JP2003264102A - Ceramic resistor and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To suppress resistance variations of a ceramic resistor that uses a resistor made of a chemical compound or a complex compound obtained by using metals of more than four kinds and/or a half metal simple substrate as the starting material and mixing and molding then sintering them. <P>SOLUTION: The mixing is carried out by using a first stirring blade (2) to make the starting material flow all around inside a mixer (1), and a second stirring blade (3) to release the starting material adhering inside the mixer (1). <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a ceramic resistor using ceramic as a resistor material and a method for manufacturing the same.

[0002]

2. Description of the Related Art A ceramic resistor using a ceramic made of a compound and / or a composite compound of four or more kinds of metal elements and / or metalloid elements containing Mg and Si as a resistor material is disclosed in Japanese Patent Application Laid-Open No. 2-272701. Japanese Patent Laid-Open No. 6-1
The disclosure is disclosed in Japanese Patent No. 04102.

This type of ceramic resistor is durable against high-voltage pulses and high-power surges, and since its main constituent material is ceramic, it can withstand use at high temperatures. Has advantages not found in

[0004]

In the production method described in the above publication, there is a step of mixing four or more kinds of starting materials (compounds of different elements) with a ball mill for 20 hours. If sufficient mixing is made here, it should be possible to suppress variations in resistance values of resistors of the same standard obtained by mass production from the starting materials.
However, in order to suppress the variation in the resistance value, mixing with a ball mill is not sufficient.

The problem to be solved by the present invention is as follows.
In a ceramic resistor using a ceramic made of a compound and / or a composite compound of four or more kinds of metal elements and / or metalloid elements as a resistor material, it is to suppress variations in resistance value.

[0006]

In order to solve the above-mentioned problems, a method of manufacturing a ceramic resistor using ceramic as a resistor material according to the present invention includes four or more kinds of metals and / or semi-metals (such as Si. Hereinafter, in the present specification, Si is treated as a metal for convenience.) A simple substance, a compound or a composite compound is used as a starting material, the starting materials are mixed, and thereafter, a molding and firing process is performed. The mixing step is characterized by means for flowing the starting raw material throughout the mixing container 1 and means for deaggregating the starting raw material in the mixing container 1.

In producing a ceramic composed of a compound and / or composite compound of four or more kinds of metal elements and / or metalloid elements, it is common to require a plurality of starting materials. Usually the starting materials are powders and they are mixed,
A ceramic is manufactured by molding and firing. Therefore, the process of mixing is an important factor in producing a ceramic composed of a compound and / or a composite compound of four or more kinds of metal elements and / or metalloid elements. The reason is that if a specific element (starting material) is agglomerated and subjected to the subsequent molding and firing steps, it is difficult to obtain the desired ceramic function. The above process is particularly important when utilizing the electrical characteristics of ceramics, such as ceramic resistors using ceramics as the resistor material.

It is considered that it is difficult to obtain the effect of releasing the agglomeration by mixing with a conventional ball mill. The reason is that (1) in the case of dry mixing, static electricity that induces agglomeration is likely to be generated, (2) once adhered firmly to the inner wall of the mixing container or a ball made of ceramic or the like used in a ball mill, and then there is a specific start. When the raw materials aggregate, it is not easy to break the aggregation. It is considered that there are two reasons (1) and (2).

Therefore, the mixing process according to the present invention is characterized by means for flowing the starting materials throughout the mixing container 1 and means for releasing the agglomeration of the starting materials in the mixing container 1. The means for causing the starting material to flow throughout the mixing container 1 is, for example, the first stirring blade 2 shown in FIG.
Is a means for revolving (20 to 50 rpm) while relatively slowly rotating (1 to 30 rpm). The revolution is to move the rotation axis along the rotation direction surface.

The means for releasing the agglomeration of the starting material in the mixing container 1 is, for example, means for locally stirring the second stirring blade 3 shown in FIG. 1 by rotating it at a high speed (2000 to 6000 rpm). The time required for mixing also varies depending on other conditions (rotation / revolution speed, viscosity of the material to be mixed, etc.), but it generally takes 10 to 30 minutes. Needless to say, it is acceptable to spend more mixing time.

First, the distribution of the starting material in the container is roughly made uniform by means of causing the starting material to flow throughout the mixing container 1. Further, along with it, the specific starting material that has aggregated is sequentially carried to a means for deagglomerating, which will be described later. The means may, but need not, have the function of deaggregating the starting material. Next, the aggregated starting materials in the mixing container 1 are dispersed by giving a shock to the aggregated starting materials by means of deagglomerating the starting materials. By using these two means together, it is possible to realize uniform distribution of the starting material throughout the mixing container 1 while eliminating the agglomeration of the starting material. That is, a very uniform mixed state can be realized.

