JPH04160034A - Low melting point glass composition - Google Patents
Low melting point glass compositionInfo
- Publication number
- JPH04160034A JPH04160034A JP28786890A JP28786890A JPH04160034A JP H04160034 A JPH04160034 A JP H04160034A JP 28786890 A JP28786890 A JP 28786890A JP 28786890 A JP28786890 A JP 28786890A JP H04160034 A JPH04160034 A JP H04160034A
- Authority
- JP
- Japan
- Prior art keywords
- glass
- melting point
- glass composition
- composition
- mol
- 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.)
- Pending
Links
- 239000011521 glass Substances 0.000 title claims abstract description 67
- 238000002844 melting Methods 0.000 title claims abstract description 24
- 239000000203 mixture Substances 0.000 title claims description 60
- 230000008018 melting Effects 0.000 title claims description 22
- 239000002253 acid Substances 0.000 abstract description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052681 coesite Inorganic materials 0.000 abstract description 4
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 4
- 239000000377 silicon dioxide Substances 0.000 abstract description 4
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 4
- 229910052682 stishovite Inorganic materials 0.000 abstract description 4
- 229910052905 tridymite Inorganic materials 0.000 abstract description 4
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 abstract 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 abstract 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 abstract 2
- 238000001354 calcination Methods 0.000 abstract 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 abstract 2
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 abstract 2
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 abstract 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract 1
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 abstract 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 abstract 1
- NOTVAPJNGZMVSD-UHFFFAOYSA-N potassium monoxide Inorganic materials [K]O[K] NOTVAPJNGZMVSD-UHFFFAOYSA-N 0.000 abstract 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 abstract 1
- 238000010304 firing Methods 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000007747 plating Methods 0.000 description 6
- 238000007639 printing Methods 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 238000011038 discontinuous diafiltration by volume reduction Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 229910052573 porcelain Inorganic materials 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 210000003754 fetus Anatomy 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 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
- 238000000465 moulding Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
- 238000004506 ultrasonic cleaning 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)
Abstract
Description
【発明の詳細な説明】 「産業上の利用分野」 この発明は低融点のガラス組成物に関するものである。[Detailed description of the invention] "Industrial application field" This invention relates to a low melting point glass composition.
［従来の技術Ｊ
結晶性または非結晶性ハンダガラスを主体とする封着用
組成物は、予め成形された物品、例えば、ガラス物品、
セラミック物品、金属体、半導体素子の封着、接着、あ
るいは、被覆などのために広く用いられている。特に半
導体素子、例えば集積回路やダイオード、トランジスタ
ーを収容するアルミナ磁器、ステアタイト磁器のパッケ
ージを封着するか、半導体素子を直接被覆するために、
低温短時間の熱処理によって焼成できる低膨張性かつ高
絶縁性の強固な封着部か形成されなければならない。[Prior Art J] A sealing composition mainly composed of crystalline or amorphous solder glass can be used in pre-shaped articles, such as glass articles,
It is widely used for sealing, adhering, or coating ceramic articles, metal objects, and semiconductor devices. In particular, for sealing alumina porcelain, steatite porcelain packages containing semiconductor devices, such as integrated circuits, diodes, and transistors, or for directly coating semiconductor devices.
A strong seal with low expansion and high insulation properties must be formed that can be fired by short-time heat treatment at low temperatures.
