JP7297409B2 - Composition for thick film resistor, paste for thick film resistor, and thick film resistor - Google Patents
Composition for thick film resistor, paste for thick film resistor, and thick film resistor Download PDFInfo
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Description
本発明は、厚膜抵抗体用組成物、厚膜抵抗体用ペースト、及び厚膜抵抗体に関する。 The present invention relates to a composition for thick film resistors, a paste for thick film resistors, and a thick film resistor.
厚膜抵抗体用ペーストは、ガラスと導電粉末とを含有する厚膜抵抗体用組成物、及び樹脂と溶剤とを含有する有機ビヒクルを主成分としている。そして、電極が形成された絶縁基板上に、係る厚膜抵抗体用ペーストを印刷、乾燥、焼成することで厚膜抵抗体が形成される。また、得られた厚膜抵抗体について、さらにガラスコート処理、レーザートリミング処理、側面と裏面電極の形成を行うことで抵抗器に加工される。 The thick film resistor paste is mainly composed of a thick film resistor composition containing glass and conductive powder, and an organic vehicle containing a resin and a solvent. Then, the thick film resistor is formed by printing, drying, and baking the thick film resistor paste on the insulating substrate on which the electrodes are formed. Further, the obtained thick film resistor is processed into a resistor by further performing glass coating treatment, laser trimming treatment, and formation of side and back electrodes.
厚膜抵抗体には、所定の抵抗値であって、抵抗温度係数（ＴＣＲ）が小さいこと、電流雑音（ノイズ）等が小さいこと、静電破壊（ＥＳＤ）や短時間過負荷（ＳＴＯＬ）が小さいことが求められている。 A thick film resistor has a predetermined resistance value, a small temperature coefficient of resistance (TCR), a small current noise, etc., and is resistant to electrostatic discharge (ESD) and short-term overload (STOL). Small things are required.
これらの電気特性を満たすために、鉛を含むガラスと、ルテニウム酸鉛といった鉛を含む導電粉末を用いた厚膜抵抗体が汎用されている。しかし、鉛成分は人体や環境に対して毒性があるという問題があった。 In order to satisfy these electrical characteristics, thick film resistors using lead-containing glass and lead-containing conductive powder such as lead ruthenate are widely used. However, there is a problem that the lead component is toxic to the human body and the environment.
そこで、近年は、鉛を含まないガラスフリットと酸化イリジウムといった鉛を含まない導電粉末を用いて電気特性を満たすことができる厚膜抵抗体が提案され（特許文献１）、鉛を含まない厚膜抵抗体が用いられつつある。 Therefore, in recent years, a thick film resistor has been proposed that can satisfy electrical characteristics by using a lead-free glass frit and a lead-free conductive powder such as iridium oxide (Patent Document 1). Resistors are being used.
しかしながら、酸化イリジウムを用いた厚膜抵抗体は、イリジウムが高価であるため、コスト上の問題があった。 However, thick film resistors using iridium oxide have a cost problem because iridium is expensive.
また、鉛成分を含まないルテニウム系導電性成分と、所定の塩基度の鉛成分を含まないガラスと、有機ビヒクルとを含む抵抗体組成物が提案されている。（特許文献２）
この提案によれば、非特許文献１に開示されたガラスの塩基度が０．４～０．９であるガラスを用い、焼成して得られる厚膜抵抗体中にＭＳｉｌ２Ｏ８（Ｍ：Ｂａ及び／又はＳｒ）結晶を発生させることで優れた厚膜抵抗体が得られることが記載されている。
Also proposed is a resistor composition containing a lead-free ruthenium-based conductive component, a lead-free glass having a predetermined basicity, and an organic vehicle. (Patent document 2)
According to this proposal, MSil 2 O 8 (M: It is described that excellent thick film resistors can be obtained by generating Ba and/or Sr) crystals.
しかしながら、特許文献２に開示された抵抗体組成物によれば、ルテニウム系酸化物としてルテニウム複合酸化物を用いることを前提とした発明である。そして、ルテニウム系酸化物がルテニウム複合酸化物であれば良好な特性が得られるものの、本発明の発明者の検討によれば、ルテニウム複合酸化物よりも工業的に簡便に得られる酸化ルテニウムを用いた場合には、良好な特性が得ることができなかった。 However, according to the resistor composition disclosed in Patent Document 2, the invention is based on the assumption that a ruthenium composite oxide is used as the ruthenium-based oxide. If the ruthenium-based oxide is a ruthenium composite oxide, good characteristics can be obtained. In the case of the sintered body, good characteristics could not be obtained.
そして、厚膜抵抗体について、特にノイズ特性を高めることが求められており、中でも単位面積あたりの抵抗値が約１０ｋΩ以上の高抵抗域の厚膜抵抗体とした場合でもノイズ特性が優れた厚膜抵抗体用組成物が求められていた。 Thick film resistors are particularly required to improve their noise characteristics. There has been a demand for a composition for membrane resistors.
上記従来技術の問題に鑑み、本発明の一側面では、導電粉末として酸化ルテニウム粉末を含み、単位面積あたりの抵抗値が１０ｋΩ以上の抵抗域の膜抵抗体とした場合でもノイズ特性が優れた厚膜抵抗体用組成物を提供することを目的とする。 In view of the above-described problems of the prior art, in one aspect of the present invention, even when a film resistor containing ruthenium oxide powder as a conductive powder and having a resistance value per unit area of 10 kΩ or more is used as a film resistor, the thickness is excellent in noise characteristics. An object of the present invention is to provide a composition for membrane resistors.
上記課題を解決するため本発明は、
鉛成分を含まない酸化ルテニウム粉末と、鉛成分を含まないガラスとを含有する抵抗体用組成物であって、厚膜抵抗体とした場合にＸ線回折パターンにおいてアルミノケイ酸塩結晶相が検出されず、
前記ガラスが、ＳｉＯ
２
を４ｍｏｌ％以上５２ｍｏｌ％以下、Ａｌ２Ｏ３を１ｍｏｌ％以上６ｍｏｌ％以下含む厚膜抵抗体用組成物を提供する。
In order to solve the above problems, the present invention
A composition for a resistor containing ruthenium oxide powder containing no lead component and glass containing no lead component, wherein an aluminosilicate crystal phase is detected in an X-ray diffraction pattern when used as a thick film resistor. figure,
Provided is a composition for a thick film resistor, wherein the glass contains 4 mol % or more and 52 mol % or less of SiO 2 and 1 mol % or more and 6 mol % or less of Al 2 O 3 .
本発明の一側面によれば、導電粉末として酸化ルテニウム粉末を含み、単位面積あたりの抵抗値が１０ｋΩ以上の抵抗域の厚膜抵抗体とした場合でもノイズ特性が優れた厚膜抵抗体用組成物を提供することができる。 According to one aspect of the present invention, a composition for a thick film resistor that contains ruthenium oxide powder as a conductive powder and has excellent noise characteristics even when the thick film resistor has a resistance value of 10 kΩ or more per unit area. can provide things.
以下、本発明の厚膜抵抗体用組成物、厚膜抵抗体用ペースト、及び厚膜抵抗体の一実施形態について説明する。
［厚膜抵抗体用組成物］
本実施形態の厚膜抵抗体用組成物は、鉛成分を含まない酸化ルテニウム粉末と、鉛成分を含まないガラスとを含有することができる。そして、本実施形態の厚膜抵抗体用組成物は、厚膜抵抗体とした場合に、Ｘ線回折パターンにおいてアルミノケイ酸塩結晶相が検出されないことが好ましい。
An embodiment of the composition for a thick film resistor, the paste for a thick film resistor, and the thick film resistor of the present invention will be described below.
[Composition for thick film resistor]
The composition for a thick film resistor of the present embodiment can contain ruthenium oxide powder containing no lead component and glass containing no lead component. When the composition for a thick film resistor of the present embodiment is made into a thick film resistor, it is preferable that no aluminosilicate crystal phase is detected in the X-ray diffraction pattern.
本発明の発明者らの検討によれば、厚膜抵抗体とした場合にノイズ特性が悪い場合は、厚膜抵抗体の内部に結晶相が発生していた。そこで、厚膜抵抗体のノイズ特性が悪化する理由としては、導電粉末である酸化ルテニウム粉末の粒子の間にアルミノケイ酸塩の結晶相が介在し、導電粉末により形成される導電パスが阻害されているため、もしくは結晶相が発生することで厚膜抵抗体内部に微小のクラックが発生して導電粉末の粒子の接触状態を悪化させるためと推認される。 According to the studies by the inventors of the present invention, when a thick film resistor has poor noise characteristics, a crystalline phase occurs inside the thick film resistor. Therefore, the reason why the noise characteristics of the thick film resistor deteriorate is that the crystal phase of the aluminosilicate intervenes between the particles of the ruthenium oxide powder, which is the conductive powder, and the conductive path formed by the conductive powder is obstructed. It is presumed that the contact state of the particles of the conductive powder is deteriorated due to the generation of microcracks inside the thick film resistor due to the presence of the crystal phase or the generation of the crystal phase.
