JP2013096888A - Electrode paste for screen printing and method of manufacturing electrode using the same - Google Patents
Electrode paste for screen printing and method of manufacturing electrode using the same Download PDFInfo
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- 239000007789 gas Substances 0.000 description 21
- 238000001514 detection method Methods 0.000 description 17
- 238000005259 measurement Methods 0.000 description 17
- 239000001301 oxygen Substances 0.000 description 14
- 229910052760 oxygen Inorganic materials 0.000 description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
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- UYAAVKFHBMJOJZ-UHFFFAOYSA-N diimidazo[1,3-b:1',3'-e]pyrazine-5,10-dione Chemical compound O=C1C2=CN=CN2C(=O)C2=CN=CN12 UYAAVKFHBMJOJZ-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は、例えば固体電解質型ガスセンサの電極を製造するのに好適なスクリーン印刷用電極ペースト及びそれを用いた電極の製造方法に関する。 The present invention relates to an electrode paste for screen printing suitable for manufacturing, for example, an electrode of a solid oxide gas sensor and an electrode manufacturing method using the same.
自動車等の内燃機関の排気ガス等の被測定ガス中の特定ガス成分の濃度を測定できるガスセンサとして、ジルコニア等の酸素イオン伝導性の固体電解質層の表面に一対の電極を形成してなるセルを１つないし複数備えた構成が知られている（特許文献１参照）。ここで、各セルは、上記一対の電極間の酸素濃度の差により生じる起電力を測定してセンシングに用いており、電極には高温の排気ガス等に対する耐久性に優れたＰｔ等の貴金属が用いられている。又、被測定ガスを拡散させるため、この電極は多孔質膜から構成されている。 As a gas sensor capable of measuring the concentration of a specific gas component in a measured gas such as exhaust gas of an internal combustion engine such as an automobile, a cell formed by forming a pair of electrodes on the surface of an oxygen ion conductive solid electrolyte layer such as zirconia One or more configurations are known (see Patent Document 1). Here, each cell measures the electromotive force generated by the difference in oxygen concentration between the pair of electrodes and uses it for sensing, and the electrode is made of a noble metal such as Pt having excellent durability against high-temperature exhaust gas. It is used. Further, in order to diffuse the gas to be measured, this electrode is composed of a porous film.
ところで、上記した固体電解質型ガスセンサにおいて、低消費電力に対応するために低温活性が求められている。このため、電極のガス拡散抵抗を極力低くし、低温でも電極の検知能を高くすることが必要である。
しかしながら、従来のガスセンサの電極は厚みが１０μｍを超えるため、電極でのガス拡散抵抗が律速となる程高く、検知速度が低いという問題がある。特に、低温(例えば、６００℃以下)ではガス拡散速度が小さくなるため、検知速度がさらに低下して応答遅れが顕著になる。
By the way, in the above-mentioned solid electrolyte gas sensor, low temperature activity is required in order to cope with low power consumption. For this reason, it is necessary to reduce the gas diffusion resistance of the electrode as much as possible and to increase the detection ability of the electrode even at low temperatures.
However, since the electrode of the conventional gas sensor has a thickness exceeding 10 μm, there is a problem that the gas diffusion resistance at the electrode is higher as the rate is determined and the detection speed is lower. In particular, at low temperatures (for example, 600 ° C. or lower), the gas diffusion rate becomes small, so that the detection rate is further reduced and the response delay becomes remarkable.
従来のガスセンサの電極の厚みが１０μｍを超える理由としては以下が挙げられる。
１）ガスセンサの各セルの電極ペーストを、最も電極厚みが厚い酸素ポンピングセル用電極のペーストと兼用しているため、電極が厚くても緻密になり過ぎないよう粒径が１０μｍを超える粗大なＰｔ粒子を用いていた。
２）電極ペーストの固形分が高い(７５〜９０wt%)ため、電極厚みを薄くするために微細な（粒径が１μｍ以下の）Ｐｔ粒子を配合すると、電極が緻密になり過ぎて、かえってガス拡散抵抗が高くなる。
３）電極ペーストの固形分が高いため、電極をセラミックグリーンシート等の固体電解質層にスクリーン印刷し、シートへの溶剤浸透・乾燥・焼成といった工程を経てペーストから消失する成分の割合が少なく、薄膜化が図り難い。
The reason why the thickness of the electrode of the conventional gas sensor exceeds 10 μm is as follows.
1) Since the electrode paste of each cell of the gas sensor is also used as the electrode paste for the oxygen pumping cell with the thickest electrode, coarse Pt with a particle size exceeding 10 μm so that it does not become too dense even if the electrode is thick. Particles were used.
2) Since the solid content of the electrode paste is high (75 to 90 wt%), if fine Pt particles (with a particle size of 1 μm or less) are blended to reduce the electrode thickness, the electrode becomes too dense and gas Diffusing resistance increases.
3) Since the solid content of the electrode paste is high, the electrode is screen-printed on a solid electrolyte layer such as a ceramic green sheet, and the proportion of components that disappear from the paste through processes such as solvent penetration into the sheet, drying, and firing is small, and the thin film It is hard to plan.
