JP2021193704A - Thick film resistor composition and thick film resistance paste including the same - Google Patents
Thick film resistor composition and thick film resistance paste including the same Download PDFInfo
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Abstract
Description
本願発明は、チップ抵抗や厚膜抵抗基板、厚膜抵抗体ヒーターなどを作製する際に使用する厚膜抵抗体組成物に関する。 The present invention relates to a thick film resistor composition used for manufacturing a chip resistor, a thick film resistor substrate, a thick film resistor heater, and the like.
一般的にチップ抵抗器や厚膜抵抗体、厚膜抵抗体ヒーターなどは、たとえば基板にアルミナ基板を用い、電極に厚膜電極、抵抗には厚膜抵抗又は薄膜抵抗を用いている。これら抵抗器はその用途や特性によってさまざまな種類があり、装置の小型化に伴い抵抗器関連部品の小型化も急速に進んでいる。 Generally, a chip resistor, a thick film resistor, a thick film resistor heater, or the like uses an alumina substrate as a substrate, a thick film electrode as an electrode, and a thick film resistor or a thin film resistor as a resistor. There are various types of these resistors depending on their applications and characteristics, and with the miniaturization of equipment, the miniaturization of resistor-related parts is rapidly progressing.
さらに、チップ抵抗器の特性も、たとえば耐サージ、トリマブル品、高精度品など種々の製品が存在している。
チップ抵抗器の抵抗値の調整はレーザー光によって厚膜抵抗体の一部を切除するレーザートリミングによる方法が一般的である。しかし、レーザートリミングによる抵抗値の調整では、厚膜抵抗体の表面に切除跡が残る。そこで、切除跡を残さない厚膜抵抗体の抵抗値の調整方法として、レーザー光を照射し厚膜抵抗体の特性変化を起こさせることにより抵抗値を下げる方法や、パルス電圧を厚膜抵抗体に加えて抵抗値を下げる方法などがある。
Further, as for the characteristics of the chip resistor, there are various products such as surge-resistant, trimable products, and high-precision products.
The resistance value of the chip resistor is generally adjusted by laser trimming, which excises a part of the thick film resistor by laser light. However, when the resistance value is adjusted by laser trimming, a cut mark remains on the surface of the thick film resistor. Therefore, as a method of adjusting the resistance value of the thick film resistor that does not leave a cut mark, a method of lowering the resistance value by irradiating a laser beam to cause a change in the characteristics of the thick film resistor, or a pulse voltage of the thick film resistor. In addition, there is a method to lower the resistance value.
これらのレーザー光によって特性変化を起こさせる方法や、パルス電圧を厚膜抵抗体に加えて抵抗値を下げる方法は、厚膜抵抗体の外観に物理的な破壊を与えない程度のエネルギーのレーザー光やパルス電圧を加えることで抵抗値が低くなることを利用した調整方法である。
その中で、高電圧パルスを厚膜抵抗体に加えて抵抗値を下げる方法は、パルストリミング法として知られている。特許文献１および２には、パルストリミング法に関する技術が開示されている。
今後更なる部品の小型化などによりこのような物理的な破壊を伴わない抵抗値の調整方法が今以上に必要になると考えられている。
The method of causing the characteristic change by these laser beams and the method of applying a pulse voltage to the thick film resistor to lower the resistance value are laser beams with enough energy to not physically destroy the appearance of the thick film resistor. This is an adjustment method that utilizes the fact that the resistance value is lowered by applying a pulse voltage or a pulse voltage.
Among them, a method of applying a high voltage pulse to a thick film resistor to lower the resistance value is known as a pulse trimming method. Patent Documents 1 and 2 disclose a technique relating to a pulse trimming method.
In the future, it is considered that a method for adjusting the resistance value without such physical destruction will be required more than ever due to the further miniaturization of parts.
ところで、厚膜抵抗体組成物の組成によっては、得られる厚膜抵抗体にパルストリミング法で抵抗値調整を試みても、抵抗値の調整、すなわち抵抗値の変化が十分ではない場合がある。
このような状況に鑑み、本実施形態の課題は、厚膜抵抗体の抵抗値をパルストリミング法で効率的に調整できる厚膜抵抗体組成物を提供することである。
By the way, depending on the composition of the thick film resistor composition, even if the resistance value of the obtained thick film resistor is adjusted by the pulse trimming method, the resistance value adjustment, that is, the change in the resistance value may not be sufficient.
In view of such a situation, an object of the present embodiment is to provide a thick film resistor composition capable of efficiently adjusting the resistance value of the thick film resistor by a pulse trimming method.
本発明の第１の発明は、ガラスフリットとルテニウム化合物粉末を含み、前記ルテニウム化合物粉末が針状粒子であることを特徴とする厚膜抵抗体組成物である。 The first aspect of the present invention is a thick film resistor composition containing glass frit and ruthenium compound powder, wherein the ruthenium compound powder is needle-like particles.
本発明の第２の発明は、第１の発明におけるルテニウム化合物粉末が、前記針状粒子の粒子長方向に対して垂直な断面の最大幅が１００ｎｍ以下であり、前記粒子長（Ｌ）と、前記最大幅（φ１）から求められる「粒子長（Ｌ）／最大幅（φ１）」の式で表されるアスペクト比が１．５以上であることを特徴とする厚膜抵抗体組成物である。 In the second aspect of the present invention, the ruthenium compound powder in the first invention has a maximum width of 100 nm or less in a cross section perpendicular to the particle length direction of the needle-shaped particles, and the particle length (L) and the like. said maximum width (phi 1) "particle length (L) / maximum width (phi 1)" obtained from the thick film resistor composition aspect ratio of the formula is equal to or less than 1.5 of Is.
本発明の第３の発明は、第１および第２の発明におけるルテニウム化合物粉末が、二酸化ルテニウム粉末であることを特徴とする厚膜抵抗体組成物である。 A third aspect of the present invention is a thick film resistor composition, wherein the ruthenium compound powder in the first and second inventions is a ruthenium dioxide powder.
本発明の第４の発明は、第１から第３の発明のいずれかの発明に記載の厚膜抵抗体組成物と、有機溶剤に樹脂を溶解したビヒクルを含むことを特徴とする厚膜抵抗ペーストである。 A fourth invention of the present invention comprises a thick film resistor composition according to any one of the first to third inventions and a vehicle in which a resin is dissolved in an organic solvent. It is a paste.
