JPH10321408A - Thermistor and manufacture thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To realize less change in resistance value and stable characteristics even in thermal hysteresis, by mixing an oxide of each element selected from elements of a specified group on the periodic table and yttrium oxide so as to form a mixed sintered body. SOLUTION: In a perovskite material (M1M2)O3 , the element of M1 is one or more kinds of elements selected from Mg, Ca, Sr and Ba as group 2A elements on the periodic table and Y, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ha, Er, Yb and Sc except for La as group 3A elements. The element of M2 is one or more kinds of elements selected from group 2B, group 3B, group 4A, group 5A, group 6A, group 7A and group 8A elements. (M1M2)O3 and yttrium oxide (Y2 O3 ) are mixed to form a mixed sintered body (M1M2)O3 .Y2 O3 .

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a method for producing a material from room temperature to about 100
The present invention relates to a thermistor element capable of detecting a temperature over a high temperature range of 0 ° C., that is, a so-called wide-range thermistor element, and is particularly suitable for use as a temperature sensor for automobile exhaust gas.

[0002]

2. Description of the Related Art Thermistor elements for temperature sensors are used to measure the temperature of exhaust gas for automobiles, the temperature of gas flames in gas water heaters and the like, the temperature of heating furnaces, and the like in the medium to high temperature range of 400 to 1300 ° C. The characteristics of this type of thermistor element are represented by a resistance value and a resistance temperature coefficient (temperature dependence of the resistance value). Here, in order to correspond to a practical resistance value range of the temperature detection circuit constituting the temperature sensor, it is desired that the resistance value of the thermistor element be within a predetermined range. Therefore, a perovskite-based material or the like is mainly used as a material having resistance characteristics suitable for a wide-range thermistor element.

As a thermistor element using a perovskite-based material, for example, those disclosed in JP-A-6-325907 and JP-A-7-201528 have been proposed. These are Y, Sr, Cr, Fe, to realize a thermistor element usable in a wide temperature range.
An oxide such as Ti is mixed in a predetermined composition ratio and fired to form a complete solid solution to obtain a thermistor element.

[0004]

The resistance characteristics of a wide-range thermistor element are represented by a resistance value and a resistance temperature coefficient. In a normal temperature sensor, considering the resistance value range of the temperature detection circuit, the resistance value of the thermistor element is:
It is necessary that the resistance is 50Ω to 100kΩ in the operating temperature range. In addition, a room temperature to 1000 ° C.
In this case, it is preferable that the change between the resistance value after the heat history and the initial resistance value is small.

In each of the above publications, various thermistor elements made of a complete solid solution are proposed.
Only the data on the resistance value of the thermistor element described above is disclosed. Therefore, the present inventors have investigated the resistance value characteristics of various thermistor elements in each of the above publications near room temperature. As a result, those having resistance value stability in a thermal history or the like at room temperature to 1000 ° C. are 300
In the temperature range of ° C., the resistance value becomes high and the temperature cannot be detected because it cannot be determined that the insulation is provided. On the other hand, 50Ω ~
Those satisfying a low resistance value of 100 kΩ changed the resistance value by 10% or more with respect to the initial resistance value in heat history and the like, and were found to lack stability.

In any case, a thermistor element (so-called wide-range thermistor element) capable of satisfying two resistance characteristics that are inconsistent with each other in a low resistance value characteristic over a high temperature range from room temperature to 1000 ° C. and a resistance value stability in heat history and the like.
Never before. SUMMARY OF THE INVENTION In view of the above problems, the present invention has a small resistance change characteristic even in a thermal history from room temperature to 1000 ° C., and has a stable characteristic, and has a resistance of 50Ω to 100 kΩ in a temperature range from room temperature to 1000 ° C. The purpose is to obtain an element.

[0007]

The conventional thermistor element is a complete solid solution having a perovskite structure. However, the present inventors have found that a complete solid solution, which is a single compound, has the above-mentioned conflicting tendency. It was considered difficult to satisfy certain resistance characteristics. Therefore, a novel thermistor material is not a complete solid solution but a mixed sintered body in which two compounds of a perovskite-based material (oxide) having a relatively low resistance value and a material having a relatively high resistance value are mixed. To achieve the above object.

[0008] As a result of experimental studies on various perovskite-based materials, a composition (M1M2) as a material having an appropriate resistance characteristic in order to achieve the above object is described.
O ₃ (where M1 is Group 2A of the Periodic Table of the Elements and La
M2 is at least one element selected from the elements of Group 3A excluding
At least one element selected from Group B, Group 4A, Group 5A, Group 6A, Group 7A and Group 8).

Here, La is not used as M2 because it has a high hygroscopicity and has a problem that it reacts with moisture in the air to form an unstable hydroxide and destroy the thermistor element. On the other hand, the material of the other party to be mixed, the result of the study, was the use of Y ₂ O ₃ to stabilize the resistance value of and thermistor material has a relatively high resistance value (yttrium oxide).

[0010] Then, (M1M2) by the O _3, Y ₂ O ₃ and the mixed sintered body, as described in the claim 1, the mixed sintered body _{(M1M2) O 3 · Y 2} O _A thermistor element consisting of ₃ is obtained. When the resistance characteristics of the thermistor element were incorporated into a temperature sensor and the resistance characteristics of the element were examined, the change in resistance value was small and stable at several percent even in a thermal history from room temperature to 1000 ° C. It was confirmed that the resistance value was 50Ω to 100kΩ.

Therefore, in the first aspect of the present invention,
It is possible to provide a thermistor element capable of detecting a temperature over a high temperature range from room temperature to 1000 ° C. and having a stable characteristic in which a change in resistance is small even in a thermal history from room temperature to 1000 ° C., that is, a so-called wide-range type thermistor element. . According to the study of the present inventors, each element in the perovskite compound (M1M2) O ₃ is, as in the invention of claim 3, M1 is Y, Ce, Pr,
Nd, Sm, Eu, Gd, Dy, Ho, Er, Yb, M
g, one or more elements selected from Ca, Sr, Ba, and Sc, and M2 is Ti, V, Cr, Mn, Fe, C
o, Ni, Zn, Al, Ga, Zr, Nb, Mo, H
It is practically preferable to be at least one element selected from f, Ta, and W.

Further, as a result of studying the mixing ratio of (M1M2) O ₃ and Y ₂ O ₃ , if the mixing ratio is within a predetermined range, that is, as in the second aspect of the present invention,
The mole fraction of (M1M2) O ₃ is a, and the above Y ₂ O
Assuming that the mole fraction of ₃ is b, these mole fractions a and b are 0.05 ≦ a <1.0, 0 <b ≦ 0.95, a
It has been found that the effect of claim 1 can be more reliably achieved if the relationship of + b = 1.

Since the molar fraction can be changed in such a wide range, the resistance value and the temperature coefficient of resistance can be reduced by appropriately mixing and firing both (M1M2) O ₃ and Y ₂ O _3. Various controls can be performed in a wide range. In the sintered body, a sintering aid is added in order to improve the sinterability of each particle. For the mixed sintered body,
It has been found that it is preferable to use a sintering aid comprising at least one of CaO, CaCO ₃ and CaSiO ₃ and SiO ₂ , as in the invention of claim 6.
Thereby, a wide-range thermistor element having excellent sintering density and the like can be obtained.

By the way, as the experiment progresses, in the temperature sensor using the thermistor element according to the first to sixth aspects, the detection temperature accuracy of each manufactured sensor is ± 2.
It was found to vary from 0 to 30 ° C. Therefore, from the viewpoint of improving the temperature accuracy (reducing the variation in the detection temperature accuracy for each sensor), investigations were made on various conditions in the manufacturing process of the thermistor element, such as preparation, molding, and firing conditions.

As a result, the variation in the temperature accuracy is due to the perovskite-based material obtained by calcination (M1
M2) The average particle size of O ₃ is greater than the average particle diameter of Y ₂ O _3, both variations in composition of the mixed sintered body not uniformly mixed, as a result, due to the resistance of the thermistor element is varied I understand. Therefore, if the average particle size of (M1M2) O ₃ in the mixed state before sintering was made equal to the average particle size of Y ₂ O ₃ , it was considered that uniform mixing of the composition could be realized, and an experimental study was conducted. As a result, (M1M2) O ₃ obtained by calcination is converted to Y
This was mixed with ₂ O ₃ and pulverized, and this mixture ((M1M2) O ₃
It has been found that the average particle size of Y ₂ O ₃ ) should be equal to or less than the average particle size of Y ₂ O ₃ before mixing.

That is, according to the manufacturing method of claim 8, (M1M2) O ₃ and Y ₂ O ₃ are uniformly mixed by atomization, and the mixed sintered body (M1M2) O ₃ .Y ₂ O _{3 is obtained.}
Of the thermistor element can be reduced, so that the variation in the resistance value of the thermistor element can be reduced. Accordingly, it is possible to provide a wide-range thermistor element that enables better sensor temperature accuracy (less variation in temperature accuracy between sensors) than the conventional level in a temperature range from room temperature to 1000 ° C.

The mixed sintered body (Y (C
rMn) O ₃ ) .Y ₂ O ₃ is composed of Y (CrMn) O ₃ and Y
Not be the method of mixing sintering a ₂ O _3, and obtained by calcination at a mixture of an oxide of oxides and Mn of Cr 1000 ° C. or more _{(Mn 1 .5 Cr 1.5) O} 4, the (Mn _1.5 Cr
_1.5 ) It can also be obtained by directly mixing and sintering O ₄ and Y ₂ O ₃ . In this case, if the manufacturing method described in claim 9 is adopted, the same effect as the invention described in claim 8 can be obtained.

The mixed sintered body (Y (C
rMnTi) O ₃ ) .Y ₂ O ₃ is composed of Cr oxide and Mn.
And calcination at 1000 ° C. or more (Mn
Newsletter _{1 .5} Cr _1.5) O _4, the (Mn _{1 .5} Cr _1.5)
It can also be obtained by mixing and sintering O ₄ , Y ₂ O ₃ and TiO ₂ . In this case, if the manufacturing method described in claim 10 is adopted, the same effect as the invention described in claim 8 can be obtained.

Further, from the viewpoint of improving the detection temperature accuracy of the temperature sensor using the thermistor element according to the first to sixth aspects, investigations have been made on a method of manufacturing the thermistor element.
As a result, the composition variation of the (M1M2) O ₃ itself obtained by the preliminary firing results in the mixed sintered body (M1M2) O 3
It has been found that it affects the variation in the composition of ₃ · Y ₂ O ₃ (that is, the variation in the resistance value of the thermistor element).

Here, the mixed fired body (M1M2) O_Three・ Y
_TwoO_Three(M1)
M2) O_Three(M1M2)
O_ThreeIn the case where M1 = Y and M2 = Cr and Mn,
That is, Y (Cr_0.5Mn_0.5) O_ThreeUsing the example
I will say. Y (Cr_0.5Mn_0.5) O_ThreeThe preparation of
For example, the following is performed (see FIG. 31). With raw material of M1
Some Y_TwoO_Three(Average particle size of about 1 μm)
Cr _TwoO_Three(Average particle size of about 4 μm) and Mn_TwoO_Three(flat
Y: Cr: Mn = 1: 0.5:
Compound at a molar ratio of 0.5 (Formulation 1) and mix with a ball mill or the like.
The mixture is crushed, and the mixture is calcined at 1000 ° C. or more.
Y (Cr_0.5Mn_0.5) O_ThreeGet.

The present inventors have found that during the above process, there is a problem in mixing and pulverization with a ball mill or the like. That is, in the mixing and grinding in a ball mill or the like, the average particle size after the mixing and grinding is about 2μm limitations, also Cr ₂ O ₃ and Mn
The average particle size of ₂ O ₃ is larger than the average particle diameter of Y ₂ O _3. Therefore, a mixture of Y ₂ O ₃ , Cr ₂ O _3, and Mn ₂ O ₃ is prepared by a calcination reaction to obtain Y (Cr _0.5 Mn _0.5 ) O _3.
Is a composition deviated from Y: Cr: Mn = 1: 0.5: 0.5 due to the particle size difference between Y ₂ O ₃ , Cr ₂ O ₃ and Mn ₂ O ₃ of each raw material, for example, Y: Cr: Mn = 1: 0.6:
0.4: Y: Cr: Mn = 1: 0.4: 0.6
It becomes a mixture containing various compositions up to the composition.

These Y: Cr: Mn = 1: 0.6: 0.
From the four compositions, the Y: Cr: Mn = 1: 0.4: 0.6 compositions have different resistance values and different temperature coefficients of resistance (β values), so that the resistance fluctuates from element to element and the element resistance value Is the cause of the variation. The raw materials Y ₂ O ₃ , Cr
_{When a part of 2} O ₃ and Mn ₂ O ₃ (which deviates from the composition ratio) remains as an unreacted substance, it also causes a variation in element resistance value.

Here, the present inventors preliminarily fired (M1
M2) In a step before obtaining O ₃ , the resulting (M1M
2) Various studies were conducted to suppress problems such as variation in the composition of O ₃ and the presence of unreacted materials as raw materials. As a result, the raw material of M2 and the raw material of M1 are mixed and pulverized by a medium stirring mill or the like having a higher pulverizing ability than a ball mill, and the average particle size of the mixed and pulverized raw material mixture (mixed and pulverized product) is determined before mixing. Less than the average particle size of the raw material of M1 and 0.5 μm
It was found that the above problems could be suppressed if the particle size was reduced to m or less, and the temperature accuracy would be ± 10 ° C. or less, which is a practical level.

The inventions of claims 11 to 14 have been made based on the above findings. That is, in the invention according to claim 11, in the mixing step of mixing and pulverizing the raw material of M1 and the raw material of M2, the raw material of M2 is mixed and pulverized with the raw material of M1, and the average particle size of the mixed and pulverized product is obtained. Is not more than the average particle size of the raw material of M1 before mixing and not more than 0.5 μm. Then, (M1M2) O ₃ was obtained by preliminary firing,
(M1M2) It is characterized in that after mixing O ₃ and Y ₂ O ₃ , the mixture is molded into a predetermined shape and fired.

According to the present invention, uniform mixing of the composition is achieved by uniform atomization of the raw materials of M1 and M2, so that the variation in the composition of (M1M2) O ₃ produced after the calcination is reduced, and the unreacted raw materials are reduced. The suppression of the presence can be realized, and the variation in the resistance value of the thermistor element can be reduced. Therefore,
In the temperature range from room temperature to 1000 ° C., it is possible to provide a wide-range thermistor element which enables better sensor temperature accuracy (less variation in temperature accuracy between sensors) than the conventional level.

Also, at least Y ₂ O
_In the case where a material containing M3 is used, the raw material of M2 is mixed with the raw material of M1, mixed, pulverized and calcined, and the target mixed sintered body (M1
M2) A thermistor element can also be obtained by generating a precursor having the same composition as O ₃ · Y ₂ O _3, and molding and firing this precursor into a predetermined shape. Here, the precursor is (M1M
2) It is represented by O ₃ · Y ₂ O ₃ , but the above (M1M2) O
_{In 3} (perovskite structure), an excess of Y over the theoretical amount is attached to (M1M2) O ₃ as Y ₂ O ₃ . Therefore, in this manufacturing method, M
By mixing the raw materials 1 and M2 so as to have the composition of the target mixed sintered body, a mixed sintered body, that is, a thermistor element can be obtained without mixing Y ₂ O ₃ again after calcination. .

The twelfth aspect of the present invention is directed to a production method using a material containing at least Y ₂ O ₃ as a raw material for M1.
The raw material is mixed with the raw material of Example 1 and ground, and after the average particle diameter of the mixed and ground product after the grinding is set to be equal to or less than the average particle diameter of the raw material of M1 before mixing and 0.5 μm or less, the above precursor is obtained by calcination. It is characterized by the following.

As a result, uniform mixing of the composition is achieved by uniform atomization of the raw materials of M1 and M2, and it is possible to reduce the variation in the composition of the precursor formed after the calcination and to suppress the presence of unreacted raw materials. Therefore, as a result, even in a mixed sintered body having the same composition as the precursor, variation in composition is reduced, and the same effect as that of the invention described in claim 11 can be obtained.

Here, the invention of claim 13 is a combination of the manufacturing method of claim 11 and the manufacturing method of claim 8, and the combination of the effects of the two manufacturing methods provides a higher level. Variations in the resistance value of the thermistor element can be reduced. The invention according to claim 14 is a combination of the production method according to claim 12 and the production method according to claim 8, but the precursor (M1M2) O _3. by atomizing the Y ₂ O ₃ to an average particle diameter or less of a level of Y ₂ O ₃ as a raw material before mixing the M1, forming a subsequent step, at the time of baking, (M1M
2) O ₃ and Y ₂ O ₃ are uniformly mixed, and the composition variation of the mixed sintered body is reduced, so that the variation in the resistance value of the thermistor element can be reduced.

That is, also in the present invention, the variation in the resistance value of the thermistor element can be reduced at a higher level.

