JP2020193137A - Method for producing lead ruthenate powder - Google Patents
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- 239000000843 powder Substances 0.000 title claims abstract description 80
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 83
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 37
- 238000002844 melting Methods 0.000 claims abstract description 34
- 230000008018 melting Effects 0.000 claims abstract description 33
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052796 boron Inorganic materials 0.000 claims abstract description 32
- 239000000156 glass melt Substances 0.000 claims abstract description 25
- 238000007496 glass forming Methods 0.000 claims abstract description 19
- 239000011521 glass Substances 0.000 claims abstract description 18
- 239000011812 mixed powder Substances 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 21
- 238000004140 cleaning Methods 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 6
- 238000013329 compounding Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 abstract description 49
- 239000011362 coarse particle Substances 0.000 abstract description 24
- 238000000034 method Methods 0.000 abstract description 19
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 11
- 229910052717 sulfur Inorganic materials 0.000 abstract description 11
- 239000011593 sulfur Substances 0.000 abstract description 11
- 238000005406 washing Methods 0.000 abstract description 7
- 239000011260 aqueous acid Substances 0.000 abstract 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 12
- 229910052810 boron oxide Inorganic materials 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000004438 BET method Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 6
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000012790 confirmation Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- XMFOQHDPRMAJNU-UHFFFAOYSA-N lead(ii,iv) oxide Chemical compound O1[Pb]O[Pb]11O[Pb]O1 XMFOQHDPRMAJNU-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000006060 molten glass Substances 0.000 description 4
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 3
- 229910000464 lead oxide Inorganic materials 0.000 description 3
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 150000003303 ruthenium Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 2
- 238000010309 melting process Methods 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- TZRXHJWUDPFEEY-UHFFFAOYSA-N Pentaerythritol Tetranitrate Chemical compound [O-][N+](=O)OCC(CO[N+]([O-])=O)(CO[N+]([O-])=O)CO[N+]([O-])=O TZRXHJWUDPFEEY-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Abstract
Description
本発明は、ルテニウム酸鉛粉末の製造方法に関し、更に詳しくは、含鉛化合物および含ホウ素化合物を含むガラス形成用化合物と、含ルテニウム化合物との混合粉末を溶融して得たガラス融体から、ガラス成分を除去してルテニウム酸鉛粉末を製造する方法に関する。 The present invention relates to a method for producing a ruthenium-containing lead powder, and more specifically, from a glass melt obtained by melting a mixed powder of a glass-forming compound containing a lead-containing compound and a boron-containing compound and a ruthenium-containing compound. The present invention relates to a method for producing lead ruthenate powder by removing a glass component.
厚膜抵抗ペーストは、導電粉末、ガラス形成用化合物粉末およびそれらを印刷に適したペースト状にするための有機ビヒクルから実質構成される。この厚膜抵抗ペーストを所定のパターンで印刷し、高温で焼結処理をすることで、例えば、厚膜チップ抵抗器を構成する抵抗体を形成することができる。導電粉末としては、ガラス形成用化合物の粉末との混合比率を変化させることで緩やかに抵抗値を変化させることができるため、酸化ルテニウム（ＲｕＯ２）粉末やルテニウム酸鉛(Ｐｂ２Ｒｕ２Ｏ７−Ｘ)粉末が広く用いられている。 The thick film resistance paste is substantially composed of a conductive powder, a compound powder for glass formation, and an organic vehicle for forming them into a paste suitable for printing. By printing this thick film resistor paste in a predetermined pattern and sintering it at a high temperature, for example, a resistor constituting a thick film chip resistor can be formed. As the conductive powder, the resistance value can be gradually changed by changing the mixing ratio of the glass-forming compound with the powder. Therefore, ruthenium oxide (RuO 2 ) powder or lead ruthenium acid (Pb 2 Ru 2 O 7) -X ) Powder is widely used.
近年、厚膜チップ抵抗器のような電子素子の小型化が進むとともに、電気的特性の向上が求められており、より詳しくは、抵抗体の小型化にともなう高精細化、および電子素子当たりの抵抗値ばらつきを小さくすることが求められている。このような電子素子の小型化に対応し、かつ電気的特性の良好な厚膜抵抗体を形成するためには、導電粉末を微細化し、かつ、粗大粒子を極力少なくして粒度分布を狭くすることが必要である。粒径が１μｍを超える粗大粒子が存在すると、導電粉末とガラス形成用化合物粉末を含有する厚膜抵抗ペースト内の各成分の分布が不均一となり、形成される抵抗体内の導電部の分布構造も不均一となってしまい、抵抗値ばらつきが大きくなったり、粗大粒子による短絡が生じたりする。このように、導電粉末の粒径、特に粗大粒子の存在は、形成する抵抗体の抵抗値、抵抗温度係数、等の電気的特性に影響を与えるため、粒径の制御された微細な導電粉末が望まれている。 In recent years, with the progress of miniaturization of electronic devices such as thick film chip resistors, improvement of electrical characteristics is required. More specifically, higher definition with miniaturization of resistors and per electronic device. It is required to reduce the variation in resistance value. In order to cope with such miniaturization of electronic devices and to form a thick film resistor having good electrical characteristics, the conductive powder is made finer and the coarse particles are made as small as possible to narrow the particle size distribution. It is necessary. When coarse particles having a particle size of more than 1 μm are present, the distribution of each component in the thick film resistance paste containing the conductive powder and the glass-forming compound powder becomes non-uniform, and the distribution structure of the conductive portion in the formed resistor is also formed. It becomes non-uniform, the resistance value varies widely, and a short circuit occurs due to coarse particles. As described above, the particle size of the conductive powder, particularly the presence of coarse particles, affects the electrical characteristics such as the resistance value and the temperature coefficient of resistance of the formed resistor. Therefore, the fine conductive powder having a controlled particle size. Is desired.
