JPH10144503A - Resistance-type temperature sensor and its manufacture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To increase the heat resistance and the shock resistance by forming a substrate by a mutually laminated construction of conductor materials mainly of a metallic silicide such as a molybdenum silicide, etc., and insulating ceramic materials having alumina as their main ingredients. SOLUTION: Concerning to a resistance-type temperature sensor, an insulating part 3 composed by laminating insulating materials is interposed between connecting terminals 1 and 2 composed by laminating resistance materials, and conductive parts 4 and 5 are connected to these connecting terminals 1 and 2, and a temperature sensing unit 6 is connected between the conductive parts 4 and 5. Besides, protective layers 7 and 8 are provided on the top and underside surfaces of the temperature sensing unit 6. And individual thick-film layers are made into a rectangular shape by combining resistance materials composed of 90vol.% of molybdenum silicide and 10vol.% of alumina, and insulating material having a composition containing 3wt.% of magnesia and 0.3wt.% of silica added to a fundamental composition composed of 90vol.% of alumina and 10vol.% of mullite in addition, into respective patterns. Consequently, it becomes possible to obtain a sensor having a high heat resistance and a high environment resistance.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resistance type temperature sensor for detecting the temperature of a high-temperature atmosphere such as automobile exhaust gas, an oil stove, and a gas stove.

[0002]

2. Description of the Related Art In a temperature sensor for detecting a high temperature in a short time, it is required that the temperature sensor be excellent in heat resistance, environment resistance, thermal shock resistance and small in heat capacity. In other words, even if the temperature sensor is exposed to the high temperature for a long period of time, the temperature sensor is unlikely to undergo chemical change, and has sufficient corrosion resistance to corrosive gases such as sulfur oxides present in automobile exhaust gas and fuel combustion gas. Is required.

Conventionally, a thermocouple sensor or a resistance type temperature sensor has been used as a sensor for detecting a high temperature.
There is no one that has quick response and excellent heat resistance and environmental resistance. Therefore, when a temperature-sensitive material that does not have sufficient heat resistance and environmental resistance is used, its surface is coated with a heat-resistant and environment-resistant material.

In general, in applications in which a high temperature is detected in a short time, a temperature sensor may be installed in an environment where there is a sudden change in temperature, and the temperature is detected. Therefore, the temperature sensor has excellent thermal shock resistance. Must be composed of material. Also,
In order for the temperature of the temperature sensing section to follow the temperature change of the environment in a short time, the heat capacity of the temperature sensing section needs to be as small as possible.

Heretofore, a heat-resistant metal or metal compound such as tungsten (W) or platinum (Pt) has been used as a material of the temperature-sensitive part, but a heat-resistant metal such as tungsten or platinum is thermally expanded. When a ceramic having a small thermal expansion coefficient is used for a container or the like because of its large coefficient, the reliability is low in terms of thermal shock resistance.

On the other hand, a resistance type temperature sensor in which a thermistor made of a metal oxide is used in place of metal as a material of a temperature sensing part and a thermistor layer is formed on a ceramic substrate is disclosed in Japanese Unexamined Utility Model Publication No.
Japanese Patent Application Laid-Open No. Hei 7-190 discloses a temperature sensor in which a cermet, which is a mixture of metal and ceramic, is used and a cermet layer is formed on a ceramic substrate.
No. 863, all of which are 1,1.
Does not have heat resistance at a temperature of 000 ° C. or higher.

In order to improve the responsiveness of the measurement result of the temperature sensor to the temperature, it is necessary to secure the temperature followability by reducing the heat capacity of the temperature sensing part. Then, in order to reduce the heat capacity of the temperature sensing part, the shape and size of the temperature sensing part may be reduced. However, when a temperature sensor is used in a harsh environment such as an automobile engine, the mechanical strength to withstand vibration and impact during operation of the device and the assembling of the temperature sensor to such a device are strong. Therefore, mechanical strength that does not hinder the assembly process is required. However, in a temperature sensor formed by forming a thermistor layer or a cermet layer on a ceramic substrate, the temperature-sensitive portion is formed on a ceramic substrate that requires a certain size, so that the entire temperature-sensitive portion is formed. There is a limit to miniaturization of the shape and dimensions, and thus a limit to the reduction of heat capacity. As described above, in the related art, no temperature sensor has been able to detect the temperature in a short time over a temperature range from room temperature to a high temperature of 1,000 ° C. or more.

[0008]

SUMMARY OF THE INVENTION The invention of the present application is capable of detecting a temperature within a short time of 5 seconds or less in a temperature range from room temperature to about 1,000 ° C. to about 1,300 ° C. An object of the present invention is to provide a resistance-type temperature sensor that has excellent resistance and environmental resistance and can withstand long-term use.

[0009]

In order to solve the above problems, in the present application, a metal silicide, which is a conductive ceramic having a thermal expansion coefficient as low as that of alumina used as an insulating substrate, is used as a temperature-sensitive resistor. Further, a resistance type temperature sensor in which a temperature-sensitive resistor circuit is formed by laminating a large number of metal silicide temperature-sensitive resistor layers and alumina thick film layers used as a conductor is provided.

As the metal silicide used for the temperature-sensitive resistance material, molybdenum silicide having the same thermal expansion coefficient as that of an alumina insulating substrate is optimal, and an insulator such as alumina or mullite is mixed with the temperature-sensitive resistance material. Thereby, the resistance value can be adjusted. Further, in order to obtain a predetermined resistance value of the temperature sensing portion, an insulating material such as alumina or mullite is mixed with a resistance material to adjust the resistance value, or a plurality of resistance layers are connected by a conductor connection portion such as a through hole. Further, the temperature-sensitive resistor portion of the laminate is formed thinner than other portions.

A sheet method, a printing method, or the like is used as a method of manufacturing a substrate having a laminated structure. In any method, a paint-like material is dried into a so-called thick film, and the thick film is formed by lamination.

[0012]

According to the temperature sensor of the present invention, the temperature-sensitive part material is mainly composed of a metal silicide such as molybdenum silicide having a small coefficient of thermal expansion. Even in combination, sufficient thermal shock characteristics can be obtained. Further, by forming the base with an alternate laminated structure of a conductor material mainly composed of a metal silicide such as molybdenum silicide and an insulating ceramic material mainly composed of alumina, as a result, an insulating ceramic material mainly composed of alumina is obtained. It is possible to realize a substrate having excellent thermal shock characteristics that hardly impairs the thermal shock characteristics of a conductive material mainly composed of a metal silicide such as molybdenum silicide having more excellent thermal shock characteristics.

[0013]

EXAMPLES In describing specific examples of the present invention,
The entire invention will be described. [Basic Structure] The structure of the resistance type temperature sensor of the present invention is formed in a laminated structure. Due to this, if it is necessary to make the structure of the temperature sensitive part thinner than the thickness of the surrounding body,
Since the structure of the present invention can be easily formed by punching and laminating a portion of the material forming the base in the step of forming the temperature sensor element and punching out the portion located in the temperature-sensitive portion, it can be manufactured in almost the same manufacturing process. It is.

The device of the present invention has a structure in which two types of thick films are laminated in the same layer. Such a structure forms a thick film by a sheet method in which there is little variation in the thickness of the entire film.

The temperature sensing portion is formed by a circuit of a temperature sensing resistor. A temperature sensing resistor is constituted by a thick film layer, and an insulating thick film layer is provided between the temperature sensing resistor thick layers. A temperature-sensitive resistor circuit configured by connecting the temperature-sensitive resistor thick film layers to each other with a conductor, and a pattern of the temperature-sensitive resistor printed by screen printing on the insulator thick film, and a plurality of stacked layers. There is a temperature-sensitive resistor circuit formed by connecting the temperature-sensitive resistor patterns to each other by through holes.

In order to realize the function of the resistance type temperature sensor of the present invention, a connecting portion for transmitting a measurement signal to an external processing circuit and a structure for holding and mounting the resistance type temperature sensor are required. However, since the resistance type temperature sensor of the present invention is intended to measure high temperatures, these structures naturally require design specifications taking heat resistance into consideration.

In the resistance type temperature sensor of the present invention, a terminal connection portion for external connection is provided at an end opposite to the temperature sensing portion of the temperature sensor element, and this portion is plated with nickel (Ni). Can be connected to the lead member, and the electrical connection between the resistance type temperature sensor element and the lead member can be made by soldering with silver solder or by welding to provide a connection having heat resistance and mechanical strength. Can be realized. In addition, by using a lead member formed by baking palladium (Pd) paste on a lead member or a ceramic substrate, a connection portion having heat resistance and mechanical strength can be obtained.

In the resistance-type temperature sensor of the present invention, the resistance-type temperature sensor element is inserted into a heat-resistant tube or base such as a ceramic tube containing alumina as a main component, and is filled with heat-resistant material such as ceramic cement. The element is held and fixed with a material. With this structure, necessary heat resistance is realized.