係る知見に基づき、本実施形態の厚膜抵抗体用組成物は、厚膜抵抗体とした場合に、Ｘ線回折パターンにおいてアルミノケイ酸塩結晶相が検出されない厚膜抵抗体用組成物とすることができる。 Based on this knowledge, the composition for thick film resistors of the present embodiment is a composition for thick film resistors in which an aluminosilicate crystal phase is not detected in the X-ray diffraction pattern when used as a thick film resistor. can be done.
本実施形態の厚膜抵抗体用組成物によれば、従来ではノイズ特性を十分に高めることが困難であった、単位面積あたり（１ｍｍ×１ｍｍ）の抵抗値が１０ｋΩ以上の抵抗域の厚膜抵抗体とした場合でも、ノイズ特性を良好なものとすることができる。 According to the composition for a thick film resistor of the present embodiment, a thick film having a resistance value of 10 kΩ or more per unit area (1 mm × 1 mm), which was difficult to sufficiently improve noise characteristics in the past, Good noise characteristics can be obtained even when a resistor is used.
以下、本実施形態の厚膜抵抗体用組成物が含有する各成分について説明する。
（１）酸化ルテニウム粉末
酸化ルテニウム粉末は導電粉末であり、鉛成分を含まないことが好ましい。なお、鉛成分を含まない酸化ルテニウム粉末とは、鉛を意図して添加していないことを意味し、鉛の含有量が０であることを意味する。ただし、製造工程等で不純物成分、不可避成分として混入することを排除するものではない。
Each component contained in the composition for a thick film resistor of this embodiment will be described below.
(1) Ruthenium oxide powder The ruthenium oxide powder is a conductive powder and preferably does not contain lead. The ruthenium oxide powder containing no lead component means that lead is not intentionally added, and means that the lead content is zero. However, it does not exclude the contamination as an impurity component or an unavoidable component in the manufacturing process or the like.
酸化ルテニウム粉末の調製方法や、物性は特に限定されるものではないが、例えば、水酸化ルテニウム粉末を８００℃以上９００℃以下の焼成温度で、空気中で焼成することで得られる。焼成温度を上記範囲とすることで、酸化ルテニウム粉末の平均粒径（比表面積径）を１５ｎｍ以上１２０ｎｍ以下とすることができる。 The preparation method and physical properties of the ruthenium oxide powder are not particularly limited. By setting the firing temperature within the above range, the average particle diameter (specific surface area diameter) of the ruthenium oxide powder can be set to 15 nm or more and 120 nm or less.
なお、上記平均粒径は、酸化ルテニウム粉末の比表面積をＢＥＴ法によって測定し、その比表面積と酸化ルテニウム粉末の密度から求めることができる。具体的には、係る平均粒径（ｎｍ）は、粉末の比表面積をＳ（ｍ２／ｇ）、密度をρ（ｇ／ｃｍ３）と表したときの６×１０３／（ρ・Ｓ）の計算値とすることができる。 The average particle size can be obtained from the specific surface area of the ruthenium oxide powder measured by the BET method and the density of the ruthenium oxide powder. Specifically, the average particle size (nm) is 6 ×10 3 / (ρ S ) can be calculated.
また、酸化ルテニウム粉末は、含有する粗大粒子が少なく粒径が均一であり、結晶子径が大きいことが望ましい。その理由としては、酸化ルテニウム粉末に含まれる粗大粒子が少なく、粒径が均一であり、結晶子径が大きいと、厚膜抵抗体とした場合のノイズ値を特に抑制することが可能であるためである。 Further, it is desirable that the ruthenium oxide powder contains few coarse particles, has a uniform particle size, and has a large crystallite size. The reason for this is that when the ruthenium oxide powder contains few coarse particles, has a uniform particle size, and has a large crystallite size, it is possible to particularly suppress the noise value when used as a thick film resistor. is.
導電粉末は酸化ルテニウム粉末のみから構成することもできるが、所望の抵抗値領域に応じて、銀粉末、パラジウム粉末といった貴金属を含む粉末をさらに添加、含有することもできる。
（２）ガラス
ガラスとしては鉛成分を含まないガラス（ガラス粉末）を用いることができる。なお、鉛成分を含まないガラスとは、鉛を意図して添加していないことを意味し、鉛の含有量が０であることを意味する。ただし、製造工程等で不純物成分、不可避成分として混入することを排除するものではない。
The conductive powder can be composed of only ruthenium oxide powder, but it can also contain powders containing noble metals such as silver powder and palladium powder, depending on the desired resistance value range.
(2) Glass As the glass, glass (glass powder) containing no lead component can be used. The glass containing no lead component means that lead is not intentionally added, and means that the lead content is zero. However, it does not exclude the contamination as an impurity component or an unavoidable component in the manufacturing process or the like.
ガラスの組成は特に限定されないが、ガラスは、ＳｉＯ２とＢ２Ｏ３とＲＯ（ＲはＣａ、Ｓｒ、Ｂａから選択された１種類以上の元素）と、Ａｌ２Ｏ３とを含むことができ、Ａｌ２Ｏ３の含有割合が６ｍｏｌ％以下であることが好ましい。 The composition of the glass is not particularly limited, but the glass may contain SiO 2 , B 2 O 3 , RO (R is one or more elements selected from Ca, Sr, and Ba), and Al 2 O 3 . It is preferable that the content of Al 2 O 3 is 6 mol % or less.
なお、以下の各成分の含有割合（ｍｏｌ％）について説明する場合、特に断らない場合、酸化物として計算した場合の含有割合を意味する。すなわち例えばガラスの組成をＩＣＰ（Ｉｎｄｕｃｔｉｖｅｌｙ Ｃｏｕｐｌｅｄ Ｐｌａｓｍａ）発光分光分析等により、各元素、つまりＡｌ等の含有割合として評価した場合においては、Ａｌ２Ｏ３として酸化物に換算した後の値が対応した値であることを意味する。 When describing the content ratio (mol%) of each component below, unless otherwise specified, it means the content ratio calculated as an oxide. That is, for example, when the composition of glass is evaluated as the content ratio of each element, that is, Al or the like, by ICP (Inductively Coupled Plasma) emission spectroscopic analysis or the like, the value after conversion to oxide as Al 2 O 3 corresponds. value.
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配合にあわせて混合し、得られた混合物を溶融し急冷することによって製造できる。溶融温度は特に限定されるものではないが例えば１４００℃前後とすることができる。また、急冷の方法についても特に限定されないが、溶融物を冷水中に入れるか冷ベルト上に流すことにより行うことができる。 Glasses can generally be produced by mixing the given components or their precursors into a desired formulation, melting and quenching the resulting mixture. Although the melting temperature is not particularly limited, it can be around 1400°C, for example. Also, the method of quenching is not particularly limited, but it can be carried out by placing the melt in cold water or flowing it on a cooling belt.
ガラスの所定の成分またはそれらの前駆体を目的とする配合にあわせて混合し、得られた混合物を溶融した際に、ガラス成分の分相等が発生することがある。厚膜抵抗体を形成するガラスは、均質であることが望ましく、分相することは望ましくない。そのような分相の発生を抑制するために、本実施形態の厚膜抵抗体用組成物に用いるガラスは、Ａｌ２Ｏ３を含有することが望ましい。 When predetermined glass components or their precursors are mixed in accordance with the desired composition and the resulting mixture is melted, phase separation of the glass components may occur. The glass forming the thick film resistor should be homogeneous and should not be phase split. In order to suppress the occurrence of such phase separation, the glass used in the composition for thick film resistors of the present embodiment preferably contains Al 2 O 3 .
しかし、ＳｉＯ２とＢ２Ｏ３とＲＯとＡｌ２Ｏ３とを含むガラスは、ガラス自体が分相などしていなくても、酸化ルテニウム粉末と組み合わせて厚膜抵抗体用組成物とした時や、該厚膜抵抗体用組成物を焼成する際にアルミノケイ酸塩結晶相が発生することがある。そして、アルミノケイ酸塩結晶相が厚膜抵抗体の中に生じると、厚膜抵抗体の電気特性の１つであるノイズが劣ってしまう。 However, even if the glass containing SiO 2 , B 2 O 3 , RO and Al 2 O 3 is not phase-separated, when it is combined with ruthenium oxide powder to form a composition for a thick film resistor, Also, an aluminosilicate crystal phase may occur when the composition for thick film resistors is fired. When the aluminosilicate crystal phase occurs in the thick film resistor, noise, which is one of the electrical characteristics of the thick film resistor, is degraded.