[0031]

BEST MODE FOR CARRYING OUT THE INVENTION

(First Embodiment) The perovskite-based material (M1
M2) In O ₃ , for example, the element of M1 is Mg, Ca, Sr, Ba, 3A
As a group, excluding La, Y, Ce, Pr, Nd, Sm,
It can be selected from Eu, Gd, Dy, Ho, Er, Yb, Sc and the like.

For example, the element of M2 is Zn as Group 2B, Al, Ga as Group 3B, Ti, Zr, Hf as Group 4A, and V, N as Group 5A.
b, Ta, Group 6A as Cr, Mo, W, Group 7A as Mn, Tc, Re, Group 8 as Fe,
It can be selected from Co, Ni, Ru, Rh, Pd, Os, Ir, and Pt.

Here, the mixed sintered body (M1M2) O_Three・ Y
_TwoO_ThreeThe manufacturing process of (M1M
2) O_ThreeAnd a first preparation step to obtain (M1M
2) O _ThreeAnd Y_TwoO_ThreeAnd mixed sintered body (M1M2)
O_Three・ Y_TwoO_ThreeAnd a second preparation to obtain a thermistor element
It is divided into processes. In the first preparation step, M1 and M2
Oxide of M1 (M1O_X) And oxides of M2
(M2O_X), Etc. (Formulation 1), mixing, pulverizing (mixing)
Calcination (for example, 1000 ° C. to 1500 ° C.)
(About 1 ° C.) (preliminary firing step) to obtain (M1M2) O
_ThreeCan be obtained.

[0034] Note that when M1 is Y, in the first preparation step without obtain a pre YM2O _3, not including Y M2
Oxide M2O _X only, for example, M2 is a spinel type compound is Mn and _{Cr (Mn 1 .5 Cr 1.5)} O 4
May be obtained. Then, in the second preparation step, the obtained (M1M2) O ₃ or M2O _X is mixed with Y ₂ O ₃ so as to have a desired resistance value and a desired temperature coefficient of resistance (Formulation 2). In addition, in the preparation of M2O _X and Y ₂ O ₃ , the preparation is performed such that Y of Y ₂ O ₃ forms a solid solution in the M ₂ O _X side to become a perovskite compound YM2O ₃ at the time of calcination described later.

The (M1M2) O_Three+ Y_TwoO_Three,
Or M2O_X+ Y_TwoO_ThreeWhen mixing, the desired resistance
M1 or M1
2 oxides, and composite oxides of M1 and M2
(Eg TiO_Two, YTiO _Three)
You may. Also in this case, the calcination described later (for example,
(1500 ° C. or more), these additives (M1M
2) O_ThreeSolution of M1 or M2 in perovskite
Compound (M1M2) O_ThreeFormulate so that

Then, the prepared mixture (M1M2) O
₃ + Y ₂ O ₃ (or M2O _X + Y ₂ O ₃ ) is pulverized (pulverizing step), a lead wire such as Pt is incorporated, molded into a desired shape by a mold or the like (molding step), and the above-described firing ( (For example, 1500 ° C. or higher) (firing step), and (M1M2)
A thermistor element made of O ₃ · Y ₂ O ₃ is obtained. By the way, in the second preparation step, CaO, C
at least one of aCO ₃ and CaSiO ₃ and S
Mixture (M1M2) O ₃ + with iO ₂ as sintering aid
When added to Y ₂ O ₃ , the sintered density is further improved. As a result, the resistance value of the thermistor element can be stabilized, and the variation in the resistance value with respect to the variation in the firing temperature can be reduced.

The thermistor element thus obtained is a mixed sintered body in which (M1M2) O ₃ , which is a perovskite compound, and Y ₂ O ₃ are uniformly mixed via a grain boundary. The obtained thermistor element is incorporated into a general temperature sensor assembly to form a temperature sensor. Then, the temperature sensor is placed in a high-temperature furnace, and the temperature is changed from room temperature (for example, 27 ° C.)
Up to 000 ° C, resistance value, temperature coefficient of resistance β, room temperature to 100
Each characteristic of the resistance change rate ΔR at a heat history of 0 ° C. is measured.

Here, β is β (° K) = ln (R /
Represented by _{R 0) / (1 / K} -1 / K 0). Note that ln
Is a common logarithm, and R and R ₀ are each room temperature (300
(K) and 1000 ° C. (1273 K). The resistance change rate ΔR represents the resistance change of the temperature sensor in the high-temperature endurance test that is left at 1100 ° C. in the air for 100 hours in each temperature sensor, and is expressed by the following equation: ΔR (%) = (R ′ _t / R _t ) × 100−
It is represented by 100. Note that _Rt is a predetermined temperature t (for example, 4
(00 ° C.), R ′ _t indicates the resistance at a predetermined temperature t after being left for 100 hours.

As a result, in the temperature range from room temperature to 1000 ° C., R _t is 50Ω to 100 kΩ and β is 200
It could be adjusted to 0 to 4000 (° K), and it was confirmed that ΔR could be stably realized at a level of about several%. Here, the above R _t range, beta, to more reliably achieve the values of ΔR _{are, a (M1M2) O 3 ·} bY 2 mole fraction in the O ₃ a, b are, 0.05 ≦ a < 1.0, 0 <b ≦
0.95 and a + b = 1 are preferable.

Therefore, according to the present embodiment, the room temperature to 10
The temperature can be detected over the high temperature range of 00 ° C, from room temperature to 1
It is possible to provide a wide-range thermistor element having a small resistance value change and stable characteristics even at a heat history of 000 ° C. Further, the temperature resistance coefficient β is 2000 to 4000 (° K) smaller than that of the conventional thermistor element.
Therefore, the variation in the resistance value due to the temperature fluctuation can be reduced.

The present embodiment will be described in more detail with reference to Examples 1 to 6 and Comparative Examples 1 and 2 described later. (Second Embodiment) The second embodiment relates to a mixed sintered body (M1
M2) It provides a method for producing O ₃ · Y ₂ O ₃ and has first and second preparation steps as in the first embodiment, but in addition to the first embodiment, the following It is a characteristic that it did.

That is, during the second preparation step, (M1
M2) In the step of pulverizing by mixing O ₃ or M ₂ O _X with Y ₂ O ₃ (pulverizing step), the average particle diameter of this mixture after pulverization is set to be equal to or less than the average particle diameter of Y ₂ O ₃ before mixing.
Hereinafter, this point will be mainly described. In the manufacturing method of the second embodiment, when the temperature accuracy of the temperature sensor incorporating the thermistor element of the first embodiment is investigated, it is found based on the result that the temperature accuracy varies from sensor to sensor. Was. Here, the evaluation method of the temperature accuracy was performed as follows, for example.

From the resistance-temperature data of a large number (for example, 100) of the manufactured temperature sensors, a predetermined temperature (for example, 35) is obtained.
0 ° C.), the standard deviation σ (sigma) of the resistance value is calculated, and six times the standard deviation σ is used as the variation width of the resistance value (both sides). And evaluated by expressing the temperature accuracy ± A ° C. as a result,
It was found that the temperature accuracy ± A ° C. for each sensor varied from ± 20 ° C. to 30 ° C.

On the other hand, thermistor material is SEM, EPMA
According to the observation in the first embodiment,
(M1M2) O after calcination obtained in the first preparation step
_Since the average particle size (for example, 2 to 5 μm) such as ₃ is larger than the average particle size of Y ₂ O ₃ mixed therewith (for example, 2 μm or less), the composition of the mixed sintered body is not uniformly mixed. The distribution was found to vary.

Therefore, in the second preparation step of the first embodiment, the average particle size of the mixture (M1M2) O ₃ + Y ₂ O ₃ , M2O _X + Y ₂ O _3, etc. after being prepared and pulverized Was varied to investigate the relationship between the average particle size and the temperature accuracy ± A ° C. As a result, it was found that the temperature accuracy ± A ° C. could be reduced to ± 10 ° C. or less if the average particle size of the mixture was set to be equal to or less than the average particle size of Y ₂ O ₃ before mixing (about 1.0 μm). Was.

Here, pulverization for reducing the average particle size
As a means, a medium stirring mill or the like can be used.
ZrO 2 is used as a pulverizing medium for the medium stirring mill._TwoBo
(For example, φ1 mm or less) or the like can be used.
According to the second embodiment, (M1M2) O_ThreeAnd Y
_TwoO_ThreeOr M2O_XAnd Y_TwoO_ThreeUniform mixing by atomization of
The combined sintered body (M1M2) O_Three・ Y_TwoO _Three
Of the thermistor element
Can be reduced.

Accordingly, it is possible to provide a wide-range thermistor element capable of achieving better sensor temperature accuracy (less variation in temperature accuracy between sensors) than the conventional level in a temperature range from room temperature to 1000 ° C. Note that the second embodiment will be described in more detail with Examples 7 to 14 described later.

(Third Embodiment) The third embodiment provides a method for producing a mixed sintered body (M1M2) O ₃ · Y ₂ O _3. Although it has a second preparation step, the following points are different from the first embodiment. That is, the in the first preparation step, M1 oxide which is a raw material of M1 and M2 (M1O _X) and oxides of M2 mixed (M2O _X), etc., in the step (mixing step) of grinding, M2 of the material Is mixed and crushed with the raw material of M1,
The average particle size of the mixed and pulverized product was set to be equal to or less than the average particle size of the raw material of M1 before mixing and 0.5 μm or less.
1M2) O ₃ precursor alone or mixed sintered body (M1M
2) O ₃ · Y ₂ O ₃ is obtained.

Therefore, in the method for producing the mixed sintered body (M1M2) O ₃ · Y ₂ O ₃ according to the present embodiment, the calcined product obtained in the first preparation step has a precursor having the same composition as the mixed sintered body. Body (M1M2) O ₃ · Y ₂ O ₃ or (M1M2)
There are two production methods depending on whether O _{3 is used} alone. The former is a first manufacturing method, and the latter is a second manufacturing method. Here, as described above, the precursor (M1M2) O ₃ .Y ₂ O ₃
Means that in (M1M2) O ₃ (perovskite structure), the excess of Y over the stoichiometric ratio (theoretical amount) is Y ₂ O
₃ is attached to (M1M2) O ₃ and has the same composition as the target mixed sintered body.

Since the manufacturing method according to the third embodiment has a portion that overlaps with the first embodiment, portions different from the first embodiment will be mainly described below. In the first production method, in the first preparation step, a material containing at least Y ₂ O ₃ as a raw material of M1 is used, and the raw material of M1 and an oxide of M2 (M2O _x ) which is a raw material of M2 are used. After blending, mixing and pulverizing, calcination (for example, 1000 ° C to 1 ° C)
(About 500 ° C.) to obtain the precursor (M1M2) O ₃
- obtain a Y ₂ O _3.

Here, at the time of the mixing and pulverization (mixing step), the average particle size of the mixed and pulverized material after pulverization is determined by the medium stirring mill or the like described in the second embodiment.
The raw material of No. 1 is not more than the average particle diameter and not more than 0.5 μm, and then is preliminarily fired to obtain a precursor. Thereafter, in a second preparation step, the precursor is further mixed in a desired amount, pulverized, incorporated with a lead wire such as Pt, formed into a desired shape by a mold or the like, and fired (for example, at 1500 ° C. or higher). Is performed, a thermistor element made of the mixed sintered body (M1M2) O ₃ .Y ₂ O ₃ is obtained.

In the second production method, in the first preparation step, the oxide of M1 (M1
O _X) and oxides of M2 (M2O _X) or the like formulation, mixing, after grinding to give a (M1M2) O ₃ by calcination (e.g. 1000 ° C. to 1500 approximately ° C.). Here, at the time of mixing and pulverization (mixing step), the average particle diameter of the mixed and pulverized material after pulverization is measured by the medium stirring mill or the like described in the second embodiment, and the average particle diameter of the raw material of M1 before mixing Not more than 0.5 μm.

Thereafter, in a second preparation step, (M1M2) O ₃ and Y ₂ O ₃ are further mixed to a desired amount,
Of the mixed sintered body (M1M
2) Obtain a thermistor element made of O ₃ · Y ₂ O ₃ . As a result, uniform mixing of the composition is achieved by uniform atomization of the raw materials of M1 and M2, so that the raw materials are produced after calcination (M
1M2) The composition variation in O ₃ or the precursor can be reduced, and the presence of unreacted raw materials can be suppressed, and the variation in the resistance value of the thermistor element can be reduced.

Accordingly, it is possible to provide a wide-range thermistor element capable of achieving better sensor temperature accuracy (less variation in temperature accuracy between sensors) than the conventional level in the temperature range from room temperature to 1000 ° C. In the first and second production methods, the pulverization in the pulverization step of the second preparation step may be pulverization using a ball mill or the like, but may be pulverization using a medium stirring mill or the like as in the second embodiment. Good.

That is, in the first production method, the precursor obtained by the preliminary calcination is mixed and pulverized, and the average particle size of the precursor after pulverization is determined by comparing the average particle diameter of Y ₂ before mixing in the first preparation step. The average particle size of O ₃ is not more than the average particle size. On the other hand, in the second production method, it was obtained by calcination (M1M2).
O ₃ and Y ₂ O ₃ are mixed and pulverized, and the average particle size of the mixture after the pulverization is set to be equal to or less than the average particle size of Y ₂ O ₃ before mixing.

Thus, in addition to the effect of the third embodiment described above, (M1M2) O ₃ and Y ₂ O ₃ are uniformly mixed in the forming and firing steps subsequent to the pulverization step, so that mixed firing is achieved. Since the variation in the composition of the body is reduced, the variation in the resistance value of the thermistor element can be reduced. Therefore, compared to the manufacturing method of the second embodiment, the variation in the resistance value of the thermistor element can be reduced at a higher level, and a wide sensor that can achieve better sensor temperature accuracy (less variation in temperature accuracy between sensors). A range-type thermistor element can be provided.

In the temperature sensors using the wide-range thermistor elements of the second and third embodiments, since the temperature accuracy is suppressed to ± 10 ° C. or less, a map control device requiring a high temperature accuracy is required. For example, it is suitable for use as a temperature monitor of an oxygen sensor for exhaust gas of an automobile. In addition, about this 3rd Embodiment, Examples 15-2 mentioned later.
0 and Comparative Example 3 will be described in more detail.

Next, the first embodiment will be described by Examples 1 to 6 and Comparative Examples 1 and 2, and the second embodiment will be described by Examples 7 to 14 shown below. 3
Embodiments will be described in more detail with reference to Examples 15 to 20 and Comparative Example 3 below, but the above embodiments are not limited to these examples.

[0059]

【Example】

(Example 1) In this Example 1, (M1M2) at O _3, from Y, M2 as was selected Cr and _{Mn Y (Cr 0.5 Mn 0.5)} O 3 and Y ₂ O ₃ Prefecture as M1, Y
It is intended to obtain a (Cr _{0. 5} Mn _0.5) mixed sintered body of O ₃ · Y ₂ O _3.

The manufacturing process of the thermistor element of the first embodiment will be described.
As shown in FIG. This manufacturing process is roughly based on Formulation 1 in the figure.
To Y (Cr_0.5Mn_0.5) O_ThreeFirst preparation until obtaining
Process and the resulting Y (Cr_0.5Mn_0.5) O_ThreeAnd Y_TwoO
_ThreeUntil the thermistor element is obtained by blending
And a preparation step. In the first preparation step, first,
Any purity of 99.9% or more Y_TwoO_ThreeAnd Cr _TwoO_Three
And Mn_TwoO_ThreeAnd the molar ratio of Y: Cr: Mn is
Y to be 2: 1: 1_TwoO_ThreeAnd Cr_TwoO_ThreeAnd Mn_Two
O_ThreeIs weighed to make the total amount 500 g (Formulation 1).

In order to mix the weighed material, a ball mill φ15 made of Al ₂ O ₃ or Zr ₂ O ₃ was used as a ball mill.
kg, φ20 2.5kg resin pot (capacity 5
Liter) and add Y ₂ O ₃ and Cr ₂ O to this pot.
After adding the total amount of ₃ and Mn ₂ O ₃ , adding 1500 cc of pure water, and mixing at 60 rpm for 6 to 12 hours (mixing step).

Y obtained after the mixing treatment_TwoO_ThreeAnd Cr_TwoO
_ThreeAnd Mn_TwoO_ThreeTransfer the mixed slurry to a porcelain evaporating dish.
And dried in a hot air dryer at 150 ° C. for 12 hours or more.
_TwoO_ThreeAnd Cr_TwoO_ThreeAnd Mn_TwoO_ThreeTo obtain a mixed solid with
You. Subsequently, this mixed solid was roughly pulverized with a raikai machine,
通 し Pass through 30 mesh sieve, Y_TwoO_ThreeAnd Cr_TwoO_ThreeAnd M
n _TwoO_ThreeTo obtain a mixed powder.