第１図はチップ抵抗の一構造例を示すものである。この
チップ抵抗を製造するには、まず、アルミナ製の基板ｌ
の両端部側にＡｇ製の主電極２を印刷と焼成（８５０℃
加熱）により形成し、続いて抵抗層３をペースト印刷と
焼成（８５０℃加熱）により形成する。□次に、ガラス
皮膜４を印刷と焼成（５８０〜６２０℃加熱）により形
成し、トリミングを行って抵抗値を均質化する。続いて
ガラス皮膜７を印刷と焼成（５８０〜６２０℃加熱）に
より形成し、抵抗値表示用のマーキングガラスを印刷と
焼成（５８０〜６２０℃加熱）を行ってマーキングガラ
ス８を形成し、更に基板■の両側面に電極９を形成し、
最後にめっき処理を行って完成している。FIG. 1 shows an example of the structure of a chip resistor. To manufacture this chip resistor, first, an alumina substrate l
Main electrodes 2 made of Ag are printed and fired (850℃) on both end sides of the
Then, the resistance layer 3 is formed by paste printing and baking (heating at 850° C.). □Next, a glass film 4 is formed by printing and firing (heating at 580 to 620°C), and trimming is performed to homogenize the resistance value. Subsequently, a glass film 7 is formed by printing and firing (heating at 580 to 620°C), a marking glass 8 is formed by printing and firing (heating at 580 to 620°C) marking glass for displaying resistance values, and a marking glass 8 is formed by printing and firing (heating at 580 to 620°C). Form electrodes 9 on both sides of
Finally, it is completed by plating.
前記のチップ抵抗においては、抵抗層３とガラス皮膜４
とガラス皮膜７が、いずれもガラス組成物を含む層とな
っている。In the above chip resistor, the resistance layer 3 and the glass film 4 are
and glass film 7, both of which are layers containing a glass composition.
「発明が解決しようとする課題」
ところか、前記のガラス皮膜７を印刷して焼成する工程
から、電極９を形成する工程において、焼成時の熱によ
り抵抗値か変化することがあり、高精度品の商品化がで
きずに歩留りが悪い問題があった。これは、各層を構成
するガラス組成物の融点が高く、焼成温度が高いために
、高温に加熱して焼成している間に抵抗値が変動するこ
とが原因と思われる。"Problem to be Solved by the Invention" However, in the process from printing and firing the glass film 7 to forming the electrode 9, the resistance value may change due to the heat during firing, making it difficult to achieve high accuracy. There was a problem that the product could not be commercialized and the yield was poor. This seems to be because the glass compositions constituting each layer have a high melting point and a high firing temperature, so the resistance value fluctuates during firing at high temperatures.
なお、これらの抵抗値の変化の大きさは、製品サイズ、
抵抗値範囲によって異なる。Note that the magnitude of these changes in resistance values depends on the product size,
Varies depending on resistance value range.
なお、前記めっき処理工程においては、酸性の溶液にチ
ップ抵抗を浸漬することになるので、酸によって、各層
が侵されるおそれが高かった。低融点ガラス組成物は、
酸に弱いものが多いので、耐酸性にも優れたガラス組成
物の登場が期待されている。In addition, in the plating process, since the chip resistor is immersed in an acidic solution, there is a high possibility that each layer will be attacked by the acid. The low melting point glass composition is
Many glass compositions are sensitive to acids, so the emergence of glass compositions with excellent acid resistance is expected.
本発明は前記課題を解決するためになされたもので、製
造時に焼成工程を経るチップ抵抗用に好適であって、低
融点のガラス組成物を提供すること、あるいは、融点が
低い上に耐酸性の良好なガラス組成物を提供することを
目的とする。The present invention has been made in order to solve the above-mentioned problems, and is to provide a glass composition suitable for chip resistors that undergoes a firing process during manufacture and which has a low melting point, or which has a low melting point and is resistant to acid. The purpose is to provide a good glass composition.
「課題を解決するための手段」
請求項１に記載した発明に係るガラス組成物は、モル％
で下記酸化物を、下記の範囲の組成成分、２１．３７≦
ＰｂＯ≦４５．３１．４２’、５５≦５ｉＯ７≦６６５
４．６≦ＲＯ≦Ｉ２．０＜ＣｕＯ≦２．５、（ただし、
上８己ＲＯはＬ ＋ｔＯ、ＮａｔＯ、Ｓ ｂｙｏ ３、
Ｋ 、Ｏのいずれか１種または２種以上を示す。"Means for Solving the Problem" The glass composition according to the invention described in claim 1 has a mol%
The following oxide, composition components in the following range, 21.37≦
PbO≦45.31.42', 55≦5iO7≦665
4.6≦RO≦I2.0<CuO≦2.5, (however,
Upper 8 RO is L +tO, NatO, S byo 3,
Represents one or more of K and O.
