JPH0764582B2 - Binder glass for ceramic capacitors - Google Patents
Binder glass for ceramic capacitorsInfo
- Publication number
- JPH0764582B2 JPH0764582B2 JP13407389A JP13407389A JPH0764582B2 JP H0764582 B2 JPH0764582 B2 JP H0764582B2 JP 13407389 A JP13407389 A JP 13407389A JP 13407389 A JP13407389 A JP 13407389A JP H0764582 B2 JPH0764582 B2 JP H0764582B2
- Authority
- JP
- Japan
- Prior art keywords
- glass
- ceramic capacitor
- binder
- dielectric material
- binder glass
- 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
- 239000011521 glass Substances 0.000 title claims description 21
- 239000003985 ceramic capacitor Substances 0.000 title claims description 17
- 239000011230 binding agent Substances 0.000 title claims description 13
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 239000003989 dielectric material Substances 0.000 description 14
- 238000005245 sintering Methods 0.000 description 10
- 238000007747 plating Methods 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 229910020220 Pb—Sn Inorganic materials 0.000 description 5
- 229910052718 tin Inorganic materials 0.000 description 5
- 229910001252 Pd alloy Inorganic materials 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 3
- 229910002113 barium titanate Inorganic materials 0.000 description 3
- 238000004031 devitrification Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004017 vitrification 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
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/24—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
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)
- Ceramic Capacitors (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は、ハイブリッドIC等の電子部品に使用されるセ
ラミックコンデンサーの誘電体材料を低温で燒結するち
めに用いるバインダーガラスに関するものである。Description: TECHNICAL FIELD The present invention relates to a binder glass used as a binder for sintering a dielectric material of a ceramic capacitor used in an electronic component such as a hybrid IC at a low temperature.
［従来の技術］ 近年電子部品が小型化、高機能化されるのに伴ってこれ
らに使用されるセラミックコンデンサーも小型化、大容
量化が要求されており、現在この要求を満足すべく誘電
体と電極とを交互に層状に組み合わせて一体焼成してな
る積層セラミックコンデンサーが実用化されている。積
層セラミックコンデンサーの誘電体材料としては、チタ
ン酸バリウム系セラミックスが広く使用されているが、
このチタン酸バリウム系セラミックスの燒結温度は1300
℃以上である。そのため各誘電体の間に形成する電極
（内部電極）の材料としては融点が高く、高温で焼成し
ても劣化しにくい貴金属が使用され、この中でも比較的
安価な銀ーパラジウム合金（以下Ag−Pd合金という）が
最も多く用いられている。[Prior Art] With the recent miniaturization and high functionality of electronic components, ceramic capacitors used for these are also required to be miniaturized and to have a large capacity. At present, dielectric materials are required to satisfy these requirements. A multilayer ceramic capacitor has been put to practical use in which electrodes and electrodes are alternately combined in a layered form and integrally fired. Barium titanate-based ceramics are widely used as a dielectric material for a monolithic ceramic capacitor.
The sintering temperature of this barium titanate-based ceramics is 1300.
℃ or above. Therefore, as the material of the electrodes (internal electrodes) formed between the dielectrics, noble metals that have a high melting point and do not easily deteriorate even when fired at high temperatures are used. Among these, relatively inexpensive silver-palladium alloys (hereinafter Ag-Pd Alloy) is most often used.
ところでAg−Pd合金は全率固溶する特性を有する物質で
あり、Pdの比率が減少するほど融点が低下し、コストの
低減を計るためにも高価なPdの含有量が少ない方が好ま
しい。しかしながら誘電体材料の燒結温度は電極材料の
融点よりも低くなければならないのでAg−Pd合金のPdの
含有量を減少させて融点を低くすると、それに伴って誘
電体材料の燒結温度も低くする必要があり、そのため誘
電体材料にバインダーガラスを混合することによって低
温で焼結する方法が採られており、従来より各種のバイ
ンダーガラスが提案されている。By the way, the Ag-Pd alloy is a substance having a characteristic of being solid-solved in all proportions, and the melting point is lowered as the proportion of Pd is reduced, and it is preferable that the content of expensive Pd is small in order to reduce the cost. However, the sintering temperature of the dielectric material must be lower than the melting point of the electrode material, so if the Pd content of the Ag-Pd alloy is reduced to lower the melting point, the sintering temperature of the dielectric material must also be lowered accordingly. Therefore, a method of mixing a dielectric material with a binder glass and sintering at a low temperature has been adopted, and various binder glasses have been conventionally proposed.