なお、電極の製造方法としては、スクリーン印刷の他にインクジェット方式があり、インクジェット方式では電極の薄膜化が可能であるが、技術的課題(印刷速度、位置精度、インク安定性等)が多く、実用化には至っていない。
すなわち、本発明は、厚さ１０μｍ以下の多孔質の電極をスクリーン印刷で容易かつ安定して製造可能なスクリーン印刷用電極ペースト及びそれを用いた電極の製造方法の提供を目的とする。
As an electrode manufacturing method, there is an inkjet method in addition to screen printing, and it is possible to reduce the thickness of the electrode in the inkjet method, but there are many technical problems (printing speed, positional accuracy, ink stability, etc.) It has not been put into practical use.
That is, an object of the present invention is to provide a screen printing electrode paste capable of easily and stably producing a porous electrode having a thickness of 10 μm or less by screen printing, and a method of producing an electrode using the same.
上記課題を解決するため、本発明のスクリーン印刷用電極ペーストは、セラミックグリーンシート上にスクリーン印刷されるためのスクリーン印刷用電極ペーストであって、固形分としての、レーザー回折法により測定した平均粒径が０．１〜５μｍの貴金属又はその合金の粒子からなる電極金属材料、及び、平均粒径が、前記電極金属材料の平均粒径以下であるセラミックス粒子と、バインダーと、溶剤とを含み、前記固形分のペースト全体における含有量が２５〜７０ｗｔ％である。 In order to solve the above problems, the electrode paste for screen printing of the present invention is an electrode paste for screen printing to be screen-printed on a ceramic green sheet, and has an average particle size measured by a laser diffraction method as a solid content. An electrode metal material comprising particles of a noble metal having a diameter of 0.1 to 5 μm or an alloy thereof, and ceramic particles having an average particle size equal to or less than the average particle size of the electrode metal material, a binder, and a solvent, Content in the whole paste of the said solid content is 25-70 wt%.
このスクリーン印刷用電極ペーストによれば、従来のペーストに比べて固形分が７０ｗｔ％以下と少ないので、電極をスクリーン印刷して焼成後にペーストから消失する成分の割合が多く、電極の薄膜化が図られる。 According to this electrode paste for screen printing, since the solid content is less than 70 wt% compared to the conventional paste, the ratio of components disappearing from the paste after screen printing and baking the electrode is large, and the electrode is made thinner. It is done.
前記バインダーの粘度が１５０Ｐａ・ｓ以上であることが好ましい。
このような構成とすると、バインダーの粘性が高い分、溶剤の配合割合を多くすることができ、スクリーン印刷用電極ペーストの固形分を７０ｗｔ％以下に調整し易くなる。
The binder preferably has a viscosity of 150 Pa · s or more.
With such a configuration, the blending ratio of the solvent can be increased because the viscosity of the binder is high, and the solid content of the electrode paste for screen printing can be easily adjusted to 70 wt% or less.
前記貴金属がＰｔ、Ｐｄ、Ｒｈ、Ｉｒ、Ｒｕ又はＡｇであると、高温耐久性を高めることができる。 When the noble metal is Pt, Pd, Rh, Ir, Ru, or Ag, high temperature durability can be improved.
前記セラミックス粒子は、アルミナ及び／又はジルコニアからなることが好ましい。
このような構成とすると、固体電解質体に対する電極の密着性を高めることができる。なお、セラミック粒子は、印刷対象である固体電解質体と同種の成分で構成することで、固体電解質体に対する電極の密着性をより高めることができる。
The ceramic particles are preferably made of alumina and / or zirconia.
With such a configuration, the adhesion of the electrode to the solid electrolyte body can be enhanced. The ceramic particles can be made of the same type of component as the solid electrolyte body to be printed, thereby further improving the adhesion of the electrode to the solid electrolyte body.
本発明の電極の製造方法は、セラミックグリーンシート上にスクリーン印刷されるためのスクリーン印刷用電極ペーストであって、固形分としての、レーザー回折法により測定した平均粒径が０．１〜５μｍの貴金属の粒子からなる電極金属材料、及び、平均粒径が、前記電極金属材料の平均粒径以下であるセラミックス粒子と、バインダーと、溶剤とを含み、前記固形分のペースト全体における含有量が２５〜７０ｗｔ％であるスクリーン印刷用電極ペーストを用い、スクリーン印刷により厚さ１０μｍ以下の電極を製造する。 The electrode manufacturing method of the present invention is an electrode paste for screen printing for screen printing on a ceramic green sheet, and has an average particle size of 0.1 to 5 μm as a solid content measured by a laser diffraction method. An electrode metal material composed of noble metal particles, and ceramic particles whose average particle size is equal to or less than the average particle size of the electrode metal material, a binder, and a solvent, and the content in the entire paste of the solid content is 25 An electrode having a thickness of 10 μm or less is manufactured by screen printing using an electrode paste for screen printing of ˜70 wt%.
この発明によれば、厚さ１０μｍ以下の多孔質の電極をスクリーン印刷で容易かつ安定して製造可能なスクリーン印刷用電極ペーストを得ることができる。 According to this invention, it is possible to obtain a screen printing electrode paste capable of easily and stably producing a porous electrode having a thickness of 10 μm or less by screen printing.
