JPH06294692A - Resistor paste and pressure sensor employing the same - Google Patents
Resistor paste and pressure sensor employing the sameInfo
- Publication number
- JPH06294692A JPH06294692A JP5080488A JP8048893A JPH06294692A JP H06294692 A JPH06294692 A JP H06294692A JP 5080488 A JP5080488 A JP 5080488A JP 8048893 A JP8048893 A JP 8048893A JP H06294692 A JPH06294692 A JP H06294692A
- Authority
- JP
- Japan
- Prior art keywords
- iron
- resistor
- pressure sensor
- resistor paste
- glass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- Measuring Fluid Pressure (AREA)
- Pressure Sensors (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、圧力変化に対して抵抗
体の電気抵抗が変化する圧力センサ用抵抗体ペーストお
よび圧力変化に対して抵抗体の電気抵抗の変化により圧
力を検出する圧力センサに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resistor paste for a pressure sensor in which the electric resistance of a resistor changes in response to a pressure change, and a pressure sensor for detecting pressure by a change in the electric resistance of a resistor in response to pressure change. Regarding
【０００２】[0002]
【従来の技術】近年、荷重量、圧力を検出するセンサ
は、機械，船舶，自動車等の各部に生じる応力や荷重の
大きさを検出するために広く用いられている。この種の
センサは基材の種類、感歪材料の種類によってさまざま
なものが提案されている。2. Description of the Related Art In recent years, sensors for detecting the amount of load and pressure have been widely used to detect the magnitude of stress and load generated in various parts of machines, ships, automobiles and the like. Various sensors of this type have been proposed depending on the type of base material and the type of strain-sensitive material.
【０００３】その代表的なものとして、ポリエステル，
エポキシ，ポリイミド等の樹脂からなるフィルム上に、
Ｃｕ−Ｎｉ合金、Ｎｉ−Ｃｒ合金等からなる薄膜状の抵
抗体を蒸着またはスパッタリングにより形成したセンサ
（１）がある。As a typical example thereof, polyester,
On a film made of resin such as epoxy or polyimide,
There is a sensor (1) in which a thin film resistor made of a Cu-Ni alloy, a Ni-Cr alloy or the like is formed by vapor deposition or sputtering.
【０００４】また、特公平３−２０６８２号公報に開示
されているように、上記の樹脂製フィルムの代わりにガ
ラスプレートを用いたセンサ（２）もある。Also, as disclosed in Japanese Patent Publication No. 3-20682, there is a sensor (2) using a glass plate instead of the resin film.
【０００５】さらに、特願平３−２８２６６３号に開示
されているように、金属基体と、その表面に形成された
結晶化ガラス材料からなるガラス層と、さらにそのガラ
ス層の表面に形成され、歪が加わると電気抵抗が変化す
る抵抗体からなる圧力センサ３が提案されている。Further, as disclosed in Japanese Patent Application No. 3-282663, a metal substrate, a glass layer made of a crystallized glass material formed on the surface thereof, and further formed on the surface of the glass layer, There has been proposed a pressure sensor 3 including a resistor whose electric resistance changes when strain is applied.
【０００６】応力，荷重，圧力の大きさは、次のように
して測定される。外部からの力や荷重により発生した部
材の圧力が、樹脂製フィルム，ガラスプレート，金属基
材を介して抵抗体に伝わる。この伝達された圧力によ
り、抵抗体の長さと断面積が変化することにより電気抵
抗が変化する。この電気抵抗の変化を電気信号として検
出することにより、部材に加わった応力，荷重，圧力等
の大きさが検知できる。The magnitudes of stress, load and pressure are measured as follows. The pressure of the member generated by an external force or load is transmitted to the resistor through the resin film, the glass plate, and the metal base material. Due to the transmitted pressure, the length and the cross-sectional area of the resistor change, so that the electric resistance changes. By detecting this change in electrical resistance as an electrical signal, the magnitude of stress, load, pressure, etc. applied to the member can be detected.
【０００７】ところで、圧力センサの市場が大きい用途
の１つとして、自動車等に使用される車両用サスペンシ
ョンがある。以後は車両用サスペンションを例にあげて
説明する。例えばそのシャフトの表面に圧力センサ
（１）を接着樹脂等で貼り付け、この圧力センサによ
り、車体が車輪に加わる荷重が検出される。By the way, one of the applications in which the pressure sensor has a large market is a vehicle suspension used in an automobile or the like. Hereinafter, the vehicle suspension will be described as an example. For example, the pressure sensor (1) is attached to the surface of the shaft with an adhesive resin or the like, and the load applied to the wheel by the vehicle body is detected by this pressure sensor.
