JPWO2012176696A1 - Ruthenium oxide powder, composition for thick film resistor and thick film resistor using the same - Google Patents
Ruthenium oxide powder, composition for thick film resistor and thick film resistor using the same Download PDFInfo
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- H—ELECTRICITY
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- H—ELECTRICITY
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Abstract
ルテニウムの含有率が低くても充分な性能を有するチップ抵抗器、ハイブリッドＩＣ、または、抵抗ネットワーク等の電子部品材料として安価に製造できる酸化ルテニウム粉末、それを用いた厚膜抵抗体用組成物および厚膜抵抗体を提供する。ルチル型結晶構造を有する酸化ルテニウム（ＲｕＯ２）粉末であって、Ｘ線回折法でその（１１０）面を測定した結晶子径が３〜１０ｎｍであり、かつＲｕ含有量が７３質量％以上であることを特徴とする酸化ルテニウム粉末；酸化ルテニウム粉末からなる導電性粒子とガラス粉末を主要構成成分として配合してなる厚膜抵抗体用組成物；厚膜抵抗体組成物が脂肪酸を含む有機ビヒクル中に分散した厚膜抵抗体ペーストであって、脂肪酸の含有量が酸化ルテニウム１００重量部に対して０．１〜１０重量部であることを特徴とする厚膜抵抗体ペーストなどにより提供。Ruthenium oxide powder that can be produced inexpensively as an electronic component material such as a chip resistor, a hybrid IC, or a resistor network having sufficient performance even when the ruthenium content is low, a composition for a thick film resistor using the same, and A thick film resistor is provided. A ruthenium oxide (RuO2) powder having a rutile-type crystal structure, the crystallite diameter measured by the X-ray diffraction method of the (110) plane is 3 to 10 nm, and the Ru content is 73% by mass or more. Ruthenium oxide powder characterized by: a thick film resistor composition comprising conductive particles composed of ruthenium oxide powder and glass powder as main components; thick film resistor composition in an organic vehicle containing fatty acid A thick film resistor paste dispersed in a thick film resistor paste, wherein the fatty acid content is 0.1 to 10 parts by weight with respect to 100 parts by weight of ruthenium oxide.
Description
本発明は、酸化ルテニウム粉末、それを用いた厚膜抵抗体用組成物および厚膜抵抗体に関し、ルテニウムの含有率が低くても充分な性能を有するチップ抵抗器、ハイブリッドＩＣ、または、抵抗ネットワーク等の電子部品材料として安価に製造できる酸化ルテニウム粉末、それを用いた厚膜抵抗体用組成物および厚膜抵抗体に関する。 The present invention relates to a ruthenium oxide powder, a composition for a thick film resistor and a thick film resistor using the same, and a chip resistor, a hybrid IC, or a resistor network having sufficient performance even when the ruthenium content is low The present invention relates to a ruthenium oxide powder that can be manufactured at low cost as an electronic component material such as a thick film resistor composition and a thick film resistor using the same.
一般にチップ抵抗器、ハイブリッドＩＣ、または、抵抗ネットワーク等の厚膜抵抗体は、セラミック基板に厚膜抵抗ペーストを印刷して焼成することによって形成されている。厚膜抵抗体用の組成物は、導電粒子として酸化ルテニウムを代表とするルテニウム酸化物粉末とガラス粉末を主な成分としたものが広く用いられている。 In general, a thick film resistor such as a chip resistor, a hybrid IC, or a resistor network is formed by printing and baking a thick film resistor paste on a ceramic substrate. As a composition for a thick film resistor, a composition mainly composed of ruthenium oxide powder typified by ruthenium oxide and glass powder as conductive particles is widely used.
ルテニウム酸化物とガラス粉末が厚膜抵抗体に用いられる理由は、空気中での焼成ができ、抵抗温度係数（ＴＣＲ）を０に近づける事が可能である事に加え、広い領域の抵抗値の抵抗体が形成可能である事などが挙げられる。 The reason why ruthenium oxide and glass powder are used for thick film resistors is that they can be fired in air and the resistance temperature coefficient (TCR) can be brought close to 0, and the resistance value in a wide region For example, a resistor can be formed.
ルテニウム酸化物とガラス粉末からなる厚膜抵抗用組成物では、その配合比によって抵抗値が変わる。導電粒子であるルテニウム酸化物の配合比を多くすると抵抗値が下がり、導電物の配合比を少なくすると抵抗値が上がる。この事を利用して、厚膜抵抗体では、ルテニウム酸化物とガラス粉末の配合比を調整して所望する抵抗値を出現させている。 In a thick film resistor composition composed of ruthenium oxide and glass powder, the resistance value varies depending on the blending ratio. Increasing the compounding ratio of ruthenium oxide, which is a conductive particle, decreases the resistance value, and decreasing the compounding ratio of the conductive material increases the resistance value. By utilizing this fact, in the thick film resistor, a desired resistance value appears by adjusting the mixing ratio of ruthenium oxide and glass powder.
ルテニウム酸化物として最も一般的なものは、ルチル型の結晶構造を有する酸化ルテニウム（ＲｕＯ２）であり、後述するルテニウム酸化物の種類の中では比抵抗が最も低い。そして、酸化ルテニウム（ＲｕＯ２）粉末とガラス粉末の組み合わせでは、一般に１０−２Ω・ｃｍ〜１０４Ω・ｃｍ（１０−４Ω・ｍ〜１０２Ω・ｍ）の領域の抵抗体が形成できる。The most common ruthenium oxide is ruthenium oxide (RuO 2 ) having a rutile-type crystal structure, and has the lowest specific resistance among the types of ruthenium oxides described later. A combination of ruthenium oxide (RuO 2 ) powder and glass powder generally forms a resistor in the region of 10 −2 Ω · cm to 10 4 Ω · cm (10 −4 Ω · m to 10 2 Ω · m). it can.
ルテニウム酸化物としては、ルチル型の結晶構造を有する酸化ルテニウム（ＲｕＯ２）、パイロクロア型の結晶構造を有するルテニウム酸鉛、ルテニウム酸ビスマス、ペロブスカイト型結晶構造を有するルテニウム酸カルシウム、ルテニウム酸ストロンチウム、ルテニウム酸バリウム、ルテニウム酸ランタン等があり、これらはいずれも金属的な導電性を示す酸化物である。
ルチル型の結晶構造を有する酸化ルテニウム（ＲｕＯ２）は、例えば、不定形酸化ルテニウム水和物を焙焼して得られたＲｕＯ2 粒子に、例えば、ＫＯＨおよびＮａＯＨの少なくとも一方を被覆させ、再び焙焼したのち、水洗、乾燥するなどの方法で製造されている（特許文献４参照）。Examples of the ruthenium oxide include ruthenium oxide (RuO 2 ) having a rutile crystal structure, lead ruthenate having a pyrochlore crystal structure, bismuth ruthenate, calcium ruthenate having a perovskite crystal structure, strontium ruthenate, ruthenium There are barium acid, lanthanum ruthenate, and the like, and these are oxides showing metallic conductivity.
Ruthenium oxide (RuO 2 ) having a rutile-type crystal structure is obtained by, for example, coating RuO 2 particles obtained by roasting amorphous ruthenium oxide hydrate with at least one of KOH and NaOH, for example. After roasting, it is manufactured by a method such as washing with water and drying (see Patent Document 4).
ルテニウム酸化物とガラス粉末からなる厚膜抵抗用組成物は、優れた抵抗体特性が得られるため広く用いられているが、ルテニウムは高価な貴金属であり、これを用いる厚膜抵抗体はコストが高い欠点がある。
そのためルテニウム酸化物とガラス粉末の組み合わせでは到達することが難しい、低い抵抗値領域の厚膜抵抗用組成物においては、導電物としてパラジウムと銀を添加することで所望の抵抗値を出現させている。しかし、パラジウムはルテニウムよりも高価な貴金属であり、この抵抗値が低い領域の厚膜抵抗体も同様にコストが高くなる欠点がある。また、ルテニウムとパラジウムは産出量が少ないため価格変動が激しく厚膜抵抗体の製造にかかる原料コストが安定しない。特に抵抗値が低い厚膜抵抗体程、ルテニウムもしくはパラジウム含有率が高いために価格が高く、製品価格が不安定になる。したがって、ルテニウム、抵抗値が低い領域においてはルテニウムとパラジウムの使用量を極力削減した低価格の厚膜抵抗体用組成物が望まれていた。Thick film resistors composed of ruthenium oxide and glass powder are widely used because of their excellent resistance characteristics, but ruthenium is an expensive noble metal, and thick film resistors using this composition are costly. There are high drawbacks.
Therefore, it is difficult to reach with a combination of ruthenium oxide and glass powder, and in a low resistance value thick film resistance composition, a desired resistance value appears by adding palladium and silver as a conductive material. . However, palladium is a noble metal that is more expensive than ruthenium, and the thick film resistor in the region where the resistance value is low has a disadvantage that the cost is similarly increased. In addition, since ruthenium and palladium are produced in small quantities, the price fluctuates drastically and the raw material costs for manufacturing thick film resistors are not stable. In particular, a thick film resistor having a low resistance value has a high ruthenium or palladium content, so that the price is high and the product price becomes unstable. Therefore, a low-cost composition for thick film resistors in which the amount of ruthenium and palladium used is reduced as much as possible in the region where ruthenium and resistance values are low has been desired.
