JPH0375237A - Glaze composition for ceramic substrate - Google Patents
Glaze composition for ceramic substrateInfo
- Publication number
- JPH0375237A JPH0375237A JP21191389A JP21191389A JPH0375237A JP H0375237 A JPH0375237 A JP H0375237A JP 21191389 A JP21191389 A JP 21191389A JP 21191389 A JP21191389 A JP 21191389A JP H0375237 A JPH0375237 A JP H0375237A
- Authority
- JP
- Japan
- Prior art keywords
- glaze
- glaze composition
- composition
- thermal expansion
- bao
- 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.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 30
- 239000000758 substrate Substances 0.000 title claims abstract description 18
- 239000000919 ceramic Substances 0.000 title claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 10
- 239000011521 glass Substances 0.000 abstract description 9
- 238000010438 heat treatment Methods 0.000 abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 4
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 abstract 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 abstract 2
- 229910052681 coesite Inorganic materials 0.000 abstract 2
- 229910052593 corundum Inorganic materials 0.000 abstract 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 abstract 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 abstract 2
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 abstract 2
- 239000000377 silicon dioxide Substances 0.000 abstract 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract 2
- 229910052682 stishovite Inorganic materials 0.000 abstract 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Inorganic materials [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 abstract 2
- 229910052905 tridymite Inorganic materials 0.000 abstract 2
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 2
- 238000002844 melting Methods 0.000 abstract 1
- 230000008018 melting Effects 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 238000010298 pulverizing process Methods 0.000 abstract 1
- 238000010791 quenching Methods 0.000 abstract 1
- 230000000171 quenching effect Effects 0.000 abstract 1
- 235000012255 calcium oxide Nutrition 0.000 description 6
- 230000007704 transition Effects 0.000 description 6
- 238000004031 devitrification Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000005499 meniscus Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明はサーマルプリンタヘッドに用いられるセラミッ
ク基板用のグレーズ組成物の改良に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to improvements in glaze compositions for ceramic substrates used in thermal printer heads.
（従来の技術）
サーマルプリンタヘッド用の基板としては、アルξす質
の基板の表面にグレーズと呼ばれるガラスを施釉したグ
レーズ基板が用いられ、その表面に発熱抵抗体等の回路
が形成される。このためのグレーズ組成物は８００℃以
上の高温で導体、抵抗体等を焼付けても回路パターンの
崩れが生じないように十分な耐熱性を有することが求め
られている。また回路形成時にフォトリングラフ法グレ
ーズＭ板の端部が１０〜２０μ讃の高さに盛上がるメニ
スカスと呼ばれる現象を起こしにくいものであることが
求められる。(Prior Art) As a substrate for a thermal printer head, a glaze substrate is used, in which the surface of an aluminum substrate is coated with glass called glaze, and circuits such as heating resistors are formed on the surface of the glaze substrate. The glaze composition for this purpose is required to have sufficient heat resistance so that the circuit pattern does not collapse even if conductors, resistors, etc. are baked at high temperatures of 800° C. or higher. It is also required that the edge of the photoringraph glaze M plate is unlikely to cause a phenomenon called meniscus in which it swells to a height of 10 to 20 μm during circuit formation.
このようなグレーズ組成物としては従来から多くのもの
が特許出願されている０例えば特公昭６０−５５４５３
号公報には、５ｉｆｔ、 ＢｚＯｓ、ＣａＯ、ＢａＯ。Many patent applications have been filed for such glaze compositions. For example, Japanese Patent Publication No. 60-55453.
5ift, BzOs, CaO, BaO.