以下、本発明の実施形態について説明する。
図１は、本発明の実施形態に係るスクリーン印刷用電極ペーストを用いて製造される電極を備えたガスセンサ素子（ＮＯｘセンサ素子）１０の長手方向に沿う断面図である。なお、ＮＯｘセンサ素子１０は公知の主体金具に取り付けられ、ガスセンサ（ＮＯｘセンサ）に組み付けられる。
図１において、ＮＯｘセンサ素子１０は、第１固体電解質層１１ａ、絶縁層１４ａ、第２固体電解質層１２ａ、絶縁層１４ｂ、第３固体電解質層１３ａ、及び絶縁層１４ｃ、１４ｄをこの順に積層した構造を有する。第１固体電解質層１１ａと第２固体電解質層１２ａとの層間に第１測定室１６が画成され、第１測定室１６の左端（入口）に配置された第１拡散抵抗体１５ａを介して外部から被測定ガスＧＭが導入される。
第１測定室１６のうち入口と反対端には第２拡散抵抗体１５ｂが配置され、第２拡散抵抗体１５ｂを介して第１測定室１６の右側には、第１測定室１６と連通する第２測定室１８が画成されている。第２測定室１８は、第２固体電解質層１２ａを貫通して第１固体電解質層１１ａと第３固体電解質層１３ａとの層間に形成されている。
Hereinafter, embodiments of the present invention will be described.
FIG. 1 is a cross-sectional view along the longitudinal direction of a gas sensor element (NOx sensor element) 10 including an electrode manufactured using an electrode paste for screen printing according to an embodiment of the present invention. The NOx sensor element 10 is attached to a known metal shell and assembled to a gas sensor (NOx sensor).
In FIG. 1, the NOx sensor element 10 has a first solid electrolyte layer 11a, an insulating layer 14a, a second solid electrolyte layer 12a, an insulating layer 14b, a third solid electrolyte layer 13a, and insulating layers 14c and 14d stacked in this order. It has a structure. A first measurement chamber 16 is defined between the first solid electrolyte layer 11a and the second solid electrolyte layer 12a, and the first diffusion resistor 15a disposed at the left end (inlet) of the first measurement chamber 16 is interposed therebetween. A measurement gas GM is introduced from the outside.
A second diffusion resistor 15b is disposed at the end of the first measurement chamber 16 opposite to the inlet, and communicates with the first measurement chamber 16 on the right side of the first measurement chamber 16 via the second diffusion resistor 15b. A second measurement chamber 18 is defined. The second measurement chamber 18 penetrates the second solid electrolyte layer 12a and is formed between the first solid electrolyte layer 11a and the third solid electrolyte layer 13a.
絶縁層１４ｃ、１４ｄの間にはＮＯｘセンサ素子１０の長手方向（固体電解質層１１ａ〜１３ａの積層方向に直交する方向）に沿って延びる長尺板状のヒータ５０が埋設されている。ヒータ５０はスクリーン印刷用電極ペーストを活性温度に昇温し、固体電解質層の酸素イオンの伝導性を高めて動作を安定化させるために用いられる。
絶縁層１４ａ〜１４ｄはアルミナを主体とし、第１拡散抵抗体１５ａ及び第２拡散抵抗体１５ｂはアルミナ等の多孔質物質からなる。又、ヒータ５０は白金等からなる。
A long plate-like heater 50 extending along the longitudinal direction of the NOx sensor element 10 (direction orthogonal to the stacking direction of the solid electrolyte layers 11a to 13a) is embedded between the insulating layers 14c and 14d. The heater 50 is used to raise the temperature of the electrode paste for screen printing to the activation temperature and to increase the conductivity of oxygen ions in the solid electrolyte layer to stabilize the operation.
The insulating layers 14a to 14d are mainly made of alumina, and the first diffusion resistor 15a and the second diffusion resistor 15b are made of a porous material such as alumina. The heater 50 is made of platinum or the like.
第１ポンピングセル１１は、酸素イオン伝導性を有するジルコニアを主体とする第１固体電解質層１１ａと、これを挟持するように配置された内側第１ポンプ電極１１ｃ及び対極となる第１対極電極（外側第１ポンプ電極）１１ｂとを備え、内側第１ポンプ電極１１ｃは第１測定室１６に面しており、外側第１ポンプ電極１１ｂは第１測定室１６外に面している。内側第１ポンプ電極１１ｃ及び外側第１ポンプ電極１１ｂはいずれも白金を主体とし、各電極の表面は多孔質体からなる保護層１１ｅ、１１ｄでそれぞれ覆われている。 The first pumping cell 11 includes a first solid electrolyte layer 11a mainly composed of zirconia having oxygen ion conductivity, an inner first pump electrode 11c disposed so as to sandwich the first solid electrolyte layer 11a, and a first counter electrode serving as a counter electrode ( The outer first pump electrode 11 c faces the first measurement chamber 16, and the outer first pump electrode 11 b faces the outside of the first measurement chamber 16. Both the inner first pump electrode 11c and the outer first pump electrode 11b are mainly made of platinum, and the surface of each electrode is covered with protective layers 11e and 11d made of a porous body, respectively.