）としたものである。).
請求項２に記載した発明に係るガラス組成物は、モル％
で下記酸化物を、下記の範囲の組成成分、２１．３７≦
ｐｂｏ≦４５．３１，４２゜５５≦５ｉＯ１≦６６．５
４．６≦ＲＯ≦１２．０＜ＣｕＯ≦２．５．０＜ＱＯ≦
２．０（ただし、上記ＱＯは、Ｃｒ、Ｏｓ、 Ｆ ｅｔ
ＯａのいずれかＩＮまたは２種を示す。）としたもので
ある。The glass composition according to the invention described in claim 2 has a mol%
The following oxide, composition components in the following range, 21.37≦
pbo≦45.31, 42゜55≦5iO1≦66.5
4.6≦RO≦12.0<CuO≦2.5.0<QO≦
2.0 (However, the above QO is Cr, Os, F et
Indicates either IN or two types of Oa. ).
請求項３に記載した発明に係るガラス組成物は、請求項
１または２に記載の組成のガラス組成物と４０重量％を
越えないＰ ｂＴ ｉＯａとからなるものである。The glass composition according to the invention set forth in claim 3 comprises the glass composition having the composition set forth in claim 1 or 2 and P bTiOa in an amount not exceeding 40% by weight.
以下に本発明を更に詳細に説明する。The present invention will be explained in more detail below.
請求項１に記載した発明のガラス組成物においては、モ
ル％て下記酸化物を、下記の範囲の組成成分、２１．３
７≦ＰｂＯ≦４５．３１．４２．５５≦Ｓｉｎ、≦６６
．５４．６≦ＲＯ≦１２．０＜ＣＬＩ○≦２．５、（た
だし、上記ＲＯはＬ ｉ２Ｏ３、Ｆｅ２Ｏ 、ＮａｔＯ
。In the glass composition of the invention described in claim 1, the following oxides are contained in the following range of composition components in mol%: 21.3
7≦PbO≦45.31.42.55≦Sin, ≦66
．． 54.6≦RO≦12.0<CLI○≦2.5, (However, the above RO is Li2O3, Fe2O, NatO
.
Ｓ ｂ、０３．Ｋ 、ｏのいずれか１種または２種以上
を示す。）としたものである。Sb, 03. It represents one or more of K and o. ).
ここでＰｂＯとＳｉｎ、はガラス組成物を構成するため
の主要成分であり、ＰｂＯを２１．３７モル％より少な
くするか、Ｓｉｎ、を６６．５４モル％より多くすると
、低融点のガラス組成物が得られない。また、Ｐｂｏを
４５．３１モル％より多くするか、Ｓｉｎ、を４２．５
５モル％よりも少なくすると耐酸性の良好なガラス組成
物が得られない。Here, PbO and Sin are the main components for constituting the glass composition, and if PbO is less than 21.37 mol% or Sin is more than 66.54 mol%, the glass composition has a low melting point. is not obtained. Also, increase Pbo to more than 45.31 mol% or increase Sin to 42.5 mol%.
If the amount is less than 5 mol%, a glass composition with good acid resistance cannot be obtained.
ＲＯはいずれもアルカリ金属の酸化物であり、添加量が
６モル％未満では低融点ガラス組成物が得られず、１２
モル％を越えるとガラス組成物の耐酸性が劣化する。All ROs are alkali metal oxides, and if the amount added is less than 6 mol%, a low melting point glass composition cannot be obtained;
If it exceeds mol%, the acid resistance of the glass composition will deteriorate.
また、ＣｕＯは低融点化するために添加するものである
か添加量か多すぎると融点か上昇する。Moreover, if CuO is added to lower the melting point, or if the amount added is too large, the melting point will rise.