[Material] The resistance type temperature sensor element of the present invention comprises a temperature sensing part for detecting temperature, a connection part for connecting the element to an external circuit, and a conductive part for electrically connecting the temperature sensing part and the connection part. Is done. These temperature-sensitive parts, conductive parts and connection parts are all formed by forming ceramic in a laminated structure, and a resistance material in the laminated structure and constituting the temperature-sensitive part,
The conductive material forming the conductive portion and the connection portion needs to be electrically separated appropriately by an insulating material in order to form an electric circuit. Therefore, in the present invention, a ceramic temperature-sensitive resistance material, a ceramic conductive material, and a ceramic insulating material are used.

The insulation resistance required for the insulating material is desirably 100 MΩ or more and at least 1 MΩ. The insulating material made of alumina is 10 ¹⁰ Ω ·
Since it exhibits a specific resistance of about cm, the dimensions of the temperature-sensitive portion are representative dimensions of the present invention, which will be described later: width = 1.2 mm, length = 6 m
When m and the layer thickness are 35 μm, an interlayer insulation resistance of 3 × 10 ¹² Ω is obtained, and it can be said that this is an insulator material suitable for use in the present invention.

The resistance value of the temperature-sensitive resistor portion is such that if the resistance value ratio with the insulator is approximately 1,000, the leakage current value is 1/1000.
Therefore, it is possible to measure the temperature with practical accuracy. If the resistance value of the temperature-sensitive resistor is several tens KΩ or more,
The measurement current is very small at a practical measurement voltage, and there is a difficulty in maintaining the measurement accuracy. For this reason, it is desirable that the resistance value of the temperature-sensitive resistor section be several KΩ or less. in this way,
In the case of realizing a resistance value of, for example, 1 KΩ with the above-described typical temperature-sensitive portion dimensions of the present invention, the specific resistance of the resistor is about 0.3 Ω · cm. This specific resistance can be obtained by setting the composition of molybdenum silicide, one of the metal silicides, to 30% by volume or more based on alumina. In order to obtain a predetermined resistance value of the temperature sensing portion, the resistance value can be adjusted by mixing an insulating material such as alumina or mullite with a resistance material.

The resistance value of the conductive portion and the connection portion is similar to that of the insulating portion.
/ 1,000, it is possible to obtain a resistance value, for example, several Ω, at which the temperature can be measured with practical accuracy. The specific resistance for realizing a resistance value of, for example, 1 Ω in the above-described typical temperature-sensitive portion dimensions of the present invention is about 3 × 10 ⁻⁴ Ω · cm. This specific resistance can be obtained when the composition of molybdenum silicide is 50% by volume. If the composition of molybdenum silicide is 50% by volume or more,
It is possible to obtain a resistance value of several Ω or less required for the conductive portion and the connection portion. The material of the conductive part may be made of the same material as the resistor of the temperature-sensitive part, but it is preferable that the resistance of the conductive part is lower than the resistance of the temperature-sensitive part.

Further, although thermal shock resistance is not so excellent when alumina alone is used, when a laminate is formed by combining molybdenum silicide having the same coefficient of thermal expansion as alumina used as an insulating material with alumina. Sufficient thermal shock resistance can be ensured.

Although the main materials used in the present invention are molybdenum silicide and alumina, it is necessary to control the sintering reaction during firing in a desirable state in order to form a dense sintered body. In a metal silicide such as molybdenum silicide, a metal component such as molybdenum (Mo) evaporates and volatilizes due to decomposition, and silica (SiO ₂ ) which is an oxide of silicon (Si) as another compound component remains. The specific resistance of the conductor material varies depending on the amount of molybdenum evaporating. Therefore, the resistance value control requires strict management of the process conditions.

An insulator containing alumina as a main component is mixed for the purpose of controlling the specific resistance of the conductor material. Mullite (3Al ₂ O ₃ .2SiO ₂ ) is mixed with the remaining silica and alumina.
A system of compounds is produced. Even if a conductor material is formed without containing mullite as a raw material, there is no problem if strict control of process conditions is performed in order to form the temperature sensor of the present invention, but the inclusion of mullite suppresses the decomposition of molybdenum silicide. And the resistivity of the conductive material can be more easily controlled.

If magnesia (MgO) is contained in the component, cordierite (2MgO.Al ₂ O _3.
A 5SiO ₂ ) -based compound is generated, whereby the decomposition of molybdenum silicide can be suppressed as in the case of mullite, and the specific resistance of the conductive material can be more easily controlled. However,
If the mullite content exceeds about 15% by volume and the magnesia content exceeds about 5% by weight, sintering of the conductive material is hindered, and it becomes difficult to obtain a dense sintered body. The amount has an upper limit. In this case, mullite and magnesia may coexist or may be contained independently.

The insulator material needs to have strong adhesiveness to the conductor material. Therefore, the same composition as the insulator material contained in the conductor material is desirable. By containing silica, the adhesiveness is further improved, and a more preferable element body can be formed. However, when the content exceeds approximately 0.5% by weight, sintering of the insulator is hindered, and it becomes difficult to densify the sintered body.

Since the temperature-sensitive resistor portion and the conductive portion are covered with these dense ceramics, stability to the environment can be maintained. Further, after forming the temperature sensor element, by forming a fired film containing alumina or silica as a main component on the surface thereof, environmental resistance can be improved. This calcined film is made of alumina or silica by CVD (Chemical Vapou).
r Deposition), or by immersing and adhering to these slurries followed by firing.

[Manufacture of Materials] The properties required for the raw materials when manufacturing the ceramic laminate are that drying properties and viscosity are appropriate and that cracks and drying unevenness do not occur when forming a thick film. That there is no problem in the smoothness of the surface. In order to realize the desired properties, the concentration of the coating material, the type and the amount of the binder to be added are appropriately selected according to the powder characteristics of the material. In addition, when it is necessary to form the elementary body by a sintering reaction in the firing step after forming the laminate, it is desirable to realize the optimal particle size distribution and the degree of dispersion at the time of producing the coating material of the material. .

Generally, in the case of a hardly sinterable material such as a metal silicide used in the present invention, the activity during sintering is increased by sufficiently pulverizing the material, and the lower the sintering activity, the lower the sintering activity. Sintering at the sintering temperature becomes possible. However, the manufacturing conditions of the material for achieving the optimum particle size distribution and the degree of dispersion and the optimum manufacturing conditions of the coating material are often different, so that appropriate powder characteristics are obtained before manufacturing the coating material. It is necessary to pre-process the material.

In the case of the metal silicide used in the present invention, the metal and silicon constituting the metal silicide are easily oxidized if the pulverization treatment for enhancing the activity is performed in the air. In many cases, the pretreatment conditions generally include a higher solvent concentration than the paint production conditions, that is, a lower slurry concentration. Therefore, in the pretreatment step, it is necessary to dry the material after the pulverization, and then to prepare the material constituting the paint again so as to have a predetermined paint composition.

In the case of the metal silicide used in the present invention, as described above, in the handling of the material after the pretreatment, in order to prevent oxidation, the material is handled in a non-oxidizing atmosphere such as vacuum or nitrogen or a solvent. If any residue remains, care must be taken to prevent ignition due to heat generated by oxidation. According to the method for producing a material of the present invention, the above-mentioned problems are solved and the steps are shortened.

That is, after pulverizing under the optimal pulverizing conditions, a solvent is partially removed by a concentrator such as a vacuum deaerator or a filter press, and then a coating material such as a binder and a plasticizer which is insufficient is prepared and mixed. To produce paints of the following properties: As a result, finely pulverized material powder having high activity is handled as a solvent slurry, so that oxidation in the air and ignition due to oxidation can be prevented, and the drying process and storage for preventing oxidation are performed. The steps can be omitted. Further, since the slurry viscosity in the pulverization step can be made lower than the viscosity of the paint, the material can be recovered with a high yield when the material is taken out from a dispersion device such as a ball mill or a media mill, and when the material is separated from the medium. .

[Firing Conditions] Since the element laminate of the present invention contains a so-called hard-to-sinter metal silicide as a constituent, it is fired at a temperature of at least 1,200 ° C., preferably 1,400 ° C. or more. There is a need. The metal silicide is 2
Since it is oxidized in the air even in a low temperature range of about 00 degrees, it is necessary to fire in a non-oxidizing atmosphere. The non-oxidizing atmosphere is preferably an argon gas atmosphere, and the nitrogen atmosphere is not preferable because the metal silicide tends to be nitrided, and as a result, the temperature characteristics of the resistance change.