酸素濃度検出セル１２は、ジルコニアを主体とする第２固体電解質層１２ａと、これを挟持するように配置された検知電極１２ｂ及び基準電極１２ｃとを備え、検知電極１２ｂは内側第１ポンプ電極１１ｃより下流側で第１測定室１６に面している。検知電極１２ｂ及び基準電極１２ｃはいずれも白金を主体としている。
なお、絶縁層１４ｂは、第２固体電解質層１２ａに接する基準電極１２ｃが内部に配置されるように切り抜かれ、その切り抜き部には多孔質体が充填されて基準酸素室１７を形成している。そして、酸素濃度検出セル１２に予め微弱な一定値の電流を流すことにより、酸素を第１測定室１６から基準酸素室１７内に送り込み、酸素基準とする。
The oxygen concentration detection cell 12 includes a second solid electrolyte layer 12a mainly composed of zirconia, and a detection electrode 12b and a reference electrode 12c arranged to sandwich the second solid electrolyte layer 12a. The detection electrode 12b is an inner first pump electrode 11c. It faces the first measurement chamber 16 on the further downstream side. Both the detection electrode 12b and the reference electrode 12c are mainly made of platinum.
The insulating layer 14b is cut out so that the reference electrode 12c in contact with the second solid electrolyte layer 12a is disposed inside, and the cutout portion is filled with a porous body to form the reference oxygen chamber 17. . Then, a weak constant value of current is passed through the oxygen concentration detection cell 12 in advance to send oxygen from the first measurement chamber 16 into the reference oxygen chamber 17 to be an oxygen reference.
第２ポンピングセル１３は、ジルコニアを主体とする第３固体電解質層１３ａと、第３固体電解質層１３ａのうち第２測定室１８に面した表面に配置された内側第２ポンプ電極１３ｂ及び対極となる第２対極電極（対極第２ポンプ電極１３ｃ）とを備えている。内側第２ポンプ電極１３ｂ及び対極第２ポンプ電極１３ｃはいずれも白金を主体とする。
なお、対極第２ポンプ電極１３ｃは、第３固体電解質層１３ａ上における絶縁層１４ｂの切り抜き部に配置され、基準電極１２ｃに対向して基準酸素室１７に面している。
The second pumping cell 13 includes a third solid electrolyte layer 13a mainly composed of zirconia, an inner second pump electrode 13b and a counter electrode disposed on the surface of the third solid electrolyte layer 13a facing the second measurement chamber 18. And a second counter electrode (counter electrode second pump electrode 13c). Both the inner second pump electrode 13b and the counter second pump electrode 13c are mainly composed of platinum.
In addition, the counter electrode 2nd pump electrode 13c is arrange | positioned in the cutout part of the insulating layer 14b on the 3rd solid electrolyte layer 13a, and faces the reference | standard oxygen chamber 17 facing the reference electrode 12c.
本発明の実施形態に係るスクリーン印刷用電極ペーストは、上記した各電極１１ｂ、１１ｃ、１２ｂ、１２ｃ、１３ｂ、１３ｃのいずれにも用いることができるが、特に低温での検知速度を向上させる点から少なくとも検知電極１２ｂに用いることが好ましい。
又、本発明の実施形態に係るスクリーン印刷用電極ペーストを他の電極１１ｂ、１１ｃ、１２ｃ、１３ｂ、１３ｃに用いても何ら問題はない。
なお、本発明の実施形態に係るスクリーン印刷用電極ペーストは、電極本体だけでなく、電極から延びるリードや電極パッド等にも適用可能である。
The electrode paste for screen printing according to the embodiment of the present invention can be used for any of the above-described electrodes 11b, 11c, 12b, 12c, 13b, and 13c, but from the viewpoint of improving the detection speed particularly at a low temperature. It is preferable to use at least the detection electrode 12b.
Moreover, there is no problem even if the electrode paste for screen printing according to the embodiment of the present invention is used for the other electrodes 11b, 11c, 12c, 13b, and 13c.
Note that the electrode paste for screen printing according to the embodiment of the present invention can be applied not only to the electrode body but also to leads, electrode pads and the like extending from the electrodes.
次に、スクリーン印刷用電極ペーストの組成について説明する。
スクリーン印刷用電極ペーストは、電極金属材料と、セラミックス粒子と、バインダーと、溶剤とを含む。このうち、電極金属材料及びセラミックス粒子が固形分に相当する。
電極金属材料は、レーザー回折法により測定した平均粒径が０．１〜５μｍの貴金属又はその合金の粒子からなる。貴金属は、Ａｕ、Ａｇ、Ｐｔ、Ｐｄ、Ｒｈ、Ｉｒ、Ｒｕ、Ｏｓであり、貴金属の合金は、これら貴金属の１種以上からなる。特に、貴金属としては、Ｐｔ、Ｐｄ、Ｒｈ、Ｉｒ、Ｒｕ又はＡｇが好ましい。又、貴金属の合金としてはＰｔ、Ｐｄ、Ｒｈ、Ｉｒ、Ｒｕ及びＡｇの群から選ばれる１種以上からなる合金が好ましく、具体的には、Ｐｔ−Ｐｄ合金、Ｐｔ−Ｒｈ合金、Ｐｔ−Ｐｄ−Ｒｈ合金、Ｐｔ−Ｒｕ合金、Ｐｔ−Ｒｕ−Ｉｒ合金、Ｐｔ−Ａｕ合金、Ｐｔ−Ａｇ合金等が挙げられる。
電極金属材料の平均粒径が０．１μｍ未満であると、電極が緻密になり過ぎて、かえってガス拡散抵抗が高くなる。電極金属材料の平均粒径が５μｍを超えると、厚さ１０μｍ以下の電極を製造することが困難になる。
Next, the composition of the screen printing electrode paste will be described.