ルテニウム酸鉛粉末の製造方法に関しては、既に多くの技術が開示されている。例えば、次の特許文献１には、金属ルテニウムを酸化剤共存下でアルカリ溶解し、得たルテニウム酸溶液に、鉛イオンを含む溶液を添加して沈殿物を発生させ、得た沈殿物を洗浄、乾燥した後、焙焼処理することでルテニウム酸鉛微粉末を得る技術が開示されている。 Many techniques have already been disclosed regarding the method for producing lead ruthenate powder. For example, in the following Patent Document 1, metallic ruthenium is alkaline-dissolved in the presence of an oxidizing agent, and a solution containing lead ions is added to the obtained ruthenic acid solution to generate a precipitate, and the obtained precipitate is washed. , A technique for obtaining lead ruthenate fine powder by roasting after drying is disclosed.
また、次の特許文献２には、ルテニウム酸アルカリ金属塩の水溶液と鉛化合物を含む水溶液、及び低級アルコールを混合し、アルコールで還元することで、ルテニウムと鉛の水和酸化物または水酸化物の共沈物スラリーを生成させ、該スラリーから分離した共沈物を乾燥させた後、焙焼することでルテニウム酸鉛微粉末を得る技術が開示されている。 Further, in the following Patent Document 2, an aqueous solution of an alkali metal ruthenate, an aqueous solution containing a lead compound, and a lower alcohol are mixed and reduced with alcohol to hydrate or hydroxide the ruthenium and lead. Disclosed is a technique for producing a co-precipitate slurry of the above, drying the co-precipitate separated from the slurry, and then roasting to obtain a fine powder of lead ruthenate.
しかしながら、これらの製造方法を用いて形成したルテニウム酸鉛粉末は、製造条件の差異や残留した不純物量によって、さまざまな粒径のルテニウム酸鉛粉末が生成し、粒径ばらつきが大きいため、１μｍを超える粗大粒子も生成しやすくなり、厚膜抵抗体の抵抗値ばらつきを低く抑えることができず、電気的特性を向上させることが困難である。 However, in the lead ruthenate powder formed by using these production methods, lead ruthenate powder having various particle sizes is produced depending on the difference in production conditions and the amount of residual impurities, and the particle size varies widely. Therefore, 1 μm is used. It becomes easy to generate coarse particles exceeding that, and it is not possible to suppress the variation in resistance value of the thick film resistor to a low level, and it is difficult to improve the electrical characteristics.
このような粗大粒子の発生を抑制する方法として、例えば、次の特許文献３には、ルテニウム酸鉛水酸化物に硫黄を添加した後、焙焼することで粗大粒子の発生を抑制する技術が開示されている。
この方法によれば、硫黄を８００質量ｐｐｍ以上１３００質量ｐｐｍ以下含有させることで、効率良く粗大粒子の発生を抑制することができる。ルテニウム酸鉛粉末に硫黄が不純物として残留していると、厚膜抵抗体の特性が低下してしまう虞があるため、特許文献３には、焼成後のルテニウム酸鉛粉末を水洗等により洗浄することが提案されている。
しかしながら、微細化の進む電子素子においては、わずかな量の硫黄であっても問題となる場合があるため、洗浄の精度をより向上させる必要があるが、硫黄を完全に除去できていることを保証することは非常に困難である。また、焙焼時にルテニウム酸鉛粉末の内部に硫黄を取り込んでしまった場合には、表面洗浄だけでは硫黄の除去が困難であり、長期使用の過程で硫黄が表面に浸みだし、電子素子の信頼性を低下させる要因となる場合もある。
As a method for suppressing the generation of such coarse particles, for example, in the following Patent Document 3, there is a technique for suppressing the generation of coarse particles by adding sulfur to lead ruthenate hydroxide and then roasting. It is disclosed.
According to this method, the generation of coarse particles can be efficiently suppressed by containing sulfur in an amount of 800 mass ppm or more and 1300 mass ppm or less. If sulfur remains as an impurity in the lead ruthenate powder, the characteristics of the thick film resistor may deteriorate. Therefore, in Patent Document 3, the lead ruthenate powder after firing is washed with water or the like. Has been proposed.
However, in electronic devices that are becoming finer, even a small amount of sulfur may cause a problem, so it is necessary to improve the cleaning accuracy, but it is necessary to completely remove sulfur. It is very difficult to guarantee. In addition, if sulfur is taken into the lead ruthenate powder during roasting, it is difficult to remove the sulfur only by surface cleaning, and the sulfur seeps into the surface during long-term use, making the electronic device reliable. It may be a factor that reduces sex.
本発明は、上述の問題を鑑みてなされたものであり、硫黄を添加することなく、生成するルテニウム酸鉛粉末の平均粒径を制御することができ、かつ、１μｍを超える粗大粒子を生成させず、粒径ばらつきの小さなルテニウム酸鉛粉末を得ることが可能なルテニウム酸鉛粉末の製造方法を提供することを目的としている。 The present invention has been made in view of the above-mentioned problems, and it is possible to control the average particle size of the lead ruthenate powder to be produced without adding sulfur, and to generate coarse particles exceeding 1 μm. It is an object of the present invention to provide a method for producing a lead ruthenate powder capable of obtaining a lead ruthenate powder having a small particle size variation.