これまでに粒径の細かい酸化ルテニウム（ＲｕＯ２）を厚膜抵抗体に用いた例として、特開平７−２２２０２（特許文献１）がある。この特許文献１では、比表面積が大きい酸化ルテニウムを使用する事によって静電放電（ＥＳＤ）に対する耐久性を改善されると述べており、比表面積が５０ｍ２／ｇ以上であり、かつ結晶子サイズが２５ｎｍ以下である酸化ルテニウムの固形物を使用した厚膜抵抗体組成物の例を挙げている。しかしながら、ここに記載された実施例では比表面積が最も大きいものでも５１．９ｍ２／ｇであり、結晶子サイズの最も小さいものでも１３．３ｎｍである。この比表面積と結晶子サイズでは、厚膜抵抗体用組成物として十分に経済的な効果が得られるほどルテニウムを削減できない。As an example of using ruthenium oxide (RuO 2 ) having a fine particle size as a thick film resistor, there is JP-A-7-22202 (Patent Document 1). This Patent Document 1 states that durability against electrostatic discharge (ESD) can be improved by using ruthenium oxide having a large specific surface area, the specific surface area is 50 m 2 / g or more, and the crystallite size. An example of a thick film resistor composition using a solid ruthenium oxide having a thickness of 25 nm or less is given. However, in the examples described herein, even the largest specific surface area is 51.9 m 2 / g, and the smallest crystallite size is 13.3 nm. With this specific surface area and crystallite size, ruthenium cannot be reduced to such an extent that a sufficiently economical effect can be obtained as a thick film resistor composition.
また、特開平８−２１７４５９（特許文献２）には、比表面積が７０ｍ２／ｇ以上の酸化ルテニウム粉末を製造した例が記載されている（実施例）。しかし、結晶子に関する記載はない。また、酸化ルテニウム中のルテニウム含有量が最大７３．９％であることから水和した結晶の完全性が低い酸化ルテニウムであり、このような酸化ルテニウム粉末を用いた厚膜抵抗体は抵抗値が高くなり、厚膜抵抗体用組成物としてルテニウムを削減する事はできない。Japanese Patent Application Laid-Open No. 8-217459 (Patent Document 2) describes an example in which a ruthenium oxide powder having a specific surface area of 70 m 2 / g or more is manufactured (Example). However, there is no description about crystallites. In addition, since the ruthenium content in ruthenium oxide is 73.9% at the maximum, it is ruthenium oxide with low integrity of hydrated crystals, and a thick film resistor using such ruthenium oxide powder has a resistance value. As a result, ruthenium cannot be reduced as a thick film resistor composition.
この他、特開平４−２９０４０１（特許文献３）にも比表面積が２００ｍ２／ｇであるルテニウム酸化物を導電粒子とする抵抗体ペーストが記載されている（実施例）。しかし、これも結晶子に関する記載はなく、Ｈ２Ｏが２０％付加されているルテニウム酸化物と記載されていることから、水和した結晶の完全性が低いものである。In addition, Japanese Patent Laid-Open No. 4-290401 (Patent Document 3) also describes a resistor paste using ruthenium oxide having a specific surface area of 200 m 2 / g as conductive particles (Example). However, there is no description about the crystallite, and it is described as a ruthenium oxide to which 20% of H 2 O is added. Therefore, the integrity of the hydrated crystal is low.
本発明の目的は、ルテニウムの含有率が低くても充分な性能を有するチップ抵抗器、ハイブリッドＩＣ、または、抵抗ネットワーク等の電子部品材料として安価に製造できる酸化ルテニウム粉末、それを用いた厚膜抵抗体用組成物および厚膜抵抗体を提供することにある。 An object of the present invention is to provide a ruthenium oxide powder that can be manufactured at low cost as an electronic component material such as a chip resistor, a hybrid IC, or a resistor network having a sufficient performance even when the content of ruthenium is low, and a thick film using the same The object is to provide a resistor composition and a thick film resistor.
本発明者らは、上述した従来の課題を解決するため鋭意研究を重ねた結果、導電性粒子とガラス粉末を主な構成成分とする厚膜抵抗体用組成物において、結晶性の高い酸化ルテニウムを用いることによって、その結晶子径が微細であっても、抵抗ペースト焼成時に粒成長が抑制されるようになることを見出し、このような酸化ルテニウム（ＲｕＯ２）を原料とすることによって、抵抗値が低くルテニウム含有率を削減した安価な厚膜抵抗体組成物を提供できることを確認して、本発明を完成するに至った。As a result of intensive studies to solve the conventional problems described above, the present inventors have found that ruthenium oxide having high crystallinity in a composition for a thick film resistor containing conductive particles and glass powder as main components. It has been found that even when the crystallite diameter is fine, grain growth is suppressed during firing of the resistance paste, and by using such ruthenium oxide (RuO 2 ) as a raw material, resistance After confirming that an inexpensive thick film resistor composition having a low value and a reduced ruthenium content can be provided, the present invention has been completed.
すなわち、本発明の第１の発明によれば、ルチル型結晶構造を有する酸化ルテニウム（ＲｕＯ２）粉末であって、Ｘ線回折法でその（１１０）面を測定した結晶子径が３〜１０ｎｍであり、かつＲｕ含有量が７３質量％以上であることを特徴とする酸化ルテニウム粉末が提供される。That is, according to the first invention of the present invention, the ruthenium oxide (RuO 2 ) powder having a rutile-type crystal structure, and the crystallite diameter of the (110) plane measured by X-ray diffraction method is 3 to 10 nm. And a ruthenium oxide powder characterized in that the Ru content is 73% by mass or more.
また、本発明の第２の発明によれば、第１の発明において、酸化ルテニウム（ＲｕＯ２）粉末の比表面積が７０〜２００ｍ２／ｇであることを特徴とする酸化ルテニウム粉末が提供される。
また、本発明の第３の発明によれば、第１または２の発明において、酸化ルテニウム（ＲｕＯ２）粉末は、結晶子径Ｄ１と比表面積径Ｄ２の比が、下記の式（１）を満たすことを特徴とする酸化ルテニウム粉末が提供される。
Ｄ１／Ｄ２≧０．７０ ・・・（１）
（ただし、結晶子径Ｄ１は、Ｘ線回折法によるルチル型結晶構造の（１１０）面での測定値（ｎｍ）であり、比表面積径Ｄ２は、粉末の比表面積をＳ（ｍ２／ｇ）、比重をρ（ｇ／ｃｍ３）と表したときの６×１０−６／（ρ・Ｓ）の計算値（ｎｍ）である）According to a second aspect of the present invention, there is provided a ruthenium oxide powder characterized in that, in the first aspect, the specific surface area of the ruthenium oxide (RuO 2 ) powder is 70 to 200 m 2 / g. .
According to the third invention of the present invention, in the first or second invention, the ruthenium oxide (RuO 2 ) powder has a ratio of the crystallite diameter D1 to the specific surface area diameter D2 of the following formula (1): A ruthenium oxide powder is provided that is characterized by filling.
D1 / D2 ≧ 0.70 (1)
(However, the crystallite diameter D1 is a value (nm) measured on the (110) plane of the rutile crystal structure by the X-ray diffraction method, and the specific surface area diameter D2 is the specific surface area of the powder as S (m 2 / g ), Calculated value (nm) of 6 × 10 −6 / (ρ · S) when the specific gravity is expressed as ρ (g / cm 3 ))
また、本発明の第４の発明によれば、第１〜３のいずれかの発明において、酸化ルテニウム粉末からなる導電性粒子とガラス粉末を主要構成成分として配合してなる厚膜抵抗体用組成物が提供される。
また、本発明の第５の発明によれば、第４の発明において、導電性粒子として、さらに銀（Ａｇ）粉、パラジウム（Ｐｄ）粉、もしくはパラジウムによりコートされた銀粉の酸化物及び貴金属粉末のいずれか1種以上が配合されることを特徴とする厚膜抵抗体用組成物が提供される。
一方、本発明の第６の発明によれば、第４又は５の発明において、導電性粒子とガラス粉末は、質量比として５：９５〜７０：３０の範囲で配合されることを特徴とする厚膜抵抗体用組成物が提供される。
また、本発明の第７の発明によれば、第４〜６のいずれかの発明において、ガラス粉末は、５０％累計粒度が５μｍ以下であることを特徴とする厚膜抵抗体用組成物が提供される。
また、本発明の第８の発明によれば、第４〜７のいずれかの発明において、厚膜抵抗体組成物が脂肪酸を含む有機ビヒクル中に分散した厚膜抵抗体ペーストであって、脂肪酸の含有量が酸化ルテニウム１００重量部に対して０．１〜１０重量部であることを特徴とする厚膜抵抗体ペーストが提供される。
また、本発明の第９の発明によれば、第８の発明において、脂肪酸が、炭素数が１２以上の高級脂肪酸であることを特徴とする厚膜抵抗体ペーストが提供される。According to a fourth invention of the present invention, in any one of the first to third inventions, a composition for a thick film resistor, comprising conductive particles made of ruthenium oxide powder and glass powder as main components. Things are provided.
Further, according to the fifth invention of the present invention, in the fourth invention, as the conductive particles, silver (Ag) powder, palladium (Pd) powder, or silver-coated oxide and noble metal powder coated with palladium. Any one or more of these may be blended, and a thick film resistor composition is provided.
On the other hand, according to a sixth invention of the present invention, in the fourth or fifth invention, the conductive particles and the glass powder are blended in a mass ratio of 5:95 to 70:30. A thick film resistor composition is provided.