The electrode paste for screen printing contains an electrode metal material, ceramic particles, a binder, and a solvent. Among these, the electrode metal material and the ceramic particles correspond to the solid content.
The electrode metal material is composed of particles of a noble metal or an alloy thereof having an average particle diameter of 0.1 to 5 μm measured by a laser diffraction method. The noble metals are Au, Ag, Pt, Pd, Rh, Ir, Ru, and Os, and the noble metal alloy is composed of one or more of these noble metals. In particular, Pt, Pd, Rh, Ir, Ru, or Ag is preferable as the noble metal. Further, the noble metal alloy is preferably an alloy of at least one selected from the group consisting of Pt, Pd, Rh, Ir, Ru and Ag, and specifically, Pt—Pd alloy, Pt—Rh alloy, Pt—Pd. -Rh alloy, Pt-Ru alloy, Pt-Ru-Ir alloy, Pt-Au alloy, Pt-Ag alloy and the like.
When the average particle diameter of the electrode metal material is less than 0.1 μm, the electrode becomes too dense, and on the contrary, the gas diffusion resistance is increased. When the average particle diameter of the electrode metal material exceeds 5 μm, it becomes difficult to produce an electrode having a thickness of 10 μm or less.
なお、レーザー回折法による粒度分布の測定は、粒子に光を照射した際、粒子径により散乱光量とパターンが異なること（Mie散乱理論）を利用したものである。但し、粒度測定機によって散乱光から粒度分布を算定する方法が異なるため、本発明においては、レーザ回折/散乱式粒度分布測定装置 （堀場製作所製の型番LA-750、光源：He-Neレーザ（632.8nm）、1mW）によって測定する。又、粒度分布の測定方法は、純水中に試料を滴下混合して均一分散体としたものをサンプルに用いて行う。
又、スクリーン印刷用電極ペーストは、電極金属材料以外にセラミックス粒子を含むので、スクリーン印刷用電極ペースト中の電極金属材料の粒径を測定する場合は、以下の手順で行う。
１）スクリーン印刷用電極ペーストを加熱(例えば、500℃×1時間保持)してバインダーと溶剤成分を除去する
２）残った固形分の粒度分布を測定する
３）固形分を加熱王水に浸漬し、貴金属成分（電極金属材料）を溶かす
４）残った固形分の粒度分布を測定する
５）２）及び４）の粒度分布の差から、電極金属材料及びセラミックス粒子の平均粒径をそれぞれ算出する
The measurement of the particle size distribution by the laser diffraction method utilizes the fact that when the particles are irradiated with light, the amount of scattered light and the pattern differ depending on the particle diameter (Mie scattering theory). However, since the method for calculating the particle size distribution from the scattered light differs depending on the particle size measuring device, in the present invention, a laser diffraction / scattering type particle size distribution measuring device (model number LA-750 manufactured by Horiba, light source: He-Ne laser ( 632.8nm), 1mW). In addition, the particle size distribution is measured using a sample obtained by dropping and mixing a sample in pure water to obtain a uniform dispersion.
Further, since the screen printing electrode paste contains ceramic particles in addition to the electrode metal material, the particle size of the electrode metal material in the screen printing electrode paste is measured by the following procedure.
1) Heat the electrode paste for screen printing (for example, hold at 500 ° C. for 1 hour) to remove the binder and solvent component 2) Measure the particle size distribution of the remaining solid 3) Soak the solid in heated aqua regia 4) Measure the particle size distribution of the remaining solids 5) Calculate the average particle size of the electrode metal material and ceramic particles from the difference in particle size distribution of 2) and 4), respectively. Do
セラミックス粒子は、固体電解質体に対する電極の密着性を高める共素地として用いられ、該セラミックス粒子の平均粒径が、電極金属材料の平均粒径以下である。又、セラミックス粒子がアルミナ及び／又はジルコニアからなることが好ましい。ジルコニアとしてはＹＳＺ（イットリア部分安定化ジルコニア）を挙げることができる。 The ceramic particles are used as a common substrate that improves the adhesion of the electrode to the solid electrolyte body, and the average particle size of the ceramic particles is equal to or less than the average particle size of the electrode metal material. The ceramic particles are preferably made of alumina and / or zirconia. Examples of zirconia include YSZ (yttria partially stabilized zirconia).