本発明者は、生成するルテニウム酸鉛粉末の粒径に対する、各種条件の影響を鋭意調査した結果、含鉛化合物、含ホウ素化合物を含むガラス形成用化合物と、含ルテニウム化合物を混合した混合粉末を溶融することで、含鉛化合物と含ルテニウム化合物が反応してルテニウム酸鉛を形成すると同時に、含鉛化合物や含ホウ素化合物などからなるガラス形成用化合物が溶融ガラスを形成し、この溶融ガラスが、ルテニウム酸鉛の粒子成長を阻害し、粒子成長速度を低下させることにより、溶融ガラス内で形成されるルテニウム酸鉛粒子が微細で、かつ粒度分布が狭くなり、粗大粒子の生成を抑制できることを見出した。なお、最終的にルテニウム酸鉛粉末を得るには、ルテニウム酸鉛を含有するガラス融体からガラス成分を除去する必要がある。このため、ガラス成分は溶融処理後に酸等により洗浄除去することができる配合にしておく必要がある。
すなわち、本発明者は、含鉛化合物および含ホウ素化合物を含むガラス形成用化合物と、含ルテニウム化合物とを混合し、適切な温度で溶融することで、溶融ガラス内に、粗粒の非常に少ない粒径の揃った微細なルテニウム酸鉛を含有する、ガラス融体を生成できること、またその後、酸等により、ルテニウム酸鉛を含有するガラス融体からガラス成分を除去するための処理を行うことで、粗大粒子の少ない微細なルテニウム酸鉛粉末を得られることを見出し、本発明を完成するに至った。
As a result of diligently investigating the influence of various conditions on the particle size of the lead ruthenate powder produced, the present inventor has obtained a mixed powder obtained by mixing a glass-forming compound containing a lead-containing compound and a boron-containing compound and a ruthenium-containing compound. By melting, the lead-containing compound and the ruthenium-containing compound react to form lead ruthenate, and at the same time, the glass-forming compound composed of the lead-containing compound and the boron-containing compound forms the molten glass, and the molten glass is formed. It was found that by inhibiting the particle growth of lead ruthenate and reducing the particle growth rate, the lead ruthenate particles formed in the molten glass are fine and the particle size distribution is narrowed, and the formation of coarse particles can be suppressed. It was. In order to finally obtain the lead ruthenate powder, it is necessary to remove the glass component from the glass melt containing lead ruthenate. Therefore, it is necessary to prepare the glass component so that it can be washed and removed with an acid or the like after the melting treatment.
That is, the present inventor mixes a glass-forming compound containing a lead-containing compound and a boron-containing compound with a ruthenium-containing compound and melts the compound at an appropriate temperature to have very few coarse particles in the molten glass. By being able to produce a glass melt containing fine lead ruthenate having a uniform particle size, and then performing a treatment for removing the glass component from the glass melt containing lead ruthenate with an acid or the like. , It has been found that a fine lead ruthenate powder having few coarse particles can be obtained, and the present invention has been completed.
本発明によるルテニウム酸鉛粉末の製造方法は、含鉛化合物および含ホウ素化合物を含み、該含ホウ素化合物に含有するホウ素の含有量が、前記含鉛化合物に含有する鉛の含有量１００質量部に対し、３質量部以上１０質量部以下となる、ガラス形成用化合物と、含ルテニウム化合物とを、該含ルテニウム化合物に含有するルテニウムの含有量に対する、前記ガラス形成用化合物中の前記含鉛化合物に含有する鉛の含有量のｍｏｌ比が１よりも大きくなる配合比で混合して混合粉末を得る混合粉末作製工程と、前記混合粉末作製工程により得られた混合粉末を溶融する溶融工程と、前記溶融工程により作製されたルテニウム酸鉛を含有するガラス融体から、酸水溶液によりガラス成分を洗浄除去するための洗浄工程と、前記洗浄工程により得られたルテニウム酸鉛を乾燥処理し、水分を除去する乾燥工程と、を有することを特徴とする。 The method for producing lead ruthenate powder according to the present invention contains a lead-containing compound and a boron-containing compound, and the content of boron contained in the boron-containing compound is 100 parts by mass of lead contained in the lead-containing compound. On the other hand, the glass-forming compound and the ruthenium-containing compound, which are 3 parts by mass or more and 10 parts by mass or less, are added to the lead-containing compound in the glass-forming compound with respect to the content of ruthenium contained in the ruthenium-containing compound. A mixed powder manufacturing step of obtaining a mixed powder by mixing at a compounding ratio in which the mol ratio of the lead content contained is greater than 1, a melting step of melting the mixed powder obtained by the mixed powder manufacturing step, and the above-mentioned From the glass melt containing lead ruthenate produced by the melting step, a cleaning step for cleaning and removing the glass component with an acid aqueous solution and the lead ruthenate obtained by the cleaning step are dried to remove water. It is characterized by having a drying step of the compound.
また、本発明のルテニウム酸鉛粉末の製造方法においては、前記溶融工程の溶融温度を６５０℃以上８００℃以下にすることが好ましい。 Further, in the method for producing lead ruthenate powder of the present invention, it is preferable that the melting temperature of the melting step is 650 ° C. or higher and 800 ° C. or lower.
また、本発明のルテニウム酸鉛粉末の製造方法においては、前記溶融工程に投入する混合粉末は、含ホウ素化合物の含有量が、含鉛化合物の含有量に対し、５質量％以下であることが好ましい。 Further, in the method for producing lead ruthenate powder of the present invention, the mixed powder to be put into the melting step has a boron-containing compound content of 5% by mass or less with respect to the lead-containing compound content. preferable.
また、本発明のルテニウム酸鉛粉末の製造方法においては、前記溶融工程処理後、得られたガラス融体を水中にて急冷することが好ましい。 Further, in the method for producing lead ruthenate powder of the present invention, it is preferable to quench the obtained glass melt in water after the melting step treatment.