本実施形態によれば、パルスにより抵抗値を調整する際に抵抗変化幅が大きい抵抗体を容易に得ることが出来、調整作業の改善に大きく寄与し、工業上顕著な効果を奏するものである。 According to the present embodiment, a resistor having a large resistance change range can be easily obtained when the resistance value is adjusted by a pulse, which greatly contributes to the improvement of the adjustment work and exerts a remarkable industrial effect. ..
本実施形態に係る厚膜抵抗体組成物は、ガラスフリットと導電物質のルテニウム化合物粉末を含み、前記ルテニウム化合物粉末が針状であることを特徴とする。さらに、そのルテニウム化合物粉末が、二酸化ルテニウム粉末であることが望ましい。 The thick film resistor composition according to the present embodiment is characterized by containing a glass frit and a ruthenium compound powder of a conductive substance, and the ruthenium compound powder is needle-shaped. Further, it is desirable that the ruthenium compound powder is ruthenium dioxide powder.
上記厚膜抵抗体組成物を用い、厚膜抵抗体組成物と後述の有機ビヒクルとを混練して厚膜抵抗ペーストを得ることができる。
この得られた厚膜抵抗ペーストを、アルミナ基板等のセラミックス基板の表面に印刷するなどして厚膜抵抗体組成物を含有する印刷膜を形成し焼成して厚膜抵抗体を得ることができる。
以下、各構成要素について説明する。
Using the above-mentioned thick film resistor composition, the thick film resistor composition and the organic vehicle described later can be kneaded to obtain a thick film resistance paste.
The obtained thick film resistance paste can be printed on the surface of a ceramic substrate such as an alumina substrate to form a printed film containing the thick film resistor composition and fired to obtain a thick film resistor. ..
Hereinafter, each component will be described.
［ガラスフリット］
ガラスフリットは、その組成や製造方法について特に限定されるものではない。
厚膜抵抗体用組成物に用いるガラスフリットは、鉛を含有するアルミノホウケイ酸鉛が多く用いられているが、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系などの鉛を含有しない組成系も用いられている。近年では環境保護の観点から鉛を含有しないガラスを用いることが望まれている。
[Glass frit]
The glass frit is not particularly limited in its composition and manufacturing method.
The glass frit used in the composition for thick film resistors often contains lead-containing lead aluminoborosilicate, but does not contain other leads such as zinc borosilicate-based, calcium borosilicate-based, and barium borosilicate-based. A composition system is also used. In recent years, it has been desired to use lead-free glass from the viewpoint of environmental protection.
以上のように、例えばガラスフリットのガラスとしては例えば、アルミノホウケイ酸鉛ガラス、ホウケイ酸亜鉛系ガラス、ホウケイ酸カルシウム系ガラス、ホウケイ酸バリウム系ガラスから選択された１種以上を用いることができる。また、鉛を含まないガラス、例えばホウケイ酸亜鉛系ガラス、ホウケイ酸カルシウム系ガラス、ホウケイ酸バリウム系ガラスから選択された１種以上を用いることもできる。 As described above, for example, as the glass frit glass, one or more selected from lead aluminoborosilicate glass, zinc borosilicate-based glass, calcium borosilicate-based glass, and barium borosilicate-based glass can be used. Further, one or more selected from lead-free glass, for example, zinc borosilicate glass, calcium borosilicate glass, and barium borosilicate glass can also be used.
そのガラスフリットに含まれるＳｉＯ２成分は、ガラス骨格を構成し、ＰｂＯ、Ｂ２Ｏ３、ＲＯ（Ｒはアルカリ土類元素）は、ガラスの溶融性を調整する。さらに、ガラスの耐候性や焼成時の流動性を調整する目的で、Ａｌ２Ｏ３、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。Ａｌ２Ｏ３はガラスの分相を抑制しやすく、ＺｒＯ２、ＴｉＯ２はガラスの耐候性を向上させる、ＳｎＯ２、ＺｎＯ、Ｌｉ２Ｏ、Ｎａ２Ｏ、Ｋ２Ｏ等はガラスの流動性を高める働きがある。 SiO 2 components contained in the glass frit is to constitute a glass skeleton, PbO, B 2 O 3, RO (R is an alkaline earth element) adjusts the meltability of glass. Further, it was selected from Al 2 O 3 , ZrO 2 , TIO 2 , SnO 2 , ZnO, Li 2 O, Na 2 O, K 2 O and the like for the purpose of adjusting the weather resistance of the glass and the fluidity during firing. One or more types can be mentioned. Al 2 O 3 tends to suppress the phase separation of glass, ZrO 2 and TiO 2 improve the weather resistance of glass, SnO 2 , ZnO, Li 2 O, Na 2 O, K 2 O and the like improve the fluidity of glass. Has the function of increasing.
このガラスは、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。
その溶融温度は特に限定されるものではないが、例えば１４００℃前後で行われている。また、急冷は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われることが多い。
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。
This glass can generally be produced by mixing predetermined components or precursors thereof according to the desired formulation, melting the resulting mixture and quenching.
The melting temperature is not particularly limited, but is, for example, around 1400 ° C. Further, quenching is often performed by putting the melt in cold water or flowing it on a cold belt.
The glass is crushed to the desired particle size with a ball mill, a vibration mill, a planetary mill, a bead mill, or the like.
ガラスフリット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により測定した５０％体積累計粒度は５μｍ以下が好ましく、３μｍ以下であることがさらに好ましい。
このように、ガラスフリット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。さらに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。このため、歩留まりを十分に高め、負荷特性を向上させる観点から、用いるガラス粒子の５０％体積累計粒度は５μｍ以下であることが好ましい。
なお、ガラスフリットの粒度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とから、ガラスフリットの５０％体積累計粒度は０．５μｍ以上が好ましい。
The particle size of the glass frit is also not limited, but the cumulative 50% volume particle size measured by the particle size distribution meter using laser diffraction is preferably 5 μm or less, and more preferably 3 μm or less.