請求項２に記載した発明に係るガラス組成物においては
、モル％て下記酸化物を、下記の範囲の組成成分、２１
．３７≦ＰｂＯ≦４５．３１，４２゜５５≦ＳｉＯ２≦
６６５４．６≦ＲＯ≦１２．０＜ＣｕＯ≦２．５、Ｏ＜
ＱＯ≦２．０（ただし、上記ＱＯはＣｒｈｏ ｚ、 Ｆ
ｅｔｏ ｙのいずれか１種または２種を示す。）とし
たものである。In the glass composition according to the invention described in claim 2, the following oxides are contained in the following range of composition components in mol%: 21
．． 37≦PbO≦45.31,42゜55≦SiO2≦
6654.6≦RO≦12.0<CuO≦2.5, O<
QO≦2.0 (however, the above QO is Crho z, F
Indicates any one or two of eto y. ).
ここで、Ｃｒ２Ｏ５とＦｅｔｕｓは耐酸性を向上させる
ために添加するものであるが、添加量が多すぎると耐酸
性が低下する。Here, Cr2O5 and Fetus are added to improve acid resistance, but if the amount added is too large, acid resistance will decrease.
前記組成のガラス組成物を半導体素子、例えば集積回路
やダイオード、トランジスタを収容するアルミナ磁器、
ステアタイト磁器のパッケージを封着しあるいは半導体
素子を直接封止するために前記ガラス組成物を利用する
場合は、従来のガラス組成物よりも低い温度で焼成する
ことができる。The glass composition having the above composition is used in alumina porcelain for housing semiconductor devices, such as integrated circuits, diodes, and transistors;
When the glass composition is used to seal steatite porcelain packages or directly seal semiconductor devices, it can be fired at a lower temperature than conventional glass compositions.
従って焼成時に抵抗値の変化が少なくなり、高精度なチ
ップ抵抗を提供することができる。また、前記ガラス組
成物は、耐酸性にも優れているので、めっき処理工程に
おいて酸に浸漬した場合に、酸に侵されることかない。Therefore, the change in resistance value during firing is reduced, and a highly accurate chip resistor can be provided. Moreover, since the glass composition has excellent acid resistance, it will not be attacked by acid when immersed in acid in the plating process.
ところで、請求項１．２に記載した組成のガラス組成物
のみでは、熱膨張係数か高いので、４０重量％より少な
い範囲でＰｂＴｉ０ｚと複合することが好ましい。この
ＰｂＴｉ０．との複合化によって、熱膨張係数を小さく
できるとともに、電気絶縁性を向上させることもできる
。Ｐ ｂＴ ｉｏ−粉末はＰｂＯ粉末とＴｉＯ，粉末と
を混合して混合粉末とした後にこの混合粉末を加圧成形
し、密閉容器内で１０００〜１２００℃で加熱焼成し、
焼成後に粉砕して得ることができる。By the way, since the glass composition having the composition described in claim 1.2 alone has a high coefficient of thermal expansion, it is preferable to combine it with PbTiOz in an amount less than 40% by weight. This PbTi0. By combining it with other materials, it is possible to reduce the coefficient of thermal expansion and improve electrical insulation. PbT io-powder is made by mixing PbO powder and TiO powder to form a mixed powder, and then press-molding this mixed powder, heating and baking it at 1000 to 1200°C in a closed container,
It can be obtained by pulverizing after firing.
このように得られたＰｂＴｉＯｓ粉末と前記組成のガラ
ス組成物の粉末とを混合し、目的の封着部分に封着材と
して使用することができる。The PbTiOs powder obtained in this way and the powder of the glass composition having the above composition can be mixed and used as a sealing material for the target sealing part.
このようにして得られるガラス封着部は、低熱膨張係数
であるので、半導体素子やセラミック基板の熱膨張係数
に近く、熱履歴を受けても歪やクラックが入りにくいも
のである。The glass sealed portion obtained in this manner has a low coefficient of thermal expansion, which is close to that of a semiconductor element or a ceramic substrate, and is resistant to distortion or cracking even when subjected to thermal history.
「実施例」 ｐｂｏと５ｉＯｔとＬＬＯとＮａｔＯとに２０とｓｂ。"Example" 20 and sb for pbo and 5iOt and LLO and NatO.