本発明によれば、硫黄を加えることなく、生成するルテニウム酸鉛粉末の平均粒径を制御することができ、かつ、１μｍを超える粗大粒子を生成させず、粒径ばらつきの小さなルテニウム酸鉛粉末を得ることが可能なルテニウム酸鉛粉末の製造方法が得られる。 According to the present invention, the average particle size of the lead ruthenate powder produced can be controlled without adding sulfur, and coarse particles exceeding 1 μm are not generated, and the lead ruthenate powder having a small particle size variation is small. A method for producing a lead ruthenate powder can be obtained.
以下、本発明の実施形態について説明するが、本発明は、下記の実施形態に制限されるものではなく、本発明の範囲内で、下記実施形態に種々の変形および置換を加えることができる。 Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments, and various modifications and substitutions can be added to the following embodiments within the scope of the present invention.
（ガラス組成物）
本発明のルテニウム酸鉛粉末の製造方法には、含鉛化合物および含ホウ素化合物を含むガラス形成用化合物を用いる。含鉛化合物としては、特に限定されないが、ガラス形成に一般的に用いられる一酸化鉛（ＰｂＯ）、四酸化三鉛（Ｐｂ３Ｏ４）、二酸化鉛（ＰｂＯ２）等が適用できる。含ホウ素化合物としては、特に限定されないが、ガラス形成に一般的に用いられる酸化ホウ素（Ｂ２Ｏ３）、ホウ酸（Ｈ３ＢＯ３）等が適用できる。
含ホウ素化合物および含鉛化合物のそれぞれの含有量は、ガラス形成用化合物がガラス化する範囲内の配合量とする。ガラス形成用化合物は、後述する溶融工程でガラス融体を形成できる範囲で、含ホウ素化合物および含鉛化合物以外の化合物を加えることができる。但し、含ホウ素化合物の含有量が多すぎると、形成したルテニウム酸鉛を、過剰なホウ素が分解してしまう場合がある。このため、含鉛化合物に含有する鉛の含有量１００質量部に対する、含ホウ素化合物に含有するホウ素の含有量は３質量部以上１０質量部以下とする。より好ましくは、５質量部以下とするのがよい。
それぞれの化合物の含有量が上記のようにガラス化する範囲内の配合量となった、上記ガラス形成用化合物が、後述する溶融工程にてガラス化すると、形成されたガラス融体がルテニウム酸鉛の粒子成長を阻害する。その結果、微細な粒子のルテニウム酸鉛を得ることができるようになる。
一方、上記ガラス形成用化合物におけるそれぞれの化合物の含有量が、後述する溶融工程でガラス化しない配合量の場合、ルテニウム酸鉛の粒子成長を十分に阻害することができなくなり、ルテニウム酸鉛の粒子が粗大化してしまう。
(Glass composition)
In the method for producing the lead ruthenate powder of the present invention, a glass-forming compound containing a lead-containing compound and a boron-containing compound is used. The lead containing compound is not particularly limited, lead monoxide, commonly used in glass-forming (PbO), triiron tetraoxide lead (Pb 3 O 4), lead dioxide (PbO 2) and the like can be applied. The boron-containing compound is not particularly limited, but boron oxide (B 2 O 3 ), boric acid (H 3 BO 3 ) and the like, which are generally used for glass formation, can be applied.
The content of each of the boron-containing compound and the lead-containing compound shall be within the range in which the glass-forming compound is vitrified. As the glass-forming compound, compounds other than the boron-containing compound and the lead-containing compound can be added as long as a glass melt can be formed in the melting step described later. However, if the content of the boron-containing compound is too large, excess boron may decompose the formed lead ruthenate. Therefore, the content of boron contained in the boron-containing compound is 3 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of lead contained in the lead-containing compound. More preferably, it is 5 parts by mass or less.
When the above-mentioned glass-forming compound, in which the content of each compound is within the range of vitrification as described above, is vitrified in the melting step described later, the formed glass melt becomes lead ruthenate. Inhibits particle growth. As a result, fine particles of lead ruthenate can be obtained.
On the other hand, when the content of each compound in the above glass-forming compound is a blending amount that does not vitrify in the melting step described later, the particle growth of lead ruthenate cannot be sufficiently inhibited, and the particles of lead ruthenate Becomes coarse.
（含ルテニウム化合物）
本発明に用いる含ルテニウム化合物としては、酸化ルテニウムが適用できる。酸化ルテニウムの製造方法は特に限定されないが、例えば次に示す方法で製造することができる。まず、金属ルテニウムをアルカリ条件下で酸化処理し、ルテニウム酸塩の水溶液を得る。あるいは、金属ルテニウムをアルカリ溶融して得られる固体のルテニウム酸塩を水で溶解してルテニウム酸塩の水溶液を得る。
これらの方法により得られたルテニウム酸塩の水溶液のｐＨを調整し、アルコール等の還元剤を用いて還元することで酸化ルテニウム粉末を得ることができる。
(Ruthenium-containing compound)
As the ruthenium-containing compound used in the present invention, ruthenium oxide can be applied. The method for producing ruthenium oxide is not particularly limited, but for example, it can be produced by the following method. First, metallic ruthenium is oxidized under alkaline conditions to obtain an aqueous solution of ruthenium salt. Alternatively, a solid ruthenium salt obtained by alkali-melting metallic ruthenium is dissolved in water to obtain an aqueous solution of ruthenium salt.
The ruthenium oxide powder can be obtained by adjusting the pH of the aqueous solution of ruthenium tetrate obtained by these methods and reducing the pH with a reducing agent such as alcohol.