In the calcination step, this mixed powder is mixed with 99.
Put into a 3% Al ₂ O ₃ crucible and place in a high-temperature furnace in air
Temporarily bake at 100 to 1300 ° C for 1 to 2 hours, and Y (Cr
_0.5 Mn _0.5 ) O ₃ is obtained. Y (Cr _0.5 Mn _0.5 ) O ₃ , which has become a massive solid by calcination, is roughly pulverized by a raikai machine and passed through a # 30 mesh sieve to obtain a powder. This Y
(Cr _0.5 Mn _0.5 ) O ₃ , when used alone as a thermistor material, has low resistance and 1000-4000 (°
K) shows the low temperature coefficient of resistance. As a wide-range thermistor material, Y (Cr _0.5 Mn _0.5 ) O ₃
Y ₂ O ₃ , which is a material for stabilizing the resistance value of the thermistor, is used.

In the second preparation step, first, Y (Cr _0.5 Mn _0.5 ) is adjusted so as to have a desired resistance value and a desired temperature coefficient of resistance.
The mixing molar ratio (mol fraction) of O ₃ : Y ₂ O ₃ was 38: 6.
Y (Cr _0.5 Mn _0.5 ) O powdered to be 2
₃ and a commercially available powder of Y ₂ O ₃ (purity of 99.9% or more) are weighed to make a total amount of 500 g. Here, Y (Cr _0.5 Mn
_0.5 ) The molar fractions of O ₃ and Y ₂ O ₃ are a and b (a + b
= 1), these a and b are equal to the above-mentioned molar ratio, and a = 0.38 and b = 0.62.

In the firing, a temperature range of 1500 to 1650 ° C.
SiO that becomes liquid phase around_Two, CaCO _ThreeAs sintering aid
The Y (Cr_0.5Mn_0.5) O_ThreeAnd Y_TwoO_Threeof
For the total amount (500 g), SiO_TwoIs 3% by weight, Ca
CO_ThreeAdd 4.5% by weight (Formulation 2). continue,
In the grinding step (mixing / grinding in the figure), the Y (Cr
_0.5Mn_0.5) O_ThreeAnd Y_TwoO_ThreeAnd SiO_TwoAnd CaCO_Three
And Al_TwoO_ThreeOr Zr_TwoO_Three1. Make boulder φ15.
5kg, 2.5kg of φ20 resin pot (capacity
5 liters) and after adding 1500 cc of pure water,
Mix and pulverize at 60 rpm for 4 hours or more.

In the above pulverizing step, Y (Cr _0.5
Mn _0.5 ) Polyvinyl alcohol (PVA) was added as a binder to Y (Cr) with respect to the solid content of O ₃ and Y ₂ O _3.
0.5 Mn _0.5 ) 1 g is added per 100 g of mixed powder of O ₃ and Y ₂ O _3, and mixed and pulverized at the same time. The mixed and pulverized slurry of Y (Cr _0.5 Mn _0.5 ) O ₃ and Y ₂ O ₃ obtained after mixing and pulverization is granulated by a spray dryer, dried, and dried.
(r _0.5 Mn _0.5 ) A mixed powder of O ₃ and Y ₂ O ₃ is obtained. This mixed powder is used as a thermistor raw material.

Subsequently, in the forming step (mold forming), using the thermistor raw material, the outer diameter × length is φ0.3 mm ×
10.5mm, material is Pt100 (pure platinum) as lead wire, insert lead wire, outer diameter φ1.74m
m with a pressure of about 1000 kgf / cm ² with a mold of m
A molded body of a thermistor element having an outer diameter of 1.75 mm on which a lead wire is formed is obtained.

In the firing step, the formed bodies of the thermistor elements were arranged on an Al ₂ O ₃ corrugated setter,
Baking at 1600 ° C. for 1 to 2 hours to obtain a mixed sintered body aY (Cr
_0.5 Mn _0.5 ) Outer diameter φ1.6 of O ₃ · bY ₂ O ₃
A 0 mm thermistor element is obtained. FIG. 2 shows the obtained thermistor element 1. Two parallel lead wires 11, 12
Are cylindrical element portions 13 having an outer diameter of 1.60 mm.
It is buried in the shape. This thermistor element 1
Is a temperature sensor incorporated in the general temperature sensor assembly shown in FIGS.

The thermistor element 1 is, as shown in FIG.
It is arranged in a cylindrical heat-resistant metal case 2. Although not shown, the lead wires 11 and 12 are connected to lead wires 31 and 32 of a metal pipe passing through the inside of the metal pipe 3. In addition, as shown in FIG. 4, the inside of the metal pipe 3 is filled with magnesia powder 33 to ensure insulation of the lead wires 31 and 32 in the metal pipe 3. The temperature sensor is configured as described above.

In the following, this embodiment and another embodiment 2 will be described.
In Examples 20 to 30 and Comparative Examples 1 to 3, the thermistor elements and temperature sensors to be manufactured have the same structures as those shown in FIGS. However, it is needless to say that the material composition of the mixed sintered body constituting the element portion 13 is that in each example. further,
In the above second preparation step, Y (Cr _0.5 M
n _0.5 ) O ₃ : Y ₂ O ₃ The mixture molar ratio is weighed so as to be 95: 5 and 5:95, and then a thermistor element is manufactured in the same procedure and incorporated into a temperature sensor. Here, each element of the present embodiment is represented by Y (Cr _0.5 Mn _0.5 ).
When the prepared molar ratio of O ₃ : Y ₂ O ₃ (corresponding to a: b) is 3
8:62, 95: 5, 5:95 in the order of element number 1, element number 2, and element number 3.

The temperature sensors incorporating the elements Nos. 1 to 3 were placed in a high-temperature furnace, and the temperature characteristics of the resistance were evaluated from room temperature (27 ° C.) to 1000 ° C. The evaluation results are shown in the table of FIG. As shown in FIG. 5, the wide-range thermistor element according to the first embodiment is composed of aY (CrMn) O ₃ .bY ₂ O
₃ (a + b = 1) is 0.05 ≦ a <1.
In the range of 0, 0 <b ≦ 0.95, the resistance value is a low resistance value of 50 Ω to 100 kΩ required as a temperature sensor, and the resistance temperature coefficient β also indicates 2000 to 4000 (° K). The coefficient can be controlled in a wide range. Therefore, the temperature can be detected over a high temperature range from room temperature to 1000 ° C.

Also from the results of the high-temperature durability test (resistance change rate), it is possible to provide a wide-range thermistor material having stable characteristics with little change in resistance value. (Embodiment 2) The present embodiment 2 is based on (Mn _1.5 Cr _1.5 ) O ₄
And a Y ₂ O _{3 Prefecture, Y (Cr 0 .5 Mn 0.5} ) O 3 · Y 2
This is to obtain a mixed sintered body of O ₃ . In the case of the present embodiment, Y of Y ₂ O ₃ forms a solid solution with (Mn _1.5 Cr _1.5 ) O ₄ at the time of mixed sintering. Therefore, in (M1M2) O ₃ , Y is defined as Y and M2 as M1. Cr and Mn are selected.

The manufacturing process of the thermistor element according to the second embodiment will be described.
As shown in FIG. This manufacturing process is roughly based on Formulation 1 in the figure.
From (Mn_1.5Cr_1.5) O_FourFirst preparation process until obtaining
(Mn_1.5Cr_1.5) O_FourAnd Y_TwoO_ThreeWhen
The second step until compounding (Formulation 2) to obtain a thermistor element
It is divided into a preparation step. In the first preparation step,
The purity of displacement is more than 99.9% Cr_TwoO_ThreeAnd Mn_TwoO_Three
Are prepared, and the C: Mn molar ratio is set to 1: 1.
r_TwoO_ThreeAnd Mn _TwoO_ThreeIs weighed to make the total amount 500 g.
(Formulation 1).

Subsequently, the prepared Cr ₂ O ₃ and Mn ₂ O
₃ is subjected to treatments such as mixing, drying, pulverization, and preliminary firing in the same manner as in Example 1 to obtain (Mn _1.5 Cr _1.5 ) O ₄ .
Then, it is coarsely pulverized and turned into powder by # 30 mesh sieve. As a wide-range thermistor material, this (M
n _1.5 Cr _1.5 ) O ₄ and Y ₂ O ₃ which is a material for stabilizing the resistance value of the thermistor are used.

In the second preparation step, first, (Mn _1.5 Cr _1.5 ) O is adjusted so as to obtain a desired resistance value and a desired temperature coefficient of resistance.
_4: Y a ₂ O ₃ formulation molar ratio of 14: 86 so as to (Mn _1.5 Cr _1.5) O ₄ and Y ₂ O ₃ were weighed whole amount 50
0 g. Further, a sintering aid is added in the same manner as in Example 1 (Formulation 2). Subsequently, the compounded (Mn _1.5 C
r _1.5 ) O ₄ + Y ₂ O ₃ + SiO ₂ + CaCO ₃ was mixed, pulverized, granulated, dried, molded and fired in the same manner as in Example 1 to _obtain Y (Cr _0.5 Mn _0.5 ) O ₃ .Y ₂ O
Obtain a thermistor element with ₃ as the element part and incorporate it into the temperature sensor.

Further, in the second preparation step,
(Mn_1.5Cr_1.5) O_Four: Y_TwoO _ThreeThe compounding molar ratio of
Weighed to be 38:62 and 3:97;
A thermistor element is manufactured in the same procedure and used as a temperature sensor.
Incorporate. Here, each element of the present embodiment corresponds to (Mn_1.5C
r_1.5) O_Four: Y_TwoO_ThreeIs 14:86,
38:62, 3:97, element number 4, element number
5, element number 6.

As described above, in this embodiment, the mixed
During sintering (Mn_1.5Cr_1.5) O _FourFor Y_TwoO_Three
Y forms a solid solution, and extra oxygen atoms
Is released to As a result, the perovskite type Y (Cr
_0.5Mn_0.5) O_ThreeAnd Y_TwoO _ThreeA which is a mixed sintered body of
(Y (Cr_0.5Mn_0.5) O_Three) ・ BY_TwoO_ThreeIs obtained
You.

Therefore, in this embodiment, a (Y (Cr (Cr
The molar ratio a: b of _0.5 Mn _0.5 ) O ₃ ) .bY ₂ O ₃ is slightly larger than that of (Mn _1.5 Cr _1.5 ) O ₄ : Y ₂ O _3. For example, even if the mixing molar ratio is 3:97, a ≧ 0.05 and b ≦ 0.9
It is 5. This has been confirmed by SEM, EPMA, and other surveys on the composition and structure of the mixed sintered body.

Then, in the same manner as in the first embodiment, numbers 4 to
The temperature sensor incorporating the element No. 6 was placed in a high-temperature furnace, and the temperature characteristics of the resistance were evaluated from room temperature (27 ° C.) to 1000 ° C. The evaluation results are shown in the table of FIG. As shown in FIG. 7, the wide-range-type thermistor material of Example 2 is a
The molar fraction (a + b = 1) of Y (Cr _0.5 Mn _0.5 ) O ₃ .b Y ₂ O ₃ is 0.05 ≦ a <1.0, 0 <b ≦
Within the range of 0.95, the same effect as described in the first embodiment can be realized.

(Embodiment 3) In Embodiment 3, Y (Cr _0.5
Mn _0.5 ) O ₃ , Y ₂ O ₃ and TiO _{2 form} Y (CrM
nTi) to obtain a mixed sintered body of O ₃ and Y ₂ O ₃ . Here, Y (CrMnTi) O ₃ has a perovskite structure, and the composition ratio of each atom is a stoichiometric ratio. For example, it is Y (Cr _0.45 Mn _0.45 Ti _0.1 ) O ₃ . Hereinafter, the same applies to Y (CrMnTi) O ₃ in each example.

In the case of the present embodiment, during mixed sintering, Y
Since Ti of TiO ₂ forms a solid solution with (Cr _0.5 Mn _0.5 ) O ₃ , Y is selected as M1 in (M1M2) O ₃ and Cr, Mn and Ti are selected as M2. FIG. 8 shows a manufacturing process of the thermistor element of the third embodiment. This manufacturing process is roughly based on Formulation 1 to Y in the figure.
A first preparation step until (Cr _0.5 Mn _0.5 ) O ₃ is obtained, and the obtained Y (Cr _0.5 Mn _0.5 ) O ₃ , Y ₂ O ₃ and TiO ₂ are mixed (mix 2) to obtain a thermistor element. And a second preparation step until the above is obtained.

The first preparation step is the same as in Example 1 described above, and is omitted here. As the wide-range thermistor material of the present embodiment, Y (Cr _0.5 Mn _0.5 ) O
₃ and Y ₂ which is a material for stabilizing the resistance value of the thermistor
O ₃ and Ti which is a resistor as a material for adjusting the resistance value
O ₂ (additive) is used. In the second preparation step, first,
In order to obtain a desired resistance value and a temperature coefficient of resistance, Y (Cr
_{0.5 Mn 0.5) O 3: Y} 2 O 3: the preparation molar ratio of TiO _2, 37: 59: so that 4 Y (Cr _0.5 M
n _0.5 ) O ₃ , Y ₂ O ₃ and TiO ₂ are weighed and the total amount is 50
0 g. Further, a sintering aid is added in the same manner as in Example 1 (Formulation 2).

Subsequently, the prepared Y (Cr_0.5M
n_0.5) O_Three+ Y_TwoO_Three+ TiO_Two+ SiO_Two+ CaC
O_Three, Mixed, crushed and produced in the same manner as in Example 1 above.
Y (CrMnTi) O after granulation, drying, molding and firing_Three
・ Y_TwoO_ThreeTo obtain a thermistor element with
Install in the sensor. Further, in the second preparation step,
And Y (Cr_0.5Mn_0.5) O_Three: Y_TwoO_Three: TiO
_TwoWere adjusted to 87: 5: 8 and 5: 94.5:
0.5 and weigh the sample in the same manner.
A mister element is manufactured and incorporated into a temperature sensor. here,
Each element of the present embodiment is Y (Cr_0.5Mn_0.5) O_Three: Y
_TwoO _Three: TiO_TwoAre 37: 59: 4, 87:
Element number 7, element number in the order of 5: 8, 5: 94.5: 0.5
The child number is 8 and the element number is 9.

Note that aY constituting each element of the present embodiment 3
(CrMnTi) O_Three・ BY_TwoO_ThreeMole fraction (a,
b) is Y (Cr_0.5Mn_0.5) O
_Three: Y _TwoO_ThreeEqual to the ratio of By the way, element number 7, element
In the order of No. 8 and Element No. 9, a: b (a + b = 1) is
0.39: 0.61, 0.95: 0.05, 0.05:
0.95.

Then, in the same manner as in the first embodiment, numbers 7 to
The temperature sensor incorporating the element No. 9 was placed in a high-temperature furnace, and the temperature characteristics of the resistance value were evaluated from room temperature (27 ° C.) to 1000 ° C. The evaluation results are shown in the table of FIG. As shown in FIG. 9, the wide-range thermistor material of Example 3 is a
The mole fraction of Y (CrMnTi) O ₃ .bY ₂ O ₃ (a +
b = 1), 0.05 ≦ a <1.0, 0 <b ≦ 0.95
Within this range, the same effect as described in the first embodiment can be realized.

(Embodiment 4) In Embodiment 4, Y (Cr _0.5
Mn _0.5 ) O ₃ , Y ₂ O ₃ and YTiO _{3 form} Y (Cr
(MnTi) O ₃ · Y ₂ O ₃ to obtain a mixed sintered body. In the case of this embodiment, Y (Cr
_0.5 Mn _0.5) for YTiO ₃ Y and Ti are solid solution with respect to O _3, becomes the selected Cr, Mn and Ti (in M1M2) O _3, as M1 as Y, M2.

FIG. 10 shows a manufacturing process of the thermistor element according to the fourth embodiment. This manufacturing process is roughly divided into a first preparation process from the preparation 1 in the drawing to Y (Cr _0.5 Mn _0.5 ) O ₃ , and the obtained Y (Cr _0.5 Mn _0.5 ) O ₃ and Y ₂
A second preparation step until O ₃ and YTiO ₃ are prepared (Formulation 2) to obtain a thermistor element; and a third preparation step for obtaining YTiO ₃ to be subjected to the second preparation step (formulation in the figure) 3 to YTiO ₃ ).

The first preparation step is the same as in Example 1 described above, and is omitted here. In the third preparation step, first,
Any of the prepared 99.9% or more Y ₂ O ₃ and TiO ₂ purity, Y: the mole ratio of Ti is 1: 1 so as to Y ₂ O
₃ and TiO ₂ are weighed to make a total amount of 500 g (formulation 3). In order to mix this weighed material, A
2.5kg of l ₂ O ₃ or Zr ₂ O ₃ grinding balls Fai15,
Using a resin pot (5 liter capacity) containing 2.5 kg of φ20, put the whole amount of Y ₂ O ₃ and TiO ₂ into the pot, add 1500 cc of pure water, and mix at 60 rpm for 6 hours (mixing Process).