０３とか第１表に示す種々の組成になるように基本組成
のガラスを製造した。また、得られた基本組成のガラス
について、その熱膨張係数（α）（×１０−’／’Ｃ）
とガラス転位点（Ｔ ｇ）と軟化点（Ｔ ｓ）と密度（
ρ）と耐酸性試験を行い、それらの結果を第１表に示し
た。なお、耐酸性試験とは、各サンプルを超音波洗浄し
た後、１２０℃で１５分間乾燥し、放冷した後に初期重
量を測定し、その後、温度２０±１℃の耐はんだめっき
液に８０分間浸漬し、超音波洗浄と乾燥処理を施して放
冷した後の重量を測定し、比重を用いて体積に換算し体
積減少量（−Δ■）を測定することで行った。Glasses having basic compositions such as 03 and various compositions shown in Table 1 were manufactured. Also, for the glass with the obtained basic composition, its thermal expansion coefficient (α) (×10-'/'C)
and glass transition point (T g), softening point (T s) and density (
ρ) and acid resistance tests were conducted, and the results are shown in Table 1. In addition, the acid resistance test means that after each sample is ultrasonically cleaned, it is dried at 120°C for 15 minutes, the initial weight is measured after it is left to cool, and then it is soaked in a solder-resistant plating solution at a temperature of 20 ± 1°C for 80 minutes. The weight was measured after being immersed, subjected to ultrasonic cleaning and drying treatment, and allowed to cool, and the weight was converted to volume using specific gravity to measure the amount of volume reduction (-Δ■).
（以下、余白）
第１表に示す基本組成のガラスの測定結果（特にサンプ
ル４．５などに示された結果）から、低融点のガラスを
得るためと、耐酸性の良好なガラスを得るためには、２
１．３７≦ｐｂｏ≦４５．３１．４２．５５≦ＳｉＯ２
≦６６．５４であることが必要であり、Ｎａ２Ｏ、Ｋ
ｔｏ 、ｓ ｂ、ｏ ３とイッたアルカリ金属酸化物の
総量は６モル％未満では低融点ガラスが得られず、１２
モル％を越えると耐酸性が劣化することが判明した。(Hereinafter, blank space) From the measurement results of glasses with the basic composition shown in Table 1 (particularly the results shown in samples 4.5, etc.), in order to obtain a glass with a low melting point and a glass with good acid resistance. There are 2
1.37≦pbo≦45.31.42.55≦SiO2
It is necessary that ≦66.54, and Na2O, K
If the total amount of alkali metal oxides such as to, s b, o 3 is less than 6 mol%, a low melting point glass cannot be obtained, and 12
It has been found that when the amount exceeds mol%, acid resistance deteriorates.
しかしながら、第１表に示す組成のガラスでは−ΔＶの
値が高く耐酸性に藺題があり、融点の高いので、これら
の基本組成のガラスに対しＶ ｔ ＯｓとＣｒｙ’ｓと
ＣＬＩＯとをそれぞれ所定量添加することによって、融
点の低下割合と耐酸性の向上効果について検討した。However, the glasses with the compositions shown in Table 1 have high values of -ΔV, have problems with acid resistance, and have high melting points. By adding a predetermined amount, we investigated the rate of decrease in melting point and the effect of improving acid resistance.
ＰｂＯとＳｉＯｘとＬ ｉ＊ｏとＮａｎｏとＫ ｔ Ｏ
とＳｂ。PbO and SiOx and Li*o and Nano and KtO
and Sb.