When a large amount of ceramic resistor material obtained by molding and firing the thus obtained starting material in a very uniform mixed state is manufactured, it is possible to suppress variations in their resistance values. The possible reasons for this are described below.

It can be said that the conduction mechanism of the ceramic resistor is due to movement of free electrons and holes (carriers) caused by imperfect covalent bonding between elements. This imperfection of covalent bond occurs when a covalent bond is formed between elemental compounds forming compounds having different valences. Therefore, if the agglomerated portion of the specific starting material (the same metal or the same metal compound) is directly fired and sintered, the covalent bond is almost complete at the portion, carrier migration is difficult to occur, and the portion is likely to become a conduction inhibition portion. In general, free electrons are easier to move than holes. Therefore, if a large number of places where free electrons can easily move are formed, they can become conduction promoting places. Also, the holes are easily moved depending on how they are formed. Considering all these factors, it can be understood that it is quite difficult to suppress the variation in the resistance value of the ceramic resistor material unless the above-mentioned very uniform mixed state is obtained.

The present inventor has found that there is a certain degree of correlation between the uniform mixed state and the resistance temperature characteristic of the ceramic resistor. The resistance temperature characteristic (TCR) referred to here is the amount of change in resistance value per unit temperature change (unit: unit) when measuring resistance values at ambient temperatures of 25 ° C. and 125 ° C. according to JIS C 5202 5.2.3. : Ppm / ° C.). Here, when the above-mentioned uniform mixed state is obtained, the resistance temperature characteristic value becomes higher than that in the conventional case (here, the resistance temperature characteristic value moving toward a positive value is expressed as “becomes higher”). )) (Fig. 4).

In a ceramic resistor using a ceramic made of a compound and / or a composite compound of four or more kinds of metal elements and / or semi-metal elements as the resistor material, the above-mentioned uniformity can be achieved to the extent that the variation of the resistance value can be suppressed. The resistance-temperature characteristic value at which various mixed states are obtained is -1150 ppm / when the specific resistance value of the resistor material is 1 kΩcm or less.
℃ or more, the specific resistance value of the resistor material is 1 kΩcm to 8
When it is kΩcm, it is −1300 ppm / ° C. or higher, and the specific resistance value of the resistor material is 8 kΩcm to 30 kΩcm.
Is −1450 ppm / ° C. or higher, the specific resistance value of the resistor material is 30 kΩcm to 70 kΩcm, −1530 ppm / ° C. or higher, and the specific resistance value of the resistor material is 70 kΩcm or higher, − 1620pp
m / ° C or higher. These resistance temperature characteristic values serve as an index of whether or not the above-mentioned uniform mixed state is obtained.

That is, by satisfying the relationship between the specific resistance value and the resistance temperature characteristic value, a ceramic made of a compound and / or a composite compound of four or more kinds of metal elements and / or metalloid elements is used as the resistor material. In the ceramic resistor, it is possible to suppress variations in resistance value.

The resistor material contains, for example, Mg and Si. All of these elements are easily available, and in general, compounds and / or composite compounds of these elements and other metal elements and / or metalloid elements have an advantage that resistor materials having a wide range of specific resistance values can be produced.

Further, when Mg and Si are indispensable and a compound or complex compound of other two or more kinds of metal elements and / or metalloid elements is used as the resistor material, the metal elements are, for example, Ca, Zn, Sr. , Cd, Ba, at least one kind (first group), Sn, Al, Sb, Ga,
At least one type (second group) selected from Pb, Cr, Mn, and Ge, and Bi, Nb, Ta, V, W, and Mo.
And at least one element (third group) selected from the above. In addition to these metals and metalloid elements, even when an impurity level element or a compound thereof and / or a complex compound with other elements is contained, they do not significantly affect the resistance temperature characteristics and the effect of suppressing resistance value variation. To the extent that they are present, ceramic resistors using them are within the scope of the invention.

The first group is a group of alkaline earth metals. Among them, the use of Cd is regarded as a problem from the viewpoint of environmental compatibility. Considering the availability, it is considered that one or more selected from Ca, Zn and Ba can be used particularly preferably.

The second group is a group of amphoteric metal elements. Among them, the use of Pb is regarded as a problem in terms of environmental compatibility. Considering the availability, one or more selected from Sn, Al, Sb, and Mn are considered to be particularly suitable.