本発明の発明者らの検討によれば、ＳｉＯ２とＢ２Ｏ３とＲＯとＡｌ２Ｏ３を含むガラスであっても、Ａｌ２Ｏ３の含有割合が６ｍｏｌ％以下の場合、厚膜抵抗体中にアルミノケイ酸塩結晶相をＸ線回折パターンで確認されることはない。すなわちＳｉＯ２とＢ２Ｏ３とＲＯとＡｌ２Ｏ３を含み、Ａｌ２Ｏ３の含有割合が６ｍｏｌ％以下のガラスは、導電粉末との混合割合等によらず、アルミノケイ酸塩結晶相が発生しないガラスとなる。そして、Ｘ線回折パターンでアルミノケイ酸塩結晶相が確認できない厚膜抵抗体は、ノイズ特性にも優れている。このため、本実施形態の厚膜抵抗体用組成物に用いるガラスは、Ａｌ２Ｏ３の含有割合が６ｍｏｌ％以下であることが好ましい。 According to studies by the inventors of the present invention, even in a glass containing SiO 2 , B 2 O 3 , RO, and Al 2 O 3 , when the content of Al 2 O 3 is 6 mol % or less, a thick film No X-ray diffraction pattern confirms an aluminosilicate crystal phase in the resistor. That is, glass containing SiO 2 , B 2 O 3 , RO, and Al 2 O 3 and having an Al 2 O 3 content of 6 mol % or less has an aluminosilicate crystal phase regardless of the mixing ratio with the conductive powder. It becomes glass that does not occur. A thick-film resistor in which an aluminosilicate crystal phase cannot be confirmed in an X-ray diffraction pattern also has excellent noise characteristics. Therefore, it is preferable that the content of Al 2 O 3 in the glass used for the thick film resistor composition of the present embodiment is 6 mol % or less.
なお、本実施形態の厚膜抵抗体用組成物に用いるガラスは、Ａｌ２Ｏ３を含有することが好ましいから、Ａｌ２Ｏ３の含有割合は０よりも多くすることができる。 The glass used for the thick film resistor composition of the present embodiment preferably contains Al 2 O 3 , so the content of Al 2 O 3 can be greater than zero.
本実施形態の厚膜抵抗体用組成物に用いるガラスは、ＳｉＯ２、Ｂ２Ｏ３、ＲＯ、Ａｌ２Ｏ３のみから構成することもできるが、その他の任意の成分をさらに含有することもできる。本実施形態の厚膜抵抗体用組成物に用いるガラスがさらに含有できる任意の成分としては、ＺｒＯ２、ＴｉＯ２、ＳｎＯ２、ＺｎＯ、Ｌｉ２Ｏ、Ｎａ２Ｏ、Ｋ２Ｏ等から選択された１種類以上が挙げられる。 The glass used for the thick film resistor composition of the present embodiment can be composed only of SiO 2 , B 2 O 3 , RO, and Al 2 O 3 , but may further contain other optional components. can. The optional component that the glass used in the composition for thick film resistors of the present embodiment can further contain is selected from ZrO 2 , TiO 2 , SnO 2 , ZnO, Li 2 O, Na 2 O, K 2 O, and the like. one or more types.
ＺｒＯ２、ＴｉＯ２はガラスの耐候性を向上させることができる。また、ＳｎＯ２、ＺｎＯ、Ｌｉ２Ｏ、Ｎａ２Ｏ、Ｋ２Ｏ等はガラスの溶融時の流動性を高める働きがある。 ZrO 2 and TiO 2 can improve the weather resistance of glass. Also, SnO 2 , ZnO, Li 2 O, Na 2 O, K 2 O, etc. have the function of increasing the fluidity of the glass when it is melted.
そして、本実施形態の厚膜抵抗体用組成物に用いるガラスは、さらにＺｎＯを含有することが好ましい。ＺｎＯの含有割合は１５ｍｏｌ％以上とすることが好ましい。ＺｎＯは、ガラスを溶融した際の流動性を高める働きを有する。なお、本実施形態の厚膜抵抗体用組成物に用いるガラスがＺｎＯを含有する場合、その含有量の上限は特に限定されないが、他の成分の含有量を十分に確保する観点から４５ｍｏｌ％以下であることが好ましい。 The glass used for the thick film resistor composition of the present embodiment preferably further contains ZnO. The content of ZnO is preferably 15 mol % or more. ZnO has the function of increasing the fluidity when the glass is melted. When the glass used for the composition for a thick film resistor of the present embodiment contains ZnO, the upper limit of the content is not particularly limited, but from the viewpoint of sufficiently securing the content of other components, it is 45 mol % or less. is preferred.
なお、本実施形態の厚膜抵抗体用組成物に用いるガラスは、既述の様にＳｉＯ２とＢ２Ｏ３とＲＯとＡｌ２Ｏ３とを含むことが好ましい。この際、ＲＯとして、ＣａＯとＢａＯとを含有することがより好ましい。係るガラスは上述のようにさらにＺｎＯを含むこともできる。また、係るガラスはさらにアルカリ金属の酸化物を含むこともできる。 The glass used for the thick film resistor composition of the present embodiment preferably contains SiO 2 , B 2 O 3 , RO and Al 2 O 3 as described above. At this time, it is more preferable to contain CaO and BaO as RO. Such glasses may additionally contain ZnO as described above. Also, such a glass may further contain oxides of alkali metals.
このため、本実施形態の厚膜抵抗体用組成物に用いるガラスは、ＳｉＯ２とＢ２Ｏ３とＡｌ２Ｏ３と、ＣａＯと、ＢａＯと、ＺｎＯとを含むこともでき、場合によってはさらにアルカリ金属の酸化物とを含むこともできる。なお、本実施形態の厚膜抵抗体用組成物のガラスは上記成分から構成することもできる。 Therefore, the glass used in the thick film resistor composition of the present embodiment may contain SiO 2 , B 2 O 3 , Al 2 O 3 , CaO, BaO, and ZnO, and in some cases, Further, it can also contain oxides of alkali metals. The glass of the composition for thick film resistors of the present embodiment can also be composed of the above components.
ガラスの熱的特性として、ガラス転移点と軟化点が知られており、ガラスの組成変化に伴う転移点と軟化点との変化は概ね比例関係を有している。 A glass transition point and a softening point are known as thermal properties of glass, and changes in the transition point and softening point due to changes in the composition of the glass generally have a proportional relationship.
そして、本発明の発明者らの検討によれば、厚膜抵抗体のノイズ特性の向上には、厚膜抵抗体用組成物に用いるガラスのガラス転移点が５８０℃以上６３０℃以下であることが好ましい。上記範囲のガラス転移点を有するガラスを選択したことにより厚膜抵抗体のノイズ特性が向上する理由は明らかではないが、実験的な検討の結果、アルミノケイ酸塩結晶相が析出しないガラスで、上記ガラス転移点を有するガラスを用いることでノイズ特性が向上する傾向がある。 According to the study by the inventors of the present invention, the glass transition point of the glass used in the composition for the thick film resistor should be 580° C. or higher and 630° C. or lower in order to improve the noise characteristics of the thick film resistor. is preferred. It is not clear why the noise characteristics of the thick film resistor are improved by selecting a glass having a glass transition point within the above range. Noise characteristics tend to be improved by using a glass having a glass transition point.
ガラス転移点は、ガラスを示差熱分析法（ＴＧ－ＤＴＡ）にて大気中、１０℃／ｍｉｎの昇温速度で昇温、加熱し、得られた示差熱曲線の最も低温側の示差熱曲線の減少が発現する温度とした。 The glass transition point is the differential thermal curve on the lowest temperature side of the differential thermal curve obtained by heating and heating the glass at a temperature rising rate of 10 ° C./min in the atmosphere by differential thermal analysis (TG-DTA). was defined as the temperature at which the decrease in
本実施形態の厚膜抵抗体用組成物に用いるガラスは、例えばＳｉＯ２の含有割合を４ｍｏｌ％以上６５ｍｏｌ％以下、Ｂ２Ｏ３の含有割合を２ｍｏｌ％以上３０ｍｏｌ％以下、Ａｌ２Ｏ３の含有割合を１ｍｏｌ％以上６ｍｏｌ％以下、ＣａＯの含有割合を２ｍｏｌ％以上２０ｍｏｌ％以下、ＺｎＯの含有割合を０以上４５ｍｏｌ％以下、ＢａＯの含有割合を５ｍｏｌ％以上５０ｍｏｌ％以下、アルカリ金属の酸化物の含有割合を０以上８ｍｏｌ％以下とすることができる。なお、ＺｎＯの含有割合は１５ｍｏｌ％以上であることが好ましい。 The glass used for the thick film resistor composition of the present embodiment has, for example, a SiO 2 content of 4 mol % to 65 mol %, a B 2 O 3 content of 2 mol % to 30 mol %, and an Al 2 O 3 content of 4 mol % to 65 mol %. The content ratio is 1 mol% to 6 mol%, the content ratio of CaO is 2 mol% to 20 mol%, the content ratio of ZnO is 0 to 45 mol%, the content ratio of BaO is 5 mol% to 50 mol%, alkali metal oxides can be 0 or more and 8 mol % or less. Note that the content of ZnO is preferably 15 mol % or more.