０、とを第２表に示す組成に固定し、この基本組成のガ
ラスにＣｕＯとＣｒ、０３とＶ、０．とをそれぞれ適量
添加してなる組成のガラス組成物のサンプルを製造した
。また、得られたガラス組成物のサングルについて、第
１表の場合と同様に熱膨張係数（α）（ｘ Ｉ Ｏ−’
／ ’Ｃ）とガラス転位点（Ｔｇ）と軟化点（Ｔ ｓ）
と密度（ρ）と耐酸性試験（体積減少量の値−ΔＶを求
める。）を行った。それらの結果を第２表に示す。0, and are fixed to the composition shown in Table 2, and to the glass of this basic composition, CuO and Cr, 03 and V, 0. Samples of glass compositions were prepared by adding appropriate amounts of and. Further, regarding the sample of the obtained glass composition, the coefficient of thermal expansion (α) (x I O-'
/ 'C), glass transition point (Tg) and softening point (Ts)
and density (ρ) and acid resistance test (calculating volume reduction value - ΔV). The results are shown in Table 2.
（以下、余白）
また、第２図は、第２表に示す組成のサンプルにおいて
、耐めっき液試験の体積減少量（−ＡＶ）と軟化点との
関係を示すものである。(Hereinafter, blank space) Further, FIG. 2 shows the relationship between the volume reduction (-AV) and the softening point in the plating solution resistance test for the samples having the compositions shown in Table 2.
前記第２表と第２図に示された結果から、基本組成のガ
ラスに対しＣｕＯを２，５モル％以下添加するならば、
軟化点の低下をなしえることが明らかになった。また、
ＣｕＯに加えてＦｅｔｅ、、とＣｒ２Ｏ、を総量で２０
モル％以下添加するならば、軟化点の上昇を抑えつつ更
に耐酸性の向上もなしえることが明らかになった。From the results shown in Table 2 and Figure 2 above, if CuO is added in an amount of 2.5 mol% or less to the glass having the basic composition,
It has become clear that the softening point can be lowered. Also,
In addition to CuO, the total amount of Fete, , and Cr2O is 20
It has become clear that if it is added in a mol% or less, it is possible to further improve acid resistance while suppressing the increase in softening point.
以上のことから、融点を下げるためには、ＣｕＯのみを
前記基本組成のガラスに対して２．５モル％以下添加す
るか、あるいは、前記基本組成のガラスに対し、ＣｕＯ
を２，５モル％含め、更に、Ｐｅ５ｏｓとＣｒｔＯ３の
少なくとも１種あるいは２種を２．０モル％以下の範囲
で添加すれば、融点が低く、耐酸性も優れたガラス組成
物を提供できることが明らかになった。From the above, in order to lower the melting point, CuO alone should be added in an amount of 2.5 mol% or less to the glass with the above basic composition, or CuO should be added to the glass with the above basic composition.
It is possible to provide a glass composition with a low melting point and excellent acid resistance by including 2.5 mol% of 2.5 mol% and further adding at least one or both of Pe5os and CrtO3 in a range of 2.0 mol% or less. It was revealed.
「発明の効果」
以上説明したように本発明は、特定量のＰｂ０と５ｉＯ
＝とＲＯとからなる基本組成のガラスに、特定量のＣｕ
Ｏを添加してなるもの、あるいは、前記基本組成のガラ
スにＣ’ｕＯを加え、更にＣｒ。"Effects of the Invention" As explained above, the present invention provides specific amounts of Pb0 and 5iO.
A specific amount of Cu is added to the glass with the basic composition of = and RO.
A glass with O added thereto, or a glass with the above basic composition added with C'uO and further Cr.
０３とＰｅｔ’３の１種以上を特定量添加してなるもの
であるので、従来のガラス組成物に比較すると、融点が
低くなっている。従って本発明のガラス組成物を用いて
チップ抵抗を製造するならば、焼成処理を従来より低温
度でできるので焼成処理を行っても抵抗値の変化を引き
起こすことが少なくなり、構成度のチップ抵抗を提供す
ることができる。Since it is made by adding a specific amount of one or more of 03 and Pet'3, the melting point is lower than that of conventional glass compositions. Therefore, if a chip resistor is manufactured using the glass composition of the present invention, the firing process can be performed at a lower temperature than before, so even if the firing process is performed, changes in the resistance value are less likely to occur, and the chip resistance of the composition degree can be provided.