As described above, if the particle size of the glass frit is too large, the area resistance value of the fired thick film resistor becomes low, but the variation in the area resistance value becomes large and the yield decreases. Furthermore, there is a high possibility that problems such as deterioration of load characteristics will occur. Therefore, from the viewpoint of sufficiently increasing the yield and improving the load characteristics, it is preferable that the 50% volume cumulative particle size of the glass particles used is 5 μm or less.
If the particle size of the glass frit is excessively small, the productivity is lowered and the contamination of impurities and the like may increase. Therefore, the cumulative 50% volume particle size of the glass frit is preferably 0.5 μm or more.
ガラスの焼成時の流動性に影響する尺度として軟化点がある。一般に、厚膜抵抗体を製造する際の、厚膜抵抗体用組成物を焼成する温度は８００℃以上、９００℃以下である。
このように、厚膜抵抗体を製造する際の厚膜抵抗体用組成物の焼成温度が８００℃以上９００℃以下の場合、本実施形態の厚膜抵抗体用組成物に用いるガラスの軟化点は、６００℃以上、９００℃以下が好ましい。
また、軟化点が６００℃以上、８００℃以下のガラスフリットと、より高い軟化点のガラスフリットを混合することもできる。
ここで、軟化点は、ガラスを示差熱分析法（ＴＧ−ＤＴＡ）にて大気中で、１０℃／ｍｉｎ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よりも高温側の次の示差熱曲線が減少するピークの温度である。
The softening point is a measure that affects the fluidity of glass during firing. Generally, the temperature at which the composition for a thick film resistor is fired when producing the thick film resistor is 800 ° C. or higher and 900 ° C. or lower.
As described above, when the firing temperature of the thick film resistor composition when producing the thick film resistor is 800 ° C. or higher and 900 ° C. or lower, the softening point of the glass used in the thick film resistor composition of the present embodiment. Is preferably 600 ° C. or higher and 900 ° C. or lower.
Further, a glass frit having a softening point of 600 ° C. or higher and 800 ° C. or lower can be mixed with a glass frit having a higher softening point.
Here, the softening point is the difference heat curve on the lowest temperature side of the obtained difference heat curve obtained by heating and heating the glass at 10 ° C./min in the atmosphere by a differential thermal analysis method (TG-DTA). It is the temperature of the peak at which the next differential thermal curve on the higher temperature side than the temperature at which the decrease occurs decreases.
厚膜抵抗体は、厚膜抵抗体組成物を焼成して得られる。厚膜抵抗体を得る際の焼成温度は後述の通り８００℃から９００℃であり、ガラスフリットは、焼成の過程で溶融し、ガラスフリットの各粒子が融着してガラスマトリックスを形成する。厚膜抵抗体を構成するルテニウム化合物粉末の各粒子は、焼成の過程でガラスフリットのように溶融することはない。そして、厚膜抵抗体組成物を焼成して得られる厚膜抵抗体は、ガラスマトリックスが保持して形成されるルテニウム化合物粒子による導電ネットワークを構成要素とする。 The thick film resistor is obtained by firing the thick film resistor composition. The firing temperature at the time of obtaining the thick film resistor is 800 ° C. to 900 ° C. as described later, and the glass frit is melted in the process of firing, and the particles of the glass frit are fused to form a glass matrix. Each particle of the ruthenium compound powder constituting the thick film resistor does not melt like a glass frit in the process of firing. The thick film resistor obtained by firing the thick film resistor composition has a conductive network made of ruthenium compound particles formed by holding the glass matrix as a constituent element.
[ルテニウム化合物粉末]
厚膜抵抗体組成物におけるルテニウム化合物粉末は、導電性成分として機能する。
このルテニウム化合物粉末には、二酸化ルテニウム粉末、ルテニウム酸鉛粉末やルテニウム酸ストロンチウム粉末のようなルテニウム複合酸化物粉末を用いることができる。
[Ruthenium compound powder]
The ruthenium compound powder in the thick film resistor composition functions as a conductive component.
As the ruthenium compound powder, ruthenium composite oxide powder such as ruthenium dioxide powder, lead ruthenium powder and strontium ruthenium powder can be used.
また、本実施の形態で使用されるルテニウム化合物粉末は、図１に示される真直な針状粒子の形態を有し、その真直な針状粒子の最大長さである粒子長Ｌと、前記粒子長の方向に対して垂直な断面の最大幅φ１が１００ｎｍ以下であり、前記粒子長Ｌと、前記断面の最大幅φ１から「粒子長Ｌ／断面の最大幅φ１」の式により求められる真直な針状粒子のアスペクト比が１．５以上であり、５．０以下が望ましい。 Further, the ruthenium compound powder used in the present embodiment has the form of straight needle-shaped particles shown in FIG. 1, and has a particle length L which is the maximum length of the straight needle-shaped particles and the particles. The maximum width φ 1 of the cross section perpendicular to the length direction is 100 nm or less, and it is obtained from the particle length L and the maximum width φ 1 of the cross section by the formula of “particle length L / maximum width φ 1 of the cross section”. The aspect ratio of the straight needle-shaped particles to be formed is 1.5 or more, preferably 5.0 or less.
厚膜抵抗体は、ガラスマトリックスが保持して形成される針状粒子のルテニウム化合物粉末による導電ネットワークを構成要素とする。
本実施形態では、ルテニウム化合物粉末を構成する各粒子が針状粒子であるため、各ルテニウム化合物粉末では長径方向の導電ネットワークと、短径方向の導電ネットワークが形成される。
そのような構造の厚膜抵抗体に、パルストリミングの際の通電により、導電ネットワークの周囲のガラスマトリックスが加熱されて再溶融することで、長径方向の導電ネットワークを構成する各ルテニウム化合物粉末を構成する各粒子の配置にズレが生じて導電ネットワークの再構築が行われる。この導電ネットワークの再構築により抵抗値が変化する。
The thick film resistor is composed of a conductive network of ruthenium compound powder of needle-like particles formed by holding the glass matrix.
In the present embodiment, since each particle constituting the ruthenium compound powder is a needle-shaped particle, a conductive network in the major axis direction and a conductive network in the minor axis direction are formed in each ruthenium compound powder.
The glass matrix around the conductive network is heated and remelted by energization during pulse trimming on the thick film resistor having such a structure, thereby forming each ruthenium compound powder constituting the conductive network in the major axis direction. The arrangement of each particle is displaced and the conductive network is reconstructed. The resistance value changes due to the reconstruction of this conductive network.