The Y ₂ O ₃ and TiO ₂ obtained after the mixing treatment
Was transferred to a porcelain evaporating dish and dried with a hot air drier at 150 ° C. for 12 hours or more, and Y ₂ O ₃ and TiO ₂
To obtain a mixed solid. Subsequently, the mixed solid was roughly pulverized with a raikai machine, passed through a # 30 mesh sieve, and then subjected to Y ₂ O
A mixed powder of ₃ and TiO ₂ is obtained. In the calcination step, the mixed powder is put into a 99.3% Al ₂ O ₃ crucible,
1100 to 1300 in a high-temperature furnace under normal pressure atmosphere (in air)
1-2 hours calcined at ° C., to obtain a YTiO _3. Lumpy YTiO ₃ which has been formed into a lump solid by calcination is roughly pulverized with a raikai machine and passed through a # 30 mesh sieve to obtain a powder.

As the wide range type thermistor material,
Y (Cr) obtained in the first preparation step _0.5Mn_0.5) O_Three
And Y_TwoO_ThreeAnd YTiO_Three(Additive). Second key
In the manufacturing process, first, the desired resistance value and resistance temperature coefficient are obtained.
Thus, Y (Cr_0.5Mn_0.5) O_Three: Y_TwoO_Three: YT
iO_ThreeIs adjusted so as to be 37: 60: 3.
(Cr_0.5Mn_0.5) O_ThreeAnd Y_TwoO_ThreeAnd YTiO_ThreeAnd
Weigh to a total of 500 g. Also, the same as in the first embodiment.
Is added with a sintering aid (Formulation 2).

Subsequently, the prepared Y (Cr_0.5M
n_0.5) O_Three+ Y_TwoO_Three+ YTiO_Three+ SiO_Two+ Ca
CO_Three, Mixed, crushed and produced in the same manner as in Example 1 above.
Y (CrMnTi) O after granulation, drying, molding and firing_Three
・ Y_TwoO_ThreeTo obtain a thermistor element with
Install in the sensor. Further, in the second preparation step,
And Y (Cr_0.5Mn_0.5) O_Three: Y_TwoO_Three: YTi
O_ThreeWere adjusted to 87: 6: 3 and 5:94.
7: 0.3 and weighed in the same manner.
A thermistor element is manufactured and incorporated into a temperature sensor. here
Therefore, each element of the fourth embodiment is represented by Y (Cr_0.5Mn_0.5) O
_Three: Y _TwoO_Three: YTiO_ThreeIs 37:60:
3, 87: 6: 3, 5: 94.7: 0.3
Number 10, element number 11, and element number 12 are assumed.

In each element of the fourth embodiment, the upper
As mentioned, YTiO_ThreeOf Y and Ti in
AY (CrMnTi) O in each element_Three・ BY_TwoO_Three
Is the molar fraction (a, b) of Y (Cr
_0.5Mn_0.5) O_Three: Y_TwoO _ThreeIs slightly more than the ratio of
It is almost the same. And, as in the first embodiment.
In addition, a temperature sensor incorporating elements of numbers 10 to 12 is
Place in a high-temperature furnace and change the temperature from room temperature (27 ° C) to 1000 ° C.
The temperature characteristics of the resistance value were evaluated. The evaluation results are shown in the table of FIG.
You.

As shown in FIG. 11, the wide-range thermistor material of the fourth embodiment is made of aY (CrMnTi) O ₃
The molar fraction of bY ₂ O ₃ (a + b = 1) is 0.05 ≦
Within the ranges of a <1.0 and 0 <b ≦ 0.95, the same effects as described in the first embodiment can be realized. (Embodiment 5) In this embodiment 5, (Mn _1.5 Cr _1.5 ) O ₄
Y (CrMnTi) O ₃ · from Y ₂ O ₃ and TiO ₂
A mixed sintered body of Y ₂ O ₃ is obtained. In the case of this example, since Y of Y ₂ O ₃ and Ti of TiO _{2 form} a solid solution with (Mn _1.5 Cr _1.5 ) O ₄ during mixed sintering, (M1M2) O ₃ has M1 as M1. Cr, Mn and Ti are selected as Y and M2.

FIG. 12 shows a manufacturing process of the thermistor element of the fifth embodiment. This manufacturing process is roughly divided into a first preparation process from the preparation 1 in the drawing to obtaining (Mn _1.5 Cr _1.5 ) O ₄ , and the obtained (Mn _1.5 Cr _1.5 ) O ₄ and Y ₂ O ₃
And TiO ₂ (Formulation 2) and a second preparation step until a thermistor element is obtained. The first preparation step is the same as in Example 2 described above, and is omitted here. The above-mentioned (Mn _1.5 Cr _1.5 ) O ₄ , Y ₂ O ₃ and TiO ₂ (additives) are used as the wide-range thermistor material of this embodiment.

In the second preparation step, first, a desired resistance value
(Mn)_1.5Cr_1.5) O
_Four: Y_TwoO_Three: TiO_TwoWas adjusted to 12:84:
(Mn_1.5Cr_1.5) O_FourAnd Y_TwoO_ThreeWhen
TiO_TwoAre weighed to make the total amount 500 g. In addition,
As in Example 1, a sintering aid is added (Formulation 2). Continued
(Mn_1.5Cr_1.5) O_Four+ Y_TwoO_Three+
TiO_Two+ SiO _Two+ CaCO_ThreeAbout the above embodiment
Mixing, pulverization, granulation, drying, molding and baking are performed in the same manner as in 1.
Yes, Y (CrMnTi) O_Three・ Y_TwoO_ThreeIs the element part
Obtain a thermistor element and incorporate it into a temperature sensor.

Further, in the second preparation step,
(Mn_1.5Cr_1.5) O_Four: Y_TwoO _Three: TiO_TwoMix
The molar ratios were 36: 61: 3 and 4: 95.7: 0.3
And weigh the thermistor following the same procedure.
An element is manufactured and incorporated into a temperature sensor. Here, this implementation
Each element of Example 5 has (Mn_1.5Cr_1.5) O_Four: Y
_TwoO _Three: TiO_TwoIs 12: 84: 4, 3
Element numbers in the order of 6: 61: 3, 4: 95.7: 0.3
13, element number 14, element number 15.

As described above, in the fifth embodiment,
During the mixing sintered, Y ₂ with respect to (Mn _1.5 Cr _1.5) O ₄
Y of O ₃ and Ti of TiO _{2 form} a solid solution, and excess oxygen atoms are released into the atmosphere during sintering. As a result, perovskite-type (Y (CrMnTi) O ₃ ) and Y ₂ O
_A (Y (CrMnTi) O ₃ )
bY ₂ O ₃ is obtained.

Therefore, a (Y (C
The molar ratio a: b of rMnTi) O ₃ ) .bY ₂ O ₃ is slightly larger than the above-mentioned molar ratio of (Mn _1.5 Cr _1.5 ) O ₄ : Y ₂ O ₃ , For example, even if the compounding molar ratio is 4: 95.7, a ≧ 0.05 and b ≦
0.95. This has been confirmed by SEM, EPMA, and other surveys on the composition and structure of the mixed sintered body.

Then, in the same manner as in the first embodiment, the number 13
The temperature sensor incorporating the elements Nos. 1 to 15 was placed in a high-temperature furnace, and the temperature characteristics of the resistance value were evaluated from room temperature (27 ° C.) to 1000 ° C. The evaluation results are shown in the table of FIG. FIG.
As shown in the figure, the wide-range thermistor material of Example 5 has a mole fraction (a + b = 1) of aY (CrMnTi) O ₃ .bY ₂ O ₃ of 0.05 ≦ a <1.0, 0 <B
Within the range of ≦ 0.95, the same effect as described in the first embodiment can be realized.

(Embodiment 6) In this embodiment 6, (Mn _1.5 C
r _1.5 ) From O ₄ , Y ₂ O ₃ and YTiO ₃ , Y (CrM
nTi) to obtain a mixed sintered body of O ₃ · Y ₂ O ₃ . In the case of this example, (Mn _1.5
Since Y and Ti of YTiO _{3 form} a solid solution with Cr _1.5 ) O ₄ , in (M1M2) O ₃ , M1 is Y, M
2, Cr, Mn and Ti are selected.

FIG. 14 shows a manufacturing process of the thermistor element according to the sixth embodiment. This manufacturing process is roughly divided into a first preparation process from the preparation 1 in the drawing to obtaining (Mn _1.5 Cr _1.5 ) O ₄ , and the obtained (Mn _1.5 Cr _1.5 ) O ₄ and Y ₂ O ₃
And YTiO ₃ (formulation 2) to obtain a thermistor element, and a third preparation step of obtaining YTiO ₃ to be subjected to the second preparation step (formulation 3 in the figure).
To YTiO ₃ ).

The first preparation step is the same as in Example 2 above, and the third preparation step is the same as in Example 4 above, and will not be described here. As a wide-range thermistor material, (Mn _1.5 Cr _1.5 ) O obtained in the first preparation step is used.
₄ , Y ₂ O ₃ and YTiO obtained in the third preparation step
_{3 Use} (additive). In the second preparation step, first, (Mn _1.5 C
r _1.5 ) O ₄ : Y ₂ O ₃ : YTiO ₃
13: 84: 3 (Mn _1.5 Cr _1.5 ) O ₄
, Y ₂ O ₃ and YTiO ₃ are weighed to make a total amount of 500 g. Further, a sintering aid is added in the same manner as in Example 1 (Formulation 2).

Subsequently, the prepared (Mn_1.5Cr_1.5)
O_Four+ Y_TwoO_Three+ YTiO_Three+ SiO_Two+ CaCO_ThreeTo
Then, mixing, crushing, granulating, and drying were performed in the same manner as in Example 1 above.
After drying, molding and firing, Y (CrMnTi) O_Three・ Y_Two
O_ThreeTo obtain a thermistor element with
Incorporate in. Further, in the second preparation step,
(Mn_1.5Cr_1.5) O_Four: Y_TwoO _Three: YTiO_ThreeKey
The combined molar ratios were 37: 61: 2 and 4: 95.8: 0.
2 and weigh the thermistor following the same procedure.
A temperature sensor is manufactured and incorporated into a temperature sensor.

Here, each element of the sixth embodiment is composed of Y (Cr
The molar ratio of _1.5 Mn _1.5 ) O ₃ : Y ₂ O ₃ : YTiO ₃ is 13: 84: 3, 37: 61: 2, 4: 95.8:
In the order of 0.2, element number 16, element number 17, and element number 18 are set. As described above, in the sixth embodiment,
During the mixing sintered, Y ₂ with respect to (Mn _1.5 Cr _1.5) O ₄
Y of O ₃ and Y and Ti of YTiO _{3 form} a solid solution,
Excess oxygen atoms are released into the atmosphere during sintering. As a result, a (Y (CrMnTi) O which is a mixed sintered body of perovskite-type (Y (CrMnTi) O ₃ ) and Y ₂ O ₃ is obtained.
₃ ) bY ₂ O ₃ is obtained.

For this reason, a (Y (C
The molar ratio a: b of rMnTi) O ₃ ) .bY ₂ O ₃ is slightly larger than the above-mentioned molar ratio of (Mn _1.5 Cr _1.5 ) O ₄ : Y ₂ O ₃ , For example, even when the blending molar ratio is 4: 95.8, a ≧ 0.05 and b ≦
0.95. This has been confirmed by SEM, EPMA, and other surveys on the composition and structure of the mixed sintered body.

Then, in the same manner as in the first embodiment, the number 16
The temperature sensors incorporating the elements No. to No. 18 were placed in a high-temperature furnace, and the temperature characteristics of the resistance value were evaluated from room temperature (27 ° C.) to 1000 ° C. The evaluation results are shown in the table of FIG. FIG.
As shown in the figure, the wide-range thermistor material of Example 6 has a mole fraction (a + b = 1) of aY (CrMnTi) O ₃ .bY ₂ O ₃ of 0.05 ≦ a <1.0, 0 <B
Within the range of ≦ 0.95, the same effect as described in the first embodiment can be realized.

Comparative Example 1 As Comparative Example 1, Y (Cr _0.5 M) was used without using Y ₂ O ₃ for stabilizing the resistance value.
A temperature sensor using a thermistor element having n _0.5 ) O ₃ alone will be described. Y (Cr _0.5 Mn _0.5 ) O ₃ is obtained by the same manufacturing method as in the first embodiment. Using Y (Cr _0.5 Mn _0.5 ) O ₃ prepared as a raw material,
The results of the evaluation as a temperature sensor are shown in the table of FIG. The evaluation method of the resistance value characteristics was performed in the same manner as in Example 1.

As is apparent from FIG. 16, when Y ₂ O ₃ for stabilizing the resistance value is not used, the temperature cannot be detected because the resistance value in the high temperature range of 1000 ° C. is too low. Also from the results of the high-temperature durability test (resistance change rate). The rate of change in resistance ΔR exceeds ± 20%, and a wide-range thermistor element having stable characteristics cannot be provided.
Therefore, Y (Cr _0.5 Mn _0.5 ) O in Comparative Example 1
₍₃₎ A thermistor element having a single composition cannot be used as an element of a temperature sensor intended for the present invention.

Comparative Example 2 As Comparative Example 2, a temperature sensor using a thermistor element having a single composition of YTiO ₃ without using Y ₂ O ₃ for stabilizing the resistance value will be described. According to the same manufacturing method as in the fourth embodiment, YTiO ₃
Get. The results of evaluation as a temperature sensor using YTiO ₃ prepared as a raw material are shown in the table of FIG. The evaluation method of the resistance value characteristics was performed in the same manner as in Example 1. FIG.
As is apparent from the above, in the thermistor element composed of YTiO ₃ alone, the resistance value is extremely high in a low temperature region at room temperature (27 ° C.), and becomes larger than 1000 kΩ, so that the temperature cannot be detected. Also, from the results of the high-temperature durability test, the resistance change rate ΔR
However, it is not possible to provide a wide-range thermistor element exceeding ± 20% and having stable characteristics.

Therefore, YTiO_ThreeSingle composition thermistor
The element is a temperature sensor element intended for the present invention.
I can not use it. (Embodiment 7) In this embodiment 7, Y (Cr_0.5Mn_0.5)
O_ThreeAnd Y_TwoO_Three(M1 = Y, M2 = C)
r, Mn), first, Y (Cr
_0.5Mn _0.5) O_ThreeIs prepared. Thermist of Example 7
FIG. 17 shows a manufacturing process of the semiconductor device. In this embodiment, the second
It is a manufacturing method according to the embodiment.

Starting materials Y ₂ O ₃ , Cr ₂ O ₃ and Mn ₂
As for O ₃ , a raw material having a high purity of 99.9% is used.
The average particle sizes of Y ₂ O ₃ , Cr ₂ O ₃ and Mn ₂ O ₃ are 1.0 μm, 2.0 to 4.0 μm, and 7.0, respectively.
１５15.0 μm. The average particle size of each raw material was the same in Examples 8 to 20 and Comparative Examples 1 and 2 described later.

In the first preparation step (formulation 1 to Y (C
In up to _{r 0.5 Mn 0.5) O 3)} , first, Y (Cr _0.5 M
n _0.5) O ₃ is, Y ₂ O ₃ and Cr ₂ O ₃ and Mn ₂ O ₃ molar ratio and (Y: Cr: Mn) is 2: 1: so that 1, Y ₂ O ₃ to 268. 8 g, 101 g of Cr ₂ O ₃ ,
Weigh 104 g of Mn ₂ O ₃ (Formulation 1). In order to mix this weighed material, Al ₂ O ₃ or Zr
Using a resin pot (capacity: 5 liters) containing 2.5 kg of O ₂ boulder φ15 and 2.5 kg of φ20, put into this pot, add 1500 cc of pure water, and then rotate at 60 rpm
For 4 hours (mixing step).

Y obtained after the mixing treatment_TwoO_ThreeAnd Cr_TwoO_ThreeWhen
Mn_TwoO_ThreeTransfer the mixed slurry to a porcelain evaporating dish
Dry in a dryer at 100-150 ° C for 12-17 hours,
Y_TwoO_ThreeAnd Cr_TwoO_ThreeAnd Mn_TwoO_ThreeTo obtain a mixture of Y
_TwoO_ThreeAnd Cr_TwoO_ThreeAnd Mn_TwoO_ThreeLeica mixed solids
Coarsely pulverized with a machine and passed through a # 30 mesh sieve._TwoO _Three
And Cr_TwoO_ThreeAnd Mn_TwoO_ThreeTo obtain a powder mixture.

In the calcination step, the Y ₂ O ₃ and the Cr ₂ O
₃ and Mn ₂ O ₃ were mixed with 99.3% Al ₂ O ₃
Put in a crucible made in a high-temperature furnace under normal pressure atmosphere (in air)
Heat-treated at 100 ° C. for 2 hours, Y (Cr _0.5 Mn _0.5 ) O
_{Get three} . Y (Cr _0.5 M
n _0.5 ) O ₃ is coarsely pulverized by a raikai machine and passed through a # 30 mesh sieve to obtain a powder.