ＳｒＯ、Ａｌｔ（ｌｓを特定の割合で含有させたグレー
ズ＆ＩＩＩｆｃ物が開示されている。しかしこのグレー
ズ組成物は実質的な転移点が６９０°Ｃであるために８
００°Ｃ以上の高温焼成を行うと回路パターンが崩れる
おそれがある。また特公昭６１−２４３４５号公報には
、ｓｔｏｗ、＾ｌ！０３ 、ＣａＯ、ＢａＯ、ＢｚＯｓ
、ＺｎＯを特定の割合で含有させたグレーズｍ酸物が開
示されており、更に特開昭６２−９６３４４号公報には
、Ｓ量０ｔ、Ａｌｔｏｓ ｓ ＣａＯｓ ＢａＯ５Ｓｒ
Ｏ５ＰｔＯｓを特定の割合で含有させたグレーズ組成物
が開示されている。しかしこれらのグレーズ組成物も実
質的な転移点が６９０℃であるために、上記したと同様
に８００°Ｃ以上の高温焼成を行うと回路パターンが崩
れるおそれがある。A glaze &IIIfc material containing SrO and Alt(ls) in a specific ratio has been disclosed. However, this glaze composition has a substantial transition point of 690°C, so
If high-temperature firing is performed at 00°C or higher, there is a risk that the circuit pattern will collapse. Moreover, in the Japanese Patent Publication No. 61-24345, stow, ^l! 03, CaO, BaO, BzOs
, a glaze m acid containing ZnO in a specific proportion is disclosed, and furthermore, in JP-A-62-96344, the amount of S is 0t, Altos s CaOs BaO 5 Sr
A glaze composition containing a specific proportion of O5PtOs is disclosed. However, since these glaze compositions also have a substantial transition point of 690°C, there is a risk that the circuit pattern will collapse if they are fired at a high temperature of 800°C or higher, as described above.
（発明が解決しようとする課題）
本発明は上記した従来の欠点を解決して、８００°Ｃ以
上の高温焼成に耐える耐熱性を備え、またグレーズ表面
の平滑性、耐酸性が良好で、アルミナ基板との熱膨張係
数の差が小さいセラミック基板用グレーズ組成物を提供
するために完成されたものである。(Problems to be Solved by the Invention) The present invention solves the above-mentioned conventional drawbacks, has heat resistance that can withstand high-temperature firing of 800°C or more, has good glaze surface smoothness and acid resistance, and has alumina This was completed in order to provide a glaze composition for ceramic substrates that has a small difference in coefficient of thermal expansion with the substrate.
（課題を解決するための手段）
上記の課題を解決するための本発明は、重量比で、Ｓｉ
ｎｇ ４５〜６０％、Ａｌ２Ｏ．５〜１４％、ＣａＯ５
〜１５％、ＢａＯ３〜２５％、ＳｒＯ５〜３０％、Ｍｇ
ＯＯ，５〜５％、ＬａｚＯ８Ｏ〜５％の組成を持つこと
を特徴とするものである。(Means for Solving the Problems) The present invention for solving the above problems is based on the weight ratio of Si
ng 45-60%, Al2O. 5-14%, CaO5
~15%, BaO3~25%, SrO5~30%, Mg
It is characterized by having a composition of OO, 5 to 5%, and LazO8O to 5%.
本発明のグレーズ組成物は、耐熱性を増加させるために
、Ｎａ、０． Ｋ！Ｏ等のアルカリ成分及びＢ２Ｏ２の
含有量をゼロとした無アルカリガラスとするとともに、
これによる溶解性と清澄性の低下を無アルカリガラスの
場合に融剤となるＣａＯ、ＢａＯ５ＳｒＯ、ＭｇＯの増
量により補った点に第１の特徴がある。これによって転
移点を７８０℃〜Ｂ２０”Ｃと従来品よりも大幅に向上
させることができ、しかも従来のグレーズ組成物と変わ
りのない溶融性を維持することができる。The glaze composition of the present invention contains Na, 0. K! In addition to creating an alkali-free glass with zero content of alkaline components such as O and B2O2,
The first feature is that the resulting decrease in solubility and clarity is compensated for by increasing the amount of CaO, BaO5SrO, and MgO, which are fluxing agents in the case of alkali-free glass. As a result, the transition point can be significantly improved from 780°C to B20''C compared to conventional products, and the meltability can be maintained as is the same as that of conventional glaze compositions.