バインダーとしては、エチルセルロース、ポリビニルブチラール、酢酸セルロース、アルキド、フェノール、アクリル、エポキシ、ポリウレタン等が挙げられる。なお、本発明において、バインダーとは、スクリーン印刷用電極ペーストに含まれる溶剤に溶けるものをいう。特に、バインダーの粘度を１５０Ｐａ・ｓ以上とすると、バインダーの粘性が高い分、溶剤の配合割合を多くすることができ、スクリーン印刷用電極ペーストの固形分を７０ｗｔ％以下に調整し易くなるので好ましい。なお、バインダーの粘度が高いほど、重合度が高い。バインダーの粘度は、粘度計で測定する。又、バインダーの粘度は、バインダー２０ｗｔ％を、このバインダーを溶かす溶媒８０ｗｔ％に溶解した液の粘度を測定して求める。
なお、スクリーン印刷用電極ペーストの固形分を２５〜７０ｗｔ％に調整するには、固形分に対するバインダーの配合量を３〜２１ｗｔ％とすることが好ましい。
溶剤としては、ブチルカルビトール、ブチルカルビトールアセテート、テルピネオール、テルピネオールアセテート、エチルカルビトール、エチルカルビトールアセテート、ジヒドロテルピネオール、プロピレングリコールジアセテート等が挙げられる。
Examples of the binder include ethyl cellulose, polyvinyl butyral, cellulose acetate, alkyd, phenol, acrylic, epoxy, polyurethane and the like. In addition, in this invention, a binder means what melt | dissolves in the solvent contained in the electrode paste for screen printing. Particularly, it is preferable that the viscosity of the binder is 150 Pa · s or more because the blending ratio of the solvent can be increased because the viscosity of the binder is high, and the solid content of the electrode paste for screen printing can be easily adjusted to 70 wt% or less. . The higher the viscosity of the binder, the higher the degree of polymerization. The viscosity of the binder is measured with a viscometer. The viscosity of the binder is determined by measuring the viscosity of a solution obtained by dissolving 20 wt% of the binder in 80 wt% of the solvent that dissolves the binder.
In addition, in order to adjust the solid content of the electrode paste for screen printing to 25 to 70 wt%, it is preferable that the compounding quantity of the binder with respect to solid content shall be 3 to 21 wt%.
Examples of the solvent include butyl carbitol, butyl carbitol acetate, terpineol, terpineol acetate, ethyl carbitol, ethyl carbitol acetate, dihydroterpineol, propylene glycol diacetate and the like.
スクリーン印刷用電極ペーストの固形分が２５〜７０ｗｔ％である必要がある。スクリーン印刷用電極ペーストの固形分が２５ｗｔ％未満であると、電極が薄くなり過ぎ（厚み１μｍ以下になり）、断線が生じ易くなる。一方、固形分が７０ｗｔ％を超えると、電極をスクリーン印刷して焼成後にペーストから消失する成分の割合が少なくなり、消失成分による膜厚収縮の割合も３０％以下に留まり、薄膜化が図り難くなる。
なお、スクリーン印刷用電極ペーストの固形分は電極金属材料とセラミックス粒子であり、バインダーは溶剤に溶けてペーストに所定の粘性を付与する。
The solid content of the electrode paste for screen printing needs to be 25 to 70 wt%. When the solid content of the electrode paste for screen printing is less than 25 wt%, the electrode becomes too thin (thickness becomes 1 μm or less), and disconnection tends to occur. On the other hand, if the solid content exceeds 70 wt%, the proportion of components disappearing from the paste after screen printing and firing is reduced, and the proportion of film thickness shrinkage due to the disappearing components remains below 30%, making it difficult to reduce the thickness. Become.
The solid content of the electrode paste for screen printing is an electrode metal material and ceramic particles, and the binder dissolves in a solvent and imparts a predetermined viscosity to the paste.
上記したスクリーン印刷用電極ペーストを用い、次のようにして電極を製造することができる。まず、所定のスクリーンマスク（メタルマスク等）の上からスクリーン印刷用電極ペーストを対象物に印刷する。次に、印刷した電極パターンを乾燥させ、所定温度（例えば１０００℃以上）で焼成して電極を製造する。
なお、本発明において「スクリーン印刷」とは、スクリーンマスクと対象物が離間した状態での印刷の他、スクリーンマスクが対象と接するコンタクト印刷も含む。
Using the above-mentioned electrode paste for screen printing, an electrode can be produced as follows. First, a screen printing electrode paste is printed on an object from above a predetermined screen mask (metal mask or the like). Next, the printed electrode pattern is dried and baked at a predetermined temperature (for example, 1000 ° C. or higher) to manufacture an electrode.
In the present invention, “screen printing” includes contact printing in which the screen mask is in contact with the object as well as printing in a state where the screen mask and the object are separated from each other.
本発明は上記実施形態に限定されず、本発明の思想と範囲に含まれる様々な変形及び均等物に及ぶことはいうまでもない。例えば、本発明は、ＮＯｘセンサの他、全領域空燃比センサ等の酸素センサに適用することができるが、これらの用途に限られない。 It goes without saying that the present invention is not limited to the above-described embodiment, but extends to various modifications and equivalents included in the spirit and scope of the present invention. For example, the present invention can be applied not only to NOx sensors but also to oxygen sensors such as full-range air-fuel ratio sensors, but is not limited to these applications.
以下、実施例を挙げて、本発明を具体的に説明するが、本発明は勿論これらの例に限定されるものではない。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited to these examples of course.