各成分の含有割合が上記範囲のガラスの場合、ガラス転移点を５８０℃以上６３０℃以下とすることができる。 When the content ratio of each component is in the above range, the glass transition point can be 580° C. or higher and 630° C. or lower.
本実施形態の厚膜抵抗体用組成物に用いるガラスの平均粒径は特に限定されないが、０．１μｍ以上５μｍ以下であることが好ましく、０．１μｍ以上３μｍ以下がより好ましい。厚膜抵抗体用組成物に含まれるガラスの平均粒径を５μｍ以下とすることで、厚膜抵抗体とした場合のノイズ特性を特に高めることができる。一方、ガラスの平均粒径を過度に小さくすると、生産性が低くなり、不純物等の混入も増える恐れがある。このため、ガラスの平均粒径は０．１μｍ以上であることが好ましい。 The average particle diameter of the glass used in the composition for thick film resistors of the present embodiment is not particularly limited, but is preferably 0.1 μm or more and 5 μm or less, more preferably 0.1 μm or more and 3 μm or less. By setting the average particle size of the glass contained in the thick film resistor composition to 5 μm or less, the noise characteristics of the thick film resistor can be particularly improved. On the other hand, if the average particle diameter of the glass is excessively small, the productivity will be lowered and there is a possibility that impurities and the like will be mixed. Therefore, the average particle size of the glass is preferably 0.1 μm or more.
ガラスの平均粒径は、レーザー回折を利用した粒度分布計により測定することができる。 The average particle size of glass can be measured with a particle size distribution meter using laser diffraction.
厚膜抵抗体用組成物の導電粉末と、ガラスとの混合比率は特に限定されるものではなく、厚膜抵抗体とした場合に要求される抵抗値等に応じて任意に選択することができる。なお、導電粉末としては、既述の様に酸化ルテニウム粉末を用いることができる。 The mixing ratio of the conductive powder and the glass in the composition for thick film resistors is not particularly limited, and can be arbitrarily selected according to the resistance value etc. required when making a thick film resistor. . As the conductive powder, ruthenium oxide powder can be used as described above.
ただし、例えば高抵抗域の厚膜抵抗体とするためにはガラスの配合割合を増やし、例えば厚膜抵抗体用組成物の導電粉末と、ガラスとの合計に対するガラスの含有率を８０質量％以上とすることになる。そして、本発明の発明者らの検討によれば、アルミノケイ酸塩結晶相が発生し易いガラスを用いた厚膜抵抗体用組成物では、厚膜抵抗体用組成物の導電粉末と、ガラスとの合計に対するガラスの含有率が８０質量％以上の場合にアルミノケイ酸塩結晶相が発生し易い。 However, for example, in order to obtain a thick film resistor in a high resistance range, the proportion of glass is increased, for example, the content of glass with respect to the total of conductive powder and glass in the composition for thick film resistor is 80% by mass or more. It will be According to the studies of the inventors of the present invention, in a composition for a thick film resistor using a glass in which an aluminosilicate crystal phase is likely to occur, the conductive powder of the composition for a thick film resistor and the glass When the content of glass with respect to the total of is 80% by mass or more, an aluminosilicate crystal phase is likely to occur.
なお、ここでいうアルミノケイ酸塩結晶相が発生し易いガラスとは、例えばＡｌ２Ｏ３の含有量が６ｍｏｌ％より過度に多いガラス等が挙げられる。 Here, the glass in which the aluminosilicate crystal phase is likely to occur includes, for example, glass in which the content of Al 2 O 3 is excessively higher than 6 mol %.
ところで、厚膜抵抗体用組成物は、単位面積あたりの抵抗値が１００ｋΩ、１ＭΩ等となるよう導電粉末とガラス等を配合された各抵抗値を示す複数の厚膜抵抗体用組成物を混合して、所望の抵抗値を得られるように調整されて使用される。混合に用いる各抵抗値を示す厚膜抵抗体用組成物は、混合の自由度のために、同じ導電粉末と同じガラスを使用するのが一般的である。これは、各抵抗値を示す厚膜抵抗体用組成物のガラスが異なれば、混合しても混合割合に応じた抵抗値やその他の電気特性は発現しないためである。このような厚膜抵抗体用組成物の使用態様から、厚膜抵抗体用組成物で用いるガラスは、導電粉末と、ガラスとの合計に対するガラスの含有率が８０質量％以上の場合であってもアルミノケイ酸塩結晶相が発生しないガラスであることが好ましい。 By the way, the composition for thick film resistors is obtained by mixing a plurality of compositions for thick film resistors, each of which has a resistance value of 100 kΩ, 1 MΩ, etc., and which contains conductive powder and glass, etc. Then, it is used after being adjusted so as to obtain the desired resistance value. Compositions for thick film resistors exhibiting respective resistance values used for mixing generally use the same conductive powder and the same glass for the degree of freedom in mixing. This is because if the glass of the thick film resistor composition showing each resistance value is different, the resistance value and other electrical properties corresponding to the mixing ratio will not be exhibited even if they are mixed. From such a usage mode of the composition for thick film resistors, the glass used in the composition for thick film resistors should have a glass content of 80% by mass or more with respect to the total of the conductive powder and the glass. It is also preferable that the glass is a glass in which an aluminosilicate crystal phase does not occur.
本実施形態の厚膜抵抗体用組成物中の導電粉末は、導電粉末とガラスとの合計に対する導電粉末の含有率は、５質量％以上６５質量％以下であることが好ましい。 The content of the conductive powder in the composition for a thick film resistor of the present embodiment is preferably 5% by mass or more and 65% by mass or less with respect to the total of the conductive powder and the glass.
厚膜抵抗体用組成物中の導電粉末の含有割合を上記範囲とすることで、厚膜抵抗体とした場合に、低抵抗領域から高抵抗領域まで抵抗値を発現させることが可能となる。なお、厚膜抵抗体用組成物には、電気特性を調整するために金属酸化物粉末を添加してもよい。電気特性を調整するための添加剤として使用される金属酸化物粉末としては、酸化銅、酸化チタン、酸化マンガンなどが適宜用いてよい。
［厚膜抵抗体用ペースト］
本実施形態の厚膜抵抗体用ペーストは、既述の厚膜抵抗体用組成物と、有機ビヒクルとを含むことができる。特に有機ビヒクル中に既述の厚膜抵抗体用組成物が分散されていることが好ましい。有機ビヒクルの組成は特に限定されないが、例えばエチルセルロースなどの樹脂と、ターピオネールなどの溶剤を含有することができる。
By setting the content of the conductive powder in the composition for a thick film resistor within the above range, the thick film resistor can exhibit a resistance value ranging from a low resistance region to a high resistance region. Metal oxide powder may be added to the composition for thick film resistors in order to adjust electrical properties. Copper oxide, titanium oxide, manganese oxide, and the like may be appropriately used as the metal oxide powder used as an additive for adjusting electrical properties.
[Paste for thick film resistors]
The thick film resistor paste of the present embodiment can contain the aforementioned thick film resistor composition and an organic vehicle. In particular, it is preferable that the composition for thick film resistors is dispersed in an organic vehicle. Although the composition of the organic vehicle is not particularly limited, it may contain, for example, a resin such as ethyl cellulose and a solvent such as terpionail.
本実施形態の厚膜抵抗体用ペーストは、厚膜抵抗体用組成物と、有機ビヒクルとから構成することもできるが、さらに任意の成分を含有することもできる。 The thick film resistor paste of the present embodiment can be composed of the thick film resistor composition and the organic vehicle, but can also contain optional components.
任意の成分としては、例えば分散剤や、可塑剤、樹脂、溶剤等が挙げられる。分散剤や可塑剤、樹脂や溶剤は、乾燥、焼成によって除去される。
厚膜抵抗体用ペーストの製造方法は特に限定されないが、例えば導電粉末である酸化ルテニウム粉末と、ガラスと、有機ビヒクルとその他原料を混合し、スリーロールミル（三本ロールミル）等で混練することで製造することができる。なお、酸化ルテニウム粉末と、ガラスとは予め混合し、厚膜抵抗体用組成物としてから用いることもできる。
［厚膜抵抗体］
本実施形態の厚膜抵抗体は、既述の厚膜抵抗体用組成物を含有することができる。
Optional components include, for example, dispersants, plasticizers, resins, and solvents. Dispersants, plasticizers, resins and solvents are removed by drying and baking.