また本発明のグレーズ組成物はＣａＯ、ＢａＯ、Ｓｒ０
１ＭｇＯをバランス良く含有させることによって失透を
防止するとともに、表面張力を適正な大きさに調整し、
更に熱膨張係数をアルミナ基板とほぼ同一の６．５〜？
、ＯＸｌ０−’／”Ｃに調整した点に第２の特徴がある
。Furthermore, the glaze composition of the present invention includes CaO, BaO, Sr0
By containing 1MgO in a well-balanced manner, devitrification is prevented and the surface tension is adjusted to an appropriate level.
Furthermore, the coefficient of thermal expansion is 6.5~, which is almost the same as that of the alumina substrate.
, OXl0-'/''C is the second feature.
以下に各成分の含有率の限定理由を示す。The reasons for limiting the content of each component are shown below.
Ｓｉｎｇはガラス構造を形成するための主成分であり、
その含有率が６０％を越えると熱膨張係数が小さくなり
すぎてアルミナ基板の熱膨張係数との差が大きくなり、
逆に４５％未満ではグレーズの耐熱性が不十分となり本
発゛明の目的が達成できない。Sing is the main component for forming the glass structure,
If the content exceeds 60%, the coefficient of thermal expansion becomes too small and the difference with the coefficient of thermal expansion of the alumina substrate becomes large.
On the other hand, if it is less than 45%, the heat resistance of the glaze will be insufficient and the object of the present invention cannot be achieved.
ＡＩｆ０３は失透を防ぐ成分であり、限定範囲より多す
ぎても少な過ぎてもグレーズ焼成時に失透が発生し易く
なる。AIf03 is a component that prevents devitrification, and if the amount is too much or too little than the limited range, devitrification tends to occur during glaze firing.
ＣａＯ、ＢａＯ、ＳｒＯ、ＭｇＯは上述したように無ア
ルカリガラスの場合に融剤となる成分であり、各数値限
定の範囲を外れると失透を生じ易くなり、不足すると表
面張力が小さくなりすぎる。また各数値限定の範囲内に
おいて、熱膨張係数を６．５〜？、ＯｘｌＯ−”／”ｃ
に調整することができる。As mentioned above, CaO, BaO, SrO, and MgO are components that act as fluxes in the case of alkali-free glass, and if they are out of the respective numerical limits, devitrification tends to occur, and if they are insufficient, the surface tension becomes too small. Also, within the range of each numerical limit, the coefficient of thermal expansion is 6.5 ~? ,OxlO−”/”c
can be adjusted to
Ｌａ、Ｏ，はガラスの骨格を強化することができる成分
であり、５％以下の添加により熱膨張係数を高めること
なく耐熱性を１５℃以上も高めることができる。La, O, are components that can strengthen the glass skeleton, and by adding 5% or less, the heat resistance can be increased by 15° C. or more without increasing the coefficient of thermal expansion.
（作用）
上記のような組成を持つ本発明のグレーズ組成物は耐熱
性が高く、後述する実施例のデータにも示されるように
転移点を７８０°Ｃ〜８２０℃と従来のグレーズ組成物
よりも大幅に高めることができ、従って厚膜タイプのサ
ーマルプリンタヘッドに使用される場合には回路形成の
ための高温焼成時においても下地のグレーズ層の耐熱性
が高く、回路パターンの変形が生じない、また薄膜タイ
プのサーマルプリンタヘッドに使用される場合には下地
のグレーズ層の耐熱性が高いために高温で抵抗体をアニ
ーリングができ、完成品の寿命を長くすることができる
。(Function) The glaze composition of the present invention having the above-mentioned composition has high heat resistance, and as shown in the data of Examples described later, the transition point is 780°C to 820°C, which is higher than that of conventional glaze compositions. Therefore, when used in thick-film type thermal printer heads, the underlying glaze layer has high heat resistance even during high-temperature baking to form circuits, and the circuit pattern does not deform. Furthermore, when used in a thin film type thermal printer head, the underlying glaze layer has high heat resistance, so the resistor can be annealed at high temperatures, extending the life of the finished product.