Since the metal silicide is easily oxidized in the air, the oxidation of the metal silicide lowers the stability of its performance under the actual use condition of the temperature sensor element of the present invention, and It needs to be suppressed. For this purpose, it is desirable to increase the density of the sintered body after sintering as much as possible. In order to increase the density of the sintered body after the sintering, a part of the heating process, or a part of the heating process and a part of the stable part, is set to a degree of vacuum of 50 Torr or more, preferably 10 Torr or more. The density of the sintered body can be increased. The effect of vacuuming a part of the firing process is that when sintering progresses and the pores of the crystal structure become closed pores due to densification, when the degree of vacuum in the firing atmosphere is high, the inside of the closed pores also When the degree of vacuum is high and the densification further proceeds, the closed pores disappear and high density is achieved.

When the degree of vacuum in all the firing steps is high,
Evaporation of components, especially silica, is remarkable and is not preferred. Also,
Firing by applying pressure during the firing process is preferable because it promotes densification. The pressure firing may be so-called hot press firing, HIP (Hot Isostatic Pressing) firing, or any other pressure firing. However, since pressure firing is more expensive than normal pressure firing, if the desired densification can be achieved by normal pressure firing, it does not go beyond that.

Firing at a temperature exceeding 1,800 ° C. is close to the melting point of a ceramic base containing alumina as a main component. Specifically, a part of the ceramic base is melted or evaporated to disappear, or metal silicide is used. It is difficult to react with a substance and form a target structure, which is not preferable.

[Manufacture of Laminated Body] The thick film layer constituting the laminated body is formed by applying a coating of a material having predetermined characteristics on a polyethylene film and drying it to remove unnecessary portions. A thick film layer having a partially different characteristic is formed by embedding a thick film layer of a material having the characteristics described above in a portion where unnecessary portions are removed, and the thick film layers thus formed are sequentially laminated. Manufactured by Further, it can also be manufactured by applying a paint thick film of a material having predetermined characteristics on a polyethylene film, drying, cutting to a required size and combining. Further, when the accuracy of the thickness dimension is not required, the thick film layer can be formed by screen printing.

The printing of the temperature-sensitive resistor pattern on the insulator thick film may be performed at any stage, that is, after the polyethylene film is peeled from the insulator thick film or after the conductor thick film is embedded in the insulator thick film. However, in the temperature-sensitive element of the present invention, it is necessary to connect the temperature-sensitive resistor pattern to the conductor thick film in order to allow a part of the conductor thick film to function as a conductive portion of the temperature-sensitive resistor circuit. Therefore, it is necessary to print the temperature-sensitive resistor pattern on the conductor thick film. Therefore, it is desirable to print the temperature-sensitive resistor pattern after embedding the conductor thick film in the insulator thick film.

Incorporating a printing process into the laminating process not only complicates the apparatus, but also necessitates changing the height position of the printing surface as the number of thick film laminations increases. It is desirable to do this after printing of the thermal resistor pattern is completed. With this configuration, the printing apparatus and the stacking apparatus can be separated from each other, so that the structure of the entire apparatus is simplified.

Next, the configuration of the temperature sensor according to the embodiment of the present invention will be described with reference to the drawings. [Embodiment 1] FIG. 1 is a diagram showing a laminated structure of a resistance type temperature sensor element according to Embodiment 1 of the present invention.
The pattern is shown as 100mm long and 80m wide
m, 35 μm thick and 9 types of thick film layers are ABCC-
(D-E-D-F-D-F-D-F-D-F-G-H-I-
HGDFDEDFDEDED) -C-
A total of 29 layers are laminated in the order of BA, and the temperature sensor layer is composed of 21 thick films shown in parentheses excluding the thick films of the patterns A, B, and C at both ends. . Note that the partition between the same layers shown in FIG. 1 has disappeared after sintering. In the embodiment shown in FIG. 1, the number of layers is reduced to facilitate the description of the invention. Actually, the resistance type temperature sensor element having 89 layers shown in FIG. used.

In the resistance type temperature sensor laminated in such a structure, connection terminals 1 and 2 in which a resistance material is laminated are formed with an insulating portion 3 in which an insulation material is laminated, and these connection terminals 1 and 2 are formed. 2, conductive portions 4 and 5 are connected, and a temperature sensing portion 6 is connected between the conductive portions 4 and 5. In addition, protective layers 7 and 8 are provided on the upper and lower surfaces of the temperature sensing unit 6.

The conductive portion 4 is formed by the resistor 9 of the pattern B and the resistor 10 of the pattern C, the conductive portion 5 is formed by the resistor 10 of the pattern C and the resistor 9 of the pattern B, and the temperature sensing portion 6 is formed by the pattern D Resistor 11, pattern E resistor 12, pattern D resistor 11, pattern F resistor 13, pattern D resistor 11, pattern E resistor 12, pattern D resistor 11, pattern F resistor Resistor 13, Resistor 11 of Pattern D, Resistor 1 of Pattern G
4, resistor 15 of pattern H, resistor 1 of pattern I
6, resistor 15 of pattern H, resistor 1 of pattern G
4, resistor D of pattern D, resistor 1 of pattern F
3, resistor D of pattern D, resistor 1 of pattern E
2, resistor D of pattern D, resistor 1 of pattern F
3, resistor D of pattern D, resistor 1 of pattern E
2, formed by the resistor 11 of the pattern D.

Each of the thick film layers shown in FIG. 2 is composed of 90% by volume of molybdenum silicide and 10% by volume of alumina. 10% by volume mullite base composition with 3 more
The insulating materials indicated by white backgrounds in the figure, which are composed of a composition to which magnesia and 0.3% by weight of magnesia are added, are A to I
Is formed in a rectangular shape in combination with the pattern shown as.

A method for manufacturing the temperature sensor according to the first embodiment will be described. (1) Preparation of Material Molybdenum silicide having a particle size of 2 μm
A volume%, alumina having a particle size of 0.4 μm is made up to a composition of 10 volume%, and these raw materials, a methacrylic resin as a binder, toluene and ethanol as a solvent, and BPBG as a plasticizer are put into a pot made of alumina porcelain, and a dispersion medium. Was dispersed using alumina balls for 15 hours to obtain a resistor paint.

As the insulator material, 90% by volume of alumina having a particle size of 0.4 μm, 10% by volume of mullite having a particle size of 0.4 μm, 3% by weight of magnesia having a particle size of 0.4 μm, and 0.3% by weight.
4 μm silica was made into a composition of 0.3% by weight, and, like the resistor material, these raw materials, methacrylic resin as a binder, toluene and ethanol as a solvent, and BPBG as a plasticizer were put into an alumina porcelain pot and dispersed. Disperse for 15 hours using alumina balls as media,
Obtain insulation paint.

(2) Production of Sheet The resistor paint and the insulator paint produced in the above process were adjusted on a polyethylene film by adjusting the height of a doctor blade so that the thickness after drying was 35 μm by a sheet coater. Then, a thick film having a width of 80 mm is formed to obtain a resistor sheet and an insulator sheet. The formed resistor and insulator sheet are each cut into a length of 100 mm according to the stack size at the time of manufacturing a laminate.

(3) Production of Thick Film Layer Each thick film layer constituting the temperature sensor is composed of a resistor and an insulator. FIG. 3 shows a method of manufacturing a laminate by forming the thick film layer indicated by C in FIG. 2 on the thick film layer also indicated by D.

(A) shows a resistor sheet manufactured in the above-mentioned sheet manufacturing, and a resistor thick film 22 is applied on a polyethylene film 21. The cuts 23 and 24 shown by broken lines are made in the resistor thick film 22, and the resistor thick films between them are peeled off according to the cuts 23 and 24, leaving the resistor thick films 25 and 26. Get the material to be.

On the other hand, (c) shows an insulator sheet produced in the above-mentioned sheet production, in which an insulator thick film 28 is applied on a polyethylene film 27. By making cuts 29 and 30 shown by broken lines in the insulator thick film 28 and leaving the insulator thick film 31 in accordance with the cuts 29 and 30, the outer insulator thick film is peeled off, as shown in FIG. Get the material.

Next, as shown in (e), the upper and lower sides of the resistor sheet shown in (c) are turned over, and the thick film layer 33 already formed as a pattern D on the polyethylene film 32 is formed. After applying a pressure of 0.1 kg / cm ² for 10 seconds, the polyethylene film 21 is removed.

Further, as shown in (f), the insulator material shown in (d) is turned upside down and the insulator material is laminated between the resistor materials 25 and 26 laminated on the thick film layer D. The laminate is aligned and positioned so that the material 31 enters, a pressure of 0.1 kg / cm ² is applied for 10 seconds, and then the polyethylene film 27 is removed to obtain a laminate shown in (g). By performing a predetermined lamination according to the process, FIG.
Are obtained.

(4) Production of Laminate After the predetermined lamination is completed, the laminate is removed from the stack substrate and put into a pressing mold, and a pressure of 1.5 kg / cm ² is applied for 300 minutes.
Add for 2 seconds and pressurize.

(5) Cutting of the laminate Next, the laminate is attached to a cutting substrate to which a double-sided tape has been attached, and cut with a diamond blade at a pitch of 2.4 mm to obtain a laminate having a length of 50 mm and a width of 3 mm. .

