JPS6177637A - Glass composition for glaze - Google Patents
Glass composition for glazeInfo
- Publication number
- JPS6177637A JPS6177637A JP19913384A JP19913384A JPS6177637A JP S6177637 A JPS6177637 A JP S6177637A JP 19913384 A JP19913384 A JP 19913384A JP 19913384 A JP19913384 A JP 19913384A JP S6177637 A JPS6177637 A JP S6177637A
- Authority
- JP
- Japan
- Prior art keywords
- glaze layer
- glass composition
- glaze
- ceramic substrate
- mgo
- 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
- 239000011521 glass Substances 0.000 title claims abstract description 21
- 239000000203 mixture Substances 0.000 title claims abstract description 16
- 239000000919 ceramic Substances 0.000 abstract description 22
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 4
- 229910052681 coesite Inorganic materials 0.000 abstract 2
- 229910052593 corundum Inorganic materials 0.000 abstract 2
- 229910052906 cristobalite Inorganic materials 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
- 229910052905 tridymite Inorganic materials 0.000 abstract 2
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 2
- 238000002156 mixing Methods 0.000 abstract 1
- 239000000758 substrate Substances 0.000 description 23
- 238000009429 electrical wiring Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000010292 electrical insulation Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 230000003746 surface roughness Effects 0.000 description 3
- LTPBRCUWZOMYOC-UHFFFAOYSA-N Beryllium oxide Chemical compound O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- WUOACPNHFRMFPN-SECBINFHSA-N (S)-(-)-alpha-terpineol Chemical compound CC1=CC[C@@H](C(C)(C)O)CC1 WUOACPNHFRMFPN-SECBINFHSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- OVKDFILSBMEKLT-UHFFFAOYSA-N alpha-Terpineol Natural products CC(=C)C1(O)CCC(C)=CC1 OVKDFILSBMEKLT-UHFFFAOYSA-N 0.000 description 1
- 229940088601 alpha-terpineol Drugs 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000003466 welding Methods 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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
- C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明はセラミック基板のグレーズに適したガラス組成
物に関し、より詳細にはメタライズ金属部を有するセラ
ミック基板のグレーズに適したガラス組成物に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a glass composition suitable for glazing ceramic substrates, and more particularly to a glass composition suitable for glazing ceramic substrates having metallized metal parts.
（従来の技術）
セラミック基板の表面にガラスから成るグレーズ層を溶
着させたグレーズドセラミック基板は基板表面の平滑性
が優れていることから薄膜電気配線を形成する基板とし
て多用されている。(Prior Art) A glazed ceramic substrate, in which a glaze layer made of glass is welded to the surface of a ceramic substrate, is often used as a substrate for forming thin-film electrical wiring because the substrate surface has excellent smoothness.
この従来のグレーズドセラミック基板は通常、アルミナ
、ベリリア等から成るセラミック基板の表面に、例えば
５１０ｇ ４０ ｗｔ％、 Ａｌ２０ａ Ｂ ｗｔ％。This conventional glazed ceramic substrate is typically made of alumina, beryllia, etc., with a surface containing, for example, 510 g 40 wt%, Al20a B wt%.
ＣａＯ８ｗｔ％、 Ｂ２Ｏ３５ｗｔ％、 Ｐｂ○２５
ｗｔ％、 ＢａＯ３Ｗｔ”Ａ 、 Ｂｉ２Ｏ３５ｗｔ％
から成るガラス粉末ｌコ適当な粘結剤及び溶剤を添加し
てペースト状となしたものをスクリーン印刷法により塗
布するとともに大気中、約１２００℃の温度で焼成し、
ガラス粉末を熔融させ、セラミ７り基板表面に溶着させ
ることによって作製されている。CaO8wt%, B2O35wt%, Pb○25
wt%, BaO3Wt”A, Bi2O35wt%
A glass powder consisting of l is applied by screen printing to make a paste by adding a suitable binder and solvent, and is fired in the atmosphere at a temperature of about 1200°C.
It is manufactured by melting glass powder and welding it to the surface of a ceramic substrate.
（発明が解決しようとする問題点）
（７かし乍ら、この従来のグレーズドセラミック基板は
、セラミック基板がタングステン（Ｗ）、モリブデン（
Ｍｏ）等から成るメタライズ金属部を有している場合、
セラミック基板表面にグレーズ層を溶着させる際、セラ
ミック基板を大気中で焼成するとセラミック基板のメタ
ライズ金属部が酸化されて完全に消滅してしまうという
欠点を有していた。(Problems to be Solved by the Invention) (7) However, in this conventional glazed ceramic substrate, the ceramic substrate is made of tungsten (W), molybdenum (
When it has a metallized metal part made of Mo) etc.