The third group is a group of elements capable of forming a trivalent or pentavalent compound. Considering availability, it is considered that one or more selected from Bi, V, and W are particularly suitable. By using a ceramic made of these first to third groups and a compound and / or composite compound of Mg and Si as a resistor material, it has durability against a high voltage pulse and a large power surge, and has a wide specific resistance value range. A ceramic resistor having a resistor can be obtained.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below.
An example will be described. (Production of Sample A) MgO, SiO_TwoAnd Mg and Si
A complex compound mixture (i) with CaCO _Three(Ii)
And BaCO_Three(Iii) and Sn_TwoO_ThreeAnd (iv),
Sb_TwoO_ThreePrepare (v). These weight ratios
(I) :( ii) :( iii) :( iv) :( v) = 1
4: 78: 1: 2: 4, and these metal compound groups are 10
If it is 0 parts by weight, CMC (carboxymethyl
Cellulose), water, ethylene glycol 1 each
Parts by weight, 21 parts by weight, 2 parts by weight in addition to these starting material groups
Is placed in the mixing container 1 shown in FIG. Then in the mixing container 1
Under reduced pressure, and in that state, the first stirring blade 2
Rotate at rpm, revolve at 40 rpm, and mix all in mixing container 1.
The starting material group was fluidized throughout the body. At the same time, the second
The stirring blade 3 is rotated at 6000 rpm at a high speed to
The raw material groups are mixed to release the agglomeration of the starting material group. The first
The maximum diameter of the stirring blade 2 in the rotating state is φ240 mm, the second diameter
The maximum diameter of the stirring blade 3 in the rotating state is φ40 mm,
The diameter was 60 mm. Here, the degree of pressure reduction is
The extent to which defoaming is possible from the pasty starting material group to be combined
did. The mixing time is about 20 minutes. This is the starting material
However, it becomes a defoamed clay-like material.

After the completion of the mixing step, the pasty (clay-like) starting material group is formed into a fixed cylindrical shape, naturally dried, and then kept at 1380 ° C. for 2 hours, followed by firing in the atmosphere for a total of 16 hours. I went to Then, CMC and water were completely scattered, and a sintered body of a metal compound, that is, a ceramic was formed. Using this ceramic as a resistor, silver paste was applied and fixed on both ends of the cylinder to obtain a ceramic resistor of the present invention.

(Preparation of Sample B) MgO, SiO_TwoOver
And a mixture (i) of a composite compound of Mg and Si, and CaC
O _Three(Ii) and BaCO_Three(Iii) and SnO_TwoWhen
(Iv), Sb_TwoO_Three(V) and Bi_TwoO_Three(Vi)
prepare. The weight mixing ratio of these is (i) :( ii):
(Iii) :( iv) :( v) :( vi) = 66: 1
3: 4: 11: 1: 4, and these metal compound groups are 10
If it is 0 parts by weight, CMC (carboxymethyl
2 parts by weight and 28 parts by weight of water, respectively.
Put these starting material groups in the mixing container 1 shown in FIG.
It After that, the same process as in Sample A is performed and the present invention is performed.
I got a ceramic resistor.

(Preparation of Sample a) The metal compound group was set to 10
The starting raw material group and the mixing ratio thereof were exactly the same as those of Sample A except that the amount of water when the amount was 0 part by weight was about 100 parts by weight. After that, these raw materials were put into a cylindrical mixing vessel, a large number of ceramic balls having a diameter of 30 mm were mixed, and mixed by a so-called ball mill. The mixing time was 20 hours. Also, after mixing, dehydration and drying are performed, and the metal compound group is set to 1
When the amount is 00 parts by weight, 1 part by weight, 21 parts by weight and 2 parts by weight of CMC, water and ethylene glycol are added thereto. Then, in order to obtain a viscosity that allows molding, the metal compound group is kneaded by a kneader for 40 to 60 minutes under atmospheric pressure to the extent that it is entangled with CMC containing water, and then defoamed under reduced pressure. Then, the ceramic resistor of sample a was obtained through the same steps of molding and firing as sample A.

(Preparation of Sample b) The metal compound group was set to 10
The starting materials and their compounding ratio were exactly the same as those of Sample B, except that the amount of water when the amount was 0 part by weight was about 100 parts by weight. After that, through the same process as the sample a,
A ceramic resistor of sample b was obtained.