【０００８】[0008]
【発明が解決しようとする課題】しかしながら、（１）
のセンサでは車両用サスペンションのように、温度範囲
が−５０℃から１５０℃、最大荷重が２トンにも達する
といった過酷な環境条件下で長期間使用したとき、接着
強度が劣下して圧力センサが部材から剥離する問題があ
る。特に、（２）の圧力センサでは、ガラスプレートを
シャフトのような曲面を有する部材に溶着した場合は、
ガラスプレートは密着性が乏しいため強固な接着が難し
くて剥離し易い。しかし、（３）の圧力センサは、金属
基体と結晶化ガラス層、結晶化ガラス層と抵抗体層間で
それぞれの成分元素が相互拡散しているため密着性が非
常に強く、過酷な環境条件で使用するセンサとしては最
適なものであるが、未だ実用化されていない。この原因
の１つとして、抵抗の温度変化率（ＴＣＲ）が１００〜
２００ＰＰｍ／℃と大きいことが挙げられる。この温度
変化による抵抗値の変化を排除するための高価な温度補
償素子を必要とし、これがセンサの大型化，コストアッ
プにつながっていた。[Problems to be Solved by the Invention] However, (1)
When used for a long time under severe environmental conditions, such as a vehicle suspension, where the temperature range is -50 ° C to 150 ° C and the maximum load reaches 2 tons, the pressure sensor has a poor adhesive strength. Is peeled off from the member. Particularly, in the pressure sensor of (2), when the glass plate is welded to a member having a curved surface such as a shaft,
Since the glass plate has poor adhesion, strong adhesion is difficult and easy to peel off. However, in the pressure sensor of (3), since the constituent elements of the metal substrate and the crystallized glass layer and between the crystallized glass layer and the resistor layer are mutually diffused, the adhesiveness is very strong, and the pressure sensor can be used under severe environmental conditions. It is the most suitable sensor to use, but it has not been put to practical use. One of the causes of this is that the temperature change rate (TCR) of resistance is 100-
It may be as high as 200 PPm / ° C. An expensive temperature compensating element is required to eliminate the change in the resistance value due to the temperature change, which leads to an increase in the size and cost of the sensor.
【０００９】本発明は上記従来技術の課題を解決し、抵
抗体の温度特性に優れた抵抗体ペースト及びこれを用い
た圧力センサを提供することを目的とする。An object of the present invention is to solve the above-mentioned problems of the prior art and to provide a resistor paste having excellent temperature characteristics of the resistor and a pressure sensor using the same.
【００１０】[0010]
【課題を解決するための手段】この目的を達成するため
に、本発明の圧力センサは、酸化ルテニウムと鉄化合物
とガラスフリットと有機ビヒクルおよび希釈剤から構成
される抵抗体ペーストおよび金属基体と、前記金属基体
の表面に形成された絶縁層と、前記絶縁層の表面に形成
され前記抵抗体の変形に伴って電気抵抗が変化する抵抗
体と、前記抵抗体の抵抗変化を検出する電極からなり、
抵抗体を酸化ルテニウムと鉄化合物とガラスフリットと
有機ビヒクルおよび希釈剤から構成される抵抗体ペース
トを焼成処理により構成したものである。In order to achieve this object, a pressure sensor of the present invention comprises a resistor paste and a metal substrate composed of ruthenium oxide, an iron compound, a glass frit, an organic vehicle and a diluent. An insulating layer formed on the surface of the metal substrate, a resistor formed on the surface of the insulating layer, the electric resistance of which changes with the deformation of the resistor, and an electrode for detecting a resistance change of the resistor. ,
The resistor is formed by firing a resistor paste composed of ruthenium oxide, an iron compound, glass frit, an organic vehicle and a diluent.
【００１１】[0011]
【作用】通常、抵抗体ペーストは導電性物質とガラスフ
リットと有機ビヒクルおよび希釈剤から構成されてお
り、一般的に導電性物質として酸化ルテニウムが用いら
れている。このような抵抗体ペーストを用いた抵抗体の
温度変化率（ＴＣＲ）の絶対値が１００〜２００ＰＰｍ
／℃程度である。本発明の抵抗体ペーストを用いると、
一般的な抵抗体ペーストの成分である導電性物質、ガラ
スフリット，有機ビヒクルおよび希釈剤の他に、さらに
鉄化合物を添加することにより、ＴＣＲが低下し、さら
に圧縮・引っ張りを加えたときの歪による抵抗変化率
（ＧＦ）が増大し、センサ増幅率を小さくすることが可
能となる。The resistor paste is usually composed of a conductive substance, a glass frit, an organic vehicle and a diluent, and ruthenium oxide is generally used as the conductive substance. The absolute value of the temperature change rate (TCR) of the resistor using such a resistor paste is 100 to 200 PPm.
/ ° C. Using the resistor paste of the present invention,
In addition to the conductive substances, glass frits, organic vehicles and diluents that are the components of general resistor paste, the addition of iron compounds lowers the TCR, and the strain when compression / tensile is applied. The rate of change in resistance (GF) due to increases, and the sensor amplification factor can be reduced.