According to a seventh aspect of the present invention, there is provided the thick film resistor composition according to any one of the fourth to sixth aspects, wherein the glass powder has a 50% cumulative particle size of 5 μm or less. Provided.
According to an eighth aspect of the present invention, there is provided the thick film resistor paste according to any one of the fourth to seventh aspects, wherein the thick film resistor composition is dispersed in an organic vehicle containing a fatty acid. The thick film resistor paste is provided in which the content of is 0.1 to 10 parts by weight with respect to 100 parts by weight of ruthenium oxide.
According to a ninth aspect of the present invention, there is provided the thick film resistor paste according to the eighth aspect, wherein the fatty acid is a higher fatty acid having 12 or more carbon atoms.
また、本発明の第１０の発明によれば、第８の発明において、導電性粒子とガラス粉末は、質量比として５：９５〜７０：３０の範囲で配合されることを特徴とする厚膜抵抗体ペーストが提供される。
さらに、本発明の第１１の発明によれば、第４〜７のいずれかの発明の厚膜抵抗体用組成物を、セラミック基板上で焼成してなる厚膜抵抗体が提供される。
また、本発明の第１２の発明によれば、第８〜１０のいずれかの発明の厚膜抵抗体ペーストを、セラミック基板に塗布した後、焼成して形成された厚膜抵抗体が提供される。
質量％According to a tenth aspect of the present invention, in the eighth aspect, the conductive particles and the glass powder are blended in a mass ratio of 5:95 to 70:30. A resistor paste is provided.
Furthermore, according to the eleventh aspect of the present invention, there is provided a thick film resistor formed by firing the thick film resistor composition of any of the fourth to seventh aspects of the invention on a ceramic substrate.
According to a twelfth aspect of the present invention, there is provided a thick film resistor formed by applying the thick film resistor paste according to any of the eighth to tenth aspects of the invention to a ceramic substrate and then firing the paste. The
mass%
本発明の方法によれば、ルチル型結晶構造を有する酸化ルテニウム（ＲｕＯ２）粉末が、Ｘ線回折法でその（１１０）面を測定した結晶子径が３〜１０ｎｍと微細であり、かつＲｕ含有量が７３質量％以上と結晶性が高いため、微細でありながら、抵抗ペースト焼成時に粒成長が抑制されるようになる。この効果は、酸化ルテニウム（ＲｕＯ２）の比表面積が特定範囲であるとより大きくなり、該比表面積と比重から算出される比表面積径が、前記Ｘ線回折法でその（１１０）面を測定した結晶子径に対して特定の範囲にあると、一層大きな効果が得られるようになる。
したがって、本発明の酸化ルテニウム（ＲｕＯ２）粉末を原料とする事によって、安価で経済性に優れた厚膜抵抗体用組成物および厚膜抵抗体ペーストを提供することができる。
さらに、本発明によれば、このルテニウム酸化物粉末を厚膜抵抗体用組成物として用い、セラミック基板上で焼成することで、高性能な厚膜抵抗体が形成できる。According to the method of the present invention, the ruthenium oxide (RuO 2 ) powder having a rutile crystal structure has a fine crystallite diameter of 3 to 10 nm as measured on the (110) plane by X-ray diffraction, and Ru. Since the crystallinity is as high as 73% by mass or more, grain growth is suppressed at the time of firing the resistance paste while being fine. This effect becomes larger when the specific surface area of ruthenium oxide (RuO 2 ) is in a specific range, and the specific surface area diameter calculated from the specific surface area and specific gravity is measured by the X-ray diffraction method. If it is within a specific range with respect to the crystallite diameter, a greater effect can be obtained.
Therefore, by using the ruthenium oxide (RuO 2 ) powder of the present invention as a raw material, it is possible to provide a thick film resistor composition and a thick film resistor paste that are inexpensive and excellent in economy.
Furthermore, according to the present invention, a high-performance thick film resistor can be formed by using this ruthenium oxide powder as a thick film resistor composition and firing it on a ceramic substrate.
以下、本発明の酸化ルテニウム粉末、それを用いた厚膜抵抗体用組成物および厚膜抵抗体について詳細に説明する。 Hereinafter, the ruthenium oxide powder of the present invention, the thick film resistor composition and the thick film resistor using the same will be described in detail.
１．酸化ルテニウム粉末
本発明の酸化ルテニウム粉末は、ルチル型結晶構造を有する酸化ルテニウム（ＲｕＯ２）粉末であって、Ｘ線回折法でその（１１０）面を測定した結晶子径が３〜１０ｎｍであり、かつＲｕ含有量が７３質量％以上であることを特徴とする。1. Ruthenium oxide powder The ruthenium oxide powder of the present invention is a ruthenium oxide (RuO 2 ) powder having a rutile-type crystal structure, and has a crystallite diameter of 3 to 10 nm as measured on the (110) plane by an X-ray diffraction method. And Ru content is 73 mass% or more, It is characterized by the above-mentioned.
厚膜抵抗体用の酸化ルテニウム（ＲｕＯ２）粉末は、一般に、湿式で合成された水和した酸化ルテニウム粉末を熱処理することによって製造されており、その合成方法や熱処理の条件によって粒径や結晶性が異なる。また、粒径や結晶性によって特性も異なっている。本発明は、酸化ルテニウム（ＲｕＯ２）粉末の粒径や結晶性が、下記（イ）の条件を満たしていることで、所望される抵抗値の厚膜抵抗体を安価に提供しようとするものである。
（イ）Ｘ線回折法によってルチル型結晶構造の（１１０）面で測定した結晶子径が３〜１０ｎｍであり、かつＲｕ含有量が７３質量％以上である酸化ルテニウム（ＲｕＯ２）粉末。Ruthenium oxide (RuO 2 ) powder for thick film resistors is generally manufactured by heat-treating wet synthesized hydrated ruthenium oxide powder. Depending on the synthesis method and heat treatment conditions, grain size and crystal Sex is different. Further, the characteristics vary depending on the particle size and crystallinity. The present invention intends to provide a thick film resistor having a desired resistance value at a low cost because the particle size and crystallinity of the ruthenium oxide (RuO 2 ) powder satisfy the following condition (a): It is.
(A) Ruthenium oxide (RuO 2 ) powder having a crystallite diameter of 3 to 10 nm and an Ru content of 73% by mass or more as measured by the X-ray diffraction method on the (110) plane of the rutile crystal structure.
厚膜抵抗体用原料の酸化ルテニウム（ＲｕＯ２）粉末は、一次粒子の粒径が小さく一次粒子をほぼ単結晶と見なす事が出来る場合、粒径をＸ線回折法によって測定された結晶子径で代用する事ができる。ルチル型の結晶構造を有する酸化ルテニウム（ＲｕＯ２）では、回折ピークのうち、結晶構造の（１１０）、（１０１）、（２１１）、（３０１）、（３２１）面の回折ピークが比較的大きいが、本発明では、（１１０）面で測定した結晶子径が３〜１０ｎｍでなければならない。The ruthenium oxide (RuO 2 ) powder, which is a raw material for thick film resistors, has a crystallite size measured by X-ray diffraction when the primary particles are small and the primary particles can be regarded as almost single crystals. Can be substituted. In ruthenium oxide (RuO 2 ) having a rutile crystal structure, the diffraction peaks on the (110), (101), (211), (301), and (321) planes of the crystal structure are relatively large among the diffraction peaks. However, in the present invention, the crystallite diameter measured in the (110) plane must be 3 to 10 nm.
厚膜抵抗体の抵抗値は、抵抗体幅と抵抗体長さの比を１：１とした面積抵抗値で評価される。酸化ルテニウム（ＲｕＯ２）粉末とガラス粉末を主な構成成分とする厚膜抵抗体用組成物では、これらの配合比が同一であっても、原料粉末の粒径によって出現する面積抵抗値が異なる。前述したように、一般に厚膜抵抗体では、粒径１５ｎｍ〜５００ｎｍの酸化ルテニウム粉末と粒径５００ｎｍ〜１０μｍのガラス粉末が用いられている。The resistance value of the thick film resistor is evaluated by an area resistance value where the ratio of the resistor width and the resistor length is 1: 1. In the thick film resistor composition comprising ruthenium oxide (RuO 2 ) powder and glass powder as the main constituents, even if these blending ratios are the same, the sheet resistance value that appears depends on the particle size of the raw material powder. . As described above, generally, in the thick film resistor, ruthenium oxide powder having a particle diameter of 15 nm to 500 nm and glass powder having a particle diameter of 500 nm to 10 μm are used.
粒径が１５ｎｍ以上の酸化ルテニウム（ＲｕＯ２）粉末を用いた場合、粒径が小さい方が抵抗値は低くなる傾向があるが、粒径を小さくしていくと３ｎｍ以下で抵抗値は逆に高くなる。そのためか３ｎｍ〜１５ｎｍの粒径の酸化ルテニウム（ＲｕＯ２）粉末を原料とした厚膜抵抗体の例はほとんど見当たらない。
粒径の小さい酸化ルテニウム（ＲｕＯ２）粉末では、抵抗ペーストを焼成し形成された厚膜抵抗膜中の酸化ルテニウム（ＲｕＯ２）粒子間の距離が小さくなり、面積抵抗値が低くなると考えられる。しかし、酸化ルテニウム（ＲｕＯ２）粉末の粒径を小さくし過ぎた場合、抵抗ペーストを焼成している間に酸化ルテニウム（ＲｕＯ２）粒子の成長が起こり、酸化ルテニウム（ＲｕＯ２）間の距離が大きくなって面積抵抗値が高くなると考えられる。When ruthenium oxide (RuO 2 ) powder having a particle size of 15 nm or more is used, the resistance value tends to be lower as the particle size is smaller. However, when the particle size is decreased, the resistance value is reversed to 3 nm or less. Get higher. For this reason, there are hardly any examples of thick film resistors made from ruthenium oxide (RuO 2 ) powder having a particle diameter of 3 nm to 15 nm.