The present thermistor material is made of the above Y (Cr_0.5M
n_0.5) O_ThreeAnd Y_TwoO_ThreeIs used. Second preparation step
(Formulation 2 and later in the figure) First, the desired resistance value and resistance
Y (Cr_0.5Mn_0.5) O
_Three(Average particle size 2-5 μm) and Y_TwoO _Three(Average particle size 1.0
μm) and the compounding molar ratio (Y (Cr_0.5Mn_0.5) O_Three:
Y_TwoO_Three) Is 100: 22 so that Y (Cr_0.5M
n_0.5) O_Three1560 g, Y_TwoO_ThreeWeighs 440 g
The total is 2,000 g.

Further, at the time of firing, a temperature range of 1500 to 1650 ° C.
SiO that becomes liquid phase around_Two, CaCO _ThreeAs sintering aid
The Y (Cr_0.5Mn_0.5) O_ThreeAnd Y_TwoO_Threetotal
For 2000g, SiO_TwoIs 60% of 3% by weight, C
aCO_ThreeAdd 90 g of 4.5% by weight (formulation
2). Therefore, Y (Cr_0.5Mn_0.5) O_ThreeAnd Y_TwoO_Three
And SiO_TwoAnd CaCO_ThreeAnd crush 2150g
Raw materials.

Next, in the pulverization step (mixing / pulverization in the figure), a pearl mill (RV1 manufactured by Ashizawa Co., Ltd.) was used as a medium stirring mill in order to atomize the thermistor raw material.
V, effective volume: 1.0 liter, actual volume: 0.5 liter). The operating conditions of this pearl mill device are as follows.
And 3.0% of the volume of the stirring tank is filled with zirconia balls.

The operating conditions are a peripheral speed of 12 m / sec and a rotation speed of 3110 rpm. Note that 4.5 liters of distilled water is used as a dispersion medium for 2150 g of the pulverized raw material, and a binder, a release agent and a dispersant are simultaneously added, and mixing and pulverization are performed for 10 hours. As the binder, 1 g of polyvinyl alcohol (PVA) is added per 100 g of the raw material.

Raw material slurry of pulverized thermistor material
The average particle size was 0.4
μm (micron meter). This is Y before mixing
_TwoO _ThreeIs smaller than 1.0 μm. The obtained sa
-The raw slurry of the mister material is dried with a spray dryer.
Granulation under conditions of drying chamber inlet temperature 200 ° C and outlet temperature 120 ° C
·dry. The granulated powder of the obtained thermistor material is averaged
It is spherical with a diameter of 30 μm.
Perform molding of the child.

The molding process is performed by a mold molding method. Pt100 (φ0.3 × 10.5) is loaded into a male die as a lead wire, and granulated powder is put into a φ1.74 female die, and the pressure is reduced. 1
It is molded at 000 kgf / cm ² to obtain a molded body of a thermistor element provided with a lead wire. In the firing step, the molded body of the thermistor element is placed on a corrugated setter made of Al ₂ O _{3 and} fired at 1500 to 1600 ° C. for 1 to 2 hours to obtain a thermistor element.

The obtained thermistor element and the thermistor
The temperature sensor incorporating the heater element is shown in FIGS.
It has the same structure as that of FIG. The result of evaluating the obtained temperature sensor was
The results are shown in FIG. In FIG. 18, Y (CrMn)
O_ThreeIs Y (Cr_0.5Mn_0.5) O_ThreeRepresents Also figure
During the pulverization process of the second preparation process,
Raw material components (in this example, Y (Cr _0.5Mn_0.5) O
_ThreeAnd Y_TwoO_Three), And the average particle size (μm) after pulverization is
The average particle size of the raw material slurry after pulverization in the second preparation step (this
In the example, the above-mentioned 0.4 μm is shown. Hereinafter, examples described later.
The same applies to the eighth to fourteenth embodiments.

With the temperature sensor according to the seventh embodiment, ± 10 ° C. can be obtained as the temperature accuracy. As described in the second embodiment, the temperature accuracy evaluation method is based on the temperature sensor 1.
The standard deviation σ (sigma) of the resistance value at 350 ° C. is calculated from the resistance value-temperature data of 00 units, and the standard deviation σ of 6 is calculated.
The variation width of the resistance value is doubled (both sides), and the value A obtained by halving the value obtained by converting the variation value of the resistance value into temperature is expressed as temperature accuracy ± A ° C. and evaluated.

(Embodiment 8) In this embodiment 8, Y (Cr
_0.5 Mn _0.5 ) Mixed sintered body of O ₃ and Y ₂ O ₃ (M1 =
As a raw material for obtaining Y, M2 = Cr, Mn), first, a mixture of an oxide of Cr and an oxide of Mn is mixed at 1000 ° C.
Obtained by calcination at above _{(Mn 1.5 Cr 1. 5) O} 4
Is prepared. FIG. 19 shows a manufacturing process of the thermistor element according to the eighth embodiment. This example is a manufacturing method according to the second embodiment.

The first preparation step (in the figure, from Formulation 1 to (Mn
_1.5 Cr _1.5 ) O ₄ ), first, Cr ₂ O ₃ and Mn
₂ O ₃ and the molar ratio (Cr: Mn) is 1: such that 1, 101g of _{Cr 2 O 3, Mn 2 0} 3 a to 104g weighed (Formulation 1). These Cr ₂ O ₃ and Mn ₂ O ₃ are mixed (6 hours), dried, pulverized, and heat-treated in the same manner as in Example 7 to obtain (Mn _1.5 Cr _1.5 ) O ₄ . (Mn _1.5 Cr _1.5 ) O turned into massive solid by heat treatment
₄ is coarsely pulverized by a raikai machine and passed through a # 30 mesh sieve to obtain a powder.

This thermistor material is made of the above (Mn _1.5 Cr
_1.5) using a O ₄ and Y ₂ O _3. In the second preparation step (formulation 2 and thereafter in the figure), first, (Mn _1.5 Cr _1.5 ) O ₄ (average particle size of 2 to 5 μm) and Y ₂ O are mixed so as to obtain a desired resistance value and a temperature coefficient of resistance. ₃ (average particle size: 1.0 μm) and a molar ratio ((Mn _1.5 Cr _1.5 ) O ₄ : Y ₂ O ₃ ) of 1
630 g of (Mn _1.5 Cr _1.5 ) O ₄ and 1370 g of Y ₂ O ₃ were weighed so as to be 00: 216, and a total of 2000 g was obtained.
Prepare Also, as in Example 7, as a sintering aid,
60 g of SiO ₂ and 90 g of CaCO ₃ are added (formulation 2).

Next, in order to atomize the thermistor material, a pearl mill device is used as in Example 7. The raw material slurry of the pulverized thermistor material was evaluated with a laser particle size meter, and as a result, the average particle size was 0.5 μm (micrometer). This is smaller than the average particle size of Y ₂ O ₃ before mixing of 1.0 μm. The raw material slurry is granulated and dried by a spray dryer to obtain a granulated powder of a thermistor material. The conditions for pulverization using a pearl mill and the conditions for drying with a spray dryer are the same as in Example 7.

The molding is performed by a mold molding method in the same manner as in the seventh embodiment to obtain a thermistor element, which is incorporated into a general temperature sensor assembly to form a temperature sensor. FIG. 18 shows the evaluation results. The temperature sensor according to the eighth embodiment has a temperature accuracy of ± 10.
° C is obtained. The evaluation method of the temperature accuracy is described in Example 7.
Is the same as (Embodiment 9) In this embodiment 9, Y (Cr _0.5 Mn _0.5 )
From O ₃ , Y ₂ O ₃ and TiO ₂ , Y (CrMnTi) O
₃ and Y ₂ O ₃ (M1 = Y, M2 = Cr, M
As a raw material for obtaining n, Ti), first, Y (Cr
_0.5 Mn _0.5 ) O ₃ is prepared. FIG. 20 shows a manufacturing process of the thermistor element of the ninth embodiment. In this embodiment, the second
It is a manufacturing method according to the embodiment.

In the first preparation step, the method described in Example 7 was used.
Y (Cr_0.5Mn_0.5) O_ThreeGet
You. The material of the thermistor is Y (Cr_0.5Mn_0.5)
O_ThreeAnd Y_TwoO_ThreeAnd TiO_TwoIs used. Second preparation step
(Formulation 2 and later in the figure) First, the desired resistance value and resistance
Y (Cr_0.5Mn_0.5) O
_Three(Average particle size 2-5 μm) and Y_TwoO _Three(Average particle size 1.0
μm) and TiO_TwoAnd the compounding molar ratio (Y (Cr_0.5Mn
_0.5) O_Three: Y_TwoO_Three: TiO_Two) Is 100: 22: 1
Y (Cr_0.5Mn_0.5) O_Three1520
g, Y_TwoO_Three400 g, TiO_TwoWeigh 80g and total
2000 g. In addition, the same as in Example 7,
And SiO_Two60 g, CaCO_ThreeAdd 90g
(Formulation 2).

Therefore, Y (Cr _0.5 Mn _0.5 ) O ₃ and Y
_A total of 2150 g of ₂ O ₃ , TiO ₂ , SiO ₂ and CaCO ₃ is used as a pulverized raw material. Next, in order to atomize the thermistor raw material, a pearl mill is used as in Example 7. As a result of evaluating the raw material slurry of the crushed thermistor material with a laser particle size analyzer, the average particle size was 0.4 μm.
m (micron meter). This is Y ₂ before mixing
The average particle size of O ₃ is smaller than 1.0 μm.

The obtained raw material slurry of the thermistor material is granulated and dried by a spray dryer. The pulverization conditions for atomization and the conditions of the spray dryer are the same as in Example 7. Molding is performed by a mold molding method as in Example 7, a thermistor element is obtained, and incorporated into a general temperature sensor assembly to form a temperature sensor.

FIG. 18 shows the evaluation result of the obtained temperature sensor. The temperature sensor according to the ninth embodiment can obtain ± 8 ° C. as the temperature accuracy. The evaluation method of the temperature accuracy is the same as that of the seventh embodiment. (Embodiment 10) In this embodiment 10, Y (Mn _1.5 Cr
_1.5 ) Y (CrMnT) from O ₄ , Y ₂ O ₃ and TiO ₂
i) Mixed sintered body of O ₃ and Y ₂ O ₃ (M1 = Y, M2 = C
r, Mn, Ti)
(Mn _1.5 Cr _1.5 ) O ₄ is prepared by calcining a mixture of the oxide of Mn and the oxide of Mn at 1000 ° C. or higher. A manufacturing process of the thermistor element of Example 10 is shown in FIG.
Shown in This example is a manufacturing method according to the second embodiment.

In the first preparation step, the method described in Example 8 was used.
In the same manner as (Mn_1.5Cr _1.5) O_FourGet.
This thermistor material has the above (Mn_1.5Cr_1.5) O_FourWhen
Y_TwoO_ThreeAnd TiO_TwoIs used. Second preparation step (Figure
Medium, Formulation 2), first, the desired resistance value and resistance temperature
(Mn_1.5Cr_1.5) O_Four(Average grain
Diameter 2-5 μm) and Y_TwoO_Three(Average particle size 1.0 μm) and T
iO_TwoAnd the molar ratio ((Mn_1.5Cr_1.5) O_Four: Y_Two
O_Three: TiO_Two) Is 30:70:10
(Mn_1.5Cr_1.5) O_Four578 g, Y_TwoO_Three13
55g, TiO_TwoWeighing 67g to prepare a total of 2000g
I do. Further, as in Example 7, SiO 2 was used as a sintering aid.
_Two60 g, CaCO_ThreeAdd 90g (mixed)
2).

Next, a pearl mill device is used as a medium stirring mill in order to atomize the thermistor material. The raw material slurry of the pulverized thermistor material was evaluated with a laser particle size meter, and as a result, the average particle size was 0.5 μm (micrometer). This is smaller than the average particle size of Y ₂ O ₃ before mixing of 1.0 μm. The obtained raw material slurry of the thermistor material is granulated and dried by a spray dryer. The pulverization conditions for atomization and the conditions of the spray dryer are the same as in Example 7.

The molding is performed by a mold molding method in the same manner as in the seventh embodiment to obtain a thermistor element, which is incorporated into a general temperature sensor assembly to form a temperature sensor. FIG. 18 shows the result of evaluating the obtained temperature sensor. The temperature sensor according to the present invention can obtain ± 8 ° C. as the temperature accuracy. The evaluation method of the temperature accuracy is the same as that of the seventh embodiment.

(Embodiment 11) FIG. 22 shows a manufacturing process of the thermistor element of Embodiment 11. Example 11
-Example 14 is an example in which mixing and pulverization (pulverization step) in the second preparation step are performed by a medium stirring mill.
For comparison with 0, the mixing and pulverization were performed by a conventional ball mill.

In the eleventh embodiment, a ball mill which is a conventional method is used in the pulverizing step in the second preparation step of the seventh embodiment. In the first preparation step, Y (Cr _0.5 Mn _0.5 ) O ₃ is obtained in the same manner as in the first preparation step of Example 7 above. In the second preparation step, first, 390 g of Y (Cr _0.5 Mn _0.5 ) O ₃ (average particle size of 2 to 5 μm) and Y ₂ O ₃ (average particle size) are set so as to obtain a desired resistance value and a temperature coefficient of resistance. 1.0μ
m) is weighed to make a total of 500 g. In addition, Si
O ₂ and CaCO ₃ are used as sintering aids, and SiO ₂ is 1
5 g and 23 g of CaCO ₃ are added (formulation 2). Therefore, Y (Cr _0.5 Mn _0.5 ) O ₃ , Y ₂ O ₃ and SiO ₂
And a total of 538 g of CaCO ₃ as a raw material to be mixed and pulverized.

The operation conditions of the mixing and pulverizing ball mill were as follows. The thermistor raw material was put into a resin pot (capacity: 5 liters) containing 2.5 kg of Al ₂ O ₃ boulder φ15 and 2.5 kg of φ20. After adding 1800 cc of pure water, the mixture is mixed and pulverized at 60 rpm for 6 hours. As a result of evaluating the raw material slurry of the pulverized thermistor material with a laser particle size meter, the average particle diameter was 3.0 μm (micrometer). This is because the average particle diameter of Y ₂ O ₃ before mixing is 1.0 μm.
Greater than.

The obtained slurry of the thermistor material is granulated and dried by a spray dryer in the same manner as in Example 7. A thermistor element is formed using the obtained granulated powder of the thermistor material. Molding is performed by a mold molding method as in Example 7, a thermistor element is obtained, and incorporated into a general temperature sensor assembly to form a temperature sensor. FIG. 18 shows the result of evaluating the obtained temperature sensor. Example 1
The temperature accuracy of the temperature sensor according to No. 1 is ± 30 ° C. The evaluation method of the temperature accuracy is the same as that of the seventh embodiment.

In the eleventh embodiment, the thermistor element incorporated in the temperature sensor shows a good resistance-temperature characteristic which is the object of the present invention. That is, room temperature (27
℃) to 1000 ℃, low resistance (50Ω ~
100 kΩ), good temperature coefficient of resistance β (2000 to 40
00 (° K)) and a small resistance change rate (± 10% or less).

(Example 12) In Example 12, a ball mill which is a conventional method is used in the grinding step (mixing / grinding) in the second preparation step in Example 8.
As raw materials for obtaining a mixed sintered body of Y (CrMn) O ₃ and Y ₂ O ₃ , (Mn _1.5 Cr _1.5 ) O ₄ and Y ₂ O ₃
Is used. In the first preparation step, (Mn _1.5 Cr _1.5 ) O ₄ is obtained in the same manner as in the first preparation step of Example 8.

In the second preparation step, first, (Mn _1.5 Cr _1.5 ) O is adjusted so as to obtain a desired resistance value and a desired temperature coefficient of resistance.
₄ Weigh 158 g of (average particle size of 2 to 5 μm) and 342 g of Y ₂ O ₃ (average particle size of 1.0 μm) to prepare a total of 500 g. In addition, SiO ₂ and CaCO ₃ are used as sintering aids, and 15 g of SiO _{2 and} 23 g of CaCO ₃ are added (formulation 2). Therefore, (Mn _1.5 Cr _1.5 ) O ₄ and Y ₂
A total of 538 g of O ₃ , SiO ₂ and CaCO ₃ is used as a pulverized raw material.

The operation conditions of the ball mill for mixing and pulverization are the same as in Example 11. As a result of evaluating the raw material slurry of the pulverized thermistor material with a laser particle size meter, the average particle size was 2.7 μm (micrometer). This is because the average particle diameter of Y ₂ O ₃ before mixing is 1.0 μm.
Greater than. The obtained raw material slurry of the thermistor material is granulated and dried by a spray dryer in the same manner as in Example 7. A thermistor element is formed using the obtained granulated powder of the thermistor material. Molding is performed by a mold molding method as in Example 7, a thermistor element is obtained, and incorporated into a general temperature sensor assembly to form a temperature sensor.

FIG. 18 shows the evaluation result of the obtained temperature sensor. The temperature accuracy of the temperature sensor according to the twelfth embodiment is ± 30 ° C. The evaluation method of the temperature accuracy is the same as that of the seventh embodiment. In the twelfth embodiment, the thermistor element incorporated in the temperature sensor also exhibits a good resistance-temperature characteristic, which is the object of the present invention, as in the eleventh embodiment.