【００１２】[0012]
【実施例】以下、本発明の圧力センサについて具体的に
説明する。図１に本発明の一実施例における圧力センサ
を示しており、図１（Ａ），（Ｂ）において１は金属基
体、２は絶縁層、３は抵抗体、４は電極である。EXAMPLES The pressure sensor of the present invention will be specifically described below. FIG. 1 shows a pressure sensor according to an embodiment of the present invention. In FIGS. 1A and 1B, 1 is a metal substrate, 2 is an insulating layer, 3 is a resistor, and 4 is an electrode.
【００１３】次に本発明のセンサにおける各構成部分に
ついて説明する。 （１）絶縁基板 （ａ）金属基体 本発明に使用される金属基体はホーロ用鋼，ステンレス
鋼，珪素鋼，ニッケル−クロム−鉄，ニッケル−鉄，コ
バール，インバーなどの各種合金材やそれらのクラッド
材などが選択されるが、絶縁層との密着性の観点からＳ
ＵＳ４３０が最も好ましい。Next, each component of the sensor of the present invention will be described. (1) Insulating Substrate (a) Metal Substrate The metal substrate used in the present invention includes various alloy materials such as hollow steel, stainless steel, silicon steel, nickel-chromium-iron, nickel-iron, kovar, invar, and the like. Although a clad material or the like is selected, from the viewpoint of adhesion with the insulating layer, S
US430 is most preferred.
【００１４】金属基体の材質が決定されれば、所望の形
状加工、穴加工等が通常の機械加工，エッチング加工，
レーザ加工等で施される。その形状は、負荷荷重の大き
さや用途により、円筒形や板状（箔状も含む）等が選択
される。Once the material of the metal substrate has been determined, the desired shape processing, hole processing, etc. can be carried out by ordinary mechanical processing, etching processing,
It is applied by laser processing or the like. A cylindrical shape, a plate shape (including a foil shape), or the like is selected as the shape depending on the size of the load applied and the application.
【００１５】これらの金属基体は絶縁層の密着性を向上
させる目的で、表面脱脂された後、サンドブラスト処理
したり、ニッケル，コバルトなどの各種メッキを施した
り、熱酸化処理によって酸化被覆層を形成したりする。For the purpose of improving the adhesion of the insulating layer, these metal substrates are degreased on the surface and then subjected to sandblasting, various platings of nickel, cobalt, etc., or an oxide coating layer is formed by thermal oxidation treatment. To do
【００１６】（ｂ）絶縁層 本発明のセンサの金属基体上に形成される絶縁層は、結
晶化ガラス層が選択される。結晶化ガラス層は、電気絶
縁性，耐熱性の観点から、無アルカル結晶化ガラス（焼
成によってたとえば、ＭｇＯ系の結晶相を析出）で構成
されることが好ましい。そのガラス組成が特に、ＭｇＯ
が１６〜５０重量％，ＳｉＯ2が７〜３０重量％，Ｂ2Ｏ
3が５〜３４重量％，ＢａＯが０〜５０重量％，Ｌａ2Ｏ
3が０〜４０重量％，ＣａＯが０〜２０重量％，Ｐ2Ｏ5
が０〜５重量％，ＭＯ2が０〜５重量％（但し、ＭはＺ
ｒ，Ｔｉ，Ｓｎのうち少なくとも一種の元素）であるこ
とが好ましい。(B) Insulating Layer As the insulating layer formed on the metal substrate of the sensor of the present invention, a crystallized glass layer is selected. From the viewpoint of electrical insulation and heat resistance, the crystallized glass layer is preferably composed of non-alcal crystallized glass (for example, a MgO-based crystal phase is deposited by firing). The glass composition is especially MgO
Of 16 to 50% by weight, SiO 2 of 7 to 30% by weight, B 2 O
3 to 5 to 34% by weight, BaO to 0 to 50% by weight, La 2 O
3 is 0 to 40% by weight, CaO is 0 to 20% by weight, P 2 O 5
Is 0 to 5% by weight, MO 2 is 0 to 5% by weight (where M is Z
At least one element of r, Ti, and Sn) is preferable.
【００１７】このように、結晶化ガラス材料が選択され
る理由の１つは、金属基体とガラス層との密着性を強固
にするためである。特に上記の組成のものは、密着性が
非常に強固である。As described above, one of the reasons for selecting the crystallized glass material is to strengthen the adhesion between the metal substrate and the glass layer. In particular, the above composition has very strong adhesion.
【００１８】上記結晶化ガラス層を金属基体上に被覆す
る方法として、スプレー法，粉末静電塗装法，電気泳動
電着法等がある。被膜のち密性，電気絶縁性等の観点か
ら、電気泳動電着法が最も好ましい。As a method for coating the above-mentioned crystallized glass layer on a metal substrate, there are a spray method, a powder electrostatic coating method, an electrophoretic electrodeposition method and the like. The electrophoretic electrodeposition method is the most preferable from the viewpoints of the denseness of the coating, the electric insulation, and the like.