When a glaze layer is welded to the surface of a ceramic substrate, the metallized metal portion of the ceramic substrate is oxidized and completely disappears if the ceramic substrate is fired in the atmosphere.
またメタライズ金属部の酸化消滅を防止するためにグレ
ーズ用ペーストが塗布されたセラミック基板を還元雰囲
気中で焼成するとガラス粉末中の主にＰｂＯが還元され
て溶着されるグレーズ層を黒色化させたり、導電性とな
してしまい、その結果、グレーズ層上に形成される微細
電気配線の各配線間が短絡し、微細電気配線基板として
の機能に支障を来たすという重大な欠点を誘発する。In addition, in order to prevent metallized metal parts from disappearing due to oxidation, when a ceramic substrate coated with a glaze paste is fired in a reducing atmosphere, mainly PbO in the glass powder is reduced and the glaze layer to be welded becomes black. This causes a serious drawback in that the fine electrical wiring formed on the glaze layer is short-circuited, which impairs its function as a fine electrical wiring board.
（発明の目的）
本発明は上記欠点に鑑み案出されたもので、その目的は
メタライズ金属部を有するセラミック基板表面憂ζグレ
ーズ層を溶着させる際、還元雰囲気中で焼成したとして
もグレーズ層が黒色化したり、微細電気配線基板として
の機能に支障を来たすような電気絶縁性の劣化が皆無で
あるグレーズ用ガラス組成物を提供することにある。(Object of the Invention) The present invention has been devised in view of the above-mentioned drawbacks, and its purpose is to weld a glaze layer to the surface of a ceramic substrate having a metallized metal portion, even if the glaze layer is fired in a reducing atmosphere. It is an object of the present invention to provide a glass composition for glaze that does not cause blackening or deterioration of electrical insulation properties that would impede its function as a fine electrical wiring board.
（問題点を解決するための手段）
本発明のグレーズ用ガラス組成物は重量百分率で５ＩＯ
Ｉ！ ５５〜７５％、ＢａＯ６〜２０％、 ＡＪｌ！０
３５〜１２％、 Ｃａ０８〜２０ ％オヨヒＭｇＯ、ｓ
ｒｏ （Ｄ少す（とも一種０．０５〜３％から成ること
を特徴とするものである〇
本発明のグレーズ用ガラス組成物において使用されるＳ
ｊ−Ｏｇはグレーズ層を構成するガラスの主成分であり
、その添加量が５５ ｗｔ％未満であれば、グレーズ層
の耐薬品性が劣化し、薄膜電気配線を形成する際等にお
いて薬品が付着すると侵蝕を受は良好な電気配線の形成
ができなくなる。また７５ｗｔ％以上であればグレーズ
層の熱膨張係数がセラミック基板のものよりも小となっ
てグレーズ層にクラックや剥離を発生してしまう。よっ
て５１０２はその添加量が５５〜７５ ｗｔ％の範囲に
特定される。(Means for Solving the Problems) The glass composition for glaze of the present invention has a weight percentage of 5IO
I! 55-75%, BaO6-20%, AJl! 0
35-12%, Ca08-20% Oyohi MgO,s
ro (S) used in the glass composition for glaze of the present invention.
j-Og is the main component of the glass that makes up the glaze layer, and if the amount added is less than 55 wt%, the chemical resistance of the glaze layer will deteriorate and chemicals will adhere when forming thin-film electrical wiring, etc. As a result, it becomes impossible to form good electrical wiring due to the corrosion. Moreover, if it is more than 75 wt%, the thermal expansion coefficient of the glaze layer will be smaller than that of the ceramic substrate, resulting in cracking or peeling of the glaze layer. Therefore, the addition amount of 5102 is specified to be in the range of 55 to 75 wt%.
またＢａＯはグレーズ層の結晶化を抑制するとともに熱
膨張係数を制御する成分であり、その添加量が６ｗｔ％
未満であれば前記性質は付与されず、また２０ ｗｔ％
以上であればグレーズ層の熱膨張係数がセラミック基板
のものよりも大となってグレーズ層にクラックや剥離を
発生してしまうことから６〜２０ ｖｔ％の範囲（２特
定される。In addition, BaO is a component that suppresses crystallization of the glaze layer and controls the coefficient of thermal expansion, and the amount added is 6 wt%.
If it is less than 20 wt%, the above properties will not be imparted, and if it is less than 20 wt%
If it is more than that, the coefficient of thermal expansion of the glaze layer will be larger than that of the ceramic substrate, causing cracks and peeling in the glaze layer.
またＡＪ２０ａはグレーズ層の結晶化を抑制するととも
に耐薬品性を改善する成分であり、その添加量が６ ｗ
ｔ％未満であれば前記性質は付与されず、また１２ｗｔ
％以上であればグレーズ層表面の表面粗さが大となって
良好な電気配線ができな（なることから６〜１２ｗｔ％
の範囲に特定される。In addition, AJ20a is a component that suppresses crystallization of the glaze layer and improves chemical resistance, and the amount added is 6 w.