含ルテニウム化合物の含有量は任意で良いが、鉛と反応させてルテニウム酸鉛を形成させるため、含ルテニウム化合物に含有するルテニウムの含有量に対する、ガラス組成物中の含鉛化合物に含有する鉛の含有量のｍｏｌ比が１よりも大きい、鉛が過剰となる配合比となるようにするのが好ましい。ルテニウムの含有量に対する鉛の含有量のｍｏｌ比が１よりも小さい場合、ルテニウム酸鉛の形成に余ったルテニウムが、含ルテニウム化合物中に酸化ルテニウムなどの状態で残留し、製造されるルテニウム酸鉛粉末中に不純物として混合してしまう場合があるため好ましくない。 The content of the ruthenium-containing compound may be arbitrary, but since it reacts with lead to form lead ruthenate, the content of lead contained in the lead-containing compound in the glass composition is relative to the content of ruthenium contained in the ruthenium-containing compound. It is preferable that the mol ratio of the content is larger than 1 and the compounding ratio is such that lead is excessive. When the mol ratio of the lead content to the ruthenium content is smaller than 1, the ruthenium surplus in the formation of lead ruthenium remains in the ruthenium-containing compound in the state of ruthenium oxide or the like, and the produced lead ruthenium is produced. It is not preferable because it may be mixed as an impurity in the powder.
（溶融工程）
上述した、含鉛化合物および含ホウ素化合物を含むガラス形成用化合物と、含ルテニウム化合物を、ボールミルやライカイ機等により十分に混合、解砕し、混合粉末を作製する。得られた混合粉末を、６５０℃以上８００℃以下の温度で溶融処理することで、ルテニウム酸鉛を包含するガラス融体が生成される。
溶融温度が６５０℃未満であると、ルテニウムと鉛の反応が不十分となり、ルテニウム酸鉛が十分形成されない場合があるので好ましくない。
また、溶融温度が８００℃以上になると、ガラス融体がルテニウム酸鉛の粒子成長を阻害する効果が十分発揮されず、粒径の制御が難しくなり、得られるルテニウム酸鉛粉末の粒径がばらついてしまい、一部の粒子が粗大化してしまう場合があるため、小型化、薄層化の進む厚膜抵抗用の導電物としては望ましくない。
溶融時間は、反応が完了する時間以上であれば、特に限定されない。
溶融後に、ガラス融体を冷却する方法は、自然放冷で冷却しても良いし、水中に投入して急冷しても良い。但し、ガラス融体を水中に投入し急冷した方が、細かく粉砕し易くなり、後工程での酸洗浄工程でより効果的にルテニウム酸鉛以外の酸化鉛や酸化ホウ素等からなるガラス成分を除去可能になるため好ましい。
(Melting process)
The above-mentioned glass-forming compound containing a lead-containing compound and a boron-containing compound and a ruthenium-containing compound are sufficiently mixed and crushed by a ball mill, a Raikai machine, or the like to prepare a mixed powder. The obtained mixed powder is melt-treated at a temperature of 650 ° C. or higher and 800 ° C. or lower to produce a glass melt containing lead ruthenate.
If the melting temperature is less than 650 ° C., the reaction between ruthenium and lead becomes insufficient, and lead ruthenium acid may not be sufficiently formed, which is not preferable.
Further, when the melting temperature becomes 800 ° C. or higher, the glass melt does not sufficiently exert the effect of inhibiting the particle growth of lead ruthenate, it becomes difficult to control the particle size, and the particle size of the obtained lead ruthenate powder varies. This is not desirable as a conductor for thick film resistance, which is becoming smaller and thinner, because some particles may become coarse.
The melting time is not particularly limited as long as it is longer than the time required for the reaction to be completed.
As a method of cooling the glass melt after melting, it may be cooled by natural cooling, or it may be put into water and rapidly cooled. However, if the glass melt is put into water and rapidly cooled, it will be easier to crush it finely, and the glass component consisting of lead oxide, boron oxide, etc. other than lead ruthenate will be removed more effectively in the acid cleaning process in the subsequent process. It is preferable because it becomes possible.
（酸洗浄工程）
溶融工程で得られたルテニウム酸鉛粉末を含むガラス融体を酸で洗浄することで、ルテニウム酸鉛以外の酸化鉛や酸化ホウ素等からなるガラス成分を溶解し、除去することが可能になる。酸洗浄するガラス融体が、細かい粉末であるほど表面積が増加することにより、効率よくガラス成分を除去可能になり、酸洗浄の時間を短くすることができ、作業効率を向上させることができる。このため、必要に応じて酸洗浄工程前に、ガラス融体を粗粉砕しても良い。このとき、上述のように、溶融工程後の冷却処理を、水中に投入して急冷する方法にすると、冷却後のガラス成分が脆くなり、より簡便にガラス融体を粉砕することができるため、より好ましい。
酸洗浄に用いる酸としては、溶融工程で形成されたガラス融体を溶解できる酸であれば特に限定されないが、例えば、硝酸等を適用することができる。
また、ルテニウム酸鉛表面から酸洗浄工程で使用した酸の残渣を除去するため、最後に水で酸を置換する水洗浄を行い、含水したルテニウム酸鉛スラリーを得る。
(Acid cleaning process)
By cleaning the glass melt containing the lead ruthenate powder obtained in the melting step with an acid, it becomes possible to dissolve and remove the glass component composed of lead oxide, boron oxide and the like other than lead ruthenate. The finer the powder of the acid-cleaned glass melt, the larger the surface area, so that the glass component can be efficiently removed, the acid-cleaning time can be shortened, and the work efficiency can be improved. Therefore, if necessary, the glass melt may be roughly pulverized before the acid cleaning step. At this time, as described above, if the cooling process after the melting step is carried out by putting it in water and quenching it, the glass component after cooling becomes brittle and the glass melt can be crushed more easily. More preferred.