一方、本実施形態と異なる、長径と前記断面における短径との比（長径方向における長径／断面における短径）が１．５未満で、粒状のルテニウム化合物粉末のみで構成される導電ネットワークでは、パルストリミングの際の通電の後の導電ネットワークの再構築が生じても、各ルテニウム化合物粉末を構成する各粒子の配置のズレが小さく、抵抗値の変化は小さい。 On the other hand, in a conductive network in which the ratio of the major axis to the minor axis in the cross section (major axis in the major axis direction / minor axis in the cross section) is less than 1.5, which is different from the present embodiment, and is composed only of granular ruthenium compound powder. Even if the conductive network is reconstructed after energization during pulse trimming, the deviation of the arrangement of each particle constituting each ruthenium compound powder is small, and the change in resistance value is small.
そのルテニウム化合物粉末は、厚膜抵抗体組成物に５質量％以上、６０質量％以下含まれることが望ましく、さらに望ましくは、１０質量％以上５５質量％以下であり、さらに好ましくは１５質量％以上５０質量％以下である。 The ruthenium compound powder is preferably contained in the thick film resistor composition in an amount of 5% by mass or more and 60% by mass or less, more preferably 10% by mass or more and 55% by mass or less, still more preferably 15% by mass or more. It is 50% by mass or less.
厚膜抵抗体組成物では、ガラスフリットとルテニウム化合物粉末の配合割合で得られる厚膜抵抗体の抵抗値を調整している。厚膜抵抗体組成物に含まれるルテニウム化合物粉末の含有率が５質量％未満では、抵抗値が高くなりすぎる。一方、厚膜抵抗体組成物に含まれるルテニウム化合物粉末の含有率が６０質量％を超えると、厚膜抵抗体の焼結面が緻密にならないので、厚膜抵抗体の機械強度が確保できない。 In the thick film resistor composition, the resistance value of the thick film resistor obtained by the blending ratio of the glass frit and the ruthenium compound powder is adjusted. If the content of the ruthenium compound powder contained in the thick film resistor composition is less than 5% by mass, the resistance value becomes too high. On the other hand, if the content of the ruthenium compound powder contained in the thick film resistor composition exceeds 60% by mass, the sintered surface of the thick film resistor does not become dense, so that the mechanical strength of the thick film resistor cannot be ensured.
粉末を構成するルテニウム化合物には、二酸化ルテニウムを用いることが望ましい。
この二酸化ルテニウムは、ルテニウム酸鉛などのルテニウム複合酸化物よりも比抵抗が小さく、低抵抗域の厚膜抵抗体の抵抗値５０Ω〜３０００Ωの領域を実現するのに適しているからである。
厚膜抵抗体で発熱抵抗とする場合は、パルストリミング性や得られる厚膜抵抗体の消費電力を考慮して厚膜抵抗体の抵抗値を５０Ω〜１００ｋΩとすることが望ましい。
It is desirable to use ruthenium dioxide as the ruthenium compound constituting the powder.
This is because ruthenium dioxide has a smaller specific resistance than a ruthenium composite oxide such as lead rutheniumate, and is suitable for realizing a resistance value of 50Ω to 3000Ω in a thick film resistor in a low resistance range.
When the thick film resistor is used as the heat generation resistance, it is desirable to set the resistance value of the thick film resistor to 50Ω to 100 kΩ in consideration of the pulse trimming property and the power consumption of the obtained thick film resistor.
本実施形態のルテニウム化合物粉末の合成の例を説明する。
針状粒子の二酸化ルテニウム粉末の製造方法の一例は、ビスマス化合物の存在下、粒状の二酸化ルテニウム粉末を熱処理することで、針状の二酸化ルテニウム粉末を形成する針状化熱処理工程の後、ビスマス化合物を溶媒に溶解して得られた溶液中から、針状の二酸化ルテニウム粉末を固液分離する分離工程を経ることができる。
An example of synthesizing the ruthenium compound powder of this embodiment will be described.
An example of a method for producing needle-shaped ruthenium dioxide powder is a needle-shaped heat treatment step of heat-treating granular ruthenium dioxide powder in the presence of a bismuth compound to form needle-shaped ruthenium dioxide powder, followed by the bismuth compound. Can be subjected to a separation step of solid-liquid separation of needle-shaped ruthenium dioxide powder from the solution obtained by dissolving the above in a solvent.
一連の工程を具体的に説明すると、針状化熱処理工程では、二酸化ルテニウム粉末とビスマス化合物とを混合して作製した第１の混合物に、熱処理を実施して第２の混合物を得て、室温まで冷却する。その冷却された第２の混合物を分離工程に処し、その分離工程では第２の混合物を、酸などに溶解して針状粒子の二酸化ルテニウム粉末を固液分離して得るものである。 Specifically, in the needle-like heat treatment step, a first mixture prepared by mixing ruthenium dioxide powder and a bismuth compound is heat-treated to obtain a second mixture at room temperature. Cool to. The cooled second mixture is subjected to a separation step, and in the separation step, the second mixture is dissolved in an acid or the like to obtain needle-like particles of ruthenium dioxide powder by solid-liquid separation.
粒状の二酸化ルテニウム粉末は、例えば、ＳＥＭを用いて観察される一次粒子の平均粒径が１００ｎｍ以下であり、粉末のアスペクト比が１．５未満の球状又は略球状粒子であることが好ましい。このような上記形状を有する二酸化ルテニウム粉末を原料として用いた場合、粒子長の方向に垂直な断面の最大幅が１００ｎｍ以下の針状の二酸化ルテニウム粉末を容易に得ることができる。 The granular ruthenium dioxide powder is preferably spherical or substantially spherical particles having, for example, an average particle size of primary particles observed using SEM of 100 nm or less and an aspect ratio of the powder of less than 1.5. When ruthenium dioxide powder having such a shape is used as a raw material, needle-shaped ruthenium dioxide powder having a maximum width of 100 nm or less in a cross section perpendicular to the direction of the particle length can be easily obtained.