【００１９】この方法は、ガラスにアルコールおよび少
量の水を加えてボールミル中で約２０時間粉砕，混合
し、ガラスの平均粒径を１〜５μｍ程度にする。得られ
たスラリーを電解槽に入れて、液を循環する。そして金
属基体を、このスラリー中に浸漬し、１００〜４００Ｖ
で陰分極させることにより、金属基体表面にガラス粒子
を析出させる。これを乾燥後、８５０〜９００℃で１０
分〜１時間焼成する。これによってガラスの微粒子が溶
融するとともに、ガラスの成分と金属材料の成分が、十
分に相互拡散するためガラス層と金属基体との強固な密
着が得られる。According to this method, alcohol and a small amount of water are added to glass and the mixture is ground and mixed in a ball mill for about 20 hours so that the average particle diameter of glass is about 1 to 5 μm. The obtained slurry is put in an electrolytic cell and the liquid is circulated. Then, the metal substrate is immersed in this slurry to obtain 100 to 400V.
The glass particles are deposited on the surface of the metal substrate by performing negative polarization with. After drying, this is heated at 850-900 ° C for 10
Bake for 1 minute to 1 hour. As a result, the glass fine particles are melted, and the glass component and the metal material component are sufficiently diffused into each other, so that strong adhesion between the glass layer and the metal substrate can be obtained.
【００２０】なお、焼成は常温から徐々に昇温して上記
温度に到達させる方法が微細針状結晶が無数に析出する
ため後述のアンカー効果がより強く働き、抵抗体との密
着性が向上し好ましい。In the firing, a method of gradually raising the temperature from room temperature to reach the above temperature causes innumerable fine needle-like crystals to be deposited, so that the anchor effect described later works more strongly and the adhesion with the resistor is improved. preferable.
【００２１】（２）抵抗体 抵抗体用の材料としては、酸化ルテニウム，酸化タンタ
ル，酸化タリウム，ルテニウム酸鉛等の種々の圧力変化
によって電気抵抗が変化する性質を含む抵抗材料が使用
可能であるが、被膜特性およびコストの点から酸化ルテ
ニウムが選択される。本発明の抵抗体ペーストは、酸化
ルテニウムと鉄化合物ガラスフリットと有機ビヒクルお
よび希釈剤から構成される。鉄化合物は、酸化鉄，硝酸
鉄，塩化鉄等の無機鉄化合物結晶、およびクエン酸鉄，
蓚酸鉄，鉄アセチルアセトナート等の有機鉄化合物結晶
のような固体状態にある材料と、ナフテン酸鉄やオクチ
ル酸鉄等の有機酸鉄、およびスルファミン酸鉄等の液体
材料がある。ペースト材料として用いる場合、混合性等
の観点から液体材料が好ましい。(2) Resistor As the material for the resistor, it is possible to use a resistance material such as ruthenium oxide, tantalum oxide, thallium oxide, lead ruthenate, etc., which has a property that the electric resistance is changed by various pressure changes. However, ruthenium oxide is selected in terms of coating properties and cost. The resistor paste of the present invention comprises ruthenium oxide, an iron compound glass frit, an organic vehicle and a diluent. Iron compounds include inorganic iron compound crystals such as iron oxide, iron nitrate and iron chloride, and iron citrate,
There are solid-state materials such as organic iron compound crystals such as iron oxalate and iron acetylacetonate, organic acid iron such as iron naphthenate and iron octylate, and liquid materials such as iron sulfamate. When used as a paste material, a liquid material is preferable from the viewpoint of mixability and the like.
【００２２】次に、具体的な実施例について説明する。 （実施例１）前述の絶縁層形成工程に従い、ＳＵＳ４３
０基体（１００mm×１００mm×０．５mm）の表面に、厚
さ１００μｍの（表１）〜（表５）に示す組成の結晶化
ガラス層を電気泳動電着し、８８０℃で１０分焼成しサ
ンプルの表面粗度，うねり性，耐熱性等の諸特性を調べ
た。その結果を組成とともに（表１）〜（表５）に示し
ている。Next, a concrete example will be described. (Example 1) In accordance with the above-mentioned insulating layer forming step, SUS43
A 100 μm thick crystallized glass layer having a composition shown in (Table 1) to (Table 5) was electrophoretically electrodeposited on the surface of a 0 substrate (100 mm × 100 mm × 0.5 mm) and baked at 880 ° C. for 10 minutes. Various properties such as surface roughness, waviness, and heat resistance of the sample were investigated. The results are shown in (Table 1) to (Table 5) together with the composition.