また積層セラミックコンデンサーは、その外部に接続用
電極（外部電極）を形成し、この外部電極を回路基板に
直接ハンダ付けすることによって使用させる。この外部
電極は低コスト化、ハンダ耐熱性及びぬれ性の向上を計
るため一般にAg−Pd合金下地外部電極の上にNi,Cu等の
メッキを施し、その上にSn,Pb−Sn等のメッキを施した
構造を有している。The monolithic ceramic capacitor is used by forming a connection electrode (external electrode) on the outside thereof and directly soldering the external electrode to the circuit board. This external electrode is generally plated with Ni, Cu, etc. on the Ag-Pd alloy base external electrode in order to reduce costs, improve solder heat resistance and wettability, and then Sn, Pb-Sn, etc. It has a structure with.
［発明が解決しようとする問題点］ 先記したように積層セラミックコンデンサーにはSn,Pb
−Sn等のメッキが施されるが、Sn,Pb−Snメッキ液の酸
性が強く、誘電体材料の耐酸性が低いと特性が劣化す
る。そのためこれに用いるバインダーガラスは耐酸性に
優れていることが要求されるが、充分満足のいく耐酸性
を有するバインダーガラスは未だ存在しないのが現状で
ある。[Problems to be Solved by the Invention] As described above, Sn, Pb are contained in the multilayer ceramic capacitor.
Although -Sn or the like is plated, the Sn, Pb-Sn plating solution has a strong acidity, and if the acid resistance of the dielectric material is low, the characteristics deteriorate. Therefore, the binder glass used for this is required to have excellent acid resistance, but at present, there is no binder glass having sufficiently satisfactory acid resistance.
本発明の目的は、セラミックコンデンサーの誘電体材料
を800〜1000℃の低温で燒結することを可能にし、しか
もSn,Pb−Snメッキ工程においてセラミックコンデンサ
ーをメッキ液中に浸漬した時、メッキ液がセラミックコ
ンデンサー内部に侵入しても誘電体の特性が劣化しない
ような優れた耐酸性を有するセラミックコンデンサー用
バインダーガラスを提供することを目的とするものであ
る。The object of the present invention makes it possible to sinter the dielectric material of the ceramic capacitor at a low temperature of 800 to 1000 ° C., and when the ceramic capacitor is immersed in the plating solution in the Sn, Pb-Sn plating process, the plating solution is It is an object of the present invention to provide a binder glass for a ceramic capacitor, which has excellent acid resistance such that the characteristics of the dielectric material do not deteriorate even if it enters the inside of the ceramic capacitor.
［問題点を解決するための手段］ 本発明のセラミックコンデンサー用バインダーガラス
は、重量百分率でZnO50.0〜70.0％、B2O320.0〜30.0
％、SiO25.0〜20.0％、Al2O38.2〜10.5％からなること
を特徴とする。[Means for Solving Problems] The binder glass for a ceramic capacitor of the present invention has a weight percentage of ZnO 50.0 to 70.0% and B 2 O 3 20.0 to 30.0.
%, SiO 2 5.0 to 20.0%, Al 2 O 3 8.2 to 10.5%.
本発明において先記のように各成分の含有量を限定した
のは以下の理由による。In the present invention, the content of each component is limited as described above for the following reason.