(Evaluation of each sample) Samples A, B,
The resistance value was measured for each of a and b (n = 10
0). FIG. 2 shows a histogram of the resistance values of Samples A and a and FIG. 3 of Samples B and b as histograms. As is clear from these figures, the sample A of the present invention has a much higher resistance value than the sample a manufactured by the conventional method, and the sample B of the present invention has a significantly higher resistance value than the sample b manufactured by the conventional method. It can be seen that the variation is suppressed.

The samples A and B of the present invention required about 20 minutes for mixing as described above, while the samples a and b according to the prior art required time for mixing as described above. Was 20 hours. From this, it is understood that the present invention can significantly reduce the time required for manufacturing the ceramic resistor.

(Preparation of Other Samples) In the preparation method of Sample A, a mixture of MgO, SiO ₂ and a complex compound of Mg and Si, CaCO ₃ and BaCO are prepared.
₃ , Sn ₂ O ₃ , and Sb ₂ O ₃ were adjusted in weight ratio to obtain specific resistance values of 1.5 Ωcm (obtained by the manufacturing method of Sample A), 10 Ωcm, 100 Ωcm, 1 kΩcm,
A ceramic resistor having a resistor was manufactured.

In addition, in the manufacturing method of the sample B, Mg
O, SiO _2, and a mixture of Mg and Si complex compounds, CaCO ₃ , BaCO ₃ , SnO ₂ , and Sb ₂
And O _3, by adjusting the ratio by weight of _Bi 2 _{O 3,} specific resistance 8kΩcm, 30kΩcm, 70kΩcm, 160
A ceramic resistor having a resistor of kΩcm (obtained by the manufacturing method of Sample B) was manufactured.

In addition, in the manufacturing method of the sample a, Mg
O, SiO _2, and a mixture of Mg and Si complex compounds, CaCO ₃ , BaCO ₃ , Sn ₂ O ₃ , and Sb.
_The specific resistance value is 1.5Ω by adjusting the mixing ratio by weight with ₂ O _3.
cm (slightly obtained by the manufacturing method of sample a), 10 Ω
A ceramic resistor having a cm, 100 Ωcm, and 1 kΩcm resistor was produced.

In addition, in the manufacturing method of the sample b, Mg
O, SiO _2, and a mixture of Mg and Si complex compounds, CaCO ₃ , BaCO ₃ , SnO ₂ , and Sb ₂
And O _3, by adjusting the ratio by weight of _Bi 2 _{O 3,} specific resistance 8kΩcm, 30kΩcm, 70kΩcm, 160
A ceramic resistor having a resistor of kΩcm (slightly obtained by the manufacturing method of sample b) was manufactured.

The guideline for adjusting the above-mentioned weight blending ratio will be described to the extent that one skilled in the art can implement it. A mixture of MgO, SiO ₂ and a complex compound of Mg and Si, CaCO ₃ , and BaC
Increasing the total compounding ratio of O ₃ and Bi ₂ O ₃ increases the specific resistance value of the resistor, and increasing the total compounding ratio of other starting materials has the effect of decreasing the specific resistance value of the resistor. . By adjusting the compounding ratio of these, it is possible to obtain a resistor having a target specific resistance value.

(Resistance-Temperature Characteristics of Other Samples) Each of the above-mentioned other samples prepared was 25 ° C.
The resistance temperature characteristic (TCR) value at 5 ° C. was measured. FIG. 4 shows the measurement results (n = 10).

For the samples having the same specific resistance value, comparing the resistor produced by the starting material mixing method according to the present invention with the resistor produced by the conventional starting material mixing method, it was produced by the mixing method according to the present invention. The produced resistors are 150 to 300 pp more than the resistors produced by the conventional mixing method.
It can be seen that the value is higher by m / ° C.

From FIG. 4, it is clear that the resistor produced by the mixing method according to the present invention has a relationship between the specific resistance value and the resistance temperature characteristic, which are generally shown in (1) to (5) below. Became. (1) When the specific resistance value of the resistor material is 1 kΩcm or less, -1150 ppm / ° C or more. (2) The specific resistance value of the resistor material is 1 kΩcm to 8 kΩcm
If above, -1300 ppm / ° C or higher. (3) The specific resistance value of the resistor material is 8 kΩcm to 30 kΩc
When it is m, it is -1450 ppm / ° C or higher. (4) The specific resistance value of the resistor material is 30 kΩcm to 70 kΩ
When it is cm, it is -1530 ppm / ° C or higher. (5) -1620 ppm / ° C or higher when the specific resistance value of the resistor material is 70 kΩcm or higher.