ビスマス化合物は、ビスマスを含む化合物であり、熱処理の際に、二酸化ルテニウムと合金化しないものであれば、公知のビスマス化合物を用いることができる。
ビスマス化合物は、例えば、塩化ビスマス、オキシ塩化ビスマス、酸化ビスマス、これらの混合物などを用いることができる。中でも、塩化ビスマス及びオキシ塩化ビスマスのうち少なくとも一つを用いることが好ましく、オキシ塩化ビスマスを用いることがより好ましい。
The bismuth compound is a compound containing bismuth, and a known bismuth compound can be used as long as it does not alloy with ruthenium dioxide during heat treatment.
As the bismuth compound, for example, bismuth chloride, bismuth oxychloride, bismuth oxide, a mixture thereof, or the like can be used. Among them, it is preferable to use at least one of bismuth chloride and bismuth oxychloride, and it is more preferable to use bismuth oxychloride.
第１の混合物は、上記粒状の二酸化ルテニウム粉末と、上記ビスマス化合物とを混合して得られる。粒状の二酸化ルテニウム粉末とビスマス化合物との混合比率は、粒状の二酸化ルテニウム粉末に対するビスマス化合物のモル比が、例えば、０．１倍以上、５倍以下であり、０．５倍以上、３倍以下が好ましく、０．５倍以上、２倍以下がより好ましい。 The first mixture is obtained by mixing the granular ruthenium dioxide powder and the bismuth compound. Regarding the mixing ratio of the granular ruthenium dioxide powder and the bismuth compound, the molar ratio of the bismuth compound to the granular ruthenium dioxide powder is, for example, 0.1 times or more and 5 times or less, and 0.5 times or more and 3 times or less. Is preferable, and 0.5 times or more and 2 times or less are more preferable.
粒状の二酸化ルテニウム粉末とビスマス化合物とを混合する方法は、両者が十分に混合できる方法であれば特に限定されず、公知の混合装置を用いて混合することができる。たとえば、ボールミル、ライカイ機、シェーカーミキサーなどの一般的な混合装置を用いて混合することができる。 The method for mixing the granular ruthenium dioxide powder and the bismuth compound is not particularly limited as long as they can be sufficiently mixed, and can be mixed using a known mixing device. For example, it can be mixed using a general mixing device such as a ball mill, a Raikai machine, or a shaker mixer.
針状化熱処理工程は、酸化性雰囲気下６００℃以上、９００℃以下の温度で行うことができる。熱処理温度を上記範囲で調整することにより、得られる針状粒子の二酸化ルテニウム粉末の長さである粒子長（Ｌ）や太さ（粒子長の方向に垂直な断面の最大幅φ１）を容易に制御することができる。
この熱処理の諸条件は、原料となる粒状の二酸化ルテニウム粉末及びビスマス化合物の種類や形状、混合割合などに応じて、針状の二酸化ルテニウム粉末が得られる範囲で適宜調整することができる。
例えば、熱処理の雰囲気は、酸化性雰囲気下とすることができ、大気雰囲気で行うことができる。なお、酸化性雰囲気とは、酸素を１０容積％以上含む気体をいい、例えば、空気を使用することができる。また、熱処理時間は、特に限定されず、例えば、１時間以上４時間以下程度とすることができ、１時間以上３時間未満とすることが好ましい。
The needle-shaped heat treatment step can be performed at a temperature of 600 ° C. or higher and 900 ° C. or lower in an oxidizing atmosphere. By adjusting the heat treatment temperature within the above range, the particle length (L) and the thickness (maximum width φ1 of the cross section perpendicular to the direction of the particle length), which are the lengths of the ruthenium dioxide powder of the obtained needle-shaped particles, can be easily obtained. Can be controlled.
The conditions of this heat treatment can be appropriately adjusted within a range in which needle-shaped ruthenium dioxide powder can be obtained, depending on the type and shape of the granular ruthenium dioxide powder and the bismuth compound as raw materials, the mixing ratio, and the like.
For example, the atmosphere of the heat treatment can be an oxidizing atmosphere, and can be performed in an atmospheric atmosphere. The oxidizing atmosphere means a gas containing 10% by volume or more of oxygen, and for example, air can be used. The heat treatment time is not particularly limited, and may be, for example, about 1 hour or more and 4 hours or less, and preferably 1 hour or more and less than 3 hours.
分離工程では、第２の混合物（針状の二酸化ルテニウム粉末及びビスマス化合物を含む混合粉末）に含まれるビスマス化合物を溶剤に溶解させた後、得られた溶液中から、針状の二酸化ルテニウム粉末を固液分離する。
ビスマス化合物の溶解に用いられる溶剤は、二酸化ルテニウム粉末を溶解せずにビスマス化合物のみを溶解するものであれば、特に限定されず、例えば、無機化合物の酸（鉱酸）や有機酸などが使用できる。ビスマス化合物を溶剤に溶解させる際の条件は、特に限定されず、ビスマス化合物が溶剤に十分溶ければよい。例えば、溶解時の液温は、３０〜６０℃程度とすることができる。
In the separation step, the bismuth compound contained in the second mixture (needle-shaped ruthenium dioxide powder and mixed powder containing the bismuth compound) is dissolved in a solvent, and then the needle-shaped ruthenium dioxide powder is added to the obtained solution. Solid-liquid separation.
The solvent used for dissolving the bismuth compound is not particularly limited as long as it dissolves only the bismuth compound without dissolving the ruthenium dioxide powder, and for example, an inorganic compound acid (mineral acid) or an organic acid is used. can. The conditions for dissolving the bismuth compound in the solvent are not particularly limited, and the bismuth compound may be sufficiently dissolved in the solvent. For example, the liquid temperature at the time of dissolution can be about 30 to 60 ° C.
溶剤へのビスマス化合物の溶解後、針状粒子の二酸化ルテニウム粉末が分散し、溶解されたビスマス化合物を含む溶液が得られる。その得られた溶液から、固液分離処理を経て、針状粒子の二酸化ルテニウム粉末を得ることができる。固液分離して得られた針状粒子の二酸化ルテニウム粉末は、さらに、乾燥を行ってもよく、その乾燥温度や時間は、水分が除去できる温度であれば良い。 After dissolving the bismuth compound in the solvent, the ruthenium dioxide powder of the acicular particles is dispersed to obtain a solution containing the dissolved bismuth compound. From the obtained solution, ruthenium dioxide powder of needle-like particles can be obtained through a solid-liquid separation treatment. The ruthenium dioxide powder of needle-shaped particles obtained by solid-liquid separation may be further dried, and the drying temperature and time may be any temperature at which water can be removed.