ZnOが50.0％より少ない場合は、ガラスの軟化温度が高
くなりすぎて誘電体材料を1000℃以下で燒結することが
できなくなり、70.0％より多い場合はガラス溶液中に失
透を生成しやすくなる。When the content of ZnO is less than 50.0%, the softening temperature of the glass becomes too high so that the dielectric material cannot be sintered at 1000 ° C or less, and when it is more than 70.0%, devitrification is likely to occur in the glass solution. .
B2O3はガラスの軟化温度を下げる効果を有するが、20.0
％より少ない場合はガラス溶液中に失透を生成しやすく
なり、30.0％より多い場合は均質なガラスが得られにく
くなる。B 2 O 3 has the effect of lowering the softening temperature of glass, but 20.0
When it is less than 3%, devitrification is likely to occur in the glass solution, and when it is more than 30.0%, it becomes difficult to obtain a homogeneous glass.
SiO25.0％より少ない場合は耐酸性が悪くなり、20.0％
より多い場合はガラス化が困難になったり、軟化温度が
上昇して誘電体材料を1000℃以下で燒結することができ
なくなる。If the SiO 2 content is less than 5.0%, the acid resistance will be poor and 20.0%
If it is more than that, vitrification becomes difficult, or the softening temperature rises, and it becomes impossible to sinter the dielectric material below 1000 ° C.
Al2O3は耐酸性を向上させる効果を有するが、8.2％より
少ない場合はその効果が得られ難く、Pb−Snメッキ液に
よって誘電体の特性が劣化し易く、10.5％より多い場合
はガラス溶液中に失透を生成しやすくなる。Al 2 O 3 has the effect of improving acid resistance, but if it is less than 8.2%, it is difficult to obtain that effect, and the characteristics of the dielectric material are easily deteriorated by the Pb-Sn plating solution, and if it is more than 10.5%, it is glass. Devitrification tends to occur in the solution.
また本発明においては、上記成分以外にも軟化点の調整
のためLi2Ｏを５重量％まで添加することが可能であ
る。Further, in the present invention, it is possible to add up to 5% by weight of Li 2 O in addition to the above components for adjusting the softening point.
［実施例］ 以下本発明のセラミックコンデンサー用バインダーガラ
スを実施例に基づいて説明する。[Examples] Hereinafter, the binder glass for a ceramic capacitor of the present invention will be described based on Examples.
次表は本発明の実施例（試料No.1〜７）及び比較例（試
料No.8）を示すものである。The following table shows examples (Sample Nos. 1 to 7) and comparative examples (Sample No. 8) of the present invention.
先表の各ガラス試料は以下のように調製した。 Each glass sample in the above table was prepared as follows.
まず設計組成となるように調合した原料を1300℃で１時
間溶融した後、ロール成形し、粉砕した。その後この粉
砕物をアルミナボールミナでさらに微粉砕し、平均粒径
６μｍ程度とした。次いでチタン酸バリウム仮焼体100
重量％に対して先記ガラス微粉砕物を20重量％添加した
後、アルミナボールミナで粉砕して乾燥し、さらに有機
バインダーを加えて造粒した。その後この造粒体をプレ
スして直径20mm、厚さ2mmの円板状素体を作製し、この
円板状素体を空気中で表中の燒結温度で２時間熱処理し
た。First, raw materials prepared so as to have a designed composition were melted at 1300 ° C. for 1 hour, then roll-formed and crushed. Thereafter, this pulverized product was further finely pulverized with an alumina ball miner to have an average particle size of about 6 μm. Then barium titanate calcined 100
20% by weight of the above glass finely pulverized product was added to the weight%, pulverized with an alumina ball miner and dried, and an organic binder was further added for granulation. Thereafter, this granulated body was pressed to produce a disk-shaped element having a diameter of 20 mm and a thickness of 2 mm, and this disk-shaped element was heat-treated in air at the sintering temperature shown in the table for 2 hours.