(6) Production of Sintered Body The cut laminate is mounted on a boron nitride substrate, debindered at 600 ° C. for 2 hours in nitrogen gas, and then removed for 1 hour in argon gas for 1 hour. Calcination at 750 ° C., and 1.6 hours at 2,000 atmospheres argon gas for 2 hours.
HIP baking is performed at 50 ° C. After firing, 2 in air
A surface oxidation treatment is performed at 1,430 ° C. for a time.

(7) Connection Terminal Processing After the surface oxidation treatment, the stacked end face and the upper end member of the connection terminal section 1 and the stacked end face and the lower end member of the connection terminal section 2 shown in FIG.

Next, these connection terminals 1 and 2 are printed with a palladium catalyst for nickel plating, dried, heat-treated, and subjected to nickel electroless plating. FIG. 5A shows the resistance-type thermosensitive element body thus obtained. Note that this resistive thermosensitive element body is not the resistive thermosensitive element body shown in FIG. 1 but a thick film of the pattern shown in FIG. -D-F-D-E-D-F-D-
E-D-F-D-F-D-F-D-F-D-F-D-F-F-D-E
-D-F-D-F-D-F-D-F-D-F-F-D-F-
DFDEDFDHHIGHGH
-I-H-G-F-D-F-D-F-D-F-D-E-D-
F-D-E-D-F-D-F-D-F-F-D-F-E-D-F-F
-D-E-D-F-D-F-D-F-F-D-F-E-D-F-
DED) -CBA in the order of 89 layers.

(8) Assembly / Processing After cleaning and drying the connection terminals 1 and 2 on which the Ni electroless plating has been performed, the lead members 35 and 3 shown in FIG.
The connection terminals 1 and 2 of the resistive thermosensitive element body are held between the connection portions 37 and 38 of No. 6 and brazed with a nickel plating portion and silver braze.

The resistance type thermosensitive element body to which the lead members 35 and 36 are connected is inserted into an alumina tube 39 shown in FIG. 5 (c), and a ceramic cement 40 as shown in FIG. 5 (d). And dried at 90 ° C. for 0.5 hour.
Heat treatment at 0 ° C. for 2 hours to cure. [Embodiment 2] FIGS. 6A and 6B are schematic structural views of a resistance type temperature sensor element body according to Embodiment 2 of the present invention, FIG. 6B is a laminated structure similar to FIG. 1, and FIG. 2 shows patterns J and K of a thick film body adopted in the above. These thick film patterns J and K are obtained by forming openings 41 and 42 in the thick film patterns A and B shown in FIG. 2, respectively.

In the resistance type temperature sensor element body shown in FIG. 6, these 11 types of thick film layers are formed by JKKJKKJKK.
-JKKJK- (ABEDFDDDED
-I-H-G-H-I-D-E-D-F-D-F-D-E-B-
A) It is constituted by laminating a total of 41 layers in the order of -KJKJKKKJKKJKJ, and ten thick films each having patterns J and K at both ends. The temperature-sensitive portion 43 is constituted by the 21 thick films shown in parentheses except for the parentheses, and a protective layer of pattern B is provided on the outermost portion of the temperature-sensitive portion 43,
Openings 44 and 45 are formed above and below the temperature sensing portion 43 by the openings 41 and 42 formed in the thick film patterns J and K.

By adopting such a structure, the thickness of the temperature-sensitive portion can be reduced even if the protective layer is thickened in order to secure the strength. Can be The manufacturing method and the measurement results will be described below, but the description of the parts common to the first embodiment will be omitted, and only the parts different from the first embodiment will be described.

A resistance material and an insulator material are prepared by the same composition and method as in Example 1 except that the composition of the resistance material is 40% by volume of molybdenum silicide and 60% by volume of alumina.

In manufacturing the laminate, a plurality of holes for forming the holes 41 and 42 are punched out in advance in the thick film layer indicated by the patterns A and B in FIG. The formed thick film layers A to K are laminated in a predetermined order according to the method described with reference to FIG. 3 to obtain a laminate. This laminate was placed in a pressing mold, and a pressure of 1.5 kg / cm ² was applied for 300 minutes.
After adding for 2 seconds, cut at a pitch of 4.8mm and length 50m
m, a laminate having a thickness of 3 mm is obtained.

The laminated body after cutting is placed in a nitrogen gas at 600 ° C.
And then baking at 1700 ° C. for 2 hours in an argon gas, and further firing at 1,650 ° C. for 2 hours in an argon gas at 2,000 atm by the HIP method, followed by 1 hour in the air. The surface oxidation treatment is performed at 400 ° C. for 1 hour.

Third Embodiment FIG. 7A shows a third embodiment of the present invention.
FIG. 7 shows the laminated sectional structure of the resistance type temperature sensor element body of FIG.
FIG. 8B shows an exploded structure, and FIG. 8 shows a pattern of a thick film used. The laminate shown in FIG. 7A has a length of 100 mm, a width of 80 mm, and a thickness of 35 μm as shown in FIG.
m from the top, JKJKJ
-K-J-K-J-K- (A-L-M-L-M-N-O
-N-M-L-M-D-A-)-K-J-K-J-K-J
-KJKJ in this order. Here, a temperature-sensitive resistor is formed by printing on the thick film pattern shown in parentheses. FIG.
The partition between the same layers shown in (a) has disappeared after sintering.

This resistance type temperature sensor element body is shown in FIG.
As shown in (b), the upper protection part 51 and the temperature sensing part 52
And the lower protection portion 53 are overlapped with each other,
The temperature-sensitive resistor of the pattern P is printed on the thick film of the pattern L constituting the temperature sensing part 52 and the thick film of the pattern A disposed at the uppermost part in the thick film constituting the lower protective layer 53. ing.

In the upper protection portion 51 and the lower protection portion 53, ten thick film layers of the pattern J and ten thick film layers of the pattern K are alternately laminated, and the upper and lower ends of the thick film layers of the pattern J are formed. A part of the upper protection part 51 and a part of the lower protection part 53 are formed by an opening 41 formed in the thick film layer of the pattern J and an opening 42 formed in the thick film layer of the pattern K. The temperature-sensitive resistor of the temperature-sensitive portion 52 is provided between the apertures 54 and 55.

Although a part of the thick film pattern shown in FIG. 8 is common to those used in the first and second embodiments, the through hole used in the third embodiment has an insulating material. In some cases, a through hole is formed and a conductor is embedded in the through hole. That is, the pattern L has the through hole 56 in the pattern A, and the pattern M has the pattern C
In addition, a pattern N in which a through hole 58 is formed and a conductor is embedded and a pattern O in which a through hole 59 is formed and a conductor is embedded are newly used. The patterns A, J and K are the ones used so far in the first and second embodiments.

In this embodiment, the temperature-sensitive resistor pattern is printed on the thick film body of the patterns A, M, N and O.
The relationship between the temperature-sensitive resistor pattern and the thick film pattern will be described with reference to FIG. FIG. 7B shows the temperature-sensitive resistor pattern to be printed.
In addition to the pattern P shown in FIG. 7, similar patterns Q and patterns R and S that are not the temperature-sensitive resistor patterns are used. In FIG. 9, the through-holes are not visible under the temperature-sensitive resistor pattern. (A) shows that the thick-film patterns A and L have temperature-sensitive resistor patterns P,
(B) shows the temperature sensitive resistor pattern Q and the patterns R and S in the thick film pattern M, and (c) shows the temperature sensitive resistor pattern in the thick film patterns A and L. Q is
(D) shows the temperature-sensitive resistor pattern Q and the patterns R and S in the thick film pattern O, and (e) shows the temperature-sensitive resistor pattern Q in the thick film pattern N. Each is printed and these are stacked in the order described above.

FIG. 10 shows a temperature-sensitive resistor circuit constituted by these temperature-sensitive resistor patterns and through holes. In this figure, only the temperature-sensitive resistor pattern and the through-hole are shown, and the thick film body is omitted. In the temperature-sensitive resistor circuit shown in this figure, ten patterns Q of temperature-sensitive resistors are arranged between two patterns P of temperature-sensitive resistors, and these temperature-sensitive resistor patterns P and Q are By the through holes 56 to 59, the pattern P-the through hole 56-the pattern Q-the through hole 57-the pattern Q
-Through hole 56-Pattern Q-Through hole 57-
Pattern Q-Through hole 58-Pattern Q-Through hole 59-Pattern Q-Through hole 58-Pattern Q
-Through hole 57-Pattern Q-Through hole 56-
They are connected in series in the order of pattern Q-through hole 57-pattern Q-through hole 56-pattern P.