The acid used for the acid cleaning is not particularly limited as long as it can dissolve the glass melt formed in the melting step, but for example, nitric acid or the like can be applied.
Further, in order to remove the residue of the acid used in the acid washing step from the surface of lead ruthenate, water washing is finally carried out by replacing the acid with water to obtain a water-containing lead ruthenate slurry.
(乾燥工程)
水洗浄後の含水したルテニウム酸鉛スラリーに対し、必要に応じてろ過等の固液分離処理を行った後、空気中で乾燥することで、ルテニウム酸鉛の乾燥粉末を得ることができる。
(Drying process)
A dry powder of lead ruthenate can be obtained by subjecting the water-containing lead ruthenate slurry after washing with water to a solid-liquid separation treatment such as filtration as necessary and then drying in air.
以下、本発明をさらに詳細な実施例に基づき説明するが、本発明は、これら実施例に限定されるものではない。 Hereinafter, the present invention will be described based on more detailed examples, but the present invention is not limited to these examples.
（評価試験１：粗大粒子の生成抑制効果確認）
（実施例１）
四酸化三鉛（Ｐｂ３Ｏ４）を８０．２ｇ、酸化ホウ素（Ｂ２Ｏ３）を７．５ｇ、酸化ルテニウム（ＲｕＯ２）を１２．３ｇそれぞれ秤量した後、ライカイ機に投入して、解砕及び混合を十分に行った。本実施例では、四酸化三鉛中の鉛含有量１００質量部に対する、酸化ホウ素中のホウ素含有量は３．２質量部である。また、ルテニウムに対する鉛の含有ｍｏｌ比は３．８である。
得られた混合粉末１００ｇをアルミナるつぼに移した後、７００℃の温度で２時間溶融し、ルテニウム酸鉛粉末を包含するガラス融体を得た。溶融処理後、得られたガラス融体を水に投入して冷却した。冷却後、ガラス融体を粗粉砕し、粉末状とした。その後、２４％硝酸水溶液５００ｍＬに粉末状のガラス融体を入れて、撹拌することで、酸化ホウ素および未反応の酸化鉛からなるガラス成分を溶解した。その後、この水溶液をろ過し除去することで、ガラス成分を洗浄除去するための処理を施した粉末を得た。このような酸洗浄処理を合計２回行った。得られた酸洗浄後の粉末を、純水５００ｍＬに入れて撹拌した後、ろ過することで、粉末表面などに残留した酸を除去した。このような水洗浄処理を合計３回行った。水洗浄後のスラリー状のルテニウム酸鉛組成物を、８０℃で１２時間乾燥することでルテニウム酸鉛粉末を得た。
＜平均粒径＞
このようにして製造したルテニウム酸鉛粉末の比表面積を、吸着ガスとして窒素ガスを用いたガス吸着法(ＢＥＴ法)により測定し、その比表面積から平均粒径を算出したところ６１ｎｍであった。
＜粒子ばらつきの評価（粗大粒子の有無確認）＞
製造したルテニウム酸鉛粉末から０．３ｇ採取し、１００ｍＬビーカーに入れた後、純水１００ｍＬを加え試料溶液を作製した。作製した試料溶液を入れた１００ｍＬビーカーに超音波を照射し、ルテニウム酸鉛粉末を純水中に分散させた。その後、１０分間静置し、粗大粒子をビーカー底に沈降させた後に、ビーカー内の上澄みを除去することで微細粒子を効率的に除去した。ビーカー内に残った残液を更にフィルターでろ過することにより粗大粒子を効率的に採取する処理を行った。採取した粒子を、走査型電子顕微鏡にて倍率２０００倍で６４×４８μｍの視野を２０視野観察したところ、粒径が１μｍを超えるルテニウム酸鉛の粗大粒子は観測されなかった。
(Evaluation test 1: Confirmation of effect of suppressing the formation of coarse particles)
(Example 1)
After weighing 80.2 g of trilead tetroxide (Pb 3 O 4 ), 7.5 g of boron oxide (B 2 O 3 ), and 12.3 g of ruthenium oxide (RuO 2 ), they were put into a Raikai machine. Thorough crushing and mixing were performed. In this example, the boron content in boron oxide is 3.2 parts by mass with respect to 100 parts by mass of lead content in trilead tetroxide. The mol ratio of lead to ruthenium is 3.8.
After transferring 100 g of the obtained mixed powder to an alumina crucible, it was melted at a temperature of 700 ° C. for 2 hours to obtain a glass melt containing lead ruthenate powder. After the melting treatment, the obtained glass melt was put into water and cooled. After cooling, the glass melt was coarsely pulverized into a powder. Then, a powdery glass melt was placed in 500 mL of a 24% nitric acid aqueous solution and stirred to dissolve a glass component composed of boron oxide and unreacted lead oxide. Then, by filtering and removing this aqueous solution, a powder subjected to a treatment for washing and removing the glass component was obtained. Such acid cleaning treatment was performed twice in total. The obtained acid-cleaned powder was placed in 500 mL of pure water, stirred, and then filtered to remove the acid remaining on the surface of the powder. Such a water washing treatment was performed a total of three times. The slurry-like lead ruthenate composition after washing with water was dried at 80 ° C. for 12 hours to obtain a lead ruthenate powder.
<Average particle size>
The specific surface area of the lead ruthenate powder produced in this manner was measured by a gas adsorption method (BET method) using nitrogen gas as an adsorption gas, and the average particle size was calculated from the specific surface area and found to be 61 nm.