The method for producing the thick film resistor paste is not particularly limited, but for example, ruthenium oxide powder, which is a conductive powder, glass, an organic vehicle, and other raw materials are mixed and kneaded in a three-roll mill (three-roll mill) or the like. can be manufactured. Note that the ruthenium oxide powder and the glass can be mixed in advance and used as a composition for a thick film resistor.
[Thick film resistor]
The thick film resistor of this embodiment can contain the composition for thick film resistors described above.
既述の厚膜抵抗体用組成物や、厚膜抵抗体用ペーストを焼成することで厚膜抵抗体とすることができる。例えば、既述の厚膜抵抗体用ペーストを塗布後、乾燥、焼成すると、厚膜抵抗体用ペーストに含まれていた分散剤や、可塑剤、樹脂、溶剤は、乾燥、焼成によって除去される。一方、酸化ルテニウム粉末は、焼成後において、そのまま残留したり、ガラスに取り込まれたりすることで、機能を発現している。 A thick film resistor can be obtained by firing the composition for a thick film resistor or the paste for a thick film resistor. For example, when the thick-film resistor paste described above is applied and then dried and fired, the dispersant, plasticizer, resin, and solvent contained in the thick-film resistor paste are removed by drying and firing. . On the other hand, the ruthenium oxide powder exhibits its function by remaining as it is or by being incorporated into the glass after firing.
本発明の発明者らの検討によれば、抵抗値領域においてノイズ値が高い（悪い）場合は、厚膜抵抗体の内部に結晶相が発生している。ノイズ値が高くなる理由としては、導電粉末である酸化ルテニウム粉末の粒子の間にアルミノケイ酸塩の結晶相が介在し、導電粉末により形成される導電パスが阻害されているため、もしくは結晶相が発生することで厚膜抵抗体内部に微小のクラックが発生し導電粉末の粒子の接触状態を悪化させるためと推察している。 According to studies by the inventors of the present invention, when the noise value is high (bad) in the resistance value region, a crystalline phase occurs inside the thick film resistor. The reason for the high noise value is that the crystal phase of the aluminosilicate intervenes between the particles of the ruthenium oxide powder, which is the conductive powder, and the conductive path formed by the conductive powder is obstructed. It is presumed that this is because minute cracks are generated inside the thick film resistor and the contact state of the particles of the conductive powder is deteriorated.
厚膜抵抗体中の結晶相の存在は、厚膜抵抗体用ペーストを乾燥、焼成することで得られた厚膜抵抗体について、Ｘ線回折測定を行う方法や、厚膜抵抗体の断面ＳＥＭ像を観察する方法等により確認できる。 The presence of a crystalline phase in the thick film resistor can be determined by a method of X-ray diffraction measurement of a thick film resistor obtained by drying and firing a thick film resistor paste, or a cross-sectional SEM of the thick film resistor. It can be confirmed by a method of observing an image or the like.
本実施形態の厚膜抵抗体は既述の厚膜抵抗体用組成物を含有しており、Ｘ線回折パターンにおいてアルミノケイ酸塩結晶相が検出されないものとすることができる。 The thick film resistor of the present embodiment contains the thick film resistor composition described above, and the aluminosilicate crystal phase is not detected in the X-ray diffraction pattern.
また、従来特に高抵抗域の厚膜抵抗体においてノイズ特性が悪い場合が多かった。しかし、本実施形態の厚膜抵抗体によれば、高抵抗域においても優れたノイズ特性を発揮することができる。このため、本実施形態の厚膜抵抗体は、例えば単位面積（１ｍｍ×１ｍｍ）あたりの抵抗値が８ｋΩ以上であることが好ましく、１０ｋΩ以上であることがより好ましい。 In addition, conventional thick-film resistors, especially in the high-resistance range, often have poor noise characteristics. However, according to the thick film resistor of this embodiment, excellent noise characteristics can be exhibited even in the high resistance region. For this reason, the thick film resistor of the present embodiment preferably has a resistance value of 8 kΩ or more, more preferably 10 kΩ or more, per unit area (1 mm×1 mm), for example.
厚膜抵抗体は例えば以下の手順で製造できる。まず、厚膜抵抗体用ペーストをスクリーン印刷機等により、電極が印刷されたアルミナ基板等の絶縁基板上に印刷する。その後、乾燥により溶剤を揮発、除去した後に、例えば８００℃以上９００℃以下の焼成温度で焼成を行うことで、厚膜抵抗体を形成することができる。
［抵抗器、抵抗器の製造］
本実施形態の抵抗器は、既述の厚膜抵抗体から製造することができる。
A thick film resistor can be manufactured, for example, by the following procedure. First, a thick-film resistor paste is printed by a screen printer or the like on an insulating substrate such as an alumina substrate on which electrodes are printed. Then, after volatilizing and removing the solvent by drying, the thick film resistor can be formed by firing at a firing temperature of, for example, 800° C. or higher and 900° C. or lower.
[Manufacture of resistors and resistors]
The resistor of this embodiment can be manufactured from the thick film resistor described above.
具体的にはまず、厚膜抵抗体の表面にガラスペーストを塗布、乾燥し、８００℃よりも低い温度で焼成することでガラス膜を形成できる。その後、抵抗値調整の為のレーザートリミングを行ったり、保護コート処理、側面電極ペーストを行うことで抵抗器を製造することができる。 Specifically, a glass film can be formed by first applying a glass paste to the surface of the thick film resistor, drying it, and firing it at a temperature lower than 800°C. After that, the resistor can be manufactured by performing laser trimming for resistance value adjustment, protective coating treatment, and side electrode paste.
以下に具体的な実施例、比較例等を挙げて説明するが、本発明はこれらの実施例に限定されるものではない。
（評価方法）
（１）抵抗値測定
製造した厚膜抵抗体について、デジタルマルチメーター（ＫＥＩＴＨＬＥＹ社製、２００１番）により抵抗値を測定し、得られた抵抗値を、厚膜抵抗体の厚さが７μｍの場合に換算して、その抵抗体厚膜の抵抗値とした。
（２）ノイズ（電流雑音）測定
厚膜抵抗体のノイズについて、ノイズメーター（ノイズ研究所製ＲＣＮ－２０１１）を用いて測定した。
（３）酸化ルテニウム粉末の粒径
酸化ルテニウム粉末の粒径（比表面積径）は比表面積と密度より算出した。比表面積は測定が簡単にできるＢＥＴ１点法を用いた。酸化ルテニウム粉末の粒径（ｎｍ）は、密度をρ（ｇ／ｃｍ３）、比表面積をＳ（ｍ２／ｇ）とし、粉末を真球とみなし、以下の式（１）により算出した。
酸化ルテニウムの粒径（ｎｍ）＝６×１０３／（ρ・Ｓ） ・・・（１）
以下の実施例、比較例では、酸化ルテニウムの密度を７．０５ｇ／ｃｍ３として計算した。
（４）ガラス粉末の平均粒径
ガラス粉末を粒度分布測定器（マイクロトラック・ベル社製 型式：ＨＲＡ9320-Ｘ100）で粒度分布を測定し、その体積平均値（ｍｖ）を平均粒径（体積平均粒径）とした。
（５）ガラス粉末のガラス転移点
ガラス粉末のガラス転移点は、ガラス粉末を示差熱分析法（ＴＧ－ＤＴＡ）にて大気中にて毎分１０℃で昇温し、加熱し、得られた示差熱曲線の最も低温側の示差熱曲線の減少が発現する温度とした。
（６）アルミノケイ酸塩結晶相の確認
焼成して得られたＸＲＤ測定用厚膜抵抗体をＸ線回折装置（スペクトリス社製 型式：Ｘ'ＰＥＲＴ-ＰＲＯ）で分析した。ＸＲＤ測定用厚膜抵抗体のＸ線回折パターンからは、例えば酸化ルテニウムおよびアルミナに帰属されるピーク、ガラス成分が結晶物を含む場合はそのピークを確認できる。そして、得られたＸ線回折パターンから析出している結晶を確認し、アルミノケイ酸塩結晶相の有無を確認した。
（試料の作製条件）
以下、各実施例、比較例の試料の作製条件について説明する。
［実施例１］
ガラス粉末Ａを４５．８質量部と、酸化ルテニウム粉末を１４．２質量部との割合で含む厚膜抵抗体用組成物を調製した。
Although specific examples, comparative examples, etc. will be given and described below, the present invention is not limited to these examples.
(Evaluation method)
(1) Resistance value measurement The resistance value of the manufactured thick film resistor is measured with a digital multimeter (manufactured by KEITHLEY, No. 2001), and the obtained resistance value is measured when the thickness of the thick film resistor is 7 μm. , and used as the resistance value of the resistor thick film.