Since the material used in the resistance type temperature sensor of this embodiment is different from the material described in the first embodiment, its manufacturing method will be described. As a conductor material, molybdenum silicide having a particle size of 2 μm is 90% by volume, alumina having a particle size of 0.4 μm is 10% by volume, and toluene is used as a solvent. These materials are charged into an alumina porcelain pot and dispersed. It was dispersed with alumina balls for 15 hours as a medium for use. Ethyl cellulose resin toluene 40 as a binder after dispersion
% Solution and mix with a stirrer.

90% by volume of molybdenum silicide having a particle size of 2 μm and alumina having a particle size of 0.4 μm as 1
A composition of 0% by volume, a methacrylic resin as a binder,
Toluene, ethanol as solvent, BPB as plasticizer
Using G, these materials are put into an alumina porcelain pot and dispersed for 15 hours with alumina balls as a dispersion medium.

As a resistor material, a composition of 40% by volume of molybdenum silicide having a particle size of 2 μm, 60% by volume of alumina having a particle size of 0.4 μm, methacrylic resin as a binder, toluene and ethanol as a solvent, and BPBG as a plasticizer were used. These materials are put into an alumina porcelain pot and dispersed with alumina balls as a dispersion medium for 15 hours.

As an insulator material, 90% by volume of alumina having a particle size of 0.4 μm, 10% by volume of mullite having a particle size of 0.4 μm, 3% by weight of magnesia having a particle size of 0.4 μm, and a particle size of 0.4% were used.
A 4 μm silica composition having a composition of 0.3% by weight was charged into a pot made of alumina porcelain in the same manner as the structural conductor material, with these raw materials, methacrylic resin as a binder, toluene and ethanol as a solvent, and BPBG as a plasticizer. Disperse for 15 hours using alumina balls as a medium for use to obtain an insulating paint.

(2) Production of Sheet The conductor paint and the insulator paint produced in the above steps were coated on a polyethylene film by adjusting the height of a doctor blade so that the thickness after drying was 35 μm by a sheet coater. A coating film having a width of 80 mm is formed to obtain a resistor sheet and an insulator sheet. The formed conductor and insulator sheets are each cut to a length of 100 mm in accordance with the stack size at the time of manufacturing a laminate.

(3) Production of Thick Film Layer The thick film body can be produced by the method described with reference to FIG. 3, but can also be produced by the method described below with reference to FIG. (A) is produced in the manufacture of the sheet shown in FIG.
FIG. 3B shows a resistor sheet having substantially the same shape as that shown in FIG. 3B, in which a resistor paint is applied on a polyethylene film 65. However, unlike the element body sheet shown in FIG. The resistive paints 66 and 67 in the unremoved portions are formed slightly wider than necessary portions.

By making cuts indicated by broken lines 68 and 69 where necessary to make these resistor paints have a predetermined size, the resistor paints unnecessary for the resistor paints are peeled off according to the cuts 68 and 69 to obtain ( A material having the resistor paints 70 and 71 shown in b) is obtained.

(C) shows an insulator sheet manufactured in the manufacture of the sheet shown in FIG. 3 and having substantially the same shape as that shown in FIG. 3 (d). Although the insulating paint 73 is applied thereon, unlike the elementary sheet shown in FIG. 3D, the part of the insulator paint 73 which is not peeled off is formed a little wider than the necessary part.

Cuts indicated by broken lines 74 and 75 are made at necessary places to make the insulating paint a predetermined size.
By removing the resistor paint unnecessary for the resistor paint according to the cuts 74 and 75, a material having the insulator paint 76 shown in (d) is obtained.

Next, as shown in (e), the resistor sheet shown in (b) is turned upside down,
And 71 are laminated so that the insulator paint 76 enters between them, and after applying a pressure of 0.1 kg / cm ² for 10 seconds, the polyethylene film 65 is removed.
The element body sheet shown in (f) is obtained.

In addition, instead of forming the material having the insulating paint 76 shown in FIG. 3D, as shown in FIG. 3G, the resistor paint 70 shown in FIG. And 71
A portion corresponding to the insulator paint 76 shown in (d) can be formed by applying and drying the portion between the two. That is, after the sheet shown in (b) is prepared, the height of the doctor blade is adjusted by a sheet coater so that the height after drying becomes 35 μm, and the insulating paint 98 shown in (g) is obtained. Is applied to obtain the elementary body sheet shown in (f).

The thick films of the patterns J and K are formed by punching holes 41 and 42 for forming openings 44 and 45 in the thick film layers indicated by patterns A and B in FIG. 2 in advance. Make it by pulling it out. Also, the formation of the through hole is performed by forming a hole with a punch die in the same manner as the formation of the opening.The conductor embedded in the hole may be filled with a conductor material subsequent to the formation of the hole. The temperature-sensitive resistor pattern to be described can also be formed by embedding a resistor paint in the holes during printing.

FIG. 12 shows a process of forming a temperature-sensitive resistor thin film by printing. In this step, the unnecessary polyethylene film is removed and the necessary polyethylene film 7 is removed.
The thick film body sheet 79 (the body sheet of the pattern A in this case) placed on the substrate 8 is placed on the printing substrate 77 shown in FIG. A temperature-sensitive resistor thin film 82 is formed by printing a temperature-sensitive resistor material using a squeegee 81 via a screen 80 by such a screen printing method, and a temperature-sensitive resistor pattern is formed as shown in FIG. A temperature-sensitive thick film having P formed thereon is obtained.

In order to stack the sheets thus formed to have the structure shown in FIG. 7, sheets corresponding to the respective layers are prepared, and the types of sheets are set so that each layer has the structure shown in FIG. Instead, they are laminated in a predetermined order. In particular,
First, a sheet corresponding to the protection section 53 is prepared and laminated, then a sheet constituting the temperature sensing section 52 is prepared and laminated, and finally a sheet which is prepared and corresponds to the protection section 51 is prepared and laminated.

(4) Manufacture of the laminated body After the predetermined lamination is completed, the laminated body is removed from the stack substrate, placed in a pressing mold, and subjected to a pressure of 1.5 kg / cm ² for 300 minutes.
Pressure was applied for a second.

(5) Cutting of the laminated body After the predetermined lamination is completed, the laminated body is removed from the stack substrate, put in a pressing mold, and a pressure of 1.5 kg / cm ² is applied to the stacking substrate.
Seconds. Next, the laminate is attached to a cutting substrate to which a double-sided tape has been attached, and cut with a diamond blade at a pitch of 2.4 mm to obtain a laminate having a length of 50 mm and a thickness of 3 mm.

(6) Production of Sintered Body Since the element laminate of the present invention contains a so-called hardly sinterable metal silicide as a constituent component, at least 1,20.
It is necessary to fire at a temperature of 0 ° C., preferably 1,400 ° C. or higher. Further, the metal silicide is easily oxidized in the air at a low temperature range of about 200 degrees, and the oxidation of the metal silicide lowers the stability of its performance. Therefore, it is necessary to suppress the oxidation. It must be fired in a non-oxidizing atmosphere. The non-oxidizing atmosphere is preferably an argon gas atmosphere, and the nitrogen atmosphere has a tendency to nitride metal silicide, which undesirably changes the temperature characteristics of the resistance.

In an application for measuring the temperature of automobile exhaust gas,
It is preferable to form an insulating layer as a surface protection layer on the element surface because residual carbon in the exhaust gas adheres to the element surface and the residual carbon may cause an electrical short circuit between the conductor layers. As the surface protective layer, it is preferable to use a material having a thermal expansion coefficient substantially equal to that of the element having alumina as a main component. Since the thickness affects the response speed of the element, the thickness is preferably as thin as possible, specifically, 20 μm or less, preferably 10 μm or less.

Although a film containing silica as a main component has a higher oxidation suppressing effect than a film containing alumina as a main component, since the coefficient of thermal expansion is slightly different from that of the elementary body, cracks and the like easily occur in the film due to thermal shock. Thinner is better. For this purpose, the film containing silica as a main component must be formed with a thickness of 20 μm or less, preferably 10 μm. The film containing silica as a main component is at least 500 ° C., preferably from 1,000 ° C. to 1.4 ° C.
It can also be formed by exposing in the air at a temperature of 00 ° C. for several hours. If the temperature is lower than 500 ° C., it takes a long time to form an oxide film, which is not practical. Further, the reliability of the element can be further improved by forming a film containing alumina as a main component after forming a film containing silica as a main component. These films are CVD
It can be formed by applying a method or slurry application, dipping, printing, transfer, etc., followed by drying and heat treatment.

From the above viewpoint, the laminated body after cutting is mounted on a substrate of boron nitride, and placed in a nitrogen gas at 600 ° C. for 2 hours.
After the binder was removed, firing was performed at 1,750 ° C. for 1 hour in an argon gas. Furthermore, by HIP,
After firing at 1,650 ° C. for 2 hours in argon gas at 2,000 atm, a surface oxidation treatment was performed at 1,400 ° C. for 1 hour in air. As a result, a resistance-type thermosensitive element 6 having the shape shown in FIG.