In the case of ruthenium oxide (RuO 2 ) powder having a small particle size, it is considered that the distance between ruthenium oxide (RuO 2 ) particles in the thick film resistance film formed by firing the resistance paste is reduced and the sheet resistance value is lowered. However, when the particle size of the ruthenium oxide (RuO 2 ) powder is made too small, the ruthenium oxide (RuO 2 ) particles grow while the resistance paste is fired, and the distance between the ruthenium oxide (RuO 2 ) is small. It is considered that the sheet resistance value increases as the value increases.
このようなことから、本発明では、粒径が小さく且つ抵抗ペースト焼成時に粒成長が抑制された酸化ルテニウム（ＲｕＯ２）粉末を原料として用いる事によって、抵抗値が低くルテニウム含有率を削減した安価な厚膜抵抗体組成物を得ようとするものである。酸化ルテニウム（ＲｕＯ２）粉末の結晶子径が３ｎｍ未満であると、上記のように焼成している間に粒子の成長が起こり、面積抵抗値が高くなる問題があり、また、結晶子径が１０ｎｍを超えると面積抵抗値が高くなる問題がある。酸化ルテニウム（ＲｕＯ２）粉末の結晶子径は３．２〜９．８ｎｍがより好ましい。
また、本発明では、酸化ルテニウム（ＲｕＯ２）のＲｕ含有量が７３質量％以上でなければならない。Ｒｕ含有量が７３質量％未満であると、結晶性が低いので、抵抗ペーストの焼成中に酸化ルテニウム粒子の成長がおこり面積抵抗値が高くなる問題がある。Ｒｕ含有量は７４質量％以上であることが好ましい。For this reason, in the present invention, by using ruthenium oxide (RuO 2 ) powder having a small particle diameter and suppressing grain growth during firing of the resistance paste as a raw material, the resistance value is low and the ruthenium content is reduced. A thick film resistor composition is to be obtained. If the crystallite size of the ruthenium oxide (RuO 2 ) powder is less than 3 nm, there is a problem that the particle growth occurs during the firing as described above, resulting in a high area resistance value. If it exceeds 10 nm, there is a problem that the sheet resistance value becomes high. The crystallite diameter of the ruthenium oxide (RuO 2 ) powder is more preferably 3.2 to 9.8 nm.
In the present invention, the Ru content of ruthenium oxide (RuO 2 ) must be 73% by mass or more. If the Ru content is less than 73% by mass, the crystallinity is low, so that there is a problem that the ruthenium oxide particles grow during firing of the resistance paste and the area resistance value is increased. The Ru content is preferably 74% by mass or more.
本発明では、厚膜抵抗体用の酸化ルテニウム（ＲｕＯ２）粉末は、前記（イ）の条件を満たす必要があるが、さらに下記（ロ）の条件を満たすことが好ましく、さらには（ハ）の条件も満たすことがより好ましい。これにより厚膜抵抗体の面積抵抗値が高くならず、さらに安価な厚膜抵抗体を提供することができる。
（ロ）比表面積が７０ｍ２／ｇ以上、２００ｍ２／ｇ以下である、酸化ルテニウム（ＲｕＯ２）粉末。
（ハ）Ｘ線回折法によってルチル型結晶構造の（１１０）面で測定した結晶子径をＤ１（ｎｍ）、導電性粒子の比表面積をＳ（ｍ２／ｇ）、比重をρ（ｇ／ｃｍ３）と表した時、６×１０−６／（ρ・Ｓ）として算出される比表面積径Ｄ２（ｎｍ）として、Ｄ１／Ｄ２≧０．７０である酸化ルテニウム（ＲｕＯ２）粉末。In the present invention, the ruthenium oxide (RuO 2 ) powder for the thick film resistor needs to satisfy the condition (a), but preferably satisfies the following condition (b). It is more preferable to satisfy the above condition. Thereby, the area resistance value of the thick film resistor is not increased, and a cheaper thick film resistor can be provided.
(B) Ruthenium oxide (RuO 2 ) powder having a specific surface area of 70 m 2 / g or more and 200 m 2 / g or less.
(C) The crystallite diameter measured by the X-ray diffraction method on the (110) plane of the rutile crystal structure is D1 (nm), the specific surface area of the conductive particles is S (m 2 / g), and the specific gravity is ρ (g / When expressed as cm 3 ), a ruthenium oxide (RuO 2 ) powder having D1 / D2 ≧ 0.70 as a specific surface area diameter D2 (nm) calculated as 6 × 10 −6 / (ρ · S).
酸化ルテニウム（ＲｕＯ２）粉末の比表面積が７０ｍ２／ｇ未満の場合、厚膜抵抗体としたときの抵抗値が高くなり、ルテニウム含有率の削減効果が得られない。また、２００ｍ２／ｇを越えると厚膜抵抗体ペースト中での分散が低下し、酸化ルテニウム粉末の凝集が生じるため、厚膜抵抗体の抵抗値が高くなり、ルテニウム含有率の削減効果が得られない。好ましい比表面積は７５〜１９０ｍ２／ｇである。
厚膜抵抗体に用いられる酸化ルテニウム（ＲｕＯ２）粉末の一次粒子の粒径は小さいので、結晶子径や比表面積径で代表する事ができる。そして一次粒子をほぼ単結晶と見なす事が出来る場合、粒径をＸ線回折法によって測定された結晶子径で代用する事ができる。結晶子が小さくなると完全にＢｒａｇｇの条件を満たす結晶格子が減り、Ｘ線を照射した際の回折線プロファイルが広がる。格子歪が無いと仮定した場合、結晶子径をＤ１（ｎｍ）、Ｘ線の波長をλ（ｎｍ）、回折線プロファイルの広がりをβ、回折角をθとすると以下のＳｃｈｅｒｒｅｒの式から結晶子径が測定される。
Ｄ１（ｎｍ）＝（Ｋ・λ）／（β・ｃｏｓθ） ・・・（２）
（式中、ＫはＳｃｈｅｒｒｅｒ定数であり、０．９を用いる。）When the specific surface area of the ruthenium oxide (RuO 2 ) powder is less than 70 m 2 / g, the resistance value when the thick film resistor is formed becomes high, and the effect of reducing the ruthenium content cannot be obtained. On the other hand, if it exceeds 200 m 2 / g, the dispersion in the thick film resistor paste is reduced and the ruthenium oxide powder is agglomerated, so that the resistance value of the thick film resistor is increased and the effect of reducing the ruthenium content is obtained. I can't. A preferred specific surface area is 75 to 190 m 2 / g.
Since the primary particle size of the ruthenium oxide (RuO 2 ) powder used for the thick film resistor is small, it can be represented by a crystallite size or a specific surface area. If the primary particles can be regarded as a single crystal, the particle size can be substituted with the crystallite size measured by the X-ray diffraction method. As the crystallite becomes smaller, the number of crystal lattices that completely satisfy the Bragg condition is reduced, and the diffraction line profile when X-rays are irradiated is widened. Assuming that there is no lattice distortion, the crystallite diameter is D1 (nm), the X-ray wavelength is λ (nm), the diffraction line profile spread is β, and the diffraction angle is θ. The diameter is measured.
D1 (nm) = (K · λ) / (β · cos θ) (2)
(In the formula, K is a Scherrer constant, and 0.9 is used.)
前記したとおり、ルチル型の結晶構造を有する酸化ルテニウム（ＲｕＯ２）では、回折ピークのうち、結晶構造の（１１０）、（１０１）、（２１１）、（３０１）、（３２１）面の回折ピークが比較的大きく、これらの回折線プロファイルの広がりから結晶子径を算出する事が可能である。
一方、比表面積径は、粉末の粒径が細かくなるとその比表面積が大きくなる。これにより粉末の粒径をＤ２（ｎｍ）、密度をρ（ｇ／ｃｍ３）、比表面積をＳ（ｍ２／ｇ）とすると、粉末が真球や立方体の形状の場合は、以下の関係式が成り立つ。このＤ２によって算出される粒径は比表面積径と呼ばれている。
Ｄ２（ｎｍ）＝６×１０３／（ρ・Ｓ） ・・・（３）As described above, in ruthenium oxide (RuO 2 ) having a rutile crystal structure, among the diffraction peaks, diffraction peaks on the (110), (101), (211), (301), and (321) planes of the crystal structure. Is relatively large, and the crystallite diameter can be calculated from the broadening of these diffraction line profiles.
On the other hand, the specific surface area diameter increases as the particle diameter of the powder becomes smaller. As a result, when the particle diameter of the powder is D2 (nm), the density is ρ (g / cm 3 ), and the specific surface area is S (m 2 / g), The formula holds. The particle diameter calculated by D2 is called the specific surface area diameter.