【００２３】なお表面粗度はタリサーフ表面粗さ計で測
定し、表面中心線平均粗さＲａで示し、うねり性はタリ
サーフ表面粗さ計で得られた山と谷の差Ｒmaxで評価し
た。The surface roughness was measured by a Talysurf surface roughness meter and indicated by the surface centerline average roughness Ra, and the waviness was evaluated by the peak-valley difference R max obtained by the Talysurf surface roughness meter.
【００２４】耐熱性は、サンプルを８５０℃の電気炉中
に１０分入れ、炉から取り出し３０分間、自然放冷する
サイクルを繰り返すスポーリングテストを行って、サン
プルのクラックや剥離の状態を調べた。なおクラックは
赤インク中に浸漬しその後、表面を拭き取って目視観察
によって、その有無を調べた。表中の○，△，×は、○
が１０サイクル以上行っても異常が認められないもの、
△は５〜９サイクルで発生したもの、×は４サイクル以
下で発生したものを表す。Regarding the heat resistance, the sample was put in an electric furnace at 850 ° C. for 10 minutes, taken out of the furnace, and allowed to cool naturally for 30 minutes. A spalling test was repeated to examine the state of cracks and peeling of the sample. . The presence of cracks was examined by immersing the cracks in red ink, wiping the surface, and visually observing the cracks. ○, △, × in the table are ○
No abnormalities are observed even after 10 cycles or more,
Δ represents the one generated in 5 to 9 cycles, and × represents the one generated in 4 cycles or less.
【００２５】密着性は基体の曲げ試験を行い、ガラス層
が剥離して金属部が露出したものを×、金属部が一部だ
け露出したものを△、金属部が露出していないものを○
とした。For adhesion, a bending test of the substrate was carried out. When the glass layer was peeled off and the metal part was exposed, x was given, Δ when the metal part was partially exposed, and ◯ when the metal part was not exposed.
And
【００２６】以上の評価に基づき総合評価を行い、その
結果を○，△，×で示した。No１〜８は他の成分を一定
として、ＳｉＯ2とＢ2Ｏ3を変化させたものである。No
９〜１５はＳｉＯ2／Ｂ2Ｏ3をほぼ一定にし、ＭｇＯ量
を変化させたものである。No１６〜１９は同じく、Ｃａ
Ｏ量を変化させたものである。No２０〜２４は同じく、
ＣａＯ量を変化させたものである。No２５〜２９は同じ
く、Ｌａ2Ｏ3量を変化させたものである。No３０〜４２
はそれぞれ、ＺｒＯ2，ＴｉＯ2，ＳｎＯ2，Ｐ2Ｏ5，Ｚ
ｎＯの影響を検討したものである。A comprehensive evaluation was carried out based on the above evaluations, and the results are shown by ◯, Δ, and ×. Nos. 1 to 8 are obtained by changing SiO 2 and B 2 O 3 while keeping other components constant. No
In Nos. 9 to 15, SiO 2 / B 2 O 3 was made almost constant and the amount of MgO was changed. No16 ~ 19 is also Ca
The amount of O was changed. No. 20-24 are the same
The amount of CaO was changed. Similarly, Nos. 25 to 29 are those in which the amount of La 2 O 3 was changed. No30 ~ 42
Are ZrO 2 , TiO 2 , SnO 2 , P 2 O 5 , and Z, respectively.
This is a study of the influence of nO.
【００２７】表から明らかなようにＳｉＯ2を増加して
いけば、耐熱性は向上するが、表面性および密着性が悪
くなる。逆にＢ2Ｏ3量を増加していくと、表面性，密着
性は向上するものの耐熱性が低下する。したがってこの
両者の兼ね合いにより、本発明ではＳｉＯ2が７〜３０
重量％、Ｂ2Ｏ3が５〜３４重量％の範囲内が好ましい。As is apparent from the table, if the SiO 2 content is increased, the heat resistance is improved, but the surface property and the adhesion are deteriorated. On the contrary, when the amount of B 2 O 3 is increased, the surface property and the adhesion are improved but the heat resistance is decreased. Therefore, due to the trade-off between the two, SiO 2 is 7 to 30 in the present invention.
Wt%, B 2 O 3 is preferably in the range of 5 to 34 wt%.
【００２８】ＭｇＯ量は結晶性と相関があり、１６重量
％以下では結晶析出が不十分で耐熱性に劣る。また５０
重量％以上では結晶が析出しやすく、ガラス溶融時に簡
単に結晶化し、均質なガラスを得ることが難しく表面粗
度も大きくなる。The amount of MgO has a correlation with the crystallinity, and if it is less than 16% by weight, the precipitation of crystals is insufficient and the heat resistance is poor. Again 50
If the content is more than 10% by weight, crystals are likely to be precipitated, and when the glass is melted, it is easily crystallized, and it is difficult to obtain a homogeneous glass, and the surface roughness is increased.