(7) Connection Terminal Processing and Assembly The connection terminal is formed by subjecting the conductor portion of the laminated end face to sandblasting according to the process shown in FIG. Then, after printing a palladium catalyst for nickel plating on the connection terminals and performing a heat treatment after drying, nickel electroless plating is performed. Further, after the connection terminal is washed and dried, the connection terminal is sandwiched between the connection portions of the lead member shown in (d), and the nickel-plated portion is brazed with silver brazing. The resistance-type thermosensitive element body to which the lead member is connected is inserted into an alumina tube shown in (e), and is filled with ceramic cement 90 as shown in (f), and is heated at 90 ° C. for 0.5 hours. After drying, heat treatment is performed at 120 ° C. for 2 hours to cure.

Referring to FIGS. 13 and 14, another embodiment of the resistance type temperature sensor assembly will be described. The resistance type temperature sensor assembly shown in FIG. 5 has metal lead members 35 and 36. In addition, as shown in FIG. 13, a palladium film 9 is formed on a ceramic substrate 93 such as alumina.
The lead pattern 9 is obtained by printing 4 and 95.
4 and 95, and the palladium paste of the lead patterns 94 and 95 is used as a lead member.
Nickel-plated part is brazed with silver wax in the same way as 88,
The temperature-sensitive element body to which such a lead member is attached is inserted into a ceramic tube 91 and a ceramic cement 90 is inserted.
Thus, the resistance type temperature sensor assembly can be configured.

Further, instead of the ceramic tube 91,
The temperature-sensitive element body, to which the lead member shown in (a) is attached, is fixed to the ceramic base 96 shown in FIG. A resistance temperature sensor assembly can also be configured.

[Effects] The measurement results of the electrical characteristics of the temperature sensor assemblies of Examples 1, 2 and 3 obtained as described above are shown in Tables 1 and 2 as Sample A, Sample B and Sample C, respectively. It is shown in FIG. Table 1 shows that the change in the resistance value when the temperature is changed is represented by the resistance value itself and the normal temperature (25
(° C.). Table 2 shows the results of measuring the response speed by immersion in a nitrite melt at 400 ° C. Further, FIG. 15 shows a graph of Table 1, and FIG. 16 shows a graph of Table 2.

[0095]

[Table 1]

[0096]

[Table 2]

According to Table 1 and the corresponding graph of FIG. 15, the resistance values of the temperature sensors of the first, second and third embodiments all changed sufficiently with respect to the temperature change. it is obvious.

According to Table 2 and the corresponding graph of FIG. 16, the resistance values of the temperature sensors of Examples 1, 2 and 3 changed to desired values with a sufficient response speed. It is clear that

[Embodiment 4] The only metal silicide used in the embodiments described so far is molybdenum silicide. Various other metal silicides are known. Other metal silicides can also be used as the ceramic material constituting the resistance-type thermosensitive element.
Hereinafter, a case will be described in which a metal silicide other than molybdenum silicide is used as a ceramic material constituting a resistance-type thermosensitive element.

Various types of metal silicides are known, but the electrical characteristics, physical characteristics, and chemical characteristics differ depending on the metal constituting the silicide. In applications for temperature detection in a high-temperature atmosphere, those having excellent heat resistance and oxidation resistance in addition to the resistance temperature characteristics necessary for temperature detection are most desirable, and the maximum use temperature is 1,300 ° C. as in the present invention.
In the vicinity, silicides of molybdenum (Mo), tungsten (W), titanium (Ti), and tantalum (Ta) are suitable. Among them, silicide is considered when material prices, manufacturing difficulty, and the like are comprehensively determined. Molybdenum is preferred. But,
Even when a silicide of another metal such as tungsten silicide (WSi ₂ ) is used, it is possible to realize a resistance type temperature sensor that can sufficiently withstand use.

An example of a resistance type temperature sensor using tungsten silicide as a resistance material will be described below. This resistance type temperature sensor is different from the first embodiment shown in FIG.
Since it has the same configuration as the resistance type temperature sensor described above, the description of the common parts will be omitted.

(1) Preparation of Material Tungsten silicide having a particle size of 3 μm was used as a resistor material.
0 volume%, alumina having a particle size of 0.4 μm is made into a composition of 60 volume%, these raw materials, methacrylic resin as a binder, toluene and ethanol as a solvent, and BPBG as a plasticizer are put into an alumina porcelain pot and dispersed. Disperse for 15 hours using alumina balls as media,
Obtain resistor paint.

As the insulating material, 90% by volume of alumina having a particle size of 0.4 μm, 10% by volume of mullite having a particle size of 0.4 μm, 3% by weight of magnesia having a particle size of 0.4 μm, and 0.3% by weight were used.
4 μm silica was made into a composition of 0.3% by weight, and, like the resistor material, these raw materials, methacrylic resin as a binder, toluene and ethanol as a solvent, and BPBG as a plasticizer were put into an alumina porcelain pot and dispersed. Disperse for 15 hours using alumina balls as media,
Obtain insulation paint.

(2) Manufacture of Sheet The resistor paint and the insulator paint manufactured in the above process were adjusted on a polyethylene film by adjusting the height of a doctor blade so that the thickness after drying was 35 μm with a sheet coater. Then, an insulator paint film having a width of 80 mm is formed to obtain a resistor sheet and an insulator sheet. The formed resistor and insulator sheet are each cut into a length of 100 mm according to the stack size at the time of manufacturing a laminate.

(3) Production of Laminate A thick film layer was formed in the same manner as in Example 2, and after the predetermined lamination was completed, the laminate was placed in a pressing mold and subjected to 1.5 kg / cm ²
Is applied for 300 seconds. Next, the laminate is cut at a pitch of 4.8 mm to obtain a laminate having a length of 50 mm and a thickness of 3 mm.

(4) Production of Sintered Body The cut laminate was placed in a nitrogen gas at 600 ° C. for 2 hours.
Then, firing is performed at 1,650 ° C. for 2 hours in argon gas. Further, by the HIP method,
1600 atm for 2 hours in argon gas
After sintering at 1 ° C., a surface oxidation treatment is performed at 1,400 ° C. for 1 hour in air. After the oxidation treatment, the terminal connection is sandblasted.

(5) Assembly / Processing A palladium catalyst was printed on the terminal connection portion, dried and then heat-treated, and then subjected to nickel electroless plating. After washing and drying, the element in which the lead member is joined with silver wax is inserted into an alumina tube,
It is filled with ceramic cement and heat-cured after drying.

Tables 3 and 4 show the measurement results of the electrical characteristics of the temperature sensor element sample of Example 4 obtained in this manner. Table 3 shows the change in the resistance value of Sample D with temperature, and Table 4 shows the response speed of the resistance value measured in a nitrite melt at 400 ° C. FIG. 17 is a graph showing the change rate of the resistance value in Table 3 depending on the temperature, and FIG. 18 is a graph showing the response speed of the change rate of the resistance value in Table 4.

[0109]

[Table 3]

[0110]

[Table 4]

According to Table 3 and the corresponding graph in FIG. 17, the resistance type temperature sensor of Example 2 using tungsten silicide as the resistor material shows that the resistance value changes sufficiently with temperature change. Is evident.

According to Table 4 and the corresponding graph of FIG. 18, the temperature sensor of Example 2 using tungsten silicide as the resistor material has its resistance changed to a predetermined value with a sufficient response speed. It is clear that.

[Embodiment 5] As described above, the resistance type temperature sensor using molybdenum, tungsten, titanium and tantalum silicide as the resistance material can be used even at a high temperature of around 1,300 ° C. Temperature is 1.0
For applications in a relatively low temperature range of around 00 ° C., most other metal silicides can be used, and in particular, elements IVA, VA, VIA, V
Group III metal silicides are highly available. Above all, silicides of chromium (Cr), iron (Fe), and cobalt (Co) are desirable materials in comprehensive consideration of material cost and ease of production.

These metal silicides, chromium silicide (C
rSi ₂ ), iron silicide (FeSi ₂ ), cobalt silicide (Co
Si ₂ ) has lower heat resistance than silicides of refractory metals such as molybdenum silicide and tungsten silicide, but is sufficiently used when used in a relatively low temperature range of about 1,000 ° C. It is possible. Therefore, in place of molybdenum silicide, tungsten silicide, titanium silicide, and tantalum silicide, which have high heat resistance but are more expensive, the same structure as in Example 1 using less expensive chromium silicide, iron silicide, or cobalt silicide as a resistor material is used. The resistance type temperature sensor will be described.

(1) Preparation of Material The composition of the resistive material was determined for each of Samples E, F and G. Sample E: 40 vol% of chromium silicide having a particle size of 2.5 μm, and alumina having a particle size of 0.4 μm Sample F: 40% by volume of 3.4 μm particle size iron silicide, 60% by volume of 0.4 μm particle size alumina, Sample G: 40% by volume of 2 μm particle size cobalt silicide, 60% by volume alumina %, And the insulating material has the same composition as that of the first embodiment.