D2 (nm) = 6 × 10 3 / (ρ · S) (3)
酸化ルテニウム（ＲｕＯ２）の粉末が多結晶である場合、あるいは水和などによって結晶の完全性が乏しい場合などは、結晶子径Ｄ１よりも比表面積径Ｄ２の方が大きくなり、Ｄ２に対するＤ１の割合すなわちＤ１／Ｄ２は１より小さくなる。したがって、Ｄ１／Ｄ２の値は粒子の結晶完全性の目安となり、Ｄ１／Ｄ２が小さいほど粒子を形成している結晶の完全性は低く、Ｄ１／Ｄ２が大きいほど結晶の完全性は高いと判断できる。一般に、粉末が微細になるにつれて粒子を形成している結晶の完全性は低下し、Ｄ１／Ｄ２の値は小さくなる傾向がみられる。本発明では、結晶性が高く、単結晶に近いので、Ｄ１／Ｄ２≧０．７０となるものが好ましい。より好ましいのは、Ｄ１／Ｄ２≧０．７３となるものである。When the ruthenium oxide (RuO 2 ) powder is polycrystalline, or when the completeness of the crystal is poor due to hydration or the like, the specific surface area diameter D2 is larger than the crystallite diameter D1, and D1 relative to D2 The ratio, ie D1 / D2, is smaller than 1. Therefore, the value of D1 / D2 is a measure of the crystal perfection of the particle. The smaller the D1 / D2, the lower the completeness of the crystal forming the particle, and the higher the D1 / D2, the higher the completeness of the crystal. it can. In general, as the powder becomes finer, the completeness of the crystals forming the particles decreases and the value of D1 / D2 tends to decrease. In the present invention, since the crystallinity is high and close to a single crystal, those satisfying D1 / D2 ≧ 0.70 are preferable. More preferable is D1 / D2 ≧ 0.73.
２．ルテニウム酸化物粉末の製造方法
厚膜抵抗体用の酸化ルテニウム（ＲｕＯ２）粉末は、その製造方法によって制限されるものではないが、湿式で合成された水和した酸化ルテニウム粉末を熱処理することによって製造することが望ましい。この製造方法では、その合成方法や熱処理の条件によって粒径や結晶性が異なる。2. Method for Producing Ruthenium Oxide Powder Ruthenium oxide (RuO 2 ) powder for thick film resistors is not limited by its production method, but by heat-treating wet hydrated ruthenium oxide powder. It is desirable to manufacture. In this production method, the particle size and crystallinity differ depending on the synthesis method and heat treatment conditions.
Ｒｕ酸化物の水和物を合成する際のＲｕ溶液や合成法には、代表的な方法としてＫ２Ｒｕ２Ｏ４水溶液にエタノールを加える方法や、ＲｕＣｌ３水溶液をＫＯＨ等で中和する方法が挙げられる。
水和した酸化ルテニウム粉末は、酸化雰囲気下で４００℃を超える温度で熱処理することで結晶水がとれ、粉末の結晶性が高くなる。ここで酸化雰囲気とは、酸素を１０容積％以上含む気体であり、例えば空気を使用することができる。
熱処理の温度は４００℃より低いとルテニウム酸化物が完全に生成されず、一方、８００℃を超えると、ルテニウム酸化物の粒径が大きくなり過ぎたり、ルテニウムが６価や８価の酸化物（ＲｕＯ３やＲｕＯ４）となって揮発する割合が高くなり好ましくない。したがって、熱処理温度は、５００〜８００℃とすることが一般的である。また、適正な熱処理の時間は、熱処理温度、熱処理の雰囲気、熱処理方法等により適宜設定する。熱処理時間が１時間以上だと、特に高温ではルテニウム酸化物の粒径が大きくなり、ルテニウムが６価や８価の酸化物（ＲｕＯ３やＲｕＯ４）となって揮発する傾向がある。好ましいのは４０分以下、より好ましいのは３０分以下である。The Ru solution and the synthesis method when synthesizing the hydrate of Ru oxide include, as a typical method, a method of adding ethanol to a K 2 Ru 2 O 4 aqueous solution, or a method of neutralizing a RuCl 3 aqueous solution with KOH or the like. Is mentioned.
The hydrated ruthenium oxide powder is heat-treated at a temperature exceeding 400 ° C. in an oxidizing atmosphere to remove crystal water and increase the crystallinity of the powder. Here, the oxidizing atmosphere is a gas containing 10% by volume or more of oxygen, and for example, air can be used.
When the temperature of the heat treatment is lower than 400 ° C., the ruthenium oxide is not completely formed. On the other hand, when the temperature exceeds 800 ° C., the particle size of the ruthenium oxide becomes too large or the ruthenium is a hexavalent or octavalent oxide ( (RuO 3 or RuO 4 ) and the rate of volatilization increases, which is not preferable. Therefore, the heat treatment temperature is generally 500 to 800 ° C. In addition, an appropriate heat treatment time is appropriately set depending on a heat treatment temperature, a heat treatment atmosphere, a heat treatment method, and the like. When the heat treatment time is 1 hour or longer, the particle diameter of the ruthenium oxide increases particularly at high temperatures, and ruthenium tends to volatilize as hexavalent or octavalent oxides (RuO 3 or RuO 4 ). Preferred is 40 minutes or less, and more preferred is 30 minutes or less.
３．厚膜抵抗体組成物
本発明は、特定の結晶子径を有し、かつ特定のルテニウム含有量であるルテニウム酸化物粉末を合成し、それを厚膜抵抗体用組成物の導電成分とすることで、ルテニウム酸化物の配合量を少なくし、安価な厚膜抵抗体を得ようとするものである。
すなわち、本発明は、酸化ルテニウム粉末からなる導電性粒子とガラス粉末を主要構成成分として配合してなる厚膜抵抗体用組成物である。3. Thick film resistor composition The present invention synthesizes a ruthenium oxide powder having a specific crystallite diameter and a specific ruthenium content, and using it as a conductive component of the thick film resistor composition Thus, an attempt is made to obtain an inexpensive thick film resistor by reducing the amount of ruthenium oxide.
That is, the present invention is a thick film resistor composition comprising conductive particles made of ruthenium oxide powder and glass powder as main components.
（１）導電性粒子
本発明は、導電性粒子として前記のルテニウム酸化物粉末を使用するが、本発明の厚膜抵抗体用組成物には、必要に応じて、酸化ルテニウム（ＲｕＯ２）粉末以外の導電性粒子を含んでも良い。これらの導電性粒子としては、銀（Ａｇ）粉、パラジウム（Ｐｄ）粉もしくはパラジウムによりコートされた銀粉の酸化物粉末及び貴金属粉末を挙げることができる。形状は球状、フレーク状など特に限定されず、平均粒径は０．１〜１０μｍのものが好ましい。
また、これらの他にも、パイロクロア型の結晶構造を有するルテニウム酸鉛、ルテニウム酸ビスマス、ペロブスカイト型結晶構造を有するルテニウム酸カルシウム、ルテニウム酸ストロンチウム、ルテニウム酸バリウム、ルテニウム酸ランタン等のルテニウム酸化物等が挙げられる。(1) Conductive Particles In the present invention, the above-described ruthenium oxide powder is used as the conductive particles. In the thick film resistor composition of the present invention, as necessary, ruthenium oxide (RuO 2 ) powder. Other conductive particles may be included. Examples of the conductive particles include silver (Ag) powder, palladium (Pd) powder, or silver powder oxide powder and noble metal powder coated with palladium. The shape is not particularly limited, such as a spherical shape or flake shape, and the average particle size is preferably 0.1 to 10 μm.
In addition to these, ruthenium oxides such as lead ruthenate having a pyrochlore crystal structure, bismuth ruthenate, calcium ruthenate having a perovskite crystal structure, strontium ruthenate, barium ruthenate, lanthanum ruthenate, etc. Is mentioned.
（２）ガラス粉末
ガラス粉末は、その組成や製造方法によって限定されない。厚膜抵抗体には、一般的に鉛を含有するアルミノホウケイ酸鉛が多く用いられており、その他ホウケイ酸亜鉛系、ホウケイ酸カルシウム系、ホウケイ酸バリウムなどの鉛を含有しない組成系のガラス粉末も用いられている。ガラスは、一般的に、所定の成分またはそれらの前駆体を目的とする抵抗値が得られるような配合で混合し、これらを溶融し急冷する事によって製造される。溶融温度は１４００℃前後、急冷は溶融物を冷水中に入れるか冷ベルト上に流す事によって行われる事が多い。ガラスの粉砕はボールミル、振動ミル、遊星ミル、あるいはビーズミルなどで目的とする粒度まで行われる。(2) Glass powder Glass powder is not limited by its composition or manufacturing method. Thick film resistors are generally made of lead-containing aluminoborosilicate lead, and other glass powders containing no lead, such as zinc borosilicate, calcium borosilicate, and barium borosilicate. Are also used. Glass is generally produced by mixing predetermined components or their precursors in such a composition that a desired resistance value can be obtained, and melting and quenching them. The melting temperature is around 1400 ° C., and rapid cooling is often performed by placing the melt in cold water or flowing it on a cold belt. The glass is pulverized to a desired particle size by a ball mill, a vibration mill, a planetary mill, a bead mill, or the like.
ガラス粉末の粒径も限定されないが、レーザー回折を利用した粒度分布計の５０％累計粒度は５μｍ以下が好ましく、更に好ましくは３μｍ以下である。ガラス粉末の粒度が大き過ぎると、焼成された厚膜抵抗体の面積抵抗値は低くなるが、面積抵抗値のバラツキが大きくなり歩留まりが低下する、負荷特性が低下するなどの不具合が生じる可能性が高くなる。 The particle size of the glass powder is not limited, but the 50% cumulative particle size of the particle size distribution meter using laser diffraction is preferably 5 μm or less, more preferably 3 μm or less. If the particle size of the glass powder is too large, the area resistance value of the fired thick film resistor will be low, but the variation in the area resistance value will increase, resulting in a decrease in yield and load characteristics. Becomes higher.