表中の軟化点は、先記微粉砕したガラスを示差熱分析計
を用いて測定し、また燒結性は、先記円板状素体を燒結
した後、自動比重測定装置を用いてその燒結密度を測定
し、その結果から判定したものである。各試料とも950
℃以下で燒結し、また5.5以上の密度を有しており良好
な燒結性を有していた。さらに耐Snメッキ性は先記ガラ
ス微粉砕物をプレス成形し、650℃で10分間焼成して焼
成体を作製し、これをpHが１以下のSnメッキ液（20℃）
に１時間浸漬した後の重量損失を％表示したものであ
る。この結果、比較例であるNo.8の試料の重量損失が9.
8％であったのに対して、実施例であるNo.1〜７の試料
は、その重量損失が1.2〜1.8％と非常に小さく、Snメッ
キ液に対して優れた耐酸性を有していることがわかる。The softening point in the table, the finely pulverized glass was measured using a differential thermal analyzer, and the sintering property, after sintering the disk-shaped element described above, the sintering using an automatic specific gravity measuring device. The density was measured and judged from the results. 950 for each sample
It sinters below ℃, has a density of 5.5 or more, and has a good sinterability. Further, the Sn plating resistance is obtained by press-molding the finely pulverized glass material described above and firing at 650 ° C for 10 minutes to produce a fired body, which is a Sn plating solution (20 ° C) with a pH of 1 or less.
The weight loss after soaking in 1 hour is shown as a percentage. As a result, the weight loss of the sample No. 8 which is a comparative example is 9.
In contrast to 8%, the samples of Examples No. 1 to 7 have a very small weight loss of 1.2 to 1.8% and have excellent acid resistance to the Sn plating solution. You can see that
［発明の効果］ 以上のように本発明のセラミックコンデンサー用バイン
ダーガラスは、セラミックコンデンサーの誘電体材料を
800〜1000℃の低温で燒結することを可能にするため電
極の材料として比較的安価な金属を使用することができ
る、しかも優れた耐酸性を有するためセラミックコンデ
ンサーをSn,Pb−Snメッキ液中に浸漬しても特性の劣化
を妨ぐことができる。[Advantages of the Invention] As described above, the binder glass for a ceramic capacitor of the present invention uses the dielectric material of the ceramic capacitor.
A relatively inexpensive metal can be used as the material of the electrode to enable sintering at a low temperature of 800 to 1000 ° C, and because it has excellent acid resistance, the ceramic capacitor can be used in Sn, Pb-Sn plating solutions. It is possible to prevent deterioration of characteristics even when immersed in.
Claims (1)
0〜30.0％、SiO2 5.0〜20.0％、Al2O3 8.2〜10.5％から
なることを特徴とするセラミックコンデンサー用バイン
ダーガラス。1. A weight percentage of ZnO 50.0 to 70.0%, B 2 O 3 20.
A binder glass for a ceramic capacitor, which comprises 0 to 30.0%, SiO 2 5.0 to 20.0%, and Al 2 O 3 8.2 to 10.5%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13407389A JPH0764582B2 (en) | 1989-05-26 | 1989-05-26 | Binder glass for ceramic capacitors |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13407389A JPH0764582B2 (en) | 1989-05-26 | 1989-05-26 | Binder glass for ceramic capacitors |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02311330A JPH02311330A (en) | 1990-12-26 |
| JPH0764582B2 true JPH0764582B2 (en) | 1995-07-12 |
Family
ID=15119754
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13407389A Expired - Lifetime JPH0764582B2 (en) | 1989-05-26 | 1989-05-26 | Binder glass for ceramic capacitors |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0764582B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100355684C (en) * | 2001-11-30 | 2007-12-19 | 旭硝子株式会社 | Sealing composition and sealing material |
| JP6410089B2 (en) * | 2014-09-09 | 2018-10-24 | 日本電気硝子株式会社 | Glass for semiconductor element coating |
-
1989
- 1989-05-26 JP JP13407389A patent/JPH0764582B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02311330A (en) | 1990-12-26 |
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