表１にそれぞれ示すＰｔ粒子（電極金属材料）、セラミックス粒子、バインダー、及び所定の溶剤を混合してスクリーン印刷用電極ペーストを調製した。Ｐｔ粒子及びセラミックス粒子の平均粒径は、レーザ回折/散乱式粒度分布測定装置 （堀場製作所製の型番LA-750、光源：He-Neレーザ（632.8nm）、1mW）によって測定した。又、粒度分布の測定に際しては、純水中にそれぞれＰｔ粒子及びセラミックス粒子試料を滴下混合して均一分散体としたものをサンプルに用いた。又、バインダーの粘度は下記方法に順じて測定した。得られたスクリーン印刷用電極ペーストの粘度はRE-80U型粘度計(東機産業社)、25℃、試料重量0.1g、回転数2.5rpm、測定開始60s後の数値を測定した。
バインダーとして、エチルセルロースは、日進化成工業株式会社製のエトセル（登録商標）のグレード7,45,100,200,300を使用した。表１の「エチルセルロース（100cps）」のカッコ内の100cpsは、エトセル（登録商標）のグレード（エチルセルロース自身の粘度）を示す。又、ポリビニルブチラールは、積水化学社製の商品名BH-Sを使用した。溶剤は、エチルセルロースに対してブチルカルビトールを使用し、ポリビニルブチラールに対してブチルカルビトールを使用した。
なお、セラミックス粒子の配合量（内vol%）は、Ｐｔ粒子（電極金属材料）とセラミックス粒子の合計量に対する割合であり、配合量が33vol%である場合、Ｐｔ粒子が67vol%でセラミックス粒子が33vol%である。又、バインダーの配合量（外wt%）は固形分に対するバインダーの配合割合である。又、表１のセラミックス粒子の「ＹＳＺ」は部分安定化ジルコニアを示す。
Pt particles (electrode metal material) shown in Table 1, ceramic particles, a binder, and a predetermined solvent were mixed to prepare an electrode paste for screen printing. The average particle diameters of the Pt particles and the ceramic particles were measured by a laser diffraction / scattering particle size distribution measuring apparatus (model number LA-750, manufactured by Horiba, light source: He-Ne laser (632.8 nm), 1 mW). Further, when measuring the particle size distribution, Pt particles and ceramic particle samples were each dropped and mixed into pure water to form a uniform dispersion. The viscosity of the binder was measured according to the following method. The viscosity of the obtained electrode paste for screen printing was measured by a RE-80U viscometer (Toki Sangyo Co., Ltd.), 25 ° C., sample weight 0.1 g, rotation speed 2.5 rpm, and measurement 60 seconds after the start of measurement.
As the binder, ethyl cellulose grade 7,45,100,200,300 manufactured by Nihon Kasei Kogyo Co., Ltd. was used as the binder. 100 cps in parentheses of “Ethylcellulose (100 cps)” in Table 1 indicates the grade of Etocel (registered trademark) (the viscosity of ethylcellulose itself). Moreover, the brand name BH-S made from Sekisui Chemical Co., Ltd. was used for polyvinyl butyral. As the solvent, butyl carbitol was used for ethyl cellulose, and butyl carbitol was used for polyvinyl butyral.
In addition, the compounding amount (internal vol%) of the ceramic particles is a ratio with respect to the total amount of the Pt particles (electrode metal material) and the ceramic particles. When the compounding amount is 33 vol%, the Pt particles are 67 vol% and the ceramic particles are 33vol%. The blending amount of the binder (outside wt%) is the blending ratio of the binder to the solid content. “YSZ” of the ceramic particles in Table 1 represents partially stabilized zirconia.
次に、上記スクリーン印刷用電極ペーストを用い、図１のＮＯｘセンサの電極１２ｂを作製した。まず、所定のスクリーンマスクの上からスクリーン印刷用電極ペーストを固体電解質体上に印刷した。スクリーンマスクは、カレンダー加工（メッシュ部分に圧縮を加え、厚みを抑える加工）され、325メッシュ、メッシュ厚み46μm、乳剤厚み5μmとした。次に、印刷した電極パターンを乾燥させ、所定温度（例えば１０００℃以上）で焼成して上記電極を製造した。
得られたガスセンサについて、電極の平均厚みを、ＪＩＳ Ｂ０６５１（３．２ 接触式表面粗さ測定機）に規定する表面粗さ測定機により測定した。例えば、検知電極１２ｂの平均厚みであれば、図１の長手方向にそって、（左側に露出した）第２固体電解質層１２ａから、検知電極１２ｂを乗り越え、（右側に露出した）第２固体電解質層１２ａへ至るように検知電極１２ｂを跨ぐようにスイープすることで測定した。そして、検知電極１２ｂの平均厚みは、Ｒｚ（全）−Ｒｃ（電極）で求めることができる。ここで、Ｒｚ（全）は上記した全スイープ範囲内での最大高さであり、Ｒｃ（電極）は検知電極１２ｂをスイープした範囲内での平均高さである。
さらに、得られたガスセンサについて、ドリル等で電極をむき出しに加工し、電極面の上・下間の抵抗を常温で抵抗計で測定することで、断線の有無を測定した。
Next, the electrode 12b of the NOx sensor shown in FIG. 1 was prepared using the screen printing electrode paste. First, an electrode paste for screen printing was printed on a solid electrolyte body from above a predetermined screen mask. The screen mask was calendered (processing to compress the mesh portion to reduce the thickness) to 325 mesh, a mesh thickness of 46 μm, and an emulsion thickness of 5 μm. Next, the printed electrode pattern was dried and fired at a predetermined temperature (for example, 1000 ° C. or higher) to manufacture the electrode.