酸化ルテニウム（ＲｕＯ２）粉末などの導電性粒子とガラス粉末の割合は、目的とする面積抵抗値によって任意に変える事ができる。すなわち、目的とする抵抗値が高い場合には導電性粒子を少なく配合し、目的とする抵抗値が低い場合には導電性粒子を多く配合する。好ましい重量比は導電性粒子：ガラス粉末＝５：９５〜７０：３０の範囲である。これよりも導電性粒子が少ないと抵抗値が高くなり過ぎて不安定となる。また、これよりも導電性粒子が多いと形成される抵抗体膜が脆くなる。The ratio of conductive particles such as ruthenium oxide (RuO 2 ) powder and glass powder can be arbitrarily changed depending on the intended sheet resistance value. That is, when the target resistance value is high, less conductive particles are blended, and when the target resistance value is low, many conductive particles are blended. A preferred weight ratio is in the range of conductive particles: glass powder = 5: 95 to 70:30. If there are fewer conductive particles than this, the resistance value becomes too high and becomes unstable. Further, if there are more conductive particles than this, the formed resistor film becomes brittle.
本発明の厚膜抵抗体用組成物には、酸化ルテニウム（ＲｕＯ２）粉末、ガラス粉末の他に面積抵抗値や抵抗温度係数の調整、膨張係数の調整、耐電圧性の向上やその他の改質を目的とした添加剤を含んでもなんら差し支えない。厚膜抵抗体用組成物の添加剤としては、ＭｎＯ２、ＣｕＯ、ＴｉＯ２、Ｎｂ２Ｏ５、Ｔａ２Ｏ５、ＳｉＯ２、Ａｌ２Ｏ３、ＺｒＯ２、ＺｒＳｉＯ４などが一般に用いられている。また、添加剤の割合は、酸化ルテニウム（ＲｕＯ２）粉末とガラス粉末の重量の合計に対して０．０５〜２０％が一般的である。In addition to ruthenium oxide (RuO 2 ) powder and glass powder, the composition for thick film resistor of the present invention includes adjustment of area resistance value and resistance temperature coefficient, adjustment of expansion coefficient, improvement of voltage resistance and other improvements. There may be any additives for quality purposes. As additives for the thick film resistor composition, MnO 2 , CuO, TiO 2 , Nb 2 O 5 , Ta 2 O 5 , SiO 2 , Al 2 O 3 , ZrO 2 , ZrSiO 4 and the like are generally used. Yes. Moreover, the ratio of the additive is generally 0.05 to 20% with respect to the total weight of the ruthenium oxide (RuO 2 ) powder and the glass powder.
（３）樹脂成分
本発明の厚膜抵抗体用組成物は、ビヒクルと呼ばれる樹脂成分を溶解した溶剤中に分散すれば厚膜抵抗体ペーストになる。本発明では、ビヒクルの樹脂や溶剤の種類や配合によって限定されない。樹脂成分としては、エチルセルロース、マレイン酸樹脂、ロジンなどが一般的であり、溶剤はターピネオール、ブチルカルビトール、ブチルカルビトールアセテート等が一般に用いられている。これらの配合比は所望とする粘度によって調整される。また、ペーストの乾燥を遅らせる目的で沸点が高い溶剤を加える事もできる。抵抗体用組成物に対するビヒクルの割合は、特に限定されないが重量で３０％〜１００％が一般的である。(3) Resin component If the composition for thick film resistors of this invention is disperse | distributed in the solvent which melt | dissolved the resin component called a vehicle, it will become a thick film resistor paste. In the present invention, the present invention is not limited by the type or composition of the vehicle resin or solvent. As the resin component, ethyl cellulose, maleic resin, rosin and the like are generally used, and terpineol, butyl carbitol, butyl carbitol acetate and the like are generally used as the solvent. These blending ratios are adjusted according to the desired viscosity. Also, a solvent having a high boiling point can be added for the purpose of delaying the drying of the paste. The ratio of the vehicle to the resistor composition is not particularly limited, but is generally 30% to 100% by weight.
本発明の厚膜抵抗体用組成物をビヒクル中に分散させて厚膜抵抗体ペーストを製造するには、スリーロールミルのほか遊星ミル、ビーズミルなどを用いる事ができるが、ペーストの製造方法に限定はされない。予め本発明の厚膜抵抗体用組成物をボールミルやらいかい機で混合してから、ビヒクル中に分散させる事もできる。 In order to produce a thick film resistor paste by dispersing the composition for the thick film resistor of the present invention in a vehicle, a planetary mill, a bead mill, etc. can be used in addition to a three-roll mill, but the method is limited to the paste production method. Not done. The thick film resistor composition of the present invention can be previously mixed with a ball mill or a rough machine and then dispersed in a vehicle.
厚膜抵抗体ペーストでは、無機原料粉末の凝集を解し、樹脂成分を溶解した溶剤中に分散する事が望ましい。一般に、粉末の粒径が小さくなると凝集が強くなり、二次粒子を形成し易くなる。本発明の酸化ルテニウム（ＲｕＯ２）粉末では、二次粒子をほぐし一次粒子に分散させることを容易にするために、脂肪酸を分散剤として用いる事が有効である。脂肪酸は酸化ルテニウム（ＲｕＯ２）粉末の表面に付着して分散を容易にする働きがあると考えられる。
本発明で用いられる脂肪酸は、飽和、不飽和を問わないが、酸化ルテニウム（ＲｕＯ２）粉末を分散させ、再び凝集するのを防ぐ観点から、炭素数が１２以上の高級脂肪酸がより望ましい。脂肪酸は無機原料粉末をビヒクル中に分散させる際に加えても、あるいは予め酸化ルテニウム（ＲｕＯ２）粉末に付着させた後に、ビヒクル中に分散させても良い。In the thick film resistor paste, it is desirable to disaggregate the inorganic raw material powder and disperse it in a solvent in which the resin component is dissolved. In general, when the particle size of the powder becomes smaller, the aggregation becomes stronger and it becomes easier to form secondary particles. In the ruthenium oxide (RuO 2 ) powder of the present invention, it is effective to use a fatty acid as a dispersant in order to easily dissociate the secondary particles and disperse them in the primary particles. It is considered that the fatty acid has a function of adhering to the surface of ruthenium oxide (RuO 2 ) powder and facilitating dispersion.
The fatty acid used in the present invention may be saturated or unsaturated, but higher fatty acids having 12 or more carbon atoms are more preferable from the viewpoint of dispersing ruthenium oxide (RuO 2 ) powder and preventing aggregation again. The fatty acid may be added when the inorganic raw material powder is dispersed in the vehicle, or may be dispersed in the vehicle after preliminarily adhering to the ruthenium oxide (RuO 2 ) powder.
４．厚膜抵抗体
本発明の厚膜抵抗体は、前記厚膜抵抗体用組成物を、セラミック基板上で焼成してなる厚膜抵抗体であり、また、前記厚膜抵抗体ペーストを、セラミック基板に塗布した後、焼成して形成された厚膜抵抗体である。
厚膜抵抗体中の無機成分中のＲｕ含有量は、目的とする抵抗値の大きさによって調整する。例えば、抵抗値が１ＫΩ前後の厚膜抵抗体を得るには、Ｒｕの含有量が１８％以下、特に１５％以下とするのが経済的であり、抵抗値がより小さく１００Ωの厚膜抵抗体が必要であれば、更にＲｕ含有率は高くする必要がある。本発明では、厚膜抵抗体の無機成分中のＲｕ含有量を２３質量％以下にすることで広範な抵抗値への要求に対応できるようになる。4). Thick film resistor The thick film resistor of the present invention is a thick film resistor formed by firing the composition for a thick film resistor on a ceramic substrate, and the thick film resistor paste is applied to the ceramic substrate. It is a thick film resistor formed by firing after coating.
The Ru content in the inorganic component in the thick film resistor is adjusted according to the target resistance value. For example, in order to obtain a thick film resistor having a resistance value of about 1 KΩ, it is economical that the Ru content is 18% or less, particularly 15% or less, and a thick film resistor having a smaller resistance value and 100Ω. If it is necessary, the Ru content must be further increased. In the present invention, the requirement for a wide range of resistance values can be met by setting the Ru content in the inorganic component of the thick film resistor to 23 mass% or less.
以下に実施例を用いて、本発明によるルテニウム酸化物粉末の製造とそれを用いた厚膜抵抗体用組成物、厚膜抵抗体を説明するが、本発明はこれらの実施例によって限定されるものではない。 The production of ruthenium oxide powder according to the present invention and the composition for thick film resistor and the thick film resistor using the same will be described below with reference to examples, but the present invention is limited by these examples. It is not a thing.
ルテニウム酸化物粉末の形状・物性を評価するために、Ｘ線回折に物質同定と結晶子径を測定した。結晶子径はＸ線回折のピークの広がりより算出できる。ここではＸ線回折によって得られたルチル構造のピークをＫα１、Ｋα２に波形分離した後、測定機器の光学系による広がりを補正したＫα１のピークの広がりとして半価幅を測定し、Ｓｃｈｅｒｒｅｒの式より算出した。
形成された厚膜抵抗体は、膜厚、抵抗値、２５℃から−５５℃までの抵抗温度係数（ＣＯＬＤ−ＴＣＲ）、２５℃から１２５℃までの抵抗温度係数（ＨＯＴ−ＴＣＲ）、電流ノイズ、静電気を放電した際の抵抗値変化率（ＥＳＤ特性）を評価した。In order to evaluate the shape and physical properties of the ruthenium oxide powder, substance identification and crystallite diameter were measured by X-ray diffraction. The crystallite diameter can be calculated from the broadening of the peak of X-ray diffraction. Here, the peak of the rutile structure obtained by X-ray diffraction is waveform-separated into Kα1 and Kα2, and then the half width is measured as the spread of the peak of Kα1 corrected for the spread by the optical system of the measuring instrument. From the Scherrer equation Calculated.