針状粒子のルテニウム酸ストロンチウム粉末（ＳｒＲｕＯ３）などの針状ルテニウムの複合酸化物粉末を得るには、ストロンチウム等のルテニウム酸塩を構成するルテニウム以外の金属元素のキレート化合物の溶液と、針状の二酸化ルテニウム粉末とも混合して混合液を用意し、該混合液を乾燥によりゲル化させ、キレート錯体ゲルを得て、該キレート錯体ゲルを８００℃以下の温度で熱処理することで得ることができる。 In order to obtain a composite oxide powder of needle-shaped ruthenium such as needle-shaped particles of ruthenium ruthenium powder (SrRuO 3 ), a solution of a chelate compound of a metal element other than ruthenium constituting the ruthenium acid salt such as strontium and needle-shaped particles are used. A mixed solution is prepared by mixing with the ruthenium dioxide powder of the above, and the mixed solution is gelled by drying to obtain a chelate complex gel, which can be obtained by heat-treating the chelate complex gel at a temperature of 800 ° C. or lower. ..
［厚膜抵抗体組成物］
本実施形態に係る厚膜抵抗体組成物は、ガラスフリットとルテニウム化合物粉末を含有する。また、厚膜抵抗体組成物には、厚膜抵抗体の電気特性の一つである抵抗温度係数を調整するなどの効果がある公知のＴｉＯ２粉末等を添加することもできる。
[Thick film resistor composition]
The thick film resistor composition according to this embodiment contains a glass frit and a ruthenium compound powder. Further, a known TiO 2 powder or the like, which has an effect of adjusting the temperature coefficient of resistance, which is one of the electrical characteristics of the thick film resistor, can be added to the thick film resistor composition.
[有機ビヒクル]
本実施形態で使用する有機ビヒクルは特定のものである必要はなく、厚膜抵抗ペーストを製造するのに一般に使用されるもので良い。乾燥及び焼成時の脱バインダーの際に揮発、分解して消失してしまうものが望ましい。下記の有機溶媒、たとえばエチルセルロース、ニトロセルロース等のセルロース系樹脂、アクリル樹脂等の樹脂を用いることができる。
[Organic vehicle]
The organic vehicle used in this embodiment does not have to be specific, and may be one generally used for producing a thick film resistance paste. It is desirable that it volatilizes, decomposes and disappears during debindering during drying and baking. The following organic solvents, for example, cellulosic resins such as ethyl cellulose and nitrocellulose, and resins such as acrylic resins can be used.
これらの樹脂をターピネオール等のテルペンアルコール類、リモネン等のテルペン類、ブチルカルビトールアセテートやブチルセロソルブアセテート等のエーテル類等の有機溶剤に溶かしたものを有機ビヒクルとして使用することができる。厚膜抵抗ペーストの粘度調整の為、ターピネオール等の有機溶剤をさらに添加してもよい。
また、厚膜抵抗体組成物をビヒクルに分散させる為に、分散剤として、カルボキシル基やアミノ基を備えた高分子分散剤、ステアリン酸等の脂肪酸、レシチン等のリン脂質類を添加してもよい。
A resin obtained by dissolving these resins in an organic solvent such as terpene alcohols such as terpineol, terpenes such as limonene, and ethers such as butyl carbitol acetate and butyl cellosolve acetate can be used as an organic vehicle. In order to adjust the viscosity of the thick film resistance paste, an organic solvent such as terpineol may be further added.
Further, in order to disperse the thick film resistor composition in the vehicle, a polymer dispersant having a carboxyl group or an amino group, a fatty acid such as stearic acid, and phospholipids such as lecithin may be added as a dispersant. good.
［厚膜抵抗ペーストの製造方法］
ルテニウム化合物粉末、ガラスフリット、有機ビヒクル、有機溶媒は均一に分散させることが望ましい。方法についての限定はないが、公知の３本ロールによる分散方法が好適である。
[Manufacturing method of thick film resistance paste]
It is desirable to uniformly disperse the ruthenium compound powder, glass frit, organic vehicle, and organic solvent. Although the method is not limited, a known three-roll dispersion method is preferable.
［厚膜抵抗体の形成方法］
得られた厚膜抵抗ペーストを、スクリーン印刷によりアルミナなどのセラミックス基板上に厚膜抵抗体のパターンを印刷し、乾燥と焼成を経て厚膜抵抗体を形成することができる。
[Method of forming thick film resistors]
The obtained thick film resistance paste can be screen-printed to print a pattern of the thick film resistor on a ceramic substrate such as alumina, and dried and fired to form the thick film resistor.
焼成条件は、大気中でピーク温度８００℃から９００℃で、そのピーク温度の保持時間が５分間から６０分間とする。また室温からピーク温度までの昇温時間を５分間から６０分間とし、ピーク温度保持終了後、室温まで冷却される。焼成の過程の昇温の際に、厚膜抵抗ペーストの印刷膜に残留する有機溶剤や樹脂成分を除去する脱バインダー処理が行われる。
ピーク温度８００℃から９００℃で焼成された厚膜抵抗体は、膜厚５μｍ〜２０μｍに調整されており、より好ましい膜厚は８μｍ〜１５μｍである。
The firing conditions are a peak temperature of 800 ° C. to 900 ° C. in the atmosphere, and the holding time of the peak temperature is 5 minutes to 60 minutes. Further, the temperature rising time from room temperature to the peak temperature is set to 5 to 60 minutes, and after the peak temperature is maintained, the temperature is cooled to room temperature. When the temperature rises in the firing process, a debinder treatment is performed to remove the organic solvent and resin components remaining on the printed film of the thick film resistance paste.
The thick film resistor fired at a peak temperature of 800 ° C. to 900 ° C. is adjusted to have a film thickness of 5 μm to 20 μm, and a more preferable film thickness is 8 μm to 15 μm.