(2) Noise (current noise) measurement The noise of the thick film resistor was measured using a noise meter (RCN-2011 manufactured by Noise Laboratory).
(3) Particle size of ruthenium oxide powder The particle size (specific surface area diameter) of the ruthenium oxide powder was calculated from the specific surface area and density. The specific surface area was measured using the BET one-point method, which allows easy measurement. The particle size (nm) of the ruthenium oxide powder was calculated by the following formula (1), where ρ (g/cm 3 ) was the density, S (m 2 /g) was the specific surface area, and the powder was regarded as a true sphere.
Particle size of ruthenium oxide (nm)=6×10 3 /(ρ·S) (1)
In the following examples and comparative examples, the density of ruthenium oxide was calculated as 7.05 g/cm 3 .
(4) Average particle size of glass powder The particle size distribution of the glass powder is measured with a particle size distribution analyzer (manufactured by Microtrac Bell, model: HRA9320-X100), and the volume average value (mv) is the average particle size (volume average particle size).
(5) Glass transition point of glass powder The glass transition point of the glass powder was obtained by heating the glass powder at a rate of 10°C per minute in the atmosphere by differential thermal analysis (TG-DTA). The temperature at which a decrease in the differential thermal curve on the lowest temperature side of the differential thermal curve appears.
(6) Confirmation of Aluminosilicate Crystal Phase The fired thick-film resistor for XRD measurement was analyzed with an X-ray diffractometer (Model: X'PERT-PRO manufactured by Spectris). From the X-ray diffraction pattern of the thick film resistor for XRD measurement, peaks attributed to, for example, ruthenium oxide and alumina, and peaks when the glass component contains crystals can be confirmed. Precipitated crystals were confirmed from the obtained X-ray diffraction pattern, and the presence or absence of an aluminosilicate crystal phase was confirmed.
(Sample preparation conditions)
The conditions for producing the samples of each example and comparative example will be described below.
[Example 1]
A composition for a thick film resistor containing 45.8 parts by mass of glass powder A and 14.2 parts by mass of ruthenium oxide powder was prepared.
そして、係る厚膜抵抗体用組成物６０質量部と、有機ビヒクル４０質量部とをスリーロールミルで混練し、厚膜抵抗体用ペーストを得た。 Then, 60 parts by mass of the composition for thick film resistor and 40 parts by mass of the organic vehicle were kneaded in a three-roll mill to obtain a paste for thick film resistor.
なお、ガラス粉末Ａの組成、ガラス転移点、平均粒径は表２に示す。 Table 2 shows the composition, glass transition point, and average particle size of the glass powder A.
また、用いた酸化ルテニウム粉末は、比表面積から算出した平均粒径が４０ｎｍであった。 The ruthenium oxide powder used had an average particle size of 40 nm calculated from the specific surface area.
有機ビヒクルは、エチルセルロースを１５質量％と、ターピネオールを８５質量％の割合で含有している。 The organic vehicle contains 15% by mass of ethyl cellulose and 85% by mass of terpineol.
銀を主成分とする厚膜電極が形成されたアルミナ基板上に、調製した厚膜抵抗体用ペーストを１ｍｍ×１ｍｍの正方形パターンとなるようにスクリーン印刷した。次いで、１５０℃で乾燥し、空気中で８５０℃で１５分間焼成して、厚膜抵抗体を製造した。 The prepared thick film resistor paste was screen-printed in a square pattern of 1 mm×1 mm on an alumina substrate on which a thick film electrode containing silver as a main component was formed. It was then dried at 150° C. and fired in air at 850° C. for 15 minutes to produce a thick film resistor.
なお、焼成後において６．５μｍ以上７．５μｍ以下の膜厚になるように厚膜抵抗体を形成した。 The thick film resistor was formed so as to have a film thickness of 6.5 μm or more and 7.5 μm or less after firing.
得られた厚膜抵抗体について、抵抗値、ノイズを測定した。その結果を表１に示す。 The resistance value and noise of the obtained thick film resistor were measured. Table 1 shows the results.
また、アルミナ基板上に上記厚膜抵抗体用ペーストを印刷し、次いで１５０℃で乾燥し、空気中で８５０℃で１５分間焼成することで、１．５ｃｍ角で厚みが２０μｍのＸＲＤ測定用厚膜抵抗体を得た。得られたＸＲＤ測定用厚膜抵抗体について、Ｘ線回折装置により分析した。評価結果を表１に示す。
［実施例２］
ガラス粉末Ａを４９．６質量部と、酸化ルテニウム粉末を１０．４質量部との割合で含む厚膜抵抗体用組成物を用意した。
In addition, the thick film resistor paste was printed on an alumina substrate, then dried at 150 ° C. and fired in air at 850 ° C. for 15 minutes to obtain a thickness of 1.5 cm square and a thickness of 20 μm for XRD measurement. A membrane resistor was obtained. The obtained thick film resistor for XRD measurement was analyzed by an X-ray diffraction device. Table 1 shows the evaluation results.
[Example 2]
A composition for a thick film resistor containing 49.6 parts by mass of glass powder A and 10.4 parts by mass of ruthenium oxide powder was prepared.
そして、係る厚膜抵抗体用組成物６０質量部と、有機ビヒクル４０質量部とをスリーロールミルで混練し、厚膜抵抗体用ペーストを得た。なお、酸化ルテニウム粉末と、有機ビヒクルは実施例１と同じものを用いた。 Then, 60 parts by mass of the composition for thick film resistor and 40 parts by mass of the organic vehicle were kneaded in a three-roll mill to obtain a paste for thick film resistor. The same ruthenium oxide powder and organic vehicle as in Example 1 were used.
得られた厚膜抵抗体用ペーストを用いた点以外は実施例１と同様にして厚膜抵抗体、ＸＲＤ測定用厚膜抵抗体を製造した。また、実施例１と同様に評価を行った。評価結果を表１に示す。
［実施例３］
ガラス粉末Ａを５３．３質量部と、酸化ルテニウム粉末を６．７質量部との割合で含む厚膜抵抗体用組成物を用意した。
A thick film resistor and a thick film resistor for XRD measurement were manufactured in the same manner as in Example 1 except that the obtained thick film resistor paste was used. Moreover, evaluation was performed in the same manner as in Example 1. Table 1 shows the evaluation results.
[Example 3]
A composition for a thick film resistor containing 53.3 parts by mass of glass powder A and 6.7 parts by mass of ruthenium oxide powder was prepared.
そして、係る厚膜抵抗体用組成物６０質量部と、有機ビヒクル４０質量部とをスリーロールミルで混練し、厚膜抵抗体用ペーストを得た。なお、酸化ルテニウム粉末と、有機ビヒクルは実施例１と同じものを用いた。 Then, 60 parts by mass of the composition for thick film resistor and 40 parts by mass of the organic vehicle were kneaded in a three-roll mill to obtain a paste for thick film resistor. The same ruthenium oxide powder and organic vehicle as in Example 1 were used.
得られた厚膜抵抗体用ペーストを用いた点以外は実施例１と同様にして厚膜抵抗体、ＸＲＤ測定用厚膜抵抗体を製造した。また、実施例１と同様に評価を行った。評価結果を表１に示す。
［実施例４］
ガラス粉末Ａを５６．９質量部と、酸化ルテニウム粉末を３．１質量部との割合で含む厚膜抵抗体用組成物を用意した。
A thick film resistor and a thick film resistor for XRD measurement were manufactured in the same manner as in Example 1 except that the obtained thick film resistor paste was used. Moreover, evaluation was performed in the same manner as in Example 1. Table 1 shows the evaluation results.
[Example 4]
A composition for a thick film resistor containing 56.9 parts by mass of glass powder A and 3.1 parts by mass of ruthenium oxide powder was prepared.
そして、係る厚膜抵抗体用組成物６０質量部と、有機ビヒクル４０質量部とをスリーロールミルで混練し、厚膜抵抗体用ペーストを得た。なお、酸化ルテニウム粉末と、有機ビヒクルは実施例１と同じものを用いた。 Then, 60 parts by mass of the composition for thick film resistor and 40 parts by mass of the organic vehicle were kneaded in a three-roll mill to obtain a paste for thick film resistor. The same ruthenium oxide powder and organic vehicle as in Example 1 were used.
得られた厚膜抵抗体用ペーストを用いた点以外は実施例１と同様にして厚膜抵抗体、ＸＲＤ測定用厚膜抵抗体を製造した。また、実施例１と同様に評価を行った。評価結果を表１に示す。
［実施例５］
ガラス粉末Ｂを４６．７質量部と、酸化ルテニウム粉末を１３．３質量部との割合で含む厚膜抵抗体用組成物を用意した。
A thick film resistor and a thick film resistor for XRD measurement were manufactured in the same manner as in Example 1 except that the obtained thick film resistor paste was used. Moreover, evaluation was performed in the same manner as in Example 1. Table 1 shows the evaluation results.