The formed thick film resistor has a film thickness, a resistance value, a resistance temperature coefficient from 25 ° C. to −55 ° C. (COLD-TCR), a resistance temperature coefficient from 25 ° C. to 125 ° C. (HOT-TCR), and current noise. The rate of change in resistance value (ESD characteristics) when static electricity was discharged was evaluated.
膜厚は触針の厚さ粗さ計で５個の厚膜抵抗体の膜厚を測定した値を平均した。
また、抵抗値は２５個の厚膜抵抗体の抵抗値をデジタルマルチメーターで測定した値を平均した。The film thickness averaged the value which measured the film thickness of five thick film resistors with the thickness roughness meter of the stylus.
Moreover, the resistance value averaged the value which measured the resistance value of 25 thick film resistors with the digital multimeter.
抵抗温度係数は、厚膜抵抗体を−５５℃、２５℃、１２５℃にそれぞれ１５分保持してから、それぞれの抵抗値（Ｒ−５５、Ｒ２５、Ｒ１２５）を測定し、以下の式（４）（５）によって計算し、５個の厚膜抵抗体の平均をとった。
ＣＯＬＤ−ＴＣＲ（ｐｐｍ／℃）＝（Ｒ−５５−Ｒ２５）／Ｒ２５／（−８０）×１０６ ・・・（４）
ＨＯＴ−ＴＣＲ（ｐｐｍ／℃）＝（Ｒ１２５−Ｒ２５）／Ｒ２５／（１００）×１０６ ・・・（５）Resistance temperature coefficient, a thick film resistor -55 ° C., 25 ° C., after 15 minutes, respectively held at 125 ° C., measured the resistance values (R -55, R 25, R 125), the following formula (4) Calculated by (5) and averaged five thick film resistors.
COLD-TCR (ppm / ° C.) = (R −55 −R 25 ) / R 25 / (− 80) × 10 6 (4)
HOT-TCR (ppm / ° C.) = (R 125 −R 25 ) / R 25 / (100) × 10 6 (5)
電流ノイズは、Ｑｕａｎ−Ｔｅｃｈ社ＭＯＤＥＬ３１５Ｃで、１／１０Ｗの電圧を印加して測定された電流ノイズをノイズインデックスで表し、５個の厚膜抵抗体での平均をとった。
ＥＳＤ特性は、２００ｐＦ−０Ωのユニットに１ＫＶの電圧で電荷を充電した後、厚膜抵抗体に放電して、放電前の抵抗値をＲ０、放電後の抵抗値をＲ１として、放電後の抵抗値変化を以下の式（６）によって計算した。５個の厚膜抵抗体で変化率を測定し、平均をとった。
ＥＳＤ特性（％）＝（Ｒ１−Ｒ０）／Ｒ０×１００ ・・・（６）Current noise was measured by applying a 1/10 W voltage with a QUAN-TECH MODEL 315C, expressed as a noise index, and an average of five thick film resistors was taken.
The ESD characteristic is that after charging a unit of 200 pF-0Ω with a voltage of 1 KV, discharging to a thick film resistor, the resistance value before discharge is R 0 and the resistance value after discharge is R 1. The change in resistance value was calculated by the following equation (6). The rate of change was measured with five thick film resistors and averaged.
ESD characteristics (%) = (R 1 −R 0 ) / R 0 × 100 (6)
（実施例１〜１２）
実施例１では、ルテニウム酸カリウムを溶解した水溶液を原料にして、水溶液中で酸化ルテニウムの沈殿を合成し、これを固液分離し、洗浄後８０℃で乾燥して酸化ルテニウム粉末を得た。乾燥後の酸化ルテニウムはルテニウム含有率が６１．５質量％であり、酸化水和物であった。この乾燥後の酸化ルテニウム粉末を６５０℃で１０分熱処理し、Ｒｕ含有量７３．８質量％の酸化ルテニウム（ＲｕＯ２）粉末を得た。一方、実施例２〜１２では、実施例１とは異なり、この乾燥後の酸化ルテニウム粉末を表１のように、６８０〜８００℃、１０〜３０分の範囲で熱処理条件を変化させた。
得られた酸化ルテニウム（ＲｕＯ２）粉末を平均粒径１．５μｍのガラス粉末と共に、エチルセルロース５質量％〜１５質量％とターピネオール７５質量％〜９５質量％からなるビヒクルにスリーロールミルで分散させて厚膜抵抗ペーストを作成した。ガラス粉末としては、ガラス粉末Ａ（ＰｂＯ：５０質量％−ＳｉＯ２：３５質量％−Ｂ２Ｏ３：１０質量％−Ａｌ２Ｏ３：５質量％）を用いた。なお、実施例４，７ではガラス粉末Ｂ（ＳｉＯ２：３５質量％−Ｂ２Ｏ３：２０質量％−Ａｌ２Ｏ３：５質量％−ＣａＯ：５質量％−ＢａＯ：２０質量％−ＺｎＯ：１５質量％）を使用した。酸化ルテニウム（ＲｕＯ２）粉末とガラス粉末の配合は、実施例１〜１０では、形成された厚膜抵抗体の面積抵抗値がおよそ１ＫΩになるように調整した。
厚膜抵抗ペーストの作成では、酸化ルテニウム（ＲｕＯ２）粉末とガラス粉末の合計１００重量部に対してビヒクル４３重量部の配合にした。このとき、実施例１０以外でステアリン酸をスリーロールミルでビヒクル中に分散させて、厚膜抵抗ペーストを作成した。これらの厚膜抵抗ペーストを純度９６質量％のアルミナ基板上に印刷、乾燥、焼成して厚膜抵抗体を形成して評価した。
予めアルミナ基板に焼成して形成された１質量％Ｐｄ、９９質量％Ａｇの電極上に、作成した厚膜抵抗ペーストを印刷し、１５０℃×５分で乾燥した後、ピーク温度８５０℃×９分、トータル３０分で焼成し厚膜抵抗体を形成した。厚膜抵抗体のサイズは抵抗体幅を０．３ｍｍ、抵抗体長さを０．３ｍｍ、厚さ１０μｍとなるようにした。評価結果を表１に示した。(Examples 1-12)
In Example 1, an aqueous solution in which potassium ruthenate was dissolved was used as a raw material, a ruthenium oxide precipitate was synthesized in the aqueous solution, this was solid-liquid separated, washed and dried at 80 ° C. to obtain a ruthenium oxide powder. The ruthenium oxide after drying had a ruthenium content of 61.5% by mass and was an oxide hydrate. The dried ruthenium oxide powder was heat-treated at 650 ° C. for 10 minutes to obtain ruthenium oxide (RuO 2 ) powder having a Ru content of 73.8% by mass. On the other hand, in Examples 2 to 12, unlike Example 1, the heat-treatment conditions of the dried ruthenium oxide powder were changed in the range of 680 to 800 ° C. and 10 to 30 minutes as shown in Table 1.
The obtained ruthenium oxide (RuO 2 ) powder is dispersed together with a glass powder having an average particle diameter of 1.5 μm in a vehicle composed of 5% by mass to 15% by mass of ethyl cellulose and 75% by mass to 95% by mass of terpineol by a three roll mill. A film resistance paste was prepared. As the glass powder, glass powder A (PbO: 50% by mass—SiO 2 : 35% by mass—B 2 O 3 : 10% by mass—Al 2 O 3 : 5% by mass) was used. In Examples 4 and 7, glass powder B (SiO 2 : 35% by mass-B 2 O 3 : 20% by mass-Al 2 O 3 : 5% by mass-CaO: 5% by mass-BaO: 20% by mass-ZnO) : 15% by mass). In Examples 1 to 10, the composition of the ruthenium oxide (RuO 2 ) powder and the glass powder was adjusted so that the area resistance value of the formed thick film resistor was approximately 1 KΩ.
In the preparation of the thick film resistance paste, 43 parts by weight of the vehicle was blended with respect to 100 parts by weight of the total of ruthenium oxide (RuO 2 ) powder and glass powder. At this time, except for Example 10, stearic acid was dispersed in the vehicle with a three-roll mill to prepare a thick film resistance paste. These thick film resistor pastes were printed, dried and fired on an alumina substrate having a purity of 96% by mass to form a thick film resistor and evaluated.
The prepared thick film resistance paste is printed on an electrode of 1% by mass Pd and 99% by mass Ag previously formed by firing on an alumina substrate, dried at 150 ° C. × 5 minutes, and then a peak temperature of 850 ° C. × 9 For a total of 30 minutes to form a thick film resistor. The size of the thick film resistor was such that the resistor width was 0.3 mm, the resistor length was 0.3 mm, and the thickness was 10 μm. The evaluation results are shown in Table 1.