(Thirteenth Embodiment) A thirteenth embodiment is a modification of the ninth embodiment.
In the second preparation step, the pulverization step (mixing and pulverization)
In addition, a conventional ball mill is used. Y
(CrMn) O_ThreeAnd Y_TwoO_ThreeTo obtain a mixed sintered body with
Y (Cr.Mn) O_ThreeAnd Y_TwoO _ThreeAnd T
iO_TwoIs used. In the first preparation step, Example 7 was used.
Y (Cr) in the same manner as in the first preparation step of_0.5Mn_0.5)
O_ThreeGet.

In the second preparation step, first, a desired resistance value
Y (Cr_0.5Mn_0.5)
O_Three380 g (average particle size 2 to 5 μm), Y_TwoO_Three(flat
100 g of average particle size 1.0 μm)_ThreeWeigh 20g
To a total of 500 g. In addition, SiO_Two, CaCO_ThreeTo
Used as a sintering aid, SiO_TwoIs 15g, CaCO_ThreeIs
Add 23 g (Formulation 2). Therefore, Y (Cr_0.5M
n_0.5) O_ThreeAnd Y_TwoO _ThreeAnd SiO_TwoAnd CaCO_ThreeAnd
A total of 538 g is used as a raw material for grinding.

The operation conditions of the ball mill for mixing and pulverization are the same as in Example 11. As a result of evaluating the raw material slurry of the pulverized thermistor material with a laser particle size meter, the average particle diameter was 3.0 μm (micrometer). This is because the average particle diameter of Y ₂ O ₃ before mixing is 1.0 μm.
Greater than. The obtained raw material slurry of the thermistor material is granulated and dried by a spray dryer in the same manner as in Example 7. A thermistor element is formed using the obtained granulated powder of the thermistor material. Molding is performed by a mold molding method as in Example 7, a thermistor element is obtained, and incorporated into a general temperature sensor assembly to form a temperature sensor.

FIG. 18 shows the evaluation result of the obtained temperature sensor. The temperature accuracy of the temperature sensor according to the thirteenth embodiment is ± 25 ° C. The evaluation method of the temperature accuracy is the same as that of the seventh embodiment. Note that also in the thirteenth embodiment, the thermistor element incorporated in the temperature sensor shows a good resistance-temperature characteristic, which is the object of the present invention, as in the eleventh embodiment.

(Embodiment 14) Embodiment 14 is a modification of the above embodiment.
In the second preparation step of No. 10, the pulverization step (mixing
Crushing) using a conventional ball mill.
Y (CrMnTi) O _ThreeAnd Y_TwoO_ThreeTo obtain a mixed sintered body
(Mn_1.5Cr_1.5) O _FourAnd Y_Two
O_ThreeAnd TiO_TwoIs used. In the first preparation step,
In the same manner as in the first preparation step of Example 8, (Mn_1.5C
r_1.5) O_FourGet.

In the second preparation step, (Mn _1.5 Cr _1.5 ) O ₄ (average particle size of 2 to 5 μm) and Y ₂ O ₃ (average particle size of 1.0 μm) are obtained so as to obtain desired resistance value and temperature coefficient of resistance. 0 μm)
And TiO ₂ , and (Mn _1.5 Cr _1.5 ) O ₄
g, 338 g of Y ₂ O ₃ and 17 g of TiO ₂ are weighed to prepare a total of 500 g. Further, SiO ₂ and CaCO ₃ were used as sintering aids, and SiO ₂ was 15 g and CaCO ₃ was 2
Add 3 g (Formulation 2). Therefore, (Mn _1.5 Cr
_1.5 ) O ₄ , Y ₂ O ₃ , TiO ₂ , SiO ₂ and CaCO
538 g obtained by adding ₃ to the total was used as a pulverized raw material.

The operation conditions of the ball mill for mixing and pulverization are the same as in Example 11. As a result of evaluating the raw material slurry of the pulverized thermistor material with a laser particle size meter, the average particle diameter was 3.0 μm (micrometer). This is because the average particle diameter of Y ₂ O ₃ before mixing is 1.0 μm.
Greater than. The obtained raw material slurry of the thermistor material is granulated and dried by a spray dryer in the same manner as in Example 7. A thermistor element is formed using the obtained granulated powder of the thermistor material. Molding is performed by a mold molding method as in Example 7, a thermistor element is obtained, and incorporated into a general temperature sensor assembly to form a temperature sensor.

FIG. 18 shows the evaluation result of the obtained temperature sensor. The temperature accuracy of the temperature sensor according to the fourteenth embodiment is ± 25 ° C. The evaluation method of the temperature accuracy is the same as that of the seventh embodiment. Note that, also in the fourteenth embodiment, the thermistor element incorporated in the temperature sensor exhibits a good resistance-temperature characteristic, which is the object of the present invention, as in the eleventh embodiment.

As described above, when the embodiments 7 to 14 are compared, all thermistor elements show good resistance-temperature characteristics which are the object of the present invention. It can be said that the production methods described in Examples 7 to 10 are superior to the production methods in Examples 11 to 14. In other words, in the manufacturing methods described in Examples 7 to 10, while achieving the effects described in the first embodiment, the composition is uniformly mixed by atomizing the thermistor material, and the mixed sintered body (M1M2) O ₃ · Y ₂ by reducing the compositional variations of O _3, can reduce variations in the resistance value.

Therefore, the thermistor element of the present invention is
When produced by the production method according to the embodiment (Examples 7 to 10), compared with the production method using a conventional ball mill (Examples 11 to 14, temperature accuracy ± 20 to 30 ° C.), room temperature to 1000 ° C. Therefore, it is possible to provide a thermistor element in which the temperature accuracy is improved to ± 10 ° C. or less and the temperature sensor can be made more accurate.

(Embodiment 15) In Embodiment 15, Y_TwoO
_ThreeAnd Cr_TwoO_ThreeAnd Mn_TwoO_ThreeAnd CaCO_ThreeWith Y as the raw material
(Cr_0.5Mn_0.5) O_Three・ Y_TwoO_ThreeMixed sintered body (M
1 = Y, M2 = Cr, Mn). Example 15
FIG. 23 shows a manufacturing process of the semiconductor device. In this embodiment,
According to the first manufacturing method described in the third embodiment
It is. That is, the first preparation step (from the preparation 1 in the figure)
Y (Cr_0.5Mn_0.5) O_Three・ Y _TwoO_ThreeAbove)
Of the first preparation step.
Powder of the compounding step and the second preparation step (formulation 2 in the figure)
A medium stirring mill is used in the crushing step.

Y ₂ O _{3 having} a purity of 99.9% or more
And Cr ₂ O ₃ , Mn ₂ O ₃ and CaCO ₃ are prepared. In Formula 1, these components are blended so that the thermistor element has the desired resistance value and resistance temperature coefficient. Specifically, a of aY (Cr _0.5 Mn _0.5 ) O ₃ .bY ₂ O ₃
Y ₂ O ₃ , Cr ₂ O _3, and Mn ₂ O ₃ were weighed so that a and b (molar fraction) were a: b = 38: 62, and the total amount was 20.
00 g. Further, 36 g of CaCO ₃ was added, and Y ₂
A total of 2036 g of O ₃ , Cr ₂ O ₃ , Mn ₂ O ₃ and CaCO ₃ is used as a mixed raw material (formulation 1).

Next, in the mixing step, a medium stirring mill is used to atomize the raw materials. The medium stirring mill of the present invention
A pearl mill (Ashizawa RV1V, effective capacity: 1.0 liter, actual capacity: 0.5 liter) is used. The mixing conditions by the pearl mill device are as follows: 3.0 kg of a zirconia ball diameter of 0.5 mm is used as a grinding medium, and 80% of the volume of the stirring tank is filled with the zirconia ball.

The operating conditions are a peripheral speed of 12 m / sec and a rotation speed of 3110 rpm. To 2036 g of the mixed raw material, 4.5 liters of distilled water was used as a dispersion medium, and at the same time, a dispersant and a binder were added, followed by mixing and grinding for 10 hours. As the binder, polyvinyl alcohol (PV
A) is added in an amount of 20 g per 2036 g of the mixed raw material. In the mixing step, the raw material slurry of the thermistor material mixed and pulverized was evaluated with a laser particle sizer, and as a result, the average particle size was 0.4 μm (micrometer). This is smaller than the average particle size (1.0 μm) of Y ₂ O ₃ before mixing and smaller than 0.5 μm.

The obtained raw material slurry is dried by a spray dryer under the conditions of a drying chamber inlet temperature of 200 ° C. and an outlet temperature of 120 ° C. The obtained thermistor raw material particles have an average particle size of 30.
This raw material powder having a spherical shape of μm was put into a crucible made of 99.3% Al ₂ O ₃ , and was heated to 1100 to 1300 ° C. in the air in a high-temperature furnace.
And calcined for 1 to 2 hours with precursor Y (Cr _0.5 Mn _0.5 )
O ₃ · Y ₂ O ₃ is obtained (temporary firing step).

The precursor Y (C
r _0.5 Mn _0.5 ) O ₃ · Y ₂ O ₃ was coarsely pulverized by a raikai machine and passed through a # 30 mesh sieve to obtain a precursor Y (Cr _0.5 M
obtaining n _{0. 5)} powder O ₃ · Y ₂ O _3. Next, Formulation 2
Wherein the precursor Y (Cr _0.5 Mn _0.5 ) O ₃ .Y
2000 g of ₂ O ₃ powder is prepared.

In the pulverizing step, a pearl mill is used as in the mixing step. Then, a dispersant, a binder, and a release agent are added to the precursor prepared in Formulation 2, and the mixture is pulverized into fine particles. The conditions for pulverization by this pearl mill are the same as those in the mixing step. As a result of evaluating the raw material slurry of the pulverized thermistor material with a laser particle size meter, the average particle size was 0.3 μm (micrometer). This is smaller than the average particle size 1.0μm in front of Y ₂ O ₃ be formulated with Formulation 1.

The precursor Y obtained after the pulverization (Cr _0.5 M
n _0.5 ) The slurry of O ₃ · Y ₂ O ₃ is granulated by a spray dryer in the same manner as in the above drying step, and Y (Cr _0.5
Mn _0.5 ) Obtain a granulated powder of O ₃ · Y ₂ O ₃ . This Y (C
Thermistor element is molded using granulated powder of r _0.5 Mn _0.5 ) O ₃ · Y ₂ O ₃ . The molding process is performed by a mold molding method, and Pt100 (φ0.3 mm × 10.5 m
loaded with m) as a lead wire, the female mold having an outer diameter φ1.89mm put _{Y (Cr 0. 5 Mn 0.5)} O 3 · granulated powder Y ₂ O _3, molded under a pressure of about 1000 kgf / cm ² Then, a molded body of the thermistor element provided with the lead wire is obtained.

The molded body of the thermistor element was arranged on a corrugated setter made of Al ₂ O ₃ .
It is fired for 2 hours to obtain a thermistor element (mixed sintered body) having an outer diameter of 1.60 mm. This thermistor element is incorporated into a temperature sensor assembly to form a temperature sensor. The structures of the thermistor element and the temperature sensor are the same as those shown in FIGS.

The temperature sensor is placed in a high-temperature furnace in the same manner as in the first embodiment, and the resistance-temperature characteristic is evaluated from room temperature (27 ° C.) to 1000 ° C. FIG. 24 shows the evaluation results. FIG. 25 shows the result of evaluating the temperature accuracy of the obtained temperature sensor in the same manner as in Example 7 described above. In FIG. 25, in the figure, the raw material components at the time of pulverization are the raw material components in the pulverizing step of the second preparation step (in this example, the precursor Y
(Cr _0.5 Mn _0.5 ) O ₃ .Y ₂ O ₃ ), and the average particle size after mixing (μm) is the average particle size of the raw material slurry after pulverization in the mixing step of the first preparation step (in this example, , 0.4 μm above, and the average particle size after grinding (μm) indicates the average particle size of the raw material slurry after grinding in the grinding step of the second preparation step (0.3 μm in this example). . Hereinafter, the same applies to Comparative Examples 1 and 2 evaluated in Examples 16 to 20 and Comparative Example 3 described below.

In the temperature sensor according to the fifteenth embodiment, ± 7 ° C. can be obtained as the temperature accuracy. Further, in Formulation 1, Y (C
r _0.5 Mn _0.5 ) O ₃ : Y ₂ O ₃ molar ratio (a: b)
However, a thermistor element was similarly manufactured using thermistor raw materials prepared so as to be 95: 5 and 5:95, and the result (resistance temperature characteristic) evaluated as a temperature sensor is shown in FIG.
4 is shown. Here, in Example 15, the above molar ratios a: b were set to element number 19, element number 20, and element number 21 in the order of 38:62, 95: 5, 5:95, and FIG.
It writes in.

As shown in FIG. 24, the
Mister element is aY (Cr_0.5Mn _0.5) O_Three・ BY_Two
O_ThreeIs 0.05 ≦ a <1.
As a temperature sensor in the range of 0, 0 <b ≦ 0.95
The required resistance is 50Ω to 100kΩ, and the resistance temperature
The coefficient β also shows 2000 to 4000 (K),
Therefore, the temperature is increased over the high temperature range from room temperature to
Can be detected.

Also, from the result of the high-temperature durability test (resistance change rate), it is possible to provide a thermistor element having stable characteristics with little change in resistance value. (Embodiment 16) This embodiment 16 is based on Y (Cr _0.5 M
n _0.5 ) O ₃ and Y ₂ O _{3 form} Y (Cr _0.5 Mn _0.5 )
O ₃ · Y ₂ O ₃ mixed and fired (M1 = Y, M2 = C
r, Mn). FIG. 26 shows a manufacturing process of the thermistor element of Example 16.

The present embodiment relates to the second manufacturing method described in the third embodiment. That is, the first preparation step (in the figure, from preparation 1 to Y (Cr _0.5 Mn _0.5 ))
O ₃ ) to obtain Y (Cr _0.5 Mn _0.5 ) O ₃ , and medium stirring in the mixing step of the first preparation step and the pulverization step of the second preparation step (formulation 2 and thereafter in the figure). Use a mill.

Y ₂ O _{3 having} a purity of 99.9% or more
And Cr ₂ O ₃ , Mn ₂ O ₃ and CaCO ₃ are prepared. In Formulation 1, Y ₂ O ₃ , Cr ₂ O _3, and Mn ₂ O ₃ were weighed so that the molar ratio of Y: Cr: Mn was 2: 1: 1 to make a total amount of 644 g, and further, 36 g of CaCO ₃ . Add,
A total of 680 g of Y ₂ O ₃ , Cr ₂ O ₃ , Mn ₂ O _3, and CaCO ₃ is used as a mixed raw material.

Next, in order to atomize the raw materials in the mixing step, a medium stirring mill is used as in the fifteenth embodiment. The mixing conditions are the same as in Example 15. In this mixing step, the raw material slurry of the thermistor material mixed and pulverized was evaluated with a laser particle size meter, and as a result, the average particle size was 0.3 μm (micrometer). This is smaller than the average particle size (1.0 μm) of Y ₂ O ₃ before mixing and smaller than 0.5 μm.

The obtained raw material slurry was used in Example 15 above.
In the same manner as described above, after granulation and drying with a spray dryer, and pre-baking, Y (Cr _0.5 Mn _0.5 ) O ₃ is obtained. The Y (Cr _0.5 Mn _0.5 ) O ₃ , which has become a massive solid by calcination, is coarsely pulverized with a raikai machine, passed through a # 30 mesh sieve, and Y (C
(r _0.5 Mn _0.5 ) O ₃ powder is obtained. Next, Formulation 2
Then, the components are adjusted so as to have a desired resistance value and a resistance temperature coefficient as a thermistor element. Specifically, aY (Cr _0.5 M
n _0.5 ) O ₃ · bY ₂ O ₃ where a and b are a: b = 38:
Y (Cr _0.5 Mn _0.5 ) O ₃ (powder) and Y ₂ O ₃ are weighed to give a total weight of 2000 g so as to be 62.

In the pulverizing step, Y (Cr _0.5 Mn _0.5 ) O
₃ and Y ₂ O ₃ are mixed and pulverized by using a pearl mill device in the same manner as in the mixing step to perform atomization. The pulverization conditions by the pearl mill device are the same as the conditions in the mixing step. Also,
In this pulverization step, a dispersant, a binder, and a release agent are added, and mixed and pulverized at the same time. As a result of evaluating the raw material slurry of the pulverized thermistor material with a laser particle size meter, the average particle size was 0.4 μm (micrometer). This is because the average particle size of Y ₂ O ₃ before the preparation in Preparation 2 is 1.0.
smaller than μm.