[Example 5]
A composition for a thick film resistor containing 46.7 parts by mass of glass powder B and 13.3 parts by mass of ruthenium oxide powder was prepared.
そして、係る厚膜抵抗体用組成物６０質量部と、有機ビヒクル４０質量部とをスリーロールミルで混練し、厚膜抵抗体用ペーストを得た。 Then, 60 parts by mass of the composition for thick film resistor and 40 parts by mass of the organic vehicle were kneaded in a three-roll mill to obtain a paste for thick film resistor.
なお、ガラス粉末Ｂの組成、ガラス転移点、平均粒径は表２に示す。 Table 2 shows the composition, glass transition point, and average particle size of the glass powder B.
酸化ルテニウム粉末と、有機ビヒクルは実施例１と同じものを用いた。 The same ruthenium oxide powder and organic vehicle as in Example 1 were used.
得られた厚膜抵抗体用ペーストを用いた点以外は実施例１と同様にして厚膜抵抗体、ＸＲＤ測定用厚膜抵抗体を製造した。また、実施例１と同様に評価を行った。評価結果を表１に示す。
［実施例６］
ガラス粉末Ｂを５０．２質量部と、酸化ルテニウム粉末を９．８質量部との割合で含む厚膜抵抗体用組成物を用意した。
A thick film resistor and a thick film resistor for XRD measurement were manufactured in the same manner as in Example 1 except that the obtained thick film resistor paste was used. Moreover, evaluation was performed in the same manner as in Example 1. Table 1 shows the evaluation results.
[Example 6]
A composition for a thick film resistor containing 50.2 parts by mass of glass powder B and 9.8 parts by mass of ruthenium oxide powder was prepared.
そして、係る厚膜抵抗体用組成物６０質量部と、有機ビヒクル４０質量部とをスリーロールミルで混練し、厚膜抵抗体用ペーストを得た。なお、酸化ルテニウム粉末と、有機ビヒクルは実施例１と同じものを用いた。 Then, 60 parts by mass of the composition for thick film resistor and 40 parts by mass of the organic vehicle were kneaded in a three-roll mill to obtain a paste for thick film resistor. The same ruthenium oxide powder and organic vehicle as in Example 1 were used.
得られた厚膜抵抗体用ペーストを用いた点以外は実施例１と同様にして厚膜抵抗体、ＸＲＤ測定用厚膜抵抗体を製造した。また、実施例１と同様に評価を行った。評価結果を表１に示す。
［実施例７］
ガラス粉末Ｂを５３．３質量部と、酸化ルテニウム粉末を６．７質量部との割合で含む厚膜抵抗体用組成物を用意した。
A thick film resistor and a thick film resistor for XRD measurement were manufactured in the same manner as in Example 1 except that the obtained thick film resistor paste was used. Moreover, evaluation was performed in the same manner as in Example 1. Table 1 shows the evaluation results.
[Example 7]
A composition for a thick film resistor containing 53.3 parts by mass of glass powder B and 6.7 parts by mass of ruthenium oxide powder was prepared.
そして、係る厚膜抵抗体用組成物６０質量部と、有機ビヒクル４０質量部とをスリーロールミルで混練し、厚膜抵抗体用ペーストを得た。なお、酸化ルテニウム粉末と、有機ビヒクルは実施例１と同じものを用いた。 Then, 60 parts by mass of the composition for thick film resistors and 40 parts by mass of the organic vehicle were kneaded in a three-roll mill to obtain a paste for thick film resistors. The same ruthenium oxide powder and organic vehicle as in Example 1 were used.
得られた厚膜抵抗体用ペーストを用いた点以外は実施例１と同様にして厚膜抵抗体、ＸＲＤ測定用厚膜抵抗体を製造した。また、実施例１と同様に評価を行った。評価結果を表１に示す。
［実施例８］
ガラス粉末Ｂを５５．６質量部と、酸化ルテニウム粉末を４．４質量部との割合で含む厚膜抵抗体用組成物を用意した。
A thick film resistor and a thick film resistor for XRD measurement were manufactured in the same manner as in Example 1 except that the obtained thick film resistor paste was used. Moreover, evaluation was performed in the same manner as in Example 1. Table 1 shows the evaluation results.
[Example 8]
A composition for a thick film resistor containing 55.6 parts by mass of glass powder B and 4.4 parts by mass of ruthenium oxide powder was prepared.
そして、係る厚膜抵抗体用組成物６０質量部と、有機ビヒクル４０質量部とをスリーロールミルで混練し、厚膜抵抗体用ペーストを得た。なお、酸化ルテニウム粉末と、有機ビヒクルは実施例１と同じものを用いた。 Then, 60 parts by mass of the composition for thick film resistors and 40 parts by mass of the organic vehicle were kneaded in a three-roll mill to obtain a paste for thick film resistors. The same ruthenium oxide powder and organic vehicle as in Example 1 were used.
得られた厚膜抵抗体用ペーストを用いた点以外は実施例１と同様にして厚膜抵抗体、ＸＲＤ測定用厚膜抵抗体を製造した。また、実施例１と同様に評価を行った。評価結果を表１に示す。
［実施例９］
ガラス粉末Ｃを４８．９質量部と、酸化ルテニウム粉末を１１．１質量部との割合で含む厚膜抵抗体用組成物を用意した。
A thick film resistor and a thick film resistor for XRD measurement were manufactured in the same manner as in Example 1 except that the obtained thick film resistor paste was used. Moreover, evaluation was performed in the same manner as in Example 1. Table 1 shows the evaluation results.
[Example 9]
A composition for a thick film resistor containing 48.9 parts by mass of glass powder C and 11.1 parts by mass of ruthenium oxide powder was prepared.
そして、係る厚膜抵抗体用組成物６０質量部と、有機ビヒクル４０質量部とをスリーロールミルで混練し、厚膜抵抗体用ペーストを得た。 Then, 60 parts by mass of the composition for thick film resistor and 40 parts by mass of the organic vehicle were kneaded in a three-roll mill to obtain a paste for thick film resistor.
なお、ガラス粉末Ｃの組成、ガラス転移点、平均粒径は表２に示す。 Table 2 shows the composition, glass transition point, and average particle size of the glass powder C.
酸化ルテニウム粉末と、有機ビヒクルは実施例１と同じものを用いた。 The same ruthenium oxide powder and organic vehicle as in Example 1 were used.
得られた厚膜抵抗体用ペーストを用いた点以外は実施例１と同様にして厚膜抵抗体、ＸＲＤ測定用厚膜抵抗体を製造した。また、実施例１と同様に評価を行った。評価結果を表１に示す。
［実施例１０］
ガラス粉末Ｃを５１．２質量部と、酸化ルテニウム粉末を８．８質量部との割合で含む厚膜抵抗体用組成物を用意した。
A thick film resistor and a thick film resistor for XRD measurement were manufactured in the same manner as in Example 1 except that the obtained thick film resistor paste was used. Moreover, evaluation was performed in the same manner as in Example 1. Table 1 shows the evaluation results.
[Example 10]
A composition for a thick film resistor containing 51.2 parts by mass of glass powder C and 8.8 parts by mass of ruthenium oxide powder was prepared.
そして、係る厚膜抵抗体用組成物６０質量部と、有機ビヒクル４０質量部とをスリーロールミルで混練し、厚膜抵抗体用ペーストを得た。なお、酸化ルテニウム粉末と、有機ビヒクルは実施例１と同じものを用いた。 Then, 60 parts by mass of the composition for thick film resistor and 40 parts by mass of the organic vehicle were kneaded in a three-roll mill to obtain a paste for thick film resistor. The same ruthenium oxide powder and organic vehicle as in Example 1 were used.
得られた厚膜抵抗体用ペーストを用いた点以外は実施例１と同様にして厚膜抵抗体、ＸＲＤ測定用厚膜抵抗体を製造した。また、実施例１と同様に評価を行った。評価結果を表１に示す。
［実施例１１］
ガラス粉末Ｃを５２．４質量部と、酸化ルテニウム粉末を７．６質量部との割合で含む厚膜抵抗体用組成物を用意した。
A thick film resistor and a thick film resistor for XRD measurement were manufactured in the same manner as in Example 1 except that the obtained thick film resistor paste was used. Moreover, evaluation was performed in the same manner as in Example 1. Table 1 shows the evaluation results.
[Example 11]
A composition for a thick film resistor containing 52.4 parts by mass of glass powder C and 7.6 parts by mass of ruthenium oxide powder was prepared.
そして、係る厚膜抵抗体用組成物６０質量部と、有機ビヒクル４０質量部とをスリーロールミルで混練し、厚膜抵抗体用ペーストを得た。なお、酸化ルテニウム粉末と、有機ビヒクルは実施例１と同じものを用いた。 Then, 60 parts by mass of the composition for thick film resistor and 40 parts by mass of the organic vehicle were kneaded in a three-roll mill to obtain a paste for thick film resistor. The same ruthenium oxide powder and organic vehicle as in Example 1 were used.