（比較例１〜７）
実施例１と同様に、ルテニウム酸カリウムを溶解した水溶液を原料にして、水溶液中で酸化ルテニウムの沈殿を合成し、これを固液分離し、洗浄後８０℃で乾燥して酸化ルテニウム粉末を得た。次に、実施例１とは異なり、この乾燥後の酸化ルテニウム粉末を表２のように、２００〜８５０℃、１０〜６０分の範囲で熱処理条件を変化させた。
その後、実施例１と同様に、厚膜抵抗ペーストを作成し、厚膜抵抗体を形成して評価した。なお、全ての比較例でガラス粉末Ａを使用した。酸化ルテニウム（ＲｕＯ２）粉末とガラス粉末の配合は、比較例１〜５では、形成された厚膜抵抗体の面積抵抗値がおよそ１ＫΩになるように調整した。また、比較例２，５以外でステアリン酸を用い、スリーロールミルでビヒクル中に分散させて、厚膜抵抗ペーストを作成した。(Comparative Examples 1-7)
In the same manner as in Example 1, an aqueous solution in which potassium ruthenate is dissolved is used as a raw material, a ruthenium oxide precipitate is synthesized in the aqueous solution, this is solid-liquid separated, washed and dried at 80 ° C. to obtain a ruthenium oxide powder. It was. Next, unlike Example 1, the heat-treatment conditions of the dried ruthenium oxide powder were changed in the range of 200 to 850 ° C. and 10 to 60 minutes as shown in Table 2.
Thereafter, as in Example 1, a thick film resistor paste was prepared and a thick film resistor was formed and evaluated. Glass powder A was used in all comparative examples. In the comparative examples 1 to 5, the composition of the ruthenium oxide (RuO 2 ) powder and the glass powder was adjusted so that the area resistance value of the formed thick film resistor was about 1 KΩ. Further, stearic acid was used except in Comparative Examples 2 and 5 and dispersed in a vehicle with a three-roll mill to prepare a thick film resistance paste.
（実施例１３〜１８）
実施例１〜１２で使用した原材料に加え、平均粒径１．０μｍの銀（Ａｇ）粉、平均粒径０．３μｍのパラジウム（Ｐｄ）粉と添加剤を使用し、実施例１３〜１８では、形成された厚膜抵抗体の面積抵抗値がおよそ５Ωになるように調整した。
厚膜抵抗ペーストの作成では、酸化ルテニウム（ＲｕＯ２）粉末、Ａｇ粉、Ｐｄ粉の導電粉とガラス粉末、添加剤粉の合計１００重量部に対してビヒクル４３重量部の配合にした。このとき、ステアリン酸をスリーロールミルでビヒクル中に分散させて、厚膜抵抗ペーストを作成した。これらの厚膜抵抗ペーストを、実施例１〜１２と同様に、印刷、乾燥、焼成して評価した。評価結果を表３に示した。
実施例１３〜１８では厚膜抵抗体のＥＳＤ特性の印加電圧を３ＫＶに変更した以外は、実施例１〜１２と同じ手法で評価した。(Examples 13 to 18)
In addition to the raw materials used in Examples 1 to 12, silver (Ag) powder with an average particle diameter of 1.0 μm, palladium (Pd) powder with an average particle diameter of 0.3 μm and additives were used, and in Examples 13 to 18 The thickness resistance of the formed thick film resistor was adjusted to about 5Ω.
In the preparation of the thick film resistance paste, 43 parts by weight of the vehicle was blended with respect to 100 parts by weight in total of the conductive powder of Ruthenium oxide (RuO 2 ) powder, Ag powder, Pd powder, glass powder, and additive powder. At this time, stearic acid was dispersed in the vehicle with a three-roll mill to prepare a thick film resistance paste. These thick film resistance pastes were evaluated by printing, drying and firing in the same manner as in Examples 1-12. The evaluation results are shown in Table 3.
In Examples 13-18, evaluation was performed in the same manner as in Examples 1-12 except that the applied voltage of the ESD characteristic of the thick film resistor was changed to 3 KV.
（比較例８〜１２）
比較例１〜７と同様の方法で得た乾燥後の酸化ルテニウム粉末を、表４のように、２００〜８５０℃、１０〜６０分の範囲で熱処理条件を変化させた。
その後、実施例１３〜１８と同様に、実施例１〜１２で使用した原材料に加え、平均粒径１．０μｍの銀（Ａｇ）粉、平均粒径０．３μｍのパラジウム（Ｐｄ）粉と添加剤を使用し、比較例８〜１２では、形成された厚膜抵抗体の面積抵抗値がおよそ５Ωになるように調整した。また、比較例２，５以外でステアリン酸を用い、スリーロールミルでビヒクル中に分散させて、厚膜抵抗ペーストを作成した。これらの厚膜抵抗ペーストを、比較例１３〜１８と同じ手法で評価した。(Comparative Examples 8-12)
As shown in Table 4, the heat treatment conditions of the dried ruthenium oxide powder obtained by the same method as in Comparative Examples 1 to 7 were changed in the range of 200 to 850 ° C. and 10 to 60 minutes.
Thereafter, in the same manner as in Examples 13 to 18, in addition to the raw materials used in Examples 1 to 12, silver (Ag) powder with an average particle diameter of 1.0 μm, palladium (Pd) powder with an average particle diameter of 0.3 μm and addition In Comparative Examples 8 to 12, the area resistance value of the formed thick film resistor was adjusted to about 5Ω. Further, stearic acid was used except in Comparative Examples 2 and 5 and dispersed in a vehicle with a three-roll mill to prepare a thick film resistance paste. These thick film resistance pastes were evaluated by the same method as Comparative Examples 13-18.
「評価」
表１の実施例、表２の比較例に示したように、実施例では、本発明の特定の結晶子径、高結晶性を有する酸化ルテニウム（ＲｕＯ２）粉末を用いたため、無機成分中のＲｕ含有率が実施例１２以外は比較例よりも少なくなっている。また、実施例では、電流ノイズの値が低く、静電気を放電させた際の抵抗値変化（ＥＳＤ特性）も優れている。
また、酸化ルテニウムに加え、パラジウムと銀を添加した低い抵抗値領域においては、表３の実施例、表４の比較例に示したように、実施例では、本発明の特定の結晶子径、高結晶性を有する酸化ルテニウム（ＲｕＯ２）粉末を用いたため、無機成分中のＲｕ含有率を低下させることができている。また、静電気を放電させた際の抵抗値変化（ＥＳＤ特性）も優れている。したがって、本発明によれば、高価なルテニウムの使用量を削減した、経済的に有利なしかも電気特性にすぐれた厚膜抵抗体組成物が得られることが分かる。
これに対し比較例では、結晶子径が本発明の範囲から外れるルテニウム酸化物を用いたので、無機成分中の酸化ルテニウム（ＲｕＯ２）の含有率が全般に実施例よりも大きくなり、所望の結果が得られなかった。"Evaluation"
As shown in the examples of Table 1 and the comparative examples of Table 2, in the examples, the specific crystallite diameter and high crystallinity of the present invention used ruthenium oxide (RuO 2 ) powder. The Ru content is smaller than in the comparative example except for Example 12. In the embodiment, the value of current noise is low, and the resistance value change (ESD characteristics) when static electricity is discharged is also excellent.
In addition, in the low resistance region in which palladium and silver are added in addition to ruthenium oxide, as shown in the examples of Table 3 and the comparative examples of Table 4, in the Examples, the specific crystallite diameter of the present invention, Since ruthenium oxide (RuO2) powder having high crystallinity is used, the Ru content in the inorganic component can be reduced. Moreover, the resistance value change (ESD characteristic) when static electricity is discharged is also excellent. Therefore, according to the present invention, it can be seen that a thick film resistor composition having a reduced amount of expensive ruthenium used, economically advantageous and excellent in electrical characteristics can be obtained.
On the other hand, in the comparative example, since the ruthenium oxide having a crystallite diameter outside the scope of the present invention was used, the content of ruthenium oxide (RuO 2 ) in the inorganic component was generally larger than that of the example, and the desired No result was obtained.
本発明によって、高価なルテニウムの使用量を削減した、経済的に有利なしかも電気特性にすぐれた厚膜抵抗体組成物が提供される。この厚膜抵抗体組成物を用いることで、チップ抵抗器、ハイブリッドＩＣ、または、抵抗ネットワーク等の電子部品として充分な性能を有する厚膜抵抗体を得ることができる。 According to the present invention, there is provided a thick film resistor composition which is economically advantageous and has excellent electric characteristics, in which the amount of expensive ruthenium used is reduced. By using this thick film resistor composition, a thick film resistor having sufficient performance as an electronic component such as a chip resistor, a hybrid IC, or a resistor network can be obtained.
Claims (12)
Ｄ１／Ｄ２≧０．７０ ・・・（１）
（ただし、結晶子径Ｄ１は、Ｘ線回折法によるルチル型結晶構造の（１１０）面での測定値（ｎｍ）であり、比表面積径Ｄ２は、粉末の比表面積をＳ（ｍ２／ｇ）、比重をρ（ｇ／ｃｍ３）と表したときの６×１０−６／（ρ・Ｓ）の計算値（ｎｍ）である） 3. The ruthenium oxide powder according to claim 1, wherein the ruthenium oxide (RuO 2 ) powder satisfies a following formula (1) in a ratio of the crystallite diameter D1 to the specific surface area diameter D2.
D1 / D2 ≧ 0.70 (1)
(However, the crystallite diameter D1 is a value (nm) measured on the (110) plane of the rutile crystal structure by the X-ray diffraction method, and the specific surface area diameter D2 is the specific surface area of the powder as S (m 2 / g ), Calculated value (nm) of 6 × 10 −6 / (ρ · S) when the specific gravity is expressed as ρ (g / cm 3 ))
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