<Evaluation of particle variation (confirmation of presence of coarse particles)>
0.3 g of the produced lead ruthenate powder was collected, placed in a 100 mL beaker, and then 100 mL of pure water was added to prepare a sample solution. The 100 mL beaker containing the prepared sample solution was irradiated with ultrasonic waves to disperse the lead ruthenate powder in pure water. Then, the particles were allowed to stand for 10 minutes to allow the coarse particles to settle on the bottom of the beaker, and then the supernatant in the beaker was removed to efficiently remove the fine particles. The residual liquid remaining in the beaker was further filtered with a filter to efficiently collect coarse particles. When the collected particles were observed with a scanning electron microscope in a field of view of 64 × 48 μm at a magnification of 2000 times, no coarse particles of lead ruthenate having a particle size of more than 1 μm were observed.
（比較例１）
従来のルテニウム酸鉛粉末を得る方法として、以下の方法でルテニウム酸鉛粉末を得た。
金属ルテニウム１６００ｇを、次亜塩素酸５２Ｌ、水酸化ナトリウム１６００ｇを純水３２Ｌに溶解して作製したアルカリ溶液に加え、溶解し、純水を加えてルテニウム酸塩溶液１６０Ｌを得た。また、硝酸鉛（Ｐｂ（ＮＯ３）２）５４００ｇを過酸化水素水６．４Ｌと純水１６Ｌに溶解して硝酸鉛溶液を得た。次いで、ルテニウム酸塩溶液１６０Ｌを４０℃に維持し、攪拌しつつ、硝酸鉛溶液を添加した。硝酸を添加してｐＨを中性付近に調整し、黒色沈殿物を得た。得られた沈殿物を固液分離した後、温水で洗浄し、１１０℃で一晩乾燥した。このようにして得た黒色沈殿物を７００℃で２時間焙焼し、酸化ルテニウムを含まないＰＢ２ＲＵ２Ｏ６．５のルテニウム酸鉛パイロクロア粉末を得た。
＜平均粒径の評価＞
製造したルテニウム酸鉛パイロクロア粉末の平均粒径をＢＥＴ法にて計測したところ４２ｎｍであった。
＜粒子ばらつきの評価（粗大粒子の有無確認）＞
実施例１と同様の方法で、製造した粉末の粒子ばらつきの評価を行ったところ、１μｍを超えるルテニウム酸鉛パイロクロア粉末の粗大粒子が６８４個観測された。
(Comparative Example 1)
As a conventional method for obtaining lead ruthenate powder, lead ruthenate powder was obtained by the following method.
1600 g of metallic ruthenium was added to an alkaline solution prepared by dissolving 52 L of hypochlorite and 1600 g of sodium hydroxide in 32 L of pure water, and the solution was dissolved, and pure water was added to obtain 160 L of ruthenium acid salt solution. Further, 5400 g of lead nitrate (Pb (NO 3 ) 2 ) was dissolved in 6.4 L of hydrogen peroxide solution and 16 L of pure water to obtain a lead nitrate solution. Then, 160 L of the ruthenate solution was maintained at 40 ° C., and the lead nitrate solution was added with stirring. Nitric acid was added to adjust the pH to near neutral, and a black precipitate was obtained. The obtained precipitate was separated into solid and liquid, washed with warm water, and dried at 110 ° C. overnight. The black precipitate thus obtained was roasted at 700 ° C. for 2 hours to obtain ruthenium oxide-free lead ruthenium acid pyrochloroa powder of PB 2 RU 2 O 6.5 .
<Evaluation of average particle size>
The average particle size of the produced lead pyrochlore ruthenate powder was measured by the BET method and found to be 42 nm.
<Evaluation of particle variation (confirmation of presence of coarse particles)>
When the particle variation of the produced powder was evaluated by the same method as in Example 1, 684 coarse particles of lead ruthenate pyrochlore powder exceeding 1 μm were observed.
(評価試験２：溶融工程の処理温度による平均粒子径制御確認）
実施例２〜４では、溶融温度を表１に示す、６５０℃〜８００℃に変化させる以外は実施例１と同様な方法でルテニウム酸鉛粉末を得た。
製造したルテニウム酸鉛粉末の平均粒径をＢＥＴ法にて計測した結果、及び、実施例１と同様に行った、製造したルテニウム酸鉛粉末の粒子ばらつきの評価結果を表１に示す。
(Evaluation test 2: Confirmation of average particle size control by processing temperature in the melting process)
In Examples 2 to 4, lead ruthenate powder was obtained in the same manner as in Example 1 except that the melting temperature was changed to 650 ° C. to 800 ° C. shown in Table 1.
Table 1 shows the results of measuring the average particle size of the produced lead ruthenate powder by the BET method and the evaluation results of the particle variation of the produced lead ruthenate powder performed in the same manner as in Example 1.
（評価試験３：含鉛化合物に含有する鉛の含有量に対する、含ホウ素化合物に含有するホウ素の含有量に応じた、平均粒径、粒子ばらつき確認）
実施例５、６では、四酸化三鉛中の鉛含有量１００質量部に対する、酸化ホウ素中のホウ素含有量を夫々表２に示す配合比とした以外は実施例１と同様な方法でルテニウム酸鉛粉末を得た。
製造したルテニウム酸鉛粉末の平均粒径をＢＥＴ法にて計測した結果、及び、実施例１と同様に行った、製造したルテニウム酸鉛粉末の粒子ばらつきの評価結果を表２に示す。
(Evaluation test 3: Confirmation of average particle size and particle variation according to the content of boron contained in the boron-containing compound with respect to the content of lead contained in the lead-containing compound)
In Examples 5 and 6, ruthenic acid was prepared in the same manner as in Example 1 except that the boron content in boron oxide was set to the compounding ratio shown in Table 2 with respect to 100 parts by mass of lead content in trilead tetroxide. Lead powder was obtained.