Y (Cr _0.5 Mn _0.5 ) O ₃ obtained after pulverization
And a slurry of Y ₂ O ₃ are granulated with a spray dryer,
A granulated powder of Y (Cr _0.5 Mn _0.5 ) O ₃ and Y ₂ O ₃ is obtained. Subsequently, using this mixed granulated powder,
Molding and firing are performed in the same manner as described above to obtain a thermistor element. This thermistor element is incorporated in a temperature sensor assembly as in the fifteenth embodiment to form a temperature sensor. The structures of the thermistor element and the temperature sensor are the same as those shown in FIGS.

The above temperature sensor was evaluated in the same manner as in Example 15. FIG. 27 shows the evaluation result of the resistance-temperature characteristic, and FIG. 25 shows the evaluation result of the temperature accuracy. The temperature sensor according to Embodiment 16 has a temperature accuracy of ± 5 ° C. as shown in FIG.
Is obtained. In Example 16, pulverization and atomization by a medium stirring mill are performed in the mixing step of the first preparation step and the pulverization step of the second preparation step, and pulverization and atomization by the medium stirring mill are performed only in the latter step. Can provide a thermistor element with further improved temperature accuracy as compared with the above-described Example 7 (temperature accuracy ± 10 ° C.).

Further, in the pulverizing step, Y (Cr _0.5 Mn)
_0.5 ) The molar ratio of O ₃ : Y ₂ O ₃ (a: b) is 95: 5
And a thermistor raw material prepared to be 5:95,
Similarly, a thermistor element was manufactured and evaluated as a temperature sensor. FIG. 27 shows the result. Here, Embodiment 16
Wherein the molar ratio a: b is 38:62, 95:
Element numbers 22, element numbers 23, and element numbers 24 are shown in FIG. 27 in the order of 5, 5:95.

As shown in FIG. 27, the
Mister element is aY (Cr_0.5Mn _0.5) O_Three・ BY_Two
O_ThreeIs 0.05 ≦ a <1.
As a temperature sensor in the range of 0, 0 <b ≦ 0.95
The required resistance is 50Ω to 100kΩ, and the resistance temperature
The coefficient β also shows 2000 to 4000 (K),
Therefore, the temperature is increased over the high temperature range from room temperature to
Can be detected.

Also, from the results of the high-temperature durability test (resistance change rate), it is possible to provide a thermistor element having stable characteristics with little change in resistance value. (Embodiment 17) In this embodiment 17, Y ₂ O ₃ and Cr ₂ O
₃ and Mn ₂ O ₃ and CaCO ₃ as raw materials, and Y (Cr _0.5 M
n _0.5 ) O ₃ · Y ₂ O ₃ mixed sintered body (M1 = Y, M2
= Cr, Mn). FIG. 28 shows a manufacturing process of the thermistor element according to the seventeenth embodiment.

Example 17 relates to the first manufacturing method described in the third embodiment. That is, the first
Preparation process (in the figure, from Formulation 1 to Y (Cr _0.5 Mn _0.5 )
O ₃ · Y ₂ O ₃ ) to obtain the above-mentioned precursor. Further, in the mixing step of the first preparation step, the medium stirring mill is used, and the pulverization of the second preparation step (formulation 2 and thereafter in the figure) is performed. A ball mill is used in the process. That is, the first embodiment
A ball mill is used in place of the medium stirring mill in the pulverizing step in Step 5.

The first preparation process of this example is the same as that of Example 15 described above, and the description is omitted. Example 1
7, in Formulation 1, aY (Cr _0.5 Mn
_0.5 ) a and b (molar fraction) of O ₃ · bY ₂ O ₃ are a:
b = 38: 62, and the raw material slurry of the thermistor material mixed and pulverized in the mixing step was evaluated by a laser type particle size analyzer, and as a result, the average particle size was 0.4 μm (micrometer).
Met.

Next, in the preparation 2, in the first preparation step,
Precursor Y (Cr_0.5Mn_0.5) O_Three・ Y_TwoO_Threeof
Prepare 2000 g of powder. Next, in the grinding step,
Y (Cr_0.5Mn_0.5) O_Three・ Y _TwoO
_ThreeAdd a dispersant, binder, and release agent to the mixture, mix and pulverize
To do so, a ball mill device is used.

The grinding conditions of the ball mill were as follows: Al ₂ O ₃ cobblestone φ15 was 10 kg and φ20 was 10 kg.
In a resin pot (capacity: 20 liters) containing 2,000 kg, put 2,000 g of the powder prepared in Formulation 2 and add pure water 6
After adding 000 cc, mix and pulverize at 60 rpm for 6 hours. The raw material slurry of the pulverized thermistor material was evaluated with a laser fineness meter, and as a result, the average particle size was 1.8 μm (micrometer). This is larger than the average particle size of Y ₂ O ₃ before being prepared in Preparation 1.

Y (Cr _0.5 Mn _0.5 ) O ₃ obtained after pulverization
The slurry of and Y ₂ O ₃ is subjected to granulation, molding and firing in the same manner as in Example 15 to obtain a thermistor element. This thermistor element is incorporated in a temperature sensor assembly as in the fifteenth embodiment to form a temperature sensor. The structures of the thermistor element and the temperature sensor are the same as those shown in FIGS.

The above temperature sensor was evaluated in the same manner as in Example 15. The resistance-temperature characteristics are the same as those in Example 15 (FIG. 24).
A: b = 38: 62 resistance temperature characteristic). FIG. 25 shows the evaluation results of the temperature accuracy. In the temperature sensor according to the seventeenth embodiment, ± 10 ° C. can be obtained as the temperature accuracy. Further, in the mixing step, Y (Cr _0.5 M
n _0.5 ) O ₃ : Y ₂ O ₃ molar ratio of 95: 5 and 5: 5
A thermistor element was manufactured from a thermistor raw material prepared to be 95, and evaluated as a temperature sensor. As a result, the resistance-temperature characteristics of these thermistor elements were as good as those of Example 15 having the same molar ratio (see FIG. 24).

Therefore, in the thermistor element of Example 17, the molar fraction (a + b = 1) of aY (Cr _0.5 Mn _0.5 ) O ₃ .bY ₂ O ₃ is 0.05 ≦ a <1.0, 0 <B
50 required as a temperature sensor in the range of ≦ 0.95
And a resistance temperature coefficient β of 2000 to 4000 (K). Therefore, the temperature can be detected in a high temperature range from room temperature to 1000 ° C.

Also, from the results of the high-temperature durability test (resistance change rate), it is possible to provide a thermistor element having stable characteristics with little change in resistance value. (Embodiment 18) The present embodiment 18 is directed to a case where Y (Cr _0.5 M
n _0.5 ) O ₃ and Y ₂ O _{3 form} Y (Cr _0.5 Mn _0.5 )
Mixed sintered body of O ₃ · Y ₂ O ₃ (M1 = Y, M2 = Cr,
Mn). FIG. 29 shows a manufacturing process of the thermistor element of the eighteenth embodiment.

Example 18 relates to the second manufacturing method described in the third embodiment. That is, the first
Preparation process (in the figure, from Formulation 1 to Y (Cr _0.5 Mn _0.5 )
O ₃ ) to obtain Y (Cr _0.5 Mn _0.5 ) O ₃ , a medium stirring mill in the mixing step of the first preparation step, and a second preparation step (formulation 2 and thereafter in the figure).
A ball mill is used in the pulverizing step. That is, a ball mill is used in place of the medium stirring mill in the pulverizing step in the above Example 16.

The first preparation process of this example is the same as that of Example 16 described above, and the description will not be repeated. Example 1
Also in No. 8, as a result of evaluating the raw material slurry of the thermistor material mixed and pulverized in the mixing step in Formulation 1 with a laser particle size meter, the average particle size was 0.3 μm (micrometer). Then, from the first preparation step, a powder of Y (Cr _0.5 Mn _0.5 ) O ₃ calcined is obtained.

In Formula 2, Desired as a thermistor element
To obtain the resistance value and the temperature coefficient of resistance, aY (Cr_0.5Mn
_0.5) O_Three・ BY_TwoO_ThreeA and b are a: b = 38: 6
Y (Cr_0.5Mn_0.5) O_Three(powder)
And Y_TwoO_ThreeAre weighed to a total weight of 2000 g. Next
In the pulverizing step, Y (Cr_0.5M
n_0.5) O_ThreeAnd Y _TwoO_ThreeMix and crush the weighed material with
For this purpose, a ball mill is used. This ball mill equipment
The grinding conditions by Al_TwoO_ThreeOne boulder φ15
0 kg, resin pot containing 10 kg of φ20 (capacity
20 liters) and 2,000 g of the mixed weighed material
6 hours at 60 rpm after adding 6000 cc of pure water
Mix and crush.

The raw material slurry of the pulverized thermistor material was evaluated by a laser type particle size analyzer. As a result, the average particle size was 1.8 μm.
m (micron meter). This is greater than the average particle diameter 1.0μm previous Y ₂ O ₃ be formulated by compounding 2. In the mixing / pulverizing step, a dispersant, a binder, and a release agent are added and pulverized at the same time. Y (Cr
_0.5 Mn _0.5 ) O ₃ · Y ₂ O ₃ slurry was prepared in Example 1
Similarly to 5, granulation, molding and firing are performed to obtain a thermistor element. This thermistor element is similar to the fifteenth embodiment,
Assemble into the temperature sensor assembly and use it as a temperature sensor. The structures of the thermistor element and the temperature sensor are the same as those shown in FIGS.

The above temperature sensor was evaluated in the same manner as in Example 15. The resistance-temperature characteristics were the same as those of the above-mentioned Example 16 (the resistance-temperature characteristics of a: b = 38: 62 in FIG. 27). FIG. 25 shows the evaluation results of the temperature accuracy. The temperature sensor according to the eighteenth embodiment has a temperature accuracy of ± 10
° C is obtained.

Further, in the pulverizing step, Y (Cr _0.5 Mn)
_0.5 ) The molar ratio of O ₃ : Y ₂ O ₃ is 95: 5 and 5: 9
5, a thermistor element was manufactured from the thermistor raw material prepared to be 5, and evaluated as a temperature sensor.
The same good resistance-temperature characteristic as that of Example 16 having the same molar ratio (see FIG. 27) was exhibited. Therefore, the first embodiment
The thermistor element No. 8 is aY (Cr _0.5 Mn _0.5 ) O ₃
The molar fraction of bY ₂ O ₃ (a + b = 1) is 0.05 ≦
a <1.0, 0 <b ≦ 0.95, a resistance value of 50 Ω to 100 kΩ required as a temperature sensor,
Regarding the temperature coefficient of resistance β, 2000 to 4000 (K)
Therefore, the temperature can be detected over a high temperature range from room temperature to 1000 ° C.

The results of the high-temperature durability test (resistance change rate)
From a stable characteristic with little change in resistance.
A mister element can be provided. (Embodiment 19) This embodiment is basically similar to the embodiment 15 of the invention.
And Example 17;_TwoO _ThreeAnd Cr_TwoO_ThreeWhen
Mn_TwoO_ThreeAnd CaCO_ThreeTo produce a precursor, Y
(Cr _0.5Mn_0.5) O_Three・ Y_TwoO_ThreeMixed sintered body (M
1 = Y, M2 = Cr, Mn). Example 19
FIG. 30 shows a manufacturing process of the semiconductor device.

In the nineteenth embodiment, in the manufacturing method of the fifteenth embodiment, a conventional ball mill is used for both the mixing step and the pulverizing step. As in Example 15, the purity of each of Y ₂ O ₃ and Cr ₂ was 99.9% or more.
Prepare O ₃ , Mn ₂ O ₃ and CaCO ₃ , and in Formulation 1,
These components are blended so as to obtain a desired resistance value and a resistance temperature coefficient as a thermistor element.

More specifically, aY (Cr _0.5 Mn _0.5 ) O
_A and b (molar fraction) of ₃ · bY ₂ O ₃ are a: b = 3
8:62 so that Y ₂ O ₃ , Cr ₂ O ₃ and Mn ₂ O
₃ is weighed to a total weight of 2000 g. Further CaCo3
, And a total of 2036 g of Y ₂ O ₃ , Cr ₂ O ₃ , Mn ₂ O _3, and CaCO ₃ is used as a mixed raw material.
Next, the mixed raw material is mixed and pulverized using a ball mill in a mixing step. The operating conditions are Al
2.5 kg of ₂ O ₃ boulder φ15 and 2.5 kg of φ20
Thermistor raw material is placed in a resin pot (capacity: 20 liters) containing, and 6000 cc of pure water is added.
Mix and crush for 6 hours at rpm.

The raw material slurry of the pulverized thermistor material was evaluated with a laser type particle sizer.
m (micron meter). This is Y ₂ O before mixing
The average particle size of No. ₃ is larger than 1.0 μm. The obtained raw material slurry was dried at a drying chamber entrance temperature of 200 with a spray dryer.
Drying is performed at a temperature of 120 ° C and an outlet temperature of 120 ° C. The obtained thermistor raw material powder has a spherical shape with an average particle diameter of 30 μm. This raw material powder is put into a crucible made of 99.3% Al ₂ O _{3 and} calcined at 1100 to 1300 ° C. for 1 to 2 hours in the air in a high temperature furnace. Thus, a precursor Y (Cr _0.5 Mn _0.5 ) O ₃ .Y ₂ O ₃ is obtained.

Precursor Y (C
r_0.5Mn_0.5) O_Three・ Y_TwoO_ThreeIs coarsely crushed with a raikai machine
And passed through a # 30 mesh sieve._0.5M
n_0.5) O _Three・ Y_TwoO_ThreeTo obtain a powder. Then, crusher
In order to make this powder finer,
Use a ball mill device as described above. This ball mill equipment
The grinding conditions are the same as those in the mixing step.

The raw material slurry of the pulverized thermistor material was evaluated by a laser type particle size analyzer. As a result, the average particle size was 3.0 μm.
m (micron meter). The obtained raw material slurry of the thermistor material is subjected to granulation / drying, die molding and firing in the same manner as in Example 15 to obtain a thermistor element. This thermistor element is incorporated in a temperature sensor assembly to form a temperature sensor. The structures of the thermistor element and the temperature sensor are the same as those shown in FIGS.

The above temperature sensor was evaluated in the same manner as in Example 15. The resistance-temperature characteristics were similar to those of Example 15 having the same molar ratio (a: b = 38: 62) (see FIG. 24), and were excellent. FIG. 25 shows the evaluation results of the temperature accuracy. The temperature accuracy of the temperature sensor according to the nineteenth embodiment is ± 30 ° C.

(Embodiment 20) This embodiment 20 is basically
Is the same as in Example 16 and Example 18, and Y_TwoO _ThreeWhen
Cr_TwoO_ThreeAnd Mn_TwoO_ThreeAnd CaCO_ThreePreliminary firing using
And Y (Cr_0.5Mn _0.5) O_ThreeAnd Y (Cr_0.5
Mn_0.5) O_Three・ Y_TwoO_ThreeMixed sintered body (M1 = Y, M
2 = Cr, Mn). Example 20 Thermistor Element
FIG. 31 shows a manufacturing process of the child.

The twentieth embodiment is a manufacturing method of the sixteenth embodiment.
In the method, both the mixing step and the pulverizing step are conventional methods
A ball mill is used. Same as Example 16
In any case, the purity of any one of Y_TwoO_ThreeAnd Cr_Two
O_ThreeAnd Mn_TwoO_ThreeAnd CaCO_ThreePrepare In Formula 1
Is such that the molar ratio of Y: Cr: Mn is 2: 1: 1.
And Y_TwoO_ThreeAnd Cr_TwoO_ThreeAnd Mn_TwoO_ThreeWeigh the whole amount
644 g, and CaCO_Three36 g, Y_Two
O_ThreeAnd Cr_TwoO_ThreeAnd Mn _TwoO_ThreeAnd CaCO_ThreeAnd sum
The mixed raw material is 680 g.

In the mixing step, the mixed raw materials obtained in Preparation 1 are mixed and pulverized using a ball mill. The operating conditions were as follows: 2.5 kg of Al ₂ O ₃ boulder φ15, φ
Thermistor raw materials are placed in a resin pot (capacity: 5 liters) containing 2.5 kg of 20. After adding 1800 cc of pure water, the mixture is ground and mixed at 60 rpm for 6 hours. As a result of evaluating the raw material slurry of the pulverized thermistor material with a laser particle size meter, the average particle size was 1.7 μm (micrometer). This is because the average particle size of Y ₂ O ₃ before mixing is 1.
It is larger than 0 μm.

The obtained raw material slurry was prepared in the same manner as in Example 15 above.
In the same manner as described above, after granulation and drying with a spray dryer, and pre-baking, Y (Cr _0.5 Mn _0.5 ) O ₃ is obtained. The Y (Cr _0.5 Mn _0.5 ) O ₃ , which has become a massive solid by calcination, is coarsely pulverized with a raikai machine, passed through a # 30 mesh sieve, and Y (C
(r _0.5 Mn _0.5 ) O ₃ powder is obtained. Next, in Formula ₂ , a of aY (Cr _0.5 Mn _0.5 ) O ₃ .bY ₂ O ₃ is used in order to obtain a desired resistance value and a resistance temperature coefficient as a thermistor element.
And Y (Cr _0.5 Mn _0.5 ) O ₃ and Y ₂ O ₃ are weighed so that a and b (molar fraction) are a: b = 38: 62, to give a total amount of 2000 g.

