を必須成分として、この全成分の全組成物が
100モル％であるグレーズ組成物をセラミツクス
基板上に塗布し、焼成して形成したことを特徴と
するものと、この必須成分に副成分としてSrO10
モル％以下、B2O38モル％以下、CaO10モル％以
下、MgO3モル％以下の内、１種以上を加えて、
全組成物が100モル％であるグレーズ組成物をセ
ラミツクス基板上に塗布し、焼成して形成したこ
とを特徴とするものである。
本発明では低い熱伝導率を得るためにBaOを多
量に加え、また結晶化の防止と耐熱性を向上する
ためにAl2O3を多く含有することを特徴とするも
のである。
上記必須成分のみのものと、副成分を含有した
グレーズとを比較したとき、諸特性においては殆
んど変りないが、必須成分のみのものは若干、ガ
ラス中に気泡が残存し、やや失透しやすい性質を
有する。
上記グレーズ組成において、その限定範囲を外
れると、SiO2が56モル％以下では高膨脹係数と
なりセラミツクス基板えの密着性が低下し71モル
％以上では溶融が悪くなる。BaOが15.5モル％以
下では低い熱伝導率が得られず、28モル％以上で
はグレーズ表面の平坦なものが出来難く、熱膨脹
率が大きくなる。Al2O3が６モル％以下では安定
したガラスと成り難く、16モル％以上では溶融が
困難となる。また、B2O3が８モル％まではガラ
ス化を助長し、かつ溶融性を促進させるが、それ
以上では耐熱性が低下する。SrO、CaOは共に10
モル％まではガラス化を助長するが、それ以上に
なると失透しやすくなる。MgOはガラスの清澄
を促進し、泡を抜けやすくする作用があり３モル
％までは効果があるためである。
以下、本発明を実施例に基づき詳細に説明す
る。
実施例
下記第１表のモル％調合割合の組成ガラスが得
られるように、SiO2、Al（OH）3、BaCO3、
H3BO3、CaCO3、SrCO3、MgCO3を秤量し、ラ
イカイ機にて混合しアルミナ質ルツボにて1450℃
の最適温度で溶融した。その溶融液を水中に投入
して急冷し、それとアルミナ製のボールミルで微
粉砕してガラスフリツトを得た。以上の方法で各
組成のそれぞれのガラスフリツトを製作した。
また別にアルミナ含有量97％で50×50×1.0tmm
の寸法のアルミナ基板を製作準備した。
この基板上に下記第１表の各組成のガラスフリ
ツトをペースト状にしたものを印刷法で塗布し
て、乾燥後1220℃にて焼成して、グレーズ厚み60
±20μｍのグレーズ基板とした。
The present invention relates to facsimile glazed substrates and thin film glazed substrates for electronic components that have improved glazed surface flatness and heat resistance, and have low thermal conductivity despite not containing PbO or alkali. . In recent years, with the remarkable development of the electronics industry, various electronic components have become higher quality and more precise. A glazed ceramic substrate is a glass layer formed on an alumina or beryllia substrate.
It is used for thin film or thick film resistive elements, integrated circuits using high-precision film circuits, thermal heads of thermosensitive recording devices, etc. There are thick-film and thin-film methods for using glazed substrates as thermal heads.The thick-film method enables wiring of 6 dots/mm or more, and by inserting a heat storage glass layer, the applied voltage is halved, increasing thermal efficiency. There is. In addition, in the thin film method, the wiring is 8 dots/
mm or more, and of course there are increasing demands for glaze surface flatness, heat resistance, and alkali and PbO-free properties. Furthermore, the glaze is required to have low thermal conductivity, and the goal is to have K=
A property of 0.002 Cal/cm・sec・℃ is required. With this thermal conductivity, the glaze layer can be formed thin, resulting in a glazed ceramic substrate with a flat surface and little glaze buildup or protrusions. The present invention was made with the aim of developing a high-temperature glaze with the above-mentioned required quality and heat resistance yielding point of 700°C or higher.
The total composition of all these components is
The glaze composition is characterized by being formed by coating a glaze composition of 100 mol% on a ceramic substrate and firing it, and in addition to this essential component, SrO10 is added as a subcomponent.