また、ＣｕＯに加えてＦｅｅ’ｓとＣｒｙ’ｓを加えた
ものにあっては、融点が低い上に、チップ抵抗の耐酸性
が向上するので、めっき処理などＩこおいて酸に浸漬さ
れても変質を来すことが少なく、体積減少量が少ない高
精度のガラス組成物層を備えたチップ抵抗を提供するこ
とができる。In addition, CuO containing Fee's and Cry's has a low melting point and improves the acid resistance of the chip resistor, so it can be easily immersed in acid during plating or other processes. It is also possible to provide a chip resistor including a highly precise glass composition layer that is less likely to undergo deterioration in quality and has less volume reduction.
第１図は一般的なチップ抵抗の構造を示す断面図、第２
図は実施例で得られた複数のサンプルの軟化点と耐酸性
試験における体積減少量との関係を示すグラフである。
１・・・基板、２・主電極、３・抵抗層、４・ガラス皮
膜、７・ガラス皮膜、８・・・マーキングカラス。Figure 1 is a cross-sectional view showing the structure of a typical chip resistor, Figure 2
The figure is a graph showing the relationship between the softening point of a plurality of samples obtained in Examples and the amount of volume reduction in the acid resistance test. 1...Substrate, 2.Main electrode, 3.Resistance layer, 4.Glass film, 7.Glass film, 8.Marking crow.
Claims (1)
Ｏ＿３、Ｋ＿２Ｏのいずれか１種または２種以上を示す
。）の組成成分からなることを特徴とする低融点ガラス
組成物。 （２）モル％で、下記酸化物、 ２１．３７≦ＰｂＯ≦４５．３１ ４２．５５≦ＳｉＯ＿２≦６６．５４ ６≦ＲＯ≦１２ ０＜ＣｕＯ≦２．５ ０＜ＱＯ≦２．０ （ただし上記ＱＯはＣｒ＿２Ｏ＿３、Ｆｅ＿２Ｏ＿３の
いずれか１種または２種を示す。）の組成成分からなる
ことを特徴とする低融点ガラス組成物。 （３）請求項１または２に記載の低融点ガラス組成物と
４０重量％を越えないＰｂＴｉＯ＿３とからなる低融点
ガラス組成物。[Claims] (1) In mol%, the following oxides, 21.37≦PbO≦45.31 42.55≦SiO_2≦66.54 6≦RO≦12 0<CuO≦2.5 (however, the above RO is Li_2O, Na_2O, Sb_2
Indicates one or more of O_3 and K_2O. ) A low melting point glass composition characterized by comprising the following composition components. (2) In mol%, the following oxides, 21.37≦PbO≦45.31 42.55≦SiO_2≦66.54 6≦RO≦12 0<CuO≦2.5 0<QO≦2.0 (however A low melting point glass composition characterized in that the QO represents one or both of Cr_2O_3 and Fe_2O_3. (3) A low melting point glass composition comprising the low melting point glass composition according to claim 1 or 2 and PbTiO_3 not exceeding 40% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28786890A JPH04160034A (en) | 1990-10-25 | 1990-10-25 | Low melting point glass composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28786890A JPH04160034A (en) | 1990-10-25 | 1990-10-25 | Low melting point glass composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04160034A true JPH04160034A (en) | 1992-06-03 |
Family
ID=17722791
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28786890A Pending JPH04160034A (en) | 1990-10-25 | 1990-10-25 | Low melting point glass composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04160034A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005133216A (en) * | 2003-10-31 | 2005-05-26 | Lg Phillips Lcd Co Ltd | Susceptor for deposition process equipment, and method of fabricating the same |
-
1990
- 1990-10-25 JP JP28786890A patent/JPH04160034A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005133216A (en) * | 2003-10-31 | 2005-05-26 | Lg Phillips Lcd Co Ltd | Susceptor for deposition process equipment, and method of fabricating the same |
| US7411161B2 (en) | 2003-10-31 | 2008-08-12 | Lg. Display Co., Ltd | Susceptor for deposition process equipment and method of fabricating a heater therein |
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