Next, Y (Cr _0.5 Mn _0.5 ) O ₃ .Y ₂
In order to grind O ₃ in the grinding step, a ball mill is used as in the mixing step. The grinding operation conditions of the ball mill, 10k and made of Al ₂ O ₃ cobblestone φ15
g, φ20 into a resin pot containing 10 kg (capacity 20
Liter), thermistor raw material obtained in Formulation 2 is added, 600 cc of pure water is added, and the mixture is mixed and pulverized at 60 rpm for 6 hours.

The raw material slurry of the pulverized thermistor material was evaluated by a laser type particle size meter, and as a result, the average particle size was 2.7 μm.
m (micron meter). The obtained raw material slurry of the thermistor material is subjected to granulation, drying, molding, and firing in the same manner as in Example 15 to obtain a thermistor element. The thermistor element is incorporated into a temperature sensor assembly to form a temperature sensor. The structures of the thermistor element and the temperature sensor are the same as those shown in FIGS.

The above temperature sensor was evaluated in the same manner as in Example 15. The resistance-temperature characteristics were similar to those of Example 16 having the same molar ratio (a: b = 38: 62) (see FIG. 27), and were excellent. FIG. 25 shows the evaluation results of the temperature accuracy. The temperature accuracy of the temperature sensor according to the twentieth embodiment is ± 25 ° C.

Comparative Example 3 In Comparative Examples 1 and 2, as in Example 15, the average particle size after mixing (μm), the average particle size after pulverization (μm), and The temperature accuracy was evaluated. FIG. 25 shows the result. As described above, when the examples 15 to 20 are compared, any thermistor element shows a good resistance-temperature characteristic which is the object of the present invention.

However, with respect to the temperature accuracy of the sensor, Examples 15 to 1 according to the manufacturing method of the third embodiment are described.
The manufacturing method of Example 8 is superior to the manufacturing methods of Examples 19 and 20, and the manufacturing methods of Examples 15 and 16 can be said to be superior to the manufacturing methods of Examples 17 and 18. That is, in the mixing step in the first preparation step before calcination and in the pulverization step in the second preparation step, there are many steps in which atomization is performed using a medium stirring mill so that the particle diameter of the raw material becomes a predetermined value or less. Thus, the temperature accuracy of the sensor is improved.

(Other Modifications) By the way, in the first embodiment,
-20 and Y (Cr _0.5 Mn _0.5 ) O ₃ and (Mn
_1.5 Cr _1.5 ) O ₄ , Y ₂ O ₃ and TiO ₂ , or Y (Cr _0.5 Mn _0.5 ) O ₃ and (Mn _1.5 C
r _1.5 ) From the composition of O ₄ , Y ₂ O ₃ and YTiO ₃ , Y (CrMnTi) O ₃ and Y
It is also possible to provide a wide-range thermistor element made of a mixed sintered body with ₂ O ₃ .

Further, an yttria compound such as Y ₂ O ₃ ,
From a chromium compound such as Cr ₂ O ₃ and a manganese compound such as Mn ₂ O ₃ , Y (Cr
Mn) It goes without saying that a wide-range thermistor element composed of a mixed sintered body of O ₃ and Y ₂ O ₃ can be prepared. Further, an yttria compound such as Y ₂ O ₃ and Cr
Chromium compounds such as ₂ O _3, and manganese compounds such as Mn ₂ O _3, titanium compounds such as TiO _2, Example 3 above
Needless to say, a wide-range thermistor element composed of a mixed sintered body of Y (CrMnTi) O ₃ and Y ₂ O ₃ as described in Nos. 6 to 6 can be prepared.

[0209] In Examples 1 to 20, in the first preparation step, drying before calcination is performed with hot air drying, and the mixed solid is roughly pulverized with a raikai machine to perform calcination. A wide-range thermistor element can also be provided by adding a binder in the mixing step and calcining the granulated and dried powder mixture by a spray dryer in order to achieve uniformity of the composition.

Similarly, a wide-range thermistor element can be provided by performing preliminary firing twice or more in the process of manufacturing the thermistor element in order to achieve uniform composition. In each of Examples 1 to 20, the wire diameter and length of the lead wire are φ0.3 × 10.5 (mm), and the material is Pt1
Although 00 (pure platinum) was used, the shape, diameter and length of the lead wire can be arbitrarily selected according to the shape and dimensions of the temperature sensor and the operating environment conditions of the temperature sensor.
Not only t100 (pure platinum) but also a high melting point metal such as Pt80Ir20 (80% platinum, 20% iridium), which has a melting point that can withstand the firing temperature of the thermistor element and can provide conductivity as a lead wire, can be used. .

Further, for the purpose of preventing the lead wire from coming off,
The cross-sectional shape may be a shape other than a circle, for example, a rectangle, a semicircle, or the like. The surface of the lead wire may be provided with irregularities by knurling or the like and used as a lead wire of a thermistor element. In each of Examples 1 to 20, a lead wire is inserted as a thermistor element and die molding is performed. However, after forming a cylindrical molded body using a thermistor raw material (powder), a lead is formed. By drilling a hole for providing a wire, loading a lead wire and firing, a lead wire is formed, and a thermistor element can be obtained.

It is also possible to obtain a thermistor element by forming a lead wire after firing the above-mentioned columnar molded body. Further, a binder, a resin material and the like are mixed and added to the raw material of the thermistor element, the viscosity and the hardness suitable for extrusion molding are adjusted, and the extrusion of the thermistor element in which a hole for providing a lead wire is formed. A thermistor element having a lead wire can be obtained by obtaining a molded body, loading a lead wire, and firing.

Also, a binder, a resin material, and the like are mixed and added to the raw material of the thermistor element, and the viscosity and hardness are adjusted so as to be suitable for sheet forming, thereby obtaining a sheet-shaped thermistor sheet having a thickness of 200 μm. Five thermistor sheets were laminated to a thickness of 1 mm, and a molded body of a thermistor element having a hole for providing a lead wire having an outer diameter of 1.8 mm and a diameter of 0.4 mm was obtained by a mold. By loading and firing, a molded body of a thermistor element having a lead wire formed thereon can be obtained.

As described above, the thermistor element of the present invention has a low resistance value and a low resistance temperature coefficient (for example, 1000 to 4000 (° K)) (M1M2) O ₃ . Made of a mixed sintered body with Y ₂ O ₃ which is a material for stabilizing the resistance value of the thermistor element.
It is a material represented by the general formula of ((M1M2) O ₃ ) · b (Y ₂ O ₃ ).

Therefore, by appropriately mixing and firing the two, the resistance value and the resistance temperature coefficient can be variously controlled in a wide range, so that the temperature can be detected over a wide temperature range from room temperature to 1000 ° C. It is possible to provide a thermistor material having stable characteristics in which the resistance value does not change even from the viewpoint of reliability such as heat history of ° C. (Examples 1 to 2 above)
0).

In the method of manufacturing a thermistor element according to the present invention, the composition of the thermistor material is atomized to make the composition uniform, and the composition variation is reduced to reduce the variation in the resistance value of the thermistor element. The temperature accuracy is improved to ± 10 ° C or less at ℃.
25-30 ° C.), and a thermistor element capable of improving the accuracy of the temperature sensor can be provided (Examples 7 to 10 and Examples 15 to 18).

[Brief description of the drawings]

FIG. 1 is a manufacturing process diagram of a thermistor element according to Example 1 of the present invention.

FIG. 2 is a configuration diagram of a thermistor element according to the first embodiment.

FIG. 3 is a sectional configuration diagram of a temperature sensor using the thermistor element of FIG. 2;

FIG. 4 is a sectional configuration diagram of a metal pipe of the temperature sensor of FIG. 3;

FIG. 5 is a table showing resistance characteristics of the thermistor element according to the first embodiment.

FIG. 6 is a manufacturing process diagram of the thermistor element of Example 2 of the present invention.

FIG. 7 is a table showing resistance characteristics of the thermistor element according to the second embodiment.

FIG. 8 is a manufacturing process diagram of the thermistor element of Example 3 of the present invention.

FIG. 9 is a table showing resistance characteristics of the thermistor element according to the third embodiment.

FIG. 10 is a manufacturing process diagram of the thermistor element of Example 4 of the present invention.

FIG. 11 is a table showing resistance characteristics of the thermistor element according to the fourth embodiment.

FIG. 12 is a manufacturing process diagram of the thermistor element of Example 5 of the present invention.

FIG. 13 is a table showing the resistance characteristics of the thermistor element according to the fifth embodiment.

FIG. 14 is a manufacturing process diagram of the thermistor element according to Example 6 of the present invention.

FIG. 15 is a table showing resistance characteristics of the thermistor element according to the sixth embodiment.

FIG. 16 is a table showing resistance characteristics of the thermistor elements in Comparative Examples 1 and 2.

FIG. 17 is a manufacturing process diagram of the thermistor element of Example 7 of the present invention.

FIG. 18 is a table showing temperature accuracy characteristics of a temperature sensor using a thermistor element in Examples 7 to 14 of the present invention.

FIG. 19 is a manufacturing process diagram of the thermistor element according to Example 8 of the present invention.

FIG. 20 is a manufacturing process diagram of the thermistor element according to Example 9 of the present invention.

FIG. 21 is a manufacturing process diagram of the thermistor element according to Example 10 of the present invention.

FIG. 22 is a manufacturing process diagram of the thermistor element according to Example 11 of the present invention.

FIG. 23 is a manufacturing process diagram of the thermistor element according to Example 15 of the present invention.

FIG. 24 is a table showing resistance characteristics of the thermistor element in Example 15;

FIG. 25 shows Examples 15 to 20 and Comparative Example 1 of the present invention.
6 is a table showing temperature accuracy characteristics of a temperature sensor using a thermistor element in Comparative Example 2;

FIG. 26 is a manufacturing process diagram of the thermistor element according to Example 16 of the present invention.

FIG. 27 is a table showing resistance characteristics of the thermistor element in Example 16;

FIG. 28 is a manufacturing process diagram of the thermistor element of Example 17 of the present invention.

FIG. 29 is a manufacturing process diagram of the thermistor element according to Example 18 of the present invention.

FIG. 30 is a manufacturing process diagram of the thermistor element of Example 19 of the present invention.

FIG. 31 is a manufacturing process diagram of the thermistor element according to Example 20 of the present invention.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Thermistor element, 2 ... Metal case, 3 ... Metal pipe, 11, 12 ... Lead wire, 13 ... Element part, 31, 32
... lead wires, 33 ... magnesia powder.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Masanori Yamada 14 Iwatani, Shimowasumi-cho, Nishio-shi, Aichi Japan Inside the Japan Automotive Parts Research Institute (72) Inventor Kaoru Kuzuoka 1-1-1, Showa-cho, Kariya-shi, Aichi Stock Inside the company DENSO

Claims (14)

[Claims] 1. The composition (M1M2) O _3, wherein M1
Is at least one element selected from Group 2A elements of the periodic table and elements of Group 3A excluding La;
Are groups 2B, 3B, 4A, 5A of the periodic table of elements
At least one element selected from the group consisting of Group 6A, Group 6A, Group 7A and Group 8;
Mixed sintered body of O ₃ and Y ₂ O ₃ (M1M2) O ₃ · Y ₂
Thermistor element made of O ₃ . 2. The method according to claim 1, wherein the mole fraction of (M1M2) O ₃ is a,
The molar fraction of Y ₂ O ₃ is represented by b, and these a and b
Is 0.05 ≦ a <1.0, 0 <b ≦ 0.95, a + b
2. The thermistor element according to claim 1, wherein a relation of = 1 is satisfied. 3. M1 is Y, Ce, Pr, Nd, S
m, Eu, Gd, Dy, Ho, Er, Yb, Mg, C
a, Sr, Ba, Sc, at least one element selected from the group consisting of Ti, V, Cr, Mn, Fe, Co,
Ni, Zn, Al, Ga, Zr, Nb, Mo, Hf, T
3. The thermistor element according to claim 1, wherein the element is at least one element selected from a and W. 4. The M1 is Y, the M2 is Cr and Mn, and the mixed sintered body is (Y (CrMn) O ₃ ) · Y ₂
Thermistor device according to claim 3, characterized in that the O _3. 5. M1 is Y, M is Cr, Mn and T
i, and the mixed sintered body is (Y (CrMnTi)
4. The thermistor element according to claim 3, wherein the element is O ₃ ) .Y ₂ O ₃ . 6. CaO, CaCO ₃ and CaSiO ₃
At least one thermistor element according to any one of claims 1 to 5 sintering aid composed of SiO ₂ Metropolitan characterized in that it is contained within the. 7. A temperature sensor comprising the thermistor element according to claim 1. 8. The method for manufacturing a thermistor element according to claim 1, wherein said (M1) having a larger average particle diameter than said Y ₂ O ₃ by calcination.
M2) O ₃ is obtained, this (M1M2) O ₃ is mixed with the above-mentioned Y ₂ O ₃ and crushed, and the average particle size of the mixture after the crushing is calculated as the average particle size of the Y ₂ O ₃ before mixing. After the following, molded into a predetermined shape,
A method for manufacturing a thermistor element, characterized by firing. 9. The method for manufacturing a thermistor element according to claim 4, wherein the oxide of Cr and the oxide of Mn are mixed and calcined at 1000 ° C. or more.
₂ average particle diameter than the O ₃ is large (Mn _{1 .5} Cr _1.5) O
₄ was obtained, and the average of the _{(Mn 1 .5 Cr 1.5) O} 4 and the Y ₂ O ₃ and mixed to ground and said pre-mixing a mean particle size of the mixture after pulverization Y ₂ O ₃ A method for producing a thermistor element, comprising forming the particles into a predetermined shape and firing the particles after reducing the particle diameter to a predetermined size or less. 10. The method for manufacturing a thermistor element according to claim 5, wherein an oxide of Cr and an oxide of Mn are mixed and calcined at a temperature of 1000 ° C. or more, so that the average is lower than that of Y ₂ O _3. large particle size (Mn _{1 .5} Cr _1.5)
To give a O _4, wherein this _{(Mn 1 .5 Cr 1.5) O} 4 Y 2
O ₃ and TiO ₂ are mixed and pulverized, and after the pulverization, the average particle diameter of the mixture is set to be equal to or less than the average particle diameter of Y ₂ O ₃ before mixing, and then formed into a predetermined shape and fired. A method for manufacturing a thermistor element. 11. The method for manufacturing a thermistor element according to claim 1, wherein the raw material of M2 is mixed with the raw material of M1 and ground, and the mixed ground material after grinding is mixed. (M1M2) O ₃ was obtained by calcination, and the (M1M2) obtained by calcination was obtained. ) after the O ₃ was mixed with the Y ₂ O _3, molded into a predetermined shape, sintering method for producing a thermistor element, characterized by. 12. The method for manufacturing a thermistor element according to claim 1, wherein a material containing at least Y ₂ O ₃ is used as a material for the M1, and a material for the M2 is used as the material for the M1. The mixture is ground together with the raw material of the above, and the average particle size of the mixed ground product after the grinding is equal to or less than the average particle size of the raw material of M1 before mixing and 0.5 μm.
After that, the mixed sintered body (M1M
2) A method for producing a thermistor element, comprising obtaining a precursor having the same composition as O ₃ · Y ₂ O _3, and molding and firing the precursor obtained by the preliminary firing into a predetermined shape. 13. The method for manufacturing a thermistor element according to claim 1, wherein the raw material of M2 is mixed and ground with the raw material of M1, and an average particle size of the mixed ground product is obtained. After the diameter of the raw material of M1 before mixing was not more than the average particle diameter of the raw material of M1 and not more than 0.5 μm, (M1M2) O ₃ was obtained by calcination, and the (M1M2) O ₃ obtained by calcination was obtained. And pulverizing by mixing Y ₂ O ₃ and then reducing the average particle diameter of the mixture after the pulverization to not more than the average particle diameter of the Y ₂ O ₃ before mixing, and then forming and firing into a predetermined shape. A method for manufacturing a thermistor element. 14. The method for manufacturing a thermistor element according to claim 1, wherein a material containing at least Y ₂ O ₃ is used as a material for the M1, and a material for the M2 is used for the M1. The mixture and pulverized material are mixed together with the raw material of the above, and after the pulverization, the average particle size of the mixed and pulverized product is set to be equal to or less than the average particle size of the raw material of M1 before mixing and 0.5 μm or less, and then the mixed and sintered by pre-baking Body (M1M2)
A precursor having the same composition as O ₃ · Y ₂ O ₃ is obtained, the precursor obtained by the preliminary calcination is pulverized, and the average particle size of the precursor after pulverization is determined by mixing the raw material of the M1 before mixing. A method for producing a thermistor element, comprising: forming the sintered body into a predetermined shape after reducing the average particle diameter of Y ₂ O ₃ to be equal to or less than the average particle diameter of Y ₂ O ₃ .