If it is less than t%, the above properties are not imparted, and 12wt%
% or more, the surface roughness of the glaze layer surface becomes large and good electrical wiring is not possible (6 to 12 wt%).
specified within the range.
またＣａＯはグレーズ層の電気特性を安定化させる成分
であり、その添加量がＢ ｗｔ％未満であれば前記性質
は付与されず、また２０ｗｔ％以上であればグレーズ層
の軟化点が大きく低下するため８〜２０ ｗｔ％の範囲
に特定される。またＭｇＯ、ＳｒＯはグレーズ層の熱膨
張係数を制御する成分であり、その添加量が０．０５
ｗｔ、％未満であれば前記性質は付与されず、また３ｗ
ｔ％以上であればグレーズ層の熱膨張係数がセラミック
基板のものよりも大となってグレーズ層にクラックや剥
離を発生してしまうことから０．０５〜３ｗｔ％の範囲
に特定される。Furthermore, CaO is a component that stabilizes the electrical properties of the glaze layer, and if the amount added is less than B wt%, the above properties will not be imparted, and if it is more than 20 wt%, the softening point of the glaze layer will be significantly lowered. Therefore, it is specified in the range of 8 to 20 wt%. Furthermore, MgO and SrO are components that control the thermal expansion coefficient of the glaze layer, and the amount added is 0.05
If it is less than 3w%, the above properties are not imparted, and 3w
If it is more than t%, the coefficient of thermal expansion of the glaze layer will be larger than that of the ceramic substrate, causing cracks and peeling in the glaze layer, so it is specified in the range of 0.05 to 3 wt%.
（実施例） 次に本発明を実施例に基づいて説明する。(Example) Next, the present invention will be explained based on examples.
出発原料、！： Ｌ、 テ５１０ｇ 、 ＢａＯ、ｋ１
２ｓｓ 、 ＣａＯ。Starting materials,! : L, Te510g, BaO, k1
2ss, CaO.
ＭｇＯおよびＳｒＯを下表に示した化学組成になるよう
に秤量し、これを空気中、約１４００℃の温度で加熱溶
融し、ガラスを作成する。MgO and SrO are weighed to have the chemical compositions shown in the table below, and heated and melted in air at a temperature of about 1400° C. to create glass.
次に、前記ガラスＥこメタノールを加えてボールミルに
より湿式粉砕し、乾燥して後、２００メツシユパスさせ
整粒する。Next, methanol is added to the glass E, and the mixture is wet-pulverized using a ball mill. After drying, it is subjected to 200 mesh passes for sizing.
最後に、前記ガラス粉末にインブチルメタクリレート及
びα−テルピネオールを添加するとともに痛涜機で１時
間混練し、これによってグレーズ用ペースト試料を得た
。Finally, inbutyl methacrylate and α-terpineol were added to the glass powder, and the mixture was kneaded for 1 hour using a grinder to obtain a paste sample for glaze.
尚、試料番号２５は本発明品と比較するための比較試料
テアリ、Ｓ’ｉ、０２４０ ｗｔ％ 、 ＡＪ！０３
ｆ３ ｙｔ、 ％ 。In addition, sample number 25 is a comparative sample for comparison with the product of the present invention, S'i, 0240 wt%, AJ! 03
f3 yt, %.
ＣａＯ３ｗｔ％、 ＢｇＯ３５ｗｔ％、ＰｂＯ２５ｗ′
ｔ、％、 ＢａＯＢ ｗｔ％、 Ｂｊ−２ｏｓ ５ ｗ
ｔ％から成る従来一般に使用されているグレーズ用ペー
ストである。CaO3wt%, BgO35wt%, PbO25w'
t, %, BaOB wt%, Bj-2os 5 w
This is a conventionally commonly used glaze paste consisting of t%.
かくして得られたグレーズ用ペーストを使用してアルミ
ナから成る１００ ａ角の基板上に長さ５ＭＭ。Using the thus obtained glaze paste, a 5 mm long glaze was placed on a 100 mm square substrate made of alumina.
幅５關、厚み１００μｍのパターン１００個を印刷し、
次にこれを還元雰囲気（窒素−水素雰囲気）中、約１２
００°Ｃの温度で焼成し、セラミック基板表面にグレー
ズ層を熔着させた。Print 100 patterns with a width of 5 squares and a thickness of 100 μm,
Next, this was heated in a reducing atmosphere (nitrogen-hydrogen atmosphere) for about 12 hours.
The ceramic substrate was fired at a temperature of 0.000C to weld a glaze layer to the surface of the ceramic substrate.