Adding one or more of the following: mol% or less, B 2 O 3 8 mol% or less, CaO 10 mol% or less, MgO 3 mol% or less,
It is characterized in that it is formed by applying a glaze composition whose total composition is 100 mol % onto a ceramic substrate and firing it. The present invention is characterized in that a large amount of BaO is added in order to obtain low thermal conductivity, and a large amount of Al 2 O 3 is contained in order to prevent crystallization and improve heat resistance. When comparing a glaze containing only the above essential ingredients and a glaze containing sub-components, there is almost no difference in various properties, but the glaze containing only the essential ingredients has some air bubbles remaining in the glass and is slightly devitrified. It has the property of being easy to handle. In the above-mentioned glaze composition, if the SiO 2 content is 56 mol % or less, the expansion coefficient becomes high and the adhesion to the ceramic substrate decreases, and if it exceeds 71 mol %, the melting becomes poor. If BaO is less than 15.5 mol%, low thermal conductivity cannot be obtained, and if it is more than 28 mol%, it is difficult to obtain a flat glaze surface and the coefficient of thermal expansion becomes large. If Al 2 O 3 is less than 6 mol%, it is difficult to form a stable glass, and if it is more than 16 mol%, it becomes difficult to melt. Further, up to 8 mol % of B 2 O 3 promotes vitrification and promotes meltability, but if it exceeds 8 mol %, heat resistance decreases. Both SrO and CaO are 10
Vitrification is promoted up to mol%, but devitrification tends to occur when the amount exceeds that. This is because MgO has the effect of promoting the clarification of glass and making it easier for bubbles to come out, and is effective up to 3 mol%. Hereinafter, the present invention will be explained in detail based on examples. Example SiO 2 , Al(OH) 3 , BaCO 3 ,
H 3 BO 3 , CaCO 3 , SrCO 3 and MgCO 3 were weighed, mixed in a Raikai machine, and heated to 1450°C in an alumina crucible.
melted at the optimum temperature. The molten liquid was poured into water, rapidly cooled, and pulverized using an alumina ball mill to obtain a glass frit. Glass frits of each composition were manufactured using the above method. Additionally, 50×50×1.0tmm with alumina content of 97%
An alumina substrate with dimensions of was fabricated and prepared. A paste of glass frit having the composition shown in Table 1 below was applied onto this substrate by a printing method, dried and baked at 1220°C, resulting in a glaze thickness of 60°C.
A glaze substrate of ±20 μm was used.
【表】
上記、製作した各組成のグレーズ基板を下記第
２表に熱膨脹係数、熱伝導度、表面抵抗を測定し
て示した。
熱膨脹係数は各組成のグレーズにて５φ×20L
mmの試料を製作して測定し、この膨脹曲線の頂点
を屈伏点として示した。
表面の絶縁抵抗は各組成のグレーズ表面に２個
の銀電極を設けて、エレクトロメーターにて
100V印加し30秒経過後の電極間リーク電流を測
定し、それより表面絶縁抵抗を測定した。[Table] Table 2 below shows the measured thermal expansion coefficient, thermal conductivity, and surface resistance of the glazed substrates of each composition manufactured above. Thermal expansion coefficient is 5φ x 20L for each composition of glaze.
A sample of mm was fabricated and measured, and the peak of this expansion curve was indicated as the yield point. The surface insulation resistance was measured using an electrometer using two silver electrodes on the glaze surface of each composition.
The leakage current between the electrodes was measured after 30 seconds had elapsed after 100V was applied, and the surface insulation resistance was measured from this.
【表】
グレーズの熱膨脹係数は5.1〜7.3×10-6で従来
比較品とあまり差はないが、耐熱性は屈伏点が
740〜780℃であり、従来比較品の660℃に対して
80〜120℃の高いものとなつた。
熱伝導率においては1.5〜20×10-3であり、従
来比較品の3.3×10-3に比べて、アルカリ、PbO
がフリーであるにもかかわらず大きく改良され前
記した所期の目標値であるＫ＝0.002を達成する
ことが出来て上記した表面の平滑性、平坦性の優
れたものとなつた。
表面抵抗は１〜４×1014であり従来比較品の２
×1012に比べて絶縁性があり、電気的に安定度の
高いものとなつた。
以上、記述した如く本発明のグレーズドセラミ
ツクス基板は優れた品質のものであり、フアクシ
ミリ用グレーズド基板、薄膜基板、プリンターヘ
ツド基板等へ使用して好適なものである。[Table] The coefficient of thermal expansion of the glaze is 5.1 to 7.3×10 -6 , which is not much different from conventional comparative products, but the heat resistance is
740 to 780℃, compared to 660℃ of the conventional comparative product.