(2) Production of Laminate After the formation of the thick film layer and the completion of the prescribed lamination in the same manner as in Example 1, the laminate was placed in a pressing mold, and a pressure of 1.5 kg / cm ² was applied to the mold for 300 minutes. Add for seconds. Next, the laminate is cut at a pitch of 4.8 mm to obtain a laminate sample having a length of 50 mm and a thickness of 3 mm.

(3) Production of Sintered Body The cut laminate was placed in a nitrogen gas at 600 ° C. for 2 hours.
After removing the binder in step 1,
Bake at 250 ° C. Furthermore, 1,50 was obtained by the HIP method.
After firing at 1,200 ° C. for 2 hours in argon gas at 0 atm, a surface oxidation treatment is performed in air at 1,100 ° C. for 1 hour. After the oxidation treatment, the terminal connection is sandblasted.

(4) Assembly and Processing of Element A palladium catalyst was printed on the terminal connection part, and after drying and heat treatment, nickel electroless plating was performed. After washing and drying, the element in which the lead member is joined with silver wax is inserted into an alumina tube,
It is filled with ceramic cement and heat-cured after drying.

The results of measuring the electrical characteristics of the temperature sensor element manufactured as described above are shown in Tables 5 and 6 below. Table 5 shows the change in the resistance value with temperature, and Table 6 shows the change in the resistance value.
It shows the response speed of the resistance value measured in a nitrite melt at 0 ° C. FIG. 13 is a graph showing the rate of change of the resistance value in Table 5 with temperature, and FIG. 14 is a graph showing the response speed of Table 6 and the rate of change of the resistance value.

[0120]

[Table 5]

[0121]

[Table 6]

According to Table 5 and the corresponding graph in FIG. 19, it is clear that the resistance value of the resistance type temperature sensor using these resistance materials changes sufficiently with temperature change.

According to Table 6 and the corresponding graph of FIG. 20, it is clear that the resistance value of the resistance type temperature sensor using these resistance materials changes to a predetermined value with a sufficient response speed.

[Brief description of the drawings]

FIG. 1 is a diagram showing a laminated structure of a resistance-type temperature sensor element according to Embodiment 1 of the present invention.

FIG. 2 is a diagram showing a thick film pattern used in the resistance type temperature sensor element according to the first embodiment of the present invention.

FIG. 3 is a process chart of a thick film layer forming method performed in Embodiment 1 of the present invention.

FIG. 4 is another laminated structure diagram of the first embodiment of the present invention.

FIG. 5 is an assembly process diagram of another resistance temperature sensor according to the first embodiment of the present invention.

FIG. 6 is a structural diagram of a resistance-type temperature sensor element according to Embodiment 2 of the present invention.

FIG. 7 is a structural diagram of a resistance-type temperature sensor element according to Embodiment 3 of the present invention.

FIG. 8 is a diagram showing a thick film pattern used in the resistance type temperature sensor element according to the third embodiment of the present invention.

FIG. 9 is a diagram illustrating the relationship between a temperature-sensitive resistor pattern and a thick film pattern.

FIG. 10 is an explanatory diagram of a temperature-sensitive resistor circuit.

FIG. 11 is a process chart of another method for forming a thick film layer.

FIG. 12 is a process chart for forming a temperature-sensitive resistor thin film by printing.

FIG. 13 is an explanatory view of another embodiment of the resistance type temperature sensor assembly.

FIG. 14 is an explanatory view of still another embodiment of the resistance type temperature sensor assembly.

FIG. 15 is a graph showing the rate of change of the resistance value with temperature in Examples 1 to 3.

FIG. 16 is a graph showing the response speed of the rate of change of the resistance value in Examples 1 to 3.

FIG. 17 is a graph showing the rate of change of the resistance value with temperature in Example 4.

FIG. 18 is a graph showing the response speed of the rate of change of the resistance value in Example 4.

FIG. 19 is a graph showing the rate of change of the resistance value with temperature in Example 5.

FIG. 20 is a graph showing the response speed of the rate of change of the resistance value in Example 5.

[Explanation of symbols]

1, 2 connection terminal 3 insulating section 4, 5 conductive section 6 temperature sensing section 7, 8 protective layer 9, 10, 11, 12, 13, 14, 15, 16 resistor 21, 27, 32, 65, 72, 78 Polyethylene film 22, 25, 26 Resistor thick film 23, 24, 29, 30, 68, 69, 74, 75 Cut 28, 31 Insulator thick film 33 Thick film layer 35, 36 Lead member 37, 38 Connection 39 Alumina Pipe 40 Ceramic cement 41, 42 Opening 43, 52 Temperature sensing part 44, 45 Opening 51 Upper protective part 53 Lower protective part 54, 55 Opening 56, 57, 58, 59 Through hole 66, 67, 70, 71 Resistor paint 73,76 Insulator paint 77 Printing substrate 79 Thick film base sheet 80 Screen 81 Squeegee 82 Temperature sensitive resistor thin film 87,88 Lead member 90 Ceramic Cement 91 Ceramic tube 93 Ceramic substrate 94,95 Lead pattern 96 Ceramic base

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] January 14, 1997

[Procedure amendment 1]

[Document name to be amended] Drawing

[Correction target item name] FIG.

[Correction method] Added

[Correction contents]

FIG.

[Procedure amendment 2]

[Document name to be amended] Drawing

[Correction target item name] FIG.

[Correction method] Added

[Correction contents]

FIG.

Claims (20)