Table 2 shows the results of measuring the average particle size of the produced lead ruthenate powder by the BET method and the evaluation results of the particle variation of the produced lead ruthenate powder performed in the same manner as in Example 1.
評価試験１、評価試験２の表１、及び評価試験３の表２の結果から、本発明の製法を用いた実施例１〜７のルテニウム酸鉛粉末は、ＢＥＴ法による平均粒径が５１ｎｍ〜８９ｎｍと非常に微細な粉末であり、かつ、１μｍ以上の粗大粒子を形成することがなく、粒子ばらつきが小さいことが確認できた。また、溶融時間を一定にして、溶融温度を変化させることにより、任意にルテニウム酸鉛粉末の粒径を制御できることが確認できた。
これに対し、従来の製造方法で作製した比較例１のルテニウム酸鉛粉末は、ＢＥＴ法による平均粒径が４２ｎｍと微細な粉末を製造するような条件であっても、１μｍ以上の粗大粒子を含んでしまい、ばらつきの大きな粒度分布となってしまうことが確認できた。
なお、評価試験３において、比較例として、四酸化三鉛中の鉛含有量１００質量部に対する、酸化ホウ素中のホウ素含有量を本発明の範囲外（３質量部未満、１０質量部超）とした以外は、実施例１と同様な方法でルテニウム酸鉛粉末を得ることを試みたが、酸化ホウ素中のホウ素の含有量が３質量部未満であるとガラス化できず、また、酸化ホウ素中のホウ素の含有量が１０質量部を超えるとルテニウム酸鉛が分解してしまった。
From the results of Evaluation Test 1, Table 1 of Evaluation Test 2, and Table 2 of Evaluation Test 3, the lead ruthenate powders of Examples 1 to 7 using the production method of the present invention have an average particle size of 51 nm by the BET method. It was confirmed that the powder was a very fine powder of 89 nm, and coarse particles of 1 μm or more were not formed, and the particle variation was small. It was also confirmed that the particle size of the lead ruthenate powder can be arbitrarily controlled by changing the melting temperature while keeping the melting time constant.
On the other hand, the lead ruthenate powder of Comparative Example 1 produced by the conventional production method produces coarse particles of 1 μm or more even under the condition of producing a fine powder having an average particle size of 42 nm by the BET method. It was confirmed that the particles were included and the particle size distribution was highly variable.
In the evaluation test 3, as a comparative example, the boron content in boron oxide was outside the range of the present invention (less than 3 parts by mass and more than 10 parts by mass) with respect to 100 parts by mass of lead in trilead tetroxide. An attempt was made to obtain lead ruthenate powder by the same method as in Example 1, but if the content of boron in boron oxide was less than 3 parts by mass, it could not be vitrified, and in boron oxide. When the boron content of the diboron trioxide exceeded 10 parts by mass, lead ruthenate was decomposed.
以上説明した通り、本発明の範囲内の配合として、ガラス中でルテニウム酸鉛を生成することで粗大粒子の形成を防止することができ、溶融温度を制御することで、ルテニウム酸鉛粉末の粒径を容易に制御することが可能であることが分かった。このため、本発明の方法で製造したルテニウム酸鉛粉末は微細で粒度分布の揃った粉末とすることができ、近年要求が厳しくなっている、小型抵抗体の製造に適した抵抗ペーストに好適に用いることができる。 As described above, as a formulation within the scope of the present invention, it is possible to prevent the formation of coarse particles by producing lead ruthenate in glass, and by controlling the melting temperature, the particles of lead ruthenate powder can be prevented. It was found that the diameter can be easily controlled. Therefore, the lead ruthenate powder produced by the method of the present invention can be a fine powder having a uniform particle size distribution, and is suitable for a resistance paste suitable for producing a small resistor, which has become more and more demanding in recent years. Can be used.
本発明のルテニウム酸鉛粉末の製造方法は、電子素子の小型化に対応し、かつ電気的特性の良好な厚膜抵抗体を製造することが求められる分野に有用である。 The method for producing lead ruthenate powder of the present invention is useful in a field in which it is required to produce a thick film resistor having good electrical characteristics and corresponding to miniaturization of an electronic device.
Claims (4)
前記混合粉末作製工程により得られた混合粉末を溶融し、ルテニウム酸鉛粉末を含有するガラス融体を形成する溶融工程と、前記溶融工程により作製されたルテニウム酸鉛を含有するガラス融体から、酸水溶液によりガラス成分を洗浄除去するための洗浄工程と、前記洗浄工程により得られたルテニウム酸鉛を乾燥処理し、水分を除去する乾燥工程と、を有することを特徴とするルテニウム酸鉛粉末の製造方法。 It contains a lead-containing compound and a boron-containing compound, and the content of boron contained in the boron-containing compound is 3 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of lead contained in the lead-containing compound. , The mol ratio of the lead content of the lead-containing compound in the glass-forming compound to the ruthenium content of the glass-forming compound and the ruthenium-containing compound is 1 or more. A mixed powder manufacturing process to obtain a mixed powder by mixing at a compounding ratio that also increases
From the melting step of melting the mixed powder obtained in the mixed powder manufacturing step to form a glass melt containing lead ruthenate powder, and the glass melt containing lead ruthenate prepared in the melting step, A lead ruthenate powder having a cleaning step for cleaning and removing a glass component with an acid aqueous solution and a drying step for drying the lead ruthenate obtained by the cleaning step to remove water. Production method.
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