さらに厚膜抵抗体は、その表面を６００℃程度の焼成温度で焼成できるガラスペーストで被覆し、そのガラスペーストを焼成して厚膜抵抗体の保護膜とすることで保護膜付きの厚膜抵抗器とすることができる。このように厚膜抵抗体の表面をガラスペーストから形成された保護膜を配することで、厚膜抵抗器の表面を平滑にすることができる。
なお、厚膜抵抗体の形成に先立ち、セラミックス基板の表面に厚膜抵抗体の端子となる電極を公知の厚膜技術で形成してもよい。
Furthermore, the surface of the thick film resistor is coated with a glass paste that can be fired at a firing temperature of about 600 ° C., and the glass paste is fired to form a protective film for the thick film resistor to form a thick film resistor with a protective film. It can be a vessel. By arranging a protective film formed from glass paste on the surface of the thick film resistor in this way, the surface of the thick film resistor can be smoothed.
Prior to the formation of the thick film resistor, an electrode serving as a terminal of the thick film resistor may be formed on the surface of the ceramic substrate by a known thick film technique.
［厚膜抵抗体のパルストリミング］
焼成して得られた厚膜抵抗体の抵抗値をパルストリミング法で調整する。
具体的には、パルス電圧を厚膜抵抗体に印加し、所定の抵抗値となるまで、パルス電圧を印加する。印加電圧は、厚膜抵抗体の抵抗値により適宜選択すればよい。パルス電圧を逐次印加して印加前の抵抗値に対して印加後の抵抗値の変化率が小さいと、効率的な抵抗値の調整が困難となる。
[Pulse trimming of thick film resistors]
The resistance value of the thick film resistor obtained by firing is adjusted by the pulse trimming method.
Specifically, a pulse voltage is applied to the thick film resistor, and the pulse voltage is applied until a predetermined resistance value is reached. The applied voltage may be appropriately selected depending on the resistance value of the thick film resistor. If the pulse voltage is sequentially applied and the rate of change of the resistance value after application is small with respect to the resistance value before application, it becomes difficult to efficiently adjust the resistance value.
以下、実施例を用いて本実施の形態を詳細に説明する。 Hereinafter, the present embodiment will be described in detail using examples.
針状粒子の二酸化ルテニウム粉末Ａを１３質量％、アルミノホウケイ酸鉛ガラスフリットＢを５０質量％、残部が有機ビヒクルからなる厚膜抵抗体組成物を３本ロールミルにより、その組成物を構成する各種無機材料が、有機ビヒクル中に分散する様に混錬し、実施例１の厚膜抵抗ペーストを作製した。なお、有機ビヒクルにはエチルセルロースを溶解したターピネオールを用いた。 Various types of thick film resistor compositions consisting of needle-shaped particles of ruthenium dioxide powder A in an amount of 13% by mass, lead aluminoborosilicate glass frit B in an amount of 50% by mass, and the balance of an organic vehicle using a three-roll mill. The inorganic material was kneaded so as to be dispersed in the organic vehicle to prepare the thick film resistance paste of Example 1. As the organic vehicle, terpineol in which ethyl cellulose was dissolved was used.
針状粒子の二酸化ルテニウム粉末Ａの粒子長方向に対して垂直な断面の最大幅φ１が２５ｎｍであり、粒子長Ｌと、その最大幅φ１から求められる「粒子長（Ｌ）／断面における最大幅（φ１）」の式で表されるアスペクト比が２．０のものを使用した。針状粒子の二酸化ルテニウム粉末Ａの粒子長（Ｌ）と断面の最大幅（φ１）は、ＴＥＭ像で観測した。 The maximum width φ1 of the cross section of the needle-shaped particles of ruthenium dioxide powder A perpendicular to the particle length direction is 25 nm, and the “particle length (L) / maximum width in the cross section” obtained from the particle length L and the maximum width φ1. The one having an aspect ratio of 2.0 expressed by the formula of (φ1) ”was used. The particle length (L) and the maximum width (φ1) of the cross section of the needle-shaped particles ruthenium dioxide powder A were observed by a TEM image.
ガラスフリットＢは、５０％体積累計粒度が１．３μｍで、軟化点が８６０℃であった。
有機ビヒクルは、ターピネオール８５質量％とエチルセルロース１５質量％を混合し８０℃で溶解して調製した。
The glass frit B had a 50% cumulative volume particle size of 1.3 μm and a softening point of 860 ° C.
The organic vehicle was prepared by mixing 85% by mass of terpineol and 15% by mass of ethyl cellulose and dissolving at 80 ° C.
［厚膜抵抗体の形成方法］
予め、アルミナ基板上に形成された０．３ｍｍ間隔の５対の厚膜Ａｕ電極間に、作製した厚膜抵抗ペーストを幅０．３ｍｍで印刷し、ピーク温度１５０℃×５分のベルト炉で乾燥処理して溶剤成分のターピネオールを除去した。その後、ピーク温度８１０℃×９分のベルト炉で焼成した。同様の処理をした試料をアルミナ基板単位で５枚作製した。膜厚は、触針式の表面粗さ計（株式会社東京精密製 型番：サーフコム４８０Ｂ）を用いて、評価用試料の中からアルミナ基板単位で任意の１枚を選択し、５個の厚膜抵抗体の膜厚をそれぞれ測定したところ、５個の厚膜抵抗体の平均値は１３μｍであった。
[Method of forming thick film resistors]
The prepared thick film resistance paste was printed in advance between 5 pairs of thick film Au electrodes formed on the alumina substrate at intervals of 0.3 mm with a width of 0.3 mm, and the peak temperature was 150 ° C. × 5 minutes in a belt furnace. It was dried to remove the solvent component tarpineol. Then, it was fired in a belt furnace having a peak temperature of 810 ° C. × 9 minutes. Five samples subjected to the same treatment were prepared for each alumina substrate. For the film thickness, use a stylus type surface roughness meter (manufactured by Tokyo Precision Co., Ltd., model number: Surfcom 480B) to select any one of the evaluation samples for each alumina substrate, and five thick films. When the film thickness of each of the resistors was measured, the average value of the five thick film resistors was 13 μm.