[Claims] 1. A structure in which a conductive material containing a metal silicide such as MoSi ₂ and an insulating base mainly composed of alumina are alternately laminated, and at least a part of the laminated structure constitutes a resistance circuit, or A resistor circuit is formed on an insulating base mainly composed of alumina, and has at least one layered structure. At least the resistor circuit is formed of a temperature sensing portion and a lead portion, and the resistor circuit has two or more layers. In the case of adopting a structure, a temperature sensor in which a resistance circuit is connected with a through hole between the layers, wherein the thickness around the temperature sensing portion is smaller than the thickness of the temperature sensor body, that is, a laminated structure including the temperature sensing portion At least one of the outer upper and lower portions is a laminated structure of at least one layer of the same material as the lead portion material or the temperature sensitive portion material and the insulating base material, or the outer portion of the laminated structure including the temperature sensitive portion. The upper and lower part, near at least one of the temperature sensing portion has a notched shape, resistance type temperature sensor. 2. The material of the temperature sensing portion is 30 to 100% by volume of a metal silicide such as MoSi ₂ , and the remainder is an insulator containing alumina as a main component, and the insulator is 15% by volume or less of mullite. And 5% by weight or less of MgO, and the material of the lead portion is 50 to 100% by volume of a metal silicide such as MoSi ₂ ,
The remainder is an insulator containing alumina as a main component, and the insulator contains 15% by weight or less of mullite and 5% by weight or less of MgO. 5% by weight or less of MgO, SiO
_2. The resistance type temperature sensor according to claim 1, which has a laminated structure containing 0.5% by weight or less. 3. At least one of the outer upper and lower portions of the laminated structure including the temperature-sensitive part has at least one layered structure of a lead material or the same material as the temperature-sensitive part material and an insulating base material. The resistance type temperature sensor according to claim 1. 4. An outer periphery of a portion of the laminated structure including the temperature sensing portion is a laminated structure of at least one layer of a lead portion material or the same material as the temperature sensing portion material and an insulating base material. The resistance type temperature sensor according to claim 1, 2 or 3. 5. An at least one layer containing alumina as a main component or SiO ₂ as a main component on the outside of the element body including at least the temperature-sensitive portion except for a portion electrically connected to the outside of the lead portion. Claim 1, Claim 2, which is covered with
The resistance type temperature sensor according to claim 3 or 4. 6. A structure in which a conductor material containing a metal silicide such as MoSi ₂ and an insulating base mainly composed of alumina are alternately laminated, and at least a part of the laminated structure constitutes a resistance circuit, or A method of manufacturing a resistance type temperature sensor having a structure in which a resistance circuit is formed on an insulating base mainly composed of alumina and having at least one layer laminated, and is dispersed together with a solvent in a dispersion device such as a ball mill or a media mill. If the material particle size after dispersion is 1 μm or less and the binder is not mixed at the time of dispersion, more solvent than the final coating composition is mixed at the time of dispersion, and after dispersion or after mixing of the binder, excess is obtained by a filtration device or an evaporation device. A method for manufacturing a resistance-type temperature sensor, wherein a sheet having a predetermined coating composition by removing the solvent component is applied and dried to form a sheet and sequentially laminated to form a laminate. 7. A structure in which a conductor material containing a metal silicide such as MoSi ₂ and an insulating base mainly composed of alumina are alternately laminated, and at least a part of the laminated structure constitutes a resistance circuit, or A method for manufacturing a resistance type temperature sensor in which a resistance circuit is formed on an insulating base mainly composed of alumina and has at least one layered structure, wherein two or more kinds of layers are formed on the same layer of each layer of the stacked body. In order to form a layer composed of materials, a single material is coated and dried, and a cut is made in the sheet, and a sheet from which each unnecessary portion is peeled is formed for each material, and sequentially laminated to form a laminate. , Resistance type temperature sensor manufacturing method. 8. A structure in which a conductor material containing a metal silicide such as MoSi ₂ and an insulating base mainly composed of alumina are alternately laminated, and at least a part of the laminated structure constitutes a resistance circuit, or A method for manufacturing a resistance type temperature sensor in which a resistance circuit is formed on an insulating base mainly composed of alumina and has at least one layered structure, wherein two or more materials are formed on the same layer of each layer of the layered body. In order to form a layer composed of a single material, a cut is made in a sheet that has been applied and dried, and a sheet in which unnecessary portions have been peeled is created for each material, and for each layer, a sheet of any material In each of the stripped and removed portions, the remaining portions of the stripped and removed sheet of another material forming the same layer are embedded as a result to form each layer, and each layer is sequentially laminated to form a laminate. Resistance type temperature sensor Support manufacturing method. 9. A structure in which a conductor material containing a metal silicide such as MoSi ₂ and an insulating base mainly composed of alumina are alternately laminated, and at least a part of the laminated structure constitutes a resistance circuit, or A method for manufacturing a resistance type temperature sensor in which a resistance circuit is formed on an insulating base mainly composed of alumina and has at least one layered structure, wherein two or more kinds of layers are formed on the same layer of each layer of the stacked body. In order to form a layer composed of a material, a cut is made at a predetermined position in the running direction of a sheet on which any of the materials has been applied and dried, and a sheet in which unnecessary portions have been peeled off is formed. A method for manufacturing a resistance-type temperature sensor, comprising applying and drying a paint of the material described above, forming a sheet composed of two or more types of materials as a result, and sequentially stacking to form a laminate. 10. A structure in which a conductor material containing a metal silicide such as MoSi ₂ and an insulating base mainly composed of alumina are alternately laminated, and at least a part of the laminated structure constitutes a resistance circuit, or A method for manufacturing a resistance type temperature sensor in a structure in which a resistance circuit is formed on an insulating substrate containing alumina as a main component and at least one or more layers are stacked,
10. The resistor according to claim 6, wherein a sheet in which a resistance circuit is formed on the insulator portion of the sheet by a method such as printing or transfer is sequentially laminated to form a laminate. Method of manufacturing a temperature sensor. 11. A structure in which a conductor material containing a metal silicide such as MoSi ₂ and an insulating base mainly composed of alumina are alternately laminated, and at least a part of the laminated structure constitutes a resistance circuit, or A method for manufacturing a resistance type temperature sensor in a structure in which a resistance circuit is formed on an insulating substrate containing alumina as a main component and at least one or more layers are stacked,
Firing in the temperature range from 1,200 ° C to 1,800 ° C,
Alternatively, firing at a temperature in the range of 1,200 ° C. to 1,800 ° C. and a pressure of 0.5 Ton / cm ² or more, or firing in a temperature range of 1,200 ° C. to 1,800 ° C. Temperature range from 1,200 ° C to 1,800 ° C,
A method for manufacturing a resistance-type temperature sensor, wherein a body is formed by firing at a pressure of 000 atm or more. 12. A structure in which a conductor material containing a metal silicide such as MoSi ₂ and an insulating base mainly composed of alumina are alternately laminated, and at least a part of the laminated structure constitutes a resistance circuit, or A method for manufacturing a resistance type temperature sensor in a structure in which a resistance circuit is formed on an insulating substrate containing alumina as a main component and at least one or more layers are stacked,
The calcination according to claim 11, wherein the calcination step is an atmosphere of argon gas, or a part of the temperature raising step,
Or the temperature rise process and a part of the stable part are vacuum degree 50 Torr
A method for manufacturing a resistance-type temperature sensor, wherein the element body is formed under the above-described atmosphere under the firing conditions in which the other firing process is an argon gas atmosphere. 13. A structure in which a conductor material containing a metal silicide such as MoSi ₂ and an insulating base mainly composed of alumina are alternately laminated, and at least a part of the laminated structure constitutes a resistance circuit, or A method for manufacturing a resistance type temperature sensor in a structure in which a resistance circuit is formed on an insulating substrate containing alumina as a main component and at least one or more layers are stacked,
A method for manufacturing a resistance-type temperature sensor, wherein after sintering, a surface oxidation treatment is performed at a temperature of 500 ° C. or more to form an element having an oxide film formed on the surface. 14. A structure in which a conductive material containing a metal silicide such as MoSi ₂ and an insulating base mainly composed of alumina are alternately laminated, and at least a part of the laminated structure constitutes a resistance circuit, or A method for manufacturing a resistance-type temperature sensor in a structure in which a resistance circuit is formed on an insulating substrate containing alumina as a main component and at least one layer is stacked,
20% or less of alumina as a main component or Si
At least one layer containing O ₂ as a main component is formed on the surface by CVD or by applying a slurry by applying, dipping, printing, transferring, etc., followed by drying and heat treatment, thereby forming an element body on the surface. , Resistance type temperature sensor manufacturing method. 15. A structure in which a conductor material containing a metal silicide such as MoSi ₂ and an insulating base mainly composed of alumina are alternately laminated, and at least a part of the laminated structure constitutes a resistance circuit, or A method for manufacturing a resistance type temperature sensor in a structure in which a resistance circuit is formed on an insulating substrate containing alumina as a main component and at least one or more layers are stacked,
20% or less of alumina as a main component or Si
After forming at least one film mainly composed of O ₂ on the surface by CVD or by applying a slurry by applying, dipping, printing, transferring, etc., and then drying and heat-treating, a temperature of 500 ° C. or more is obtained. A method for manufacturing a resistance-type temperature sensor, wherein a body is formed by performing a surface oxidation treatment on the substrate. 16. A structure in which a conductor material containing a metal silicide _such as MoSi2 and an insulating base mainly composed of alumina are alternately laminated, and at least a part of the laminated structure constitutes a resistance circuit, or A circuit is formed on an insulating substrate containing alumina as a main component, and a method for manufacturing a resistance-type temperature sensor in a laminated structure of at least one or more layers,
A method for manufacturing a resistance-type temperature sensor, wherein a junction with a lead frame forms a Ni plating film and then joins the lead frame with silver wax. 17. A structure in which a conductor material containing a metal silicide such as MoSi ₂ and an insulating base mainly composed of alumina are alternately laminated, and at least a part of the laminated structure constitutes a resistance circuit, or A method for manufacturing a resistance type temperature sensor in a structure in which a resistance circuit is formed on an insulating substrate containing alumina as a main component and at least one or more layers are stacked,
A method for manufacturing a resistance-type temperature sensor, wherein a joint with a lead frame is joined to the lead frame by welding. 18. A structure in which a conductor material containing a metal silicide such as MoSi ₂ and an insulating base mainly composed of alumina are alternately laminated, and at least a part of the laminated structure constitutes a resistance circuit, or A method for manufacturing a resistance type temperature sensor in a structure in which a resistance circuit is formed on an insulating substrate containing alumina as a main component and at least one or more layers are stacked,
A resistance type temperature sensor having a structure in which a lead portion has a structure in which a conductor pattern such as Pd is baked on a ceramic substrate, and a junction with the lead portion substrate has a Ni plating film formed thereon and then is joined to the lead portion substrate with silver brazing. Production method. 19. A structure in which a conductor material containing a metal silicide such as MoSi ₂ and an insulating base mainly composed of alumina are alternately laminated, and at least a part of the laminated structure constitutes a resistance circuit, or A method for manufacturing a resistance type temperature sensor in a structure in which a resistance circuit is formed on an insulating substrate containing alumina as a main component and at least one or more layers are stacked,
A method for manufacturing a resistance-type temperature sensor, wherein a lead portion has a structure in which a conductor pattern such as Pd is baked on a ceramic substrate, and a joint portion with the lead portion substrate is joined to the lead portion substrate by welding. 20. A conductor material containing a metal silicide such as MoSi ₂ and an insulating material containing alumina as a main component are alternately laminated, and at least a part of the laminated structure constitutes a resistance circuit, or a resistance circuit is formed. A method of manufacturing a resistance type temperature sensor having a structure in which at least one layer is formed on an insulating base mainly composed of alumina and has a structure joined to a lead frame or a structure joined to a lead substrate. A structure in which a resistance-type temperature sensor element is installed inside a heat-resistant ceramic tube, ceramic base, or the like, and after injecting ceramic cement into the gap, drying and heat treatment, the ceramic cement is hardened, and embedded with ceramic cement. , Resistance type temperature sensor manufacturing method.