【００２９】ＣａＯ量は２０重量％以上入れると、表面
性が悪くなり好ましくない。ＢａＯ量は５０重量％以上
では、耐熱性および密着性が劣化し好ましくない。If the amount of CaO is 20% by weight or more, the surface property is deteriorated, which is not preferable. When the amount of BaO is 50% by weight or more, heat resistance and adhesion are deteriorated, which is not preferable.
【００３０】Ｌａ2Ｏ3は４０重量％以上では、耐熱性が
劣化し好ましくない。その他の添加可能な成分はＺｒＯ
2，ＴｉＯ2，ＳｎＯ2，Ｐ2Ｏ5，ＺｎＯなどが挙げられ
るが、５重量％以下までなら添加可能である。When La 2 O 3 is 40% by weight or more, heat resistance is deteriorated, which is not preferable. Other components that can be added are ZrO
2 , TiO 2 , SnO 2 , P 2 O 5 , ZnO and the like can be mentioned, but up to 5% by weight can be added.
【００３１】[0031]
【表１】 [Table 1]
【００３２】[0032]
【表２】 [Table 2]
【００３３】[0033]
【表３】 [Table 3]
【００３４】[0034]
【表４】 [Table 4]
【００３５】[0035]
【表５】 [Table 5]
【００３６】前述の製造方法に基づいて、抵抗体を形成
した圧力センサを図１に基づいて説明する。直系４０φ
mm、厚さ１００μｍの円盤状金属基材（ＳＵＳ４３０）
を前処理として脱脂・水洗・酸洗・水洗・ニッケルメッ
キ・水洗の各工程を行った後、（表１）でNo７で示した
組成のガラス粒子からなるスラリー中に浸漬して、対極
と金属基材間に直流電圧を印加することにより、金属基
材の表面にガラス粒子を被覆し、常温から８８０℃まで
２時間かけて昇温し、さらにこの温度で１０分間保持す
る焼成を行い、７０μｍの結晶化ガラス層を形成し絶縁
層とした。次に絶縁層の表面に、Ａｇ−Ｐｄ系ペースト
を所定のパターンにスクリーン印刷し、８５０℃で焼成
することにより電極を形成した。A pressure sensor having a resistor formed on the basis of the above-described manufacturing method will be described with reference to FIG. Direct 40φ
mm-shaped, 100 μm thick disc-shaped metal substrate (SUS430)
As pretreatment, degreasing, washing with water, pickling, washing with water, nickel plating, and washing with water are performed, and then immersed in a slurry composed of glass particles having the composition shown in No. 7 in (Table 1) to prepare a counter electrode and a metal. By applying a DC voltage between the base materials, the surface of the metal base material is coated with the glass particles, the temperature is raised from room temperature to 880 ° C. over 2 hours, and then the temperature is maintained at this temperature for 10 minutes. The crystallized glass layer of was formed as an insulating layer. Next, an electrode was formed by screen-printing an Ag-Pd-based paste in a predetermined pattern on the surface of the insulating layer and firing at 850 ° C.
【００３７】抵抗体ペーストの調製は、平均粒径０．１
５μｍの酸化ルテニウム、平均粒径１μｍのＰｂＯ−Ｓ
ｉＯ2−Ｂ2Ｏ3系のガラスフリットおよび、エチルセル
ロースとターピネオールを主成分とする有機バインダを
３：５：２になるように１００ｇ秤量し、これにナフテ
ン酸鉄を６ｇ添加してこれらを乳鉢で混合した後、さら
に３本ローラで十分混合した。途中、適時ブチルカルビ
トールアセテートを主成分とする希釈剤を加えて２５
℃、１０ｒｐｍの条件下でペースト粘度が２００±２５
ｋｃｐｓになるように調製した。The resistor paste is prepared with an average particle size of 0.1.
5 μm ruthenium oxide, PbO-S with an average particle size of 1 μm
100 g of an iO 2 -B 2 O 3 type glass frit and an organic binder containing ethyl cellulose and terpineol as main components were weighed in a ratio of 3: 5: 2, and 6 g of iron naphthenate was added thereto, and these were mortared. After being mixed with, the mixture was further thoroughly mixed with three rollers. On the way, add a diluent containing butyl carbitol acetate as a main component at a suitable time to add 25
Paste viscosity of 200 ± 25 under conditions of ℃, 10rpm
It was prepared to have kcps.
【００３８】このペーストを予め所定の電極を形成した
基材にスクリーン印刷し、室温で１０分間レベリングし
た後、１２０℃の恒温槽中で３０分間乾燥し、最終的に
６５０℃で焼成して厚さ３０μｍの抵抗体を形成して圧
力センサとした。This paste was screen-printed on a base material on which predetermined electrodes were previously formed, leveled at room temperature for 10 minutes, dried in a constant temperature bath at 120 ° C. for 30 minutes, and finally baked at 650 ° C. to a thickness. A resistor having a thickness of 30 μm was formed as a pressure sensor.