(Supplementary Explanation of Embodiments of the Present Invention) In this example, as a starting material group, MgO, SiO ₂ and a mixture of a composite compound of Mg and Si, CaCO ₃ , and
BaCO ₃ , Sn ₂ O ₃ , and Sb ₂ O ₃ are mixed in a predetermined mixing ratio and fired to obtain a ceramic resistor, and M
gO, SiO ₂ , a mixture of a composite compound of Mg and Si, CaO, BaO, SnO ₂ , Sb ₂ O ₃ , and
Only the ceramic resistor obtained by mixing Bi ₂ O ₃ with a predetermined compounding ratio and firing the mixture is shown. However, even if a ceramic resistor containing four or more metals or metalloid elements other than those shown in this example is manufactured by the method for manufacturing a ceramic resistor of the present invention, the effect of reducing the variation in resistance value is still obtained. it is conceivable that.

Examples of ceramic resistors containing four or more metals or metalloid elements are Mg and Si, Ca, Zn,
At least one selected from Sr, Cd and Ba, and S
at least one selected from n, Al, Sb, Ga, Pb, Cr, Mn, and Ge, and Bi, Nb, Ta, V, W,
It is a ceramic resistor made of a compound and / or a composite compound containing at least one element selected from Mo as a main component.

For example, in the above-mentioned sample B, a trace amount
WO_ThreeIs added to the starting materials,_TwoO_ThreeInstead of
Amount of WO_ThreeMay be one of the starting materials. in this case,
WO _ThreeIf the compounding ratio of
The resistance value increases.

In this example, the pressure inside the mixing container was reduced when the starting materials were mixed. The mixture in this example contains water and CMC, and is made into a paste by these. Therefore, bubbles are easily formed during mixing. The main purpose of the reduced pressure is defoaming. However, it is not always necessary to perform defoaming at the time of mixing, and a defoaming step may be provided after the completion of the mixing step, or a depressurizing function may be provided in the molding apparatus so that defoaming may be performed at the time of molding. It is considered preferable to proceed this defoaming step at the same time as the mixing step or the like, because this makes it possible to shorten the manufacturing time.

In this example, a stirring blade (first stirring blade 2 in FIG. 1) that rotates and revolves relatively slowly was used as the means for flowing the starting material throughout the mixing container. Not limited. For example, the starting raw material may be flowed throughout the mixing container by repeatedly tapping or turning the pasty starting raw material group with a large hammer such as mochi.

In this example, a stirring blade (second stirring blade 3 in FIG. 1) having a relatively small rotation diameter and rotating at a high speed was used as a means for releasing the agglomeration of the starting materials in the mixing container. Not limited to. For example, the starting material may be agglomerated in the mixing container by applying ultrasonic waves to the starting material from inside or outside the mixing container.

In this example, the resistance material is formed into a cylindrical shape, but the resistance material may be formed into a flat plate shape, and the resistor itself may be formed into a chip shape in consideration of the ease of handling the surface mounting mounter.

In the present example, after the mixing process, the starting material before molding was in the form of clay, but it may be in the form of flakes, that is, the starting material is in the form of a large number of flakes. It is considered that this can be obtained by reducing the water content and going through the mixing process according to the present invention. The advantage of the flake shape is that it has a disadvantage of workability in the case of molding in the subsequent step when it is made of clay, for example, it is difficult to adjust the supply amount to the molding device, and the supply work is smoothly advanced. It is considered that it is possible to avoid difficulty in automation and the like.

In this example, water is introduced into the mixing container from the beginning of the mixing process, but this is not always necessary. For example, in the starting materials of Sample A and Sample B in this example, rather in the beginning of the mixing process (about 20 minutes)
In addition, it was clarified that coagulation of individual starting materials can be suppressed by not introducing water into the mixing container. The mixing condition in this case is that the first stirring blade 2 is set to 2 at the beginning of the mixing process.
Rotating at ˜3 rpm, revolving at 40 rpm, and rotating the second stirring blade 3 at high speed at 6000 rpm to mix the starting material group, and then introduce water into the mixing container in an amount corresponding to sample A and sample B. The conditions are such that this stirring is maintained for 10 minutes, then the second stirring blade is stopped, and stirring is performed for 10 minutes only with the first stirring blade. Under these conditions, no agglomeration of the starting material due to the generation of static electricity was observed (it is possible that some were generated but it was considered to be negligible), and a better mixing state was obtained.
The quality of the mixed state here was confirmed by elemental analysis of the cut cross section of the ceramic resistor after the firing step. In sample A and sample B, CaCO ₃ and Ba
It was confirmed that CO ₃ and the Sn oxide were slightly aggregated, but the aggregation was hardly observed by the mixing step in which the water was not introduced here.