得られた厚膜抵抗体用ペーストを用いた点以外は実施例１と同様にして厚膜抵抗体、ＸＲＤ測定用厚膜抵抗体を製造した。また、実施例１と同様に評価を行った。評価結果を表１に示す。
［実施例１２］
ガラス粉末Ｃを５３．６質量部と、酸化ルテニウム粉末を６．４質量部との割合で含む厚膜抵抗体用組成物を用意した。
A thick film resistor and a thick film resistor for XRD measurement were manufactured in the same manner as in Example 1 except that the obtained thick film resistor paste was used. Moreover, evaluation was performed in the same manner as in Example 1. Table 1 shows the evaluation results.
[Example 12]
A composition for a thick film resistor containing 53.6 parts by mass of glass powder C and 6.4 parts by mass of ruthenium oxide powder was prepared.
そして、係る厚膜抵抗体用組成物６０質量部と、有機ビヒクル４０質量部とをスリーロールミルで混練し、厚膜抵抗体用ペーストを得た。なお、酸化ルテニウム粉末と、有機ビヒクルは実施例１と同じものを用いた。 Then, 60 parts by mass of the composition for thick film resistor and 40 parts by mass of the organic vehicle were kneaded in a three-roll mill to obtain a paste for thick film resistor. The same ruthenium oxide powder and organic vehicle as in Example 1 were used.
得られた厚膜抵抗体用ペーストを用いた点以外は実施例１と同様にして厚膜抵抗体、ＸＲＤ測定用厚膜抵抗体を製造した。また、実施例１と同様に評価を行った。評価結果を表１に示す。
［参考例１］
ガラス粉末Ｄを４４．６質量部と、酸化ルテニウム粉末を１５．４質量部との割合で含む厚膜抵抗体用組成物を用意した。
A thick film resistor and a thick film resistor for XRD measurement were manufactured in the same manner as in Example 1 except that the obtained thick film resistor paste was used. Moreover, evaluation was performed in the same manner as in Example 1. Table 1 shows the evaluation results.
[Reference example 1]
A composition for a thick film resistor containing 44.6 parts by mass of glass powder D and 15.4 parts by mass of ruthenium oxide powder was prepared.
そして、係る厚膜抵抗体用組成物６０質量部と、有機ビヒクル４０質量部とをスリーロールミルで混練し、厚膜抵抗体用ペーストを得た。 Then, 60 parts by mass of the composition for thick film resistor and 40 parts by mass of the organic vehicle were kneaded in a three-roll mill to obtain a paste for thick film resistor.
なお、ガラス粉末Ｄの組成、ガラス転移点、平均粒径は表２に示す。 Table 2 shows the composition, glass transition point, and average particle size of the glass powder D.
酸化ルテニウム粉末と、有機ビヒクルは実施例１と同じものを用いた。 The same ruthenium oxide powder and organic vehicle as in Example 1 were used.
得られた厚膜抵抗体用ペーストを用いた点以外は実施例１と同様にして厚膜抵抗体、ＸＲＤ測定用厚膜抵抗体を製造した。また、実施例１と同様に評価を行った。評価結果を表１に示す。
［参考例２］
ガラス粉末Ｄを４６．９質量部と、酸化ルテニウム粉末を１３．１質量部との割合で含む厚膜抵抗体用組成物を用意した。
A thick film resistor and a thick film resistor for XRD measurement were manufactured in the same manner as in Example 1 except that the obtained thick film resistor paste was used. Moreover, evaluation was performed in the same manner as in Example 1. Table 1 shows the evaluation results.
[Reference example 2]
A composition for a thick film resistor containing 46.9 parts by mass of glass powder D and 13.1 parts by mass of ruthenium oxide powder was prepared.
そして、係る厚膜抵抗体用組成物６０質量部と、有機ビヒクル４０質量部とをスリーロールミルで混練し、厚膜抵抗体用ペーストを得た。なお、酸化ルテニウム粉末と、有機ビヒクルは実施例１と同じものを用いた。 Then, 60 parts by mass of the composition for thick film resistor and 40 parts by mass of the organic vehicle were kneaded in a three-roll mill to obtain a paste for thick film resistor. The same ruthenium oxide powder and organic vehicle as in Example 1 were used.
得られた厚膜抵抗体用ペーストを用いた点以外は実施例１と同様にして厚膜抵抗体、ＸＲＤ測定用厚膜抵抗体を製造した。また、実施例１と同様に評価を行った。評価結果を表１に示す。
［比較例１］
ガラス粉末Ｄを４９．１質量部と、酸化ルテニウム粉末を１０．９質量部との割合で含む厚膜抵抗体用組成物を用意した。
A thick film resistor and a thick film resistor for XRD measurement were manufactured in the same manner as in Example 1 except that the obtained thick film resistor paste was used. Moreover, evaluation was performed in the same manner as in Example 1. Table 1 shows the evaluation results.
[Comparative Example 1]
A composition for a thick film resistor containing 49.1 parts by mass of glass powder D and 10.9 parts by mass of ruthenium oxide powder was prepared.
そして、係る厚膜抵抗体用組成物６０質量部と、有機ビヒクル４０質量部とをスリーロールミルで混練し、厚膜抵抗体用ペーストを得た。なお、酸化ルテニウム粉末と、有機ビヒクルは実施例１と同じものを用いた。 Then, 60 parts by mass of the composition for thick film resistor and 40 parts by mass of the organic vehicle were kneaded in a three-roll mill to obtain a paste for thick film resistor. The same ruthenium oxide powder and organic vehicle as in Example 1 were used.
得られた厚膜抵抗体用ペーストを用いた点以外は実施例１と同様にして厚膜抵抗体、ＸＲＤ測定用厚膜抵抗体を製造した。また、実施例１と同様に評価を行った。評価結果を表１に示す。 A thick film resistor and a thick film resistor for XRD measurement were manufactured in the same manner as in Example 1 except that the obtained thick film resistor paste was used. Moreover, evaluation was performed in the same manner as in Example 1. Table 1 shows the evaluation results.
なお、厚膜抵抗体内に析出した結晶は、ＢａＳｉ２Ａｌ２Ｏ８であることをＸ線回折パターンで確認した。
［比較例２］
ガラス粉末Ｄを５５．７質量部と、酸化ルテニウム粉末を６．３質量部との割合で含む厚膜抵抗体用組成物を用意した。
It was confirmed from the X-ray diffraction pattern that the crystals deposited in the thick film resistor were BaSi 2 Al 2 O 8 .
[Comparative Example 2]
A composition for a thick film resistor containing 55.7 parts by mass of glass powder D and 6.3 parts by mass of ruthenium oxide powder was prepared.
そして、係る厚膜抵抗体用組成物６０質量部と、有機ビヒクル４０質量部とをスリーロールミルで混練し、厚膜抵抗体用ペーストを得た。なお、酸化ルテニウム粉末と、有機ビヒクルは実施例１と同じものを用いた。 Then, 60 parts by mass of the composition for thick film resistors and 40 parts by mass of the organic vehicle were kneaded in a three-roll mill to obtain a paste for thick film resistors. The same ruthenium oxide powder and organic vehicle as in Example 1 were used.
得られた厚膜抵抗体用ペーストを用いた点以外は実施例１と同様にして厚膜抵抗体、ＸＲＤ測定用厚膜抵抗体を製造した。また、実施例１と同様に評価を行った。評価結果を表１に示す。 A thick film resistor and a thick film resistor for XRD measurement were manufactured in the same manner as in Example 1 except that the obtained thick film resistor paste was used. Moreover, evaluation was performed in the same manner as in Example 1. Table 1 shows the evaluation results.
なお、厚膜抵抗体内に析出した結晶は、ＢａＳｉ２Ａｌ２Ｏ８であることをＸ線回折パターンで確認した。 It was confirmed from the X-ray diffraction pattern that the crystals deposited in the thick film resistor were BaSi 2 Al 2 O 8 .
Claims (5)
前記ガラスが、ＳｉＯ ２ を４ｍｏｌ％以上５２ｍｏｌ％以下、Ａｌ２Ｏ３を１ｍｏｌ％以上６ｍｏｌ％以下含む厚膜抵抗体用組成物。 A composition for a resistor containing ruthenium oxide powder containing no lead component and glass containing no lead component, wherein an aluminosilicate crystal phase is detected in an X-ray diffraction pattern when used as a thick film resistor. figure,
A composition for a thick film resistor, wherein the glass contains 4 mol % or more and 52 mol % or less of SiO 2 and 1 mol % or more and 6 mol % or less of Al 2 O 3 .
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