また本発明のグレーズ組成物は、実施例のデータにも示
されるように転移点を高めたにもかかわらず熱膨張係数
をアルミナ基板の熱膨張係数と同様の値に維持できるう
え、グレーズ表面の平滑性、耐酸性が良好で電気絶縁性
の劣化のないものである。Furthermore, as shown in the data of the examples, the glaze composition of the present invention can maintain a thermal expansion coefficient similar to that of an alumina substrate even though the transition point has been raised, and the glaze composition can maintain a thermal expansion coefficient similar to that of an alumina substrate. It has good smoothness and acid resistance, and there is no deterioration in electrical insulation.
以下に本発明の実施例を示す。Examples of the present invention are shown below.
（実施例）
次頁の表に示した酸化物組成となるように原料を調合し
、高純度のるつぼに入れて１４００〜１６００″Ｃで溶
融し、急冷して得られたガラスをアルごす製ボールミル
で微粉砕した。このようにして得られたガラスの微粉末
をエチルセルロースとα−チルピノール等の混合物であ
るビしクルと混合し、ペースト状とした。このペースト
をスクリーン印刷法でアルミナ基板上に印刷して所望の
厚みの膜を形威し、１２００〜１３００’Ｃで焼成する
ことによりグレーズ基板とした。(Example) Raw materials were prepared to have the oxide composition shown in the table on the next page, placed in a high-purity crucible, melted at 1400 to 1600"C, and rapidly cooled. The resulting glass was then algorized. The glass powder thus obtained was mixed with a vehicle, which is a mixture of ethylcellulose and α-chillpinol, to form a paste.This paste was printed on an alumina substrate using a screen printing method. A film of desired thickness was formed by printing on top, and a glazed substrate was prepared by baking at 1200 to 1300'C.
表中のＮα１とＮα２は本発明の実施例であり、Ｎα３
は先に特願昭６３−１９８４４９号として出願済みのグ
レーズ＆Ｉｌ威物、Ｎａ ４は出願人会社が以前に開発
したグレーズ組成物である。またＮα５とＮα６も従来
他社から市販されているグレーズ組成物である。Nα1 and Nα2 in the table are examples of the present invention, and Nα3
is a glaze composition previously filed as Japanese Patent Application No. Sho 63-198449, and Na 4 is a glaze composition previously developed by the applicant company. Further, Nα5 and Nα6 are also conventional glaze compositions commercially available from other companies.
各グレーズ＆１１戒物の熱膨脹係数と転移点を測定した
結果を表中に記入した。表中の組成の単位は重量％、熱
膨脹係数の単位は１０−’／’Ｃである。The results of measuring the thermal expansion coefficient and transition point of each glaze and 11 precepts are entered in the table. The unit of composition in the table is % by weight, and the unit of thermal expansion coefficient is 10-'/'C.
（発明の効果）
以上に説明したとおり、本発明は従来にない新規な組成
を有し、アルミナ基板と熱膨脹係数がほぼ等しく、また
耐熱性に優れるもので、このグレーズ組成物を用いれば
８００°Ｃ以上の高温焼成を行っても回路の崩れがなく
、サーマルプリンタヘッド用発熱抵抗体の抵抗値の安定
化を図ることができる。(Effects of the Invention) As explained above, the present invention has a novel composition that has not existed before, has a coefficient of thermal expansion almost equal to that of an alumina substrate, and has excellent heat resistance. The circuit does not collapse even when fired at a high temperature of C or higher, and the resistance value of the heating resistor for a thermal printer head can be stabilized.