The temperature reached a high of 80-120℃. Thermal conductivity is 1.5 to 20 × 10 -3 , compared to 3.3 × 10 -3 of conventional comparison products, compared to alkali, PbO
Despite being free, it was greatly improved and the desired target value of K=0.002 was achieved, resulting in the excellent surface smoothness and flatness. The surface resistance is 1 to 4 × 10 14 , which is 2
It has better insulating properties and higher electrical stability than ×10 12 . As described above, the glazed ceramic substrate of the present invention is of excellent quality and is suitable for use in facsimile glazed substrates, thin film substrates, printer head substrates, and the like.
Claims (1)
Al2O36〜16モル％を必須成分として、この全成
分の全組成物が100モル％であるグレーズ組成物
をセラミツクス基板上に塗布し、焼成して形成し
たことを特徴とするグレーズドセラミツクス基
板。 ２ 特許請求の範囲第１項記載のセラミツクス基
板は、アルミナまたはベリリア基板であることを
特徴とするグレーズドセラミツクス基板。 ３ SiO256〜71モル％、BaO15.5〜28モル％、
Al2O36〜16モル％を必須成分として、これに副
成分としてSrO10モル％以下、B2O38モル％以
下、CaO10モル％以下、MgO3モル％以下の内、
１種以上を加えて、全組成物が100モル％である
グレーズ組成物をセラミツクス基板上に塗布し、
焼成して形成したことを特徴とするグレーズドセ
ラミツクス基板。 ４ 特許請求の範囲第３項記載のセラミツクス基
板は、アルミナまたはベリリア基板であることを
特徴とするグレーズドセラミツクス基板。[Claims] 1 SiO 2 56 to 71 mol%, BaO 15.5 to 28 mol%,
A glazed ceramic characterized in that it is formed by applying a glaze composition containing 6 to 16 mol% of Al 2 O 3 as an essential component and having a total composition of 100 mol% of all components on a ceramic substrate and firing. substrate. 2. A glazed ceramic substrate, wherein the ceramic substrate according to claim 1 is an alumina or beryllia substrate. 3 SiO 2 56-71 mol%, BaO 15.5-28 mol%,
Al 2 O 3 6 to 16 mol % as an essential component, and as accessory components SrO 10 mol % or less, B 2 O 3 8 mol % or less, CaO 10 mol % or less, MgO 3 mol % or less,
Applying a glaze composition in which the total composition is 100 mol % by adding one or more types onto a ceramic substrate,
A glazed ceramic substrate characterized by being formed by firing. 4. A glazed ceramic substrate, wherein the ceramic substrate according to claim 3 is an alumina or beryllia substrate.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16678081A JPS5867091A (en) | 1981-10-19 | 1981-10-19 | Glazed ceramic board |
| US06/814,177 US4634634A (en) | 1981-10-19 | 1985-12-24 | Glaze ceramic base |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16678081A JPS5867091A (en) | 1981-10-19 | 1981-10-19 | Glazed ceramic board |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5867091A JPS5867091A (en) | 1983-04-21 |
| JPS6159557B2 true JPS6159557B2 (en) | 1986-12-17 |
Family
ID=15837539
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16678081A Granted JPS5867091A (en) | 1981-10-19 | 1981-10-19 | Glazed ceramic board |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5867091A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6453072U (en) * | 1987-09-25 | 1989-03-31 |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5988337A (en) * | 1982-11-13 | 1984-05-22 | Narumi Gijutsu Kenkyusho:Kk | Glaze composition for ceramic substrate |
| JPS61114861A (en) * | 1984-11-12 | 1986-06-02 | Hitachi Ltd | Thermosensitive head |
| JPS62104772A (en) * | 1985-10-31 | 1987-05-15 | Mitsubishi Electric Corp | Thick-film thermal head |
-
1981
- 1981-10-19 JP JP16678081A patent/JPS5867091A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6453072U (en) * | 1987-09-25 | 1989-03-31 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5867091A (en) | 1983-04-21 |
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