【００３９】（実施例２）実施例１において、ナフテン
酸鉄の代わりにオクチル酸鉄５ｇ添加したペーストを作
製した。Example 2 A paste was prepared by adding 5 g of iron octylate instead of iron naphthenate in Example 1.
【００４０】（実施例３）実施例１において、ナフテン
酸鉄の代わりにスルファミン酸鉄６．５ｇ添加したペー
ストを作製した。Example 3 A paste was prepared by adding 6.5 g of iron sulfamate instead of iron naphthenate in Example 1.
【００４１】（実施例４）実施例１において、ナフテン
酸鉛の代わりに酸化鉄，硝酸鉄，塩化鉄，クエン酸鉄，
蓚酸鉄，鉄アセチルアセトナート（Ｆｅ−ＡｃＡｃと略
す）を、それぞれ酸化鉄換算にして３ｇ添加したペース
トを作製した。Example 4 In Example 1, instead of lead naphthenate, iron oxide, iron nitrate, iron chloride, iron citrate,
A paste was prepared by adding 3 g of iron oxalate and iron acetylacetonate (abbreviated as Fe-AcAc) in terms of iron oxide.
【００４２】以上の実施例１〜３および下記の比較例に
ついて、−５０℃〜１５０℃までの抵抗値から低温側
（−５０〜２５℃）と高温側（２５〜１５０℃）のＴＣ
Ｒを測定した。さらに、０〜２０００mmＨ2Ｏの圧力を
加えたときの抵抗変化率を測定し、これをＧＦ*とし
て、結果を（表６）に示す。For the above Examples 1 to 3 and the following Comparative Examples, TC values on the low temperature side (-50 to 25 ° C.) and the high temperature side (25 to 150 ° C.) were determined from the resistance value at -50 ° C. to 150 ° C.
R was measured. Further, the rate of resistance change when a pressure of 0 to 2000 mmH 2 O was applied was measured, and this was taken as GF * , and the results are shown in (Table 6).
【００４３】[0043]
【表６】 [Table 6]
【００４４】（表６）から明らかなように本実施例は、
比較例と比べてＴＣＲが一桁低く、更に１．５倍程度の
高いＧＦ値を持つことが分かる。従って本発明により温
度特性および、センサ感度に優れた圧力センサを提供す
ることが可能となる。As is clear from (Table 6), this embodiment is
It can be seen that the TCR is one digit lower than that of the comparative example, and the GF value is about 1.5 times higher. Therefore, according to the present invention, it is possible to provide a pressure sensor having excellent temperature characteristics and sensor sensitivity.
【００４５】なお本実施例では鉄化合物の一部について
説明したが、他の鉄化合物についても同様のことが言え
ることは言うまでもない。Although a part of the iron compound has been described in this embodiment, it goes without saying that the same applies to other iron compounds.
【００４６】（比較例）平均粒径０．１５μｍの酸化ル
テニウム、平均粒径１μｍのＰｂＯ−ＳｉＯ2−Ｂ2Ｏ3
系のガラスフリットおよび、エチルセルロースとターピ
ネオールを主成分とする有機バインダを３：５：２にな
るように秤量し乳鉢で混合した後、三本ローラで混合し
た。途中、適時ブチルカルビトールアセテートを主成分
とする希釈剤を加えて、ペースト粘度を２００±２５ｋ
ｃｐｓ（２５℃、１０ｒｐｍ）となるように抵抗体ペー
ストを調製した。このペーストを電極を形成した基材に
スクリーン印刷し、室温で１０分間レベリングした後１
２０℃の恒温槽中で３０分間乾燥し、最終的に６５０℃
で焼成して厚さ３０μｍの抵抗体を形成して圧力センサ
とした。Comparative Example Ruthenium oxide having an average particle diameter of 0.15 μm and PbO—SiO 2 —B 2 O 3 having an average particle diameter of 1 μm
The glass frit of the system and the organic binder containing ethyl cellulose and terpineol as main components were weighed in a ratio of 3: 5: 2, mixed in a mortar, and then mixed by a triple roller. On the way, a diluent containing butyl carbitol acetate as a main component is added at an appropriate time to increase the paste viscosity to 200 ± 25 k.
The resistor paste was prepared so as to have cps (25 ° C., 10 rpm). This paste was screen-printed on the substrate with electrodes and leveled at room temperature for 10 minutes.
Dry in a constant temperature bath at 20 ℃ for 30 minutes and finally at 650 ℃
And a resistor having a thickness of 30 μm was formed to obtain a pressure sensor.
【００４７】[0047]
【発明の効果】以上のように本発明の抵抗体ペーストお
よびこれを用いた圧力センサは、鉄化合物を抵抗体ペー
ストに加えることによりＴＣＲが小さく、ＧＦが高い高
品質なセンサを提供することが可能となる。As described above, the resistor paste of the present invention and the pressure sensor using the same can provide a high-quality sensor having a low TCR and a high GF by adding an iron compound to the resistor paste. It will be possible.