よって本発明は従来の問題点を一掃したセラミック基板
用グレーズ組成物として、産業の発展に寄与するところ
は極めて大である。Therefore, the present invention greatly contributes to the development of industry as a glaze composition for ceramic substrates that eliminates the conventional problems.
特許出願２人 代 理 人 同 同 石塚硝子株式会社 名 嶋 明 部 綿 貫 達 雄 山 本 文 夫2 patent applicants representative person same same Ishizuka Glass Co., Ltd. Name Akira Shima Watata Kan Tatsu male Mountain book text husband
Claims (1)
５〜１４％、ＣａＯ５〜１５％、ＢａＯ３〜２５％、Ｓ
ｒＯ５〜３０％、ＭｇＯ０．５〜５％、Ｌａ＿２Ｏ＿３
０〜５％の組成を持つことを特徴とするセラミック基板
用グレーズ組成物。By weight ratio, SiO_245-60%, Al_2O_3
5-14%, CaO5-15%, BaO3-25%, S
rO5-30%, MgO0.5-5%, La_2O_3
A glaze composition for a ceramic substrate characterized by having a composition of 0 to 5%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21191389A JPH0375237A (en) | 1989-08-17 | 1989-08-17 | Glaze composition for ceramic substrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21191389A JPH0375237A (en) | 1989-08-17 | 1989-08-17 | Glaze composition for ceramic substrate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0375237A true JPH0375237A (en) | 1991-03-29 |
| JPH0478572B2 JPH0478572B2 (en) | 1992-12-11 |
Family
ID=16613733
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21191389A Granted JPH0375237A (en) | 1989-08-17 | 1989-08-17 | Glaze composition for ceramic substrate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0375237A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012108345A1 (en) * | 2011-02-08 | 2012-08-16 | 旭硝子株式会社 | Glass composition, glass substrate for solar cells using glass composition, and glass substrate for display panel |
| US8343617B2 (en) | 2009-04-09 | 2013-01-01 | Industrial Technology Research Institute | Ceramic substrate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5654253A (en) * | 1979-10-11 | 1981-05-14 | Ngk Spark Plug Co Ltd | Glaze composition for alumina substrate |
| JPS6015550A (en) * | 1983-06-22 | 1985-01-26 | シ−メンス・アクチエンゲセルシヤフト | Thin-film gas sensor |
| JPS60118648A (en) * | 1983-11-30 | 1985-06-26 | Ngk Spark Plug Co Ltd | Glaze composition for ceramic base |
| JPS645927A (en) * | 1987-06-30 | 1989-01-10 | Asahi Glass Co Ltd | Glass composition |
-
1989
- 1989-08-17 JP JP21191389A patent/JPH0375237A/en active Granted
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5654253A (en) * | 1979-10-11 | 1981-05-14 | Ngk Spark Plug Co Ltd | Glaze composition for alumina substrate |
| JPS6015550A (en) * | 1983-06-22 | 1985-01-26 | シ−メンス・アクチエンゲセルシヤフト | Thin-film gas sensor |
| JPS60118648A (en) * | 1983-11-30 | 1985-06-26 | Ngk Spark Plug Co Ltd | Glaze composition for ceramic base |
| JPS645927A (en) * | 1987-06-30 | 1989-01-10 | Asahi Glass Co Ltd | Glass composition |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8343617B2 (en) | 2009-04-09 | 2013-01-01 | Industrial Technology Research Institute | Ceramic substrate |
| WO2012108345A1 (en) * | 2011-02-08 | 2012-08-16 | 旭硝子株式会社 | Glass composition, glass substrate for solar cells using glass composition, and glass substrate for display panel |
| CN103347832A (en) * | 2011-02-08 | 2013-10-09 | 旭硝子株式会社 | Glass composition, glass substrate for solar cells using glass composition, and glass substrate for display panel |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0478572B2 (en) | 1992-12-11 |
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