さらに、ＡＧＣ製ガラスペーストＡＰ５５６４を、前記厚膜抵抗体を覆うように塗布し、ピーク温度１５０℃×５分のベルト炉で乾燥処理した。その後、ピーク温度８１０℃×９分のベルト炉で焼成し、評価用サンプルとした。 Further, AGC glass paste AP5564 was applied so as to cover the thick film resistor, and dried in a belt furnace having a peak temperature of 150 ° C. × 5 minutes. Then, it was calcined in a belt furnace having a peak temperature of 810 ° C. × 9 minutes to prepare a sample for evaluation.
［厚膜抵抗体のパルストリミング］
評価試料の厚膜抵抗体に対し、電圧印加前の抵抗値Ｒｓを測定した。そして、評価試料の厚膜抵抗体に「ＥＳＳ−６００８（株式会社ノイズ研究所製）」を用いて、２００ｐＦの電気容量、内部抵抗０Ωとして電圧を１５００Ｖに設定して各電圧のパルスを印加した後、１秒の間隔をあけて、電圧１５００Ｖのパルスを再度印加する条件で電圧印加を行い、電圧印加後の抵抗値Ｒｅを測定した。その抵抗値変化率を下記式（１）にて算出した。印加電圧とその時の算出した抵抗値変化率を表１に示す。
なお、抵抗値は、デジタルマルチメーター（ＫＥＩＴＨＬＥＹ社製、２００１番）で測定した。
[Pulse trimming of thick film resistors]
The resistance value Rs before applying a voltage was measured for the thick film resistor of the evaluation sample. Then, using "ESS-6008 (manufactured by Noise Research Institute Co., Ltd.)" as the thick film resistor of the evaluation sample, the voltage was set to 1500V with an electric capacity of 200pF and an internal resistance of 0Ω, and pulses of each voltage were applied. After that, the voltage was applied under the condition that the pulse of the voltage of 1500 V was applied again at intervals of 1 second, and the resistance value Re after the voltage was applied was measured. The resistance value change rate was calculated by the following equation (1). Table 1 shows the applied voltage and the calculated resistance value change rate at that time.
The resistance value was measured with a digital multimeter (manufactured by KEITHLEY, No. 2001).
（比較例１）
略球状の粒状粒子の二酸化ルテニウム粉末Ｃを１１質量％、粒状のルテニウム酸鉛粉末Ｄを２質量％、アルミナホウケイ酸鉛ガラスフリットＥを４５質量％、残部が実施例１と同じ有機ビヒクルからなる厚膜抵抗体組成物を３本ロールミルにより、組成物を構成する各種無機材料が有機ビヒクル中に分散する様に混錬し、比較例１の厚膜抵抗ペーストを作製した。なお、粒状の二酸化ルテニウム粉末Ｃは、その粒子長の方向に垂直な断面の最大幅（φ１）が２０ｎｍであり、アスペクト比が１．１のものを使用した。二酸化ルテニウム粉末の粒子長（Ｌ）と最大幅（φ１）は、実施例１と同様に、ＴＥＭ像で観測した。
(Comparative Example 1)
11% by mass of ruthenium dioxide powder C of substantially spherical granular particles, 2% by mass of granular lead ruthenium powder D, 45% by mass of lead alumina borosilicate glass frit E, and the balance is the same organic vehicle as in Example 1. The thick film resistor composition was kneaded with a three-roll mill so that various inorganic materials constituting the composition were dispersed in the organic vehicle to prepare the thick film resistance paste of Comparative Example 1. As the granular ruthenium dioxide powder C, a powder having a maximum width (φ1) of 20 nm and an aspect ratio of 1.1 perpendicular to the direction of the particle length was used. The particle length (L) and maximum width (φ1) of the ruthenium dioxide powder were observed by TEM images in the same manner as in Example 1.
ルテニウム酸鉛粉末Ｄは、ＴＥＭ像で観測して、粒子長の方向に垂直な断面の最大幅（φ１）が５０ｎｍで、粒子長（Ｌ）と最大幅（φ１）で構成するアスペクト比が１．１の略球状の粉末であった。
ガラスフリットＥは、５０％体積累計粒度が１．４μｍで、軟化点が６６０℃であった。
The lead ruthenate powder D has a maximum width (φ1) of 50 nm in a cross section perpendicular to the direction of the particle length as observed by a TEM image, and an aspect ratio composed of the particle length (L) and the maximum width (φ1) is 1. It was a substantially spherical powder of 1.
The glass frit E had a 50% cumulative volume particle size of 1.4 μm and a softening point of 660 ° C.
また、実施例１と同様の方法で評価用試料の厚膜抵抗体を作製し、実施例１と同様の評価を行った。各評価結果を表１に示す。なお、５個の厚膜抵抗体の膜厚をそれぞれ測定したところ、５個の厚膜抵抗体の平均値は８．６μｍであった。 Further, a thick film resistor of an evaluation sample was prepared by the same method as in Example 1, and the same evaluation as in Example 1 was performed. The evaluation results are shown in Table 1. When the film thicknesses of the five thick film resistors were measured, the average value of the five thick film resistors was 8.6 μm.
表１に示す通り、本実施例の針状粒子の二酸化ルテニウム粉末を用いて作製した厚膜抵抗ペーストにより形成された実施例１の厚膜抵抗体は、粒状粒子の二酸化ルテニウム粉末を用いて作製した従来の厚膜抵抗ペーストにより形成された比較例１の厚膜抵抗体に比べ、パルストリミング評価における抵抗値変化率が負に大きく、パルストリミング性が優れていることが分かる。 As shown in Table 1, the thick film resistor of Example 1 formed by the thick film resistance paste prepared by using the ruthenium dioxide powder of the needle-shaped particles of this example was prepared by using the ruthenium dioxide powder of the granular particles. It can be seen that the rate of change in resistance value in the pulse trimming evaluation is negatively large and the pulse trimming property is excellent as compared with the thick film resistor of Comparative Example 1 formed by the conventional thick film resistance paste.
１ ルテニウム化合物粉末
Ｌ 粒子長
φ１ 断面の最大幅
1 Ruthenium compound powder L Particle length φ1 Maximum width of cross section
Claims (4)
前記ルテニウム化合物粉末が針状粒子であることを特徴とする厚膜抵抗体組成物。 Contains glass frit and ruthenium compound powder,
A thick film resistor composition, wherein the ruthenium compound powder is needle-like particles.
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