About the obtained gas sensor, the average thickness of the electrode was measured with the surface roughness measuring machine prescribed | regulated to JISB0651 (3.2 contact-type surface roughness measuring machine). For example, if the thickness of the detection electrode 12b is average, the second solid electrolyte layer 12a (exposed on the right side) is moved over the detection electrode 12b from the second solid electrolyte layer 12a (exposed on the left side) along the longitudinal direction of FIG. The measurement was performed by sweeping over the detection electrode 12b so as to reach the electrolyte layer 12a. And the average thickness of the detection electrode 12b can be calculated | required by Rz (all) -Rc (electrode). Here, Rz (total) is the maximum height within the entire sweep range described above, and Rc (electrode) is the average height within the range where the detection electrode 12b is swept.
Furthermore, about the obtained gas sensor, the electrode was processed with a drill etc., and the presence or absence of a disconnection was measured by measuring the resistance between the upper and lower sides of an electrode surface with an ohmmeter at normal temperature.
得られた結果を表１及び図２、図３に示す。
表１から明らかなように、平均粒径０．１〜５μｍのＰｔ粒子を電極金属材料に用い、固形分が２５〜７０ｗｔ％である各実施例の場合、電極を断線させずに１０μｍ以下の厚みとすることができた。又、各実施例の場合、バインダーの粘度は１５０Ｐａ・ｓ以上であった。
一方、電極ペーストの固形分が２５ｗｔ％未満である比較例１の場合、電極の厚みが１μｍ以下に薄くなり過ぎ、断線が生じた。電極ペーストの固形分が７０ｗｔ％を超えた比較例２の場合、電極の厚みが１０μｍを超えた。
又、バインダーの粘度が１５０Ｐａ・ｓ未満である比較例３の場合、バインダーの量が少な過ぎて成膜性が劣化し、断線が生じた。
さらに、Ｐｔ粒子の平均粒径が０．１μｍ未満である比較例４の場合、断線が生じた。Ｐｔ粒子の平均粒径が５μｍを超えた比較例５の場合、電極の厚みが１０μｍを超えた。
なお、図２は実施例４の電極ペーストを用いた電極の断面ＳＥＭ像であり、矢印が電極の厚み部分を示す。図３は図２の電極の表面ＳＥＭ像である。
The obtained results are shown in Table 1, FIG. 2 and FIG.
As is apparent from Table 1, in the case of each example in which Pt particles having an average particle diameter of 0.1 to 5 μm were used as the electrode metal material and the solid content was 25 to 70 wt%, the electrode was 10 μm or less without disconnecting the electrode. Thickness could be achieved. In each example, the viscosity of the binder was 150 Pa · s or more.
On the other hand, in the case of Comparative Example 1 in which the solid content of the electrode paste was less than 25 wt%, the thickness of the electrode became too thin to 1 μm or less, and disconnection occurred. In the case of Comparative Example 2 in which the solid content of the electrode paste exceeded 70 wt%, the thickness of the electrode exceeded 10 μm.
Moreover, in the case of the comparative example 3 whose viscosity of a binder is less than 150 Pa * s, the amount of binders was too small, the film formability deteriorated, and disconnection occurred.
Furthermore, in the case of the comparative example 4 whose average particle diameter of Pt particle | grains is less than 0.1 micrometer, a disconnection arose. In the case of Comparative Example 5 in which the average particle size of the Pt particles exceeded 5 μm, the thickness of the electrode exceeded 10 μm.
FIG. 2 is a cross-sectional SEM image of the electrode using the electrode paste of Example 4, and the arrow indicates the thickness of the electrode. FIG. 3 is a surface SEM image of the electrode of FIG.
１０ ＮＯｘセンサ素子
１１ 第１ポンピングセル
１２ 酸素濃度検出セル
１３ 第２ポンピングセル
１１ａ〜１３ａ 第１固体電解質層〜第３固体電解質層
１１ｂ 対極電極（外側第１電極）
１１ｃ 内側第１ポンプ電極
１２ｂ 検知電極
１２ｃ 基準電極
１３ｂ 内側第２ポンプ電極
１３ｃ 第２対極電極（対極第２ポンプ電極）
DESCRIPTION OF SYMBOLS 10 NOx sensor element 11 1st pumping cell 12 Oxygen concentration detection cell 13 2nd pumping cell 11a-13a 1st solid electrolyte layer-3rd solid electrolyte layer 11b Counter electrode (outside 1st electrode)
11c Inner first pump electrode 12b Detection electrode 12c Reference electrode 13b Inner second pump electrode 13c Second counter electrode (counter electrode second pump electrode)
Claims (5)
スクリーン印刷により厚さ１０μｍ以下の電極を製造する電極の製造方法。 An electrode paste for screen printing to be screen-printed on a ceramic green sheet, which is an electrode composed of particles of a noble metal or an alloy thereof having an average particle diameter of 0.1 to 5 μm as a solid content measured by a laser diffraction method The electrode paste for screen printing which contains a metal material and ceramic particles whose average particle diameter is equal to or less than the average particle diameter of the electrode metal material, a binder, and a solvent, and whose solid content is 25 to 70 wt% is used. ,
An electrode manufacturing method for manufacturing an electrode having a thickness of 10 μm or less by screen printing.
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