【図１】（Ａ），（Ｂ）は本発明の一実施例における圧
力センサの平面図および断面図1A and 1B are a plan view and a sectional view of a pressure sensor according to an embodiment of the present invention.
１ 金属基体 ２ 絶縁層 ３ 抵抗体 ４ 電極 1 Metal Substrate 2 Insulating Layer 3 Resistor 4 Electrode
───────────────────────────────────────────────────── フロントページの続き (72)発明者 吉田 昭彦 大阪府門真市大字門真1006番地 松下電器 産業株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akihiko Yoshida 1006 Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd.
Claims (8)
電性物質となる材料と、ガラスフリットと、有機ビヒク
ルおよび希釈剤と、鉄化合物とから構成した抵抗体ペー
スト。1. A resistor paste comprising a conductive substance or a material which becomes a conductive substance by firing, a glass frit, an organic vehicle and a diluent, and an iron compound.
徴とする請求項１記載の抵抗体ペースト。2. The resistor paste according to claim 1, wherein the iron compound is organic fatty acid iron.
チル酸鉄であることを特徴とする請求項２記載の抵抗体
ペースト。3. The resistor paste according to claim 2, wherein the organic fatty acid iron is iron naphthenate or iron octylate.
を特徴とする請求項１記載の抵抗体ペースト。4. The resistor paste according to claim 1, wherein the iron compound is iron sulfamate.
塩化鉄，クエン酸鉄，蓚酸鉄、鉄アセチルアセトナート
から選択される１種類以上の化合物を含むことを特徴と
する請求項１記載の抵抗体ペースト。5. The iron compound is at least iron oxide, iron nitrate,
2. The resistor paste according to claim 1, containing one or more compounds selected from iron chloride, iron citrate, iron oxalate, and iron acetylacetonate.
されかつ、絶縁基板変形に伴って電気抵抗が変化する抵
抗体と、前記抵抗体の抵抗変化を検出する電極とからな
り、前記抵抗体を酸化ルテニウムと鉄化合物とガラスフ
リットと有機ビヒクルおよび希釈剤とからなる抵抗体ペ
ーストにより構成したことを特徴とする圧力センサ。6. An insulating substrate, a resistor formed on the surface of the insulating substrate and having an electric resistance that changes with the deformation of the insulating substrate, and an electrode for detecting a resistance change of the resistor, A pressure sensor characterized in that the body is composed of a resistor paste comprising ruthenium oxide, an iron compound, a glass frit, an organic vehicle and a diluent.
形成したものであることを特徴とする請求項６記載の圧
力センサ。7. The pressure sensor according to claim 6, wherein the insulating substrate is a metal substrate having an insulating layer formed on the surface thereof.
ｇＯ：１６〜５０ｗｔ％、ＳｉＯ2：７〜３０ｗｔ％，
Ｂ2Ｏ3：５〜３４ｗｔ％、ＢａＯ：０〜５０ｗｔ％、Ｌ
ａ2Ｏ3：０〜４０ｗｔ％、ＣａＯ：０〜２０ｗｔ％、Ｐ
2Ｏ5：０〜５ｗｔ％、ＭＯ2：０〜５ｗｔ％（但し、Ｍ
はＺｒ，Ｔｉ，Ｓｎのうち少なくとも一種の元素）の組
成からなる結晶化ガラス層であることを特徴とする請求
項７記載の圧力センサ。8. The metal substrate is SUS430 and the insulating layer is M
gO: 16 to 50 wt%, SiO 2 : 7 to 30 wt%,
B 2 O 3: 5~34wt%, BaO: 0~50wt%, L
a 2 O 3: 0~40wt%, CaO: 0~20wt%, P
2 O 5 : 0-5 wt%, MO 2 : 0-5 wt% (however, M
The pressure sensor according to claim 7, wherein is a crystallized glass layer made of a composition of at least one element of Zr, Ti, and Sn.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5080488A JPH06294692A (en) | 1993-04-07 | 1993-04-07 | Resistor paste and pressure sensor employing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5080488A JPH06294692A (en) | 1993-04-07 | 1993-04-07 | Resistor paste and pressure sensor employing the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06294692A true JPH06294692A (en) | 1994-10-21 |
Family
ID=13719687
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5080488A Pending JPH06294692A (en) | 1993-04-07 | 1993-04-07 | Resistor paste and pressure sensor employing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06294692A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000047217A (en) * | 1998-07-24 | 2000-02-18 | Sharp Corp | Liquid crystal display device |
-
1993
- 1993-04-07 JP JP5080488A patent/JPH06294692A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000047217A (en) * | 1998-07-24 | 2000-02-18 | Sharp Corp | Liquid crystal display device |
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