そして次に前記グレーズ層を熔着させたセラミック基板
をアルカリ液中に浸漬し、しかる后、グレーズ層表面を
８１微鏡により観察し、グレーズ層の表面状態を調べる
とともに黒色化しているものの数を調べ、その変色率を
算出した。また同時に表面粗さ計でグレーズ層表面の表
面粗さを測定し、その平均値を算出した。Next, the ceramic substrate to which the glaze layer is welded is immersed in an alkaline solution, and then the surface of the glaze layer is observed with an 81 microscope to examine the surface condition of the glaze layer and to count the number of blackened particles. The color change rate was calculated. At the same time, the surface roughness of the glaze layer surface was measured using a surface roughness meter, and the average value was calculated.
その結果を表−工（こ示す。The results are shown below.
次にグレーズ層の電気絶縁抵抗を抵抗測定機で測定し、
その平均値を算出して電気絶縁抵抗の劣化を調べた。尚
、グレーズ層の電気絶縁抵抗の劣化ハクシーズ用ペース
ト中のガラス粉末が有する電気絶縁抵抗値と比較した。Next, measure the electrical insulation resistance of the glaze layer with a resistance measuring machine.
The average value was calculated to examine the deterioration of electrical insulation resistance. In addition, the deterioration of the electrical insulation resistance of the glaze layer was compared with the electrical insulation resistance value of the glass powder in the paste for haxies.
上記の結果を表−■に示す。The above results are shown in Table-■.
表−■ −印を付したものは本発明の範囲外のものである。Table -■ Items marked - are outside the scope of the present invention.
（発明の効果）
上記実験結果からも判るように、従来のグレーきく劣化
してしまうのに対し、本発明のグレーズ用ガラス組成物
を使用したグレーズ層は黒色化することが一切なく、ま
た電気絶縁抵抗もほとんど劣化することがない。(Effect of the invention) As can be seen from the above experimental results, the glaze layer using the glass composition for glazing of the present invention does not turn black at all, and is Insulation resistance also hardly deteriorates.
したがって、本発明のグレーズ用ガラス組成物はメタラ
イズ金属部を有するセラミック基板表面に溶着されるグ
レーズ層の材料として極めて有用である。Therefore, the glass composition for glazing of the present invention is extremely useful as a material for a glaze layer welded to the surface of a ceramic substrate having a metallized metal portion.
Claims (1)
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19913384A JPS6177637A (en) | 1984-09-21 | 1984-09-21 | Glass composition for glaze |
| US06/775,859 US4632846A (en) | 1984-09-17 | 1985-09-13 | Process for preparation of glazed ceramic substrate and glazing composition used therefor |
| US06/926,854 US4767672A (en) | 1984-09-17 | 1986-11-03 | Process for preparation of glazed ceramic substrate and glazing composition used therefor |
| US07/114,227 US4806334A (en) | 1984-09-17 | 1987-10-26 | Glazed ceramic substrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19913384A JPS6177637A (en) | 1984-09-21 | 1984-09-21 | Glass composition for glaze |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6177637A true JPS6177637A (en) | 1986-04-21 |
| JPH0416419B2 JPH0416419B2 (en) | 1992-03-24 |
Family
ID=16402689
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19913384A Granted JPS6177637A (en) | 1984-09-17 | 1984-09-21 | Glass composition for glaze |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6177637A (en) |
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| JP2015020927A (en) * | 2013-07-19 | 2015-02-02 | 株式会社ノリタケカンパニーリミテド | Highly heat-resistant glass bonding material |
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|---|---|---|---|---|
| EP2701182A3 (en) | 2010-12-10 | 2014-06-04 | Teijin Limited | Semiconductor laminate, semiconductor device, method for producing semiconductor laminate, and method for manufacturing semiconductor device |
| JP5930038B2 (en) | 2012-07-20 | 2016-06-08 | 旭化成株式会社 | Solar cell and method for manufacturing solar cell |
| KR20140089624A (en) * | 2012-12-27 | 2014-07-16 | 삼성정밀화학 주식회사 | metal ink composition and fabricating method thereof |
-
1984
- 1984-09-21 JP JP19913384A patent/JPS6177637A/en active Granted
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013071860A (en) * | 2011-09-27 | 2013-04-22 | Okamoto Glass Co Ltd | Lead-free white glass ceramic substrate |
| JP2015020927A (en) * | 2013-07-19 | 2015-02-02 | 株式会社ノリタケカンパニーリミテド | Highly heat-resistant glass bonding material |
| CN110981197A (en) * | 2019-12-20 | 2020-04-10 | 佛山欧神诺陶瓷有限公司 | Preparation method of wet-process dry-grain polished crystal brick and polished crystal brick |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0416419B2 (en) | 1992-03-24 |
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| EXPY | Cancellation because of completion of term |