There was a difference in whether or not minute voids were observed in the ceramic after the firing step, depending on whether the agglomeration was observed in a very small amount or when it was hardly observed. Fine voids were observed in the former, and no voids were observed in the latter. The reason for this is not clear, but it is considered that the difference in the heat shrinkage ratio between the aggregated portion and the other portion is involved in some reason. Whether or not there is such a difference depends on the resistance-temperature characteristic (FIG. 4) and the variation in resistance value (FIG. 2,
3) was not affected. It is considered that the portion involved in aggregation was extremely small in quantity. However, it is considered that the presence of voids, even if it is extremely small, reduces the strength of the resistor made of ceramic. However, there was no difference in the results of the strength test. It is considered that the existence ratio of voids was extremely low. Even if these differences do not exist, it goes without saying that it is preferable that there is no air gap so that both the person who provides the resistor and the person who uses the resistor can handle the resistor with peace of mind.

In addition, a better mixing state, that is, a further reduction in the agglomeration of the specific starting materials, can be obtained by using Sample A, Sample B
In the above, it was possible to realize by previously reducing the particle size of BaCO ₃ among the starting materials. Although the reason for this is not clear, it is considered that the particle size of BaCO ₃ is slightly larger than the others. There was a difference in whether or not a very small amount of discoloration was observed in the ceramic after the firing step, depending on whether the very small amount of aggregation was observed or not. In the former, the discolored part was observed, and in the latter, the discolored part was not observed at all. It was confirmed by elemental analysis that the discolored portion was mainly composed of a Ba compound. The presence / absence of such a discolored portion depends on the above-described resistance-temperature characteristic (FIG. 4) and resistance value variation (FIG. 2,
Naturally, it did not affect (Fig. 3). It is considered that the portion involved in aggregation was very small in quantity.

[0048]

As described above, according to the present invention, in a ceramic resistor using a ceramic made of a compound and / or a composite compound of four or more kinds of metal elements and / or metalloid elements as a resistance material, The variation was able to be suppressed significantly. In addition, the manufacturing method of the ceramic resistor of the present invention can significantly reduce the time required for manufacturing as compared with the conventional method.

[Brief description of drawings]

FIG. 1 is a diagram showing a stirring device according to the present invention.

FIG. 2 is a diagram showing resistance value variations between the ceramic resistor of the present invention and a conventional ceramic resistor.

FIG. 3 is a diagram showing variations in resistance values of the ceramic resistor of the present invention and a conventional ceramic resistor.

FIG. 4 is a diagram showing a relationship between a specific resistance value of a ceramic resistance material and a resistance temperature characteristic (TCR) by a conventional mixing method and a mixing method according to the present invention.

[Explanation of symbols]

1. Mixing container 2. First stirring blade 3. Second stirring blade

Claims (13)

[Claims] 1. A ceramic resistor using a ceramic made of a compound and / or a composite compound of four or more kinds of metal elements and / or semi-metal elements excluding Pb and Cd as a resistor material, and the specific resistance of the resistor material. A ceramic resistor having a value of 1 kΩcm or less and having a resistance temperature characteristic of -1150 ppm / ° C or more. 2. A ceramic resistor using a ceramic made of a compound and / or a composite compound of four or more kinds of metal elements and / or semi-metal elements excluding Pb and Cd as a resistor material, and the specific resistance of the resistor material. A ceramic resistor having a value of 1 kΩcm to 8 kΩcm, and the resistor exhibits a resistance temperature characteristic of -1300 ppm / ° C or higher. 3. A ceramic resistor having a ceramic made of a compound and / or a composite compound of four or more kinds of metal elements and / or metalloid elements excluding Pb and Cd as a resistor material, and the specific resistance of the resistor material. Value is 8 kΩcm to 30 kΩcm
A ceramic resistor, wherein the resistor exhibits a resistance temperature characteristic of -1450 ppm / ° C or higher. 4. A ceramic resistor having a ceramic made of a compound and / or a composite compound of four or more kinds of metal elements and / or semi-metal elements excluding Pb and Cd as a resistor material, and the specific resistance of the resistor material. Value is 30kΩcm-70kΩc
m, the ceramic resistor having a resistance temperature characteristic of -1530 ppm / ° C. or higher. 5. A ceramic resistor using a ceramic made of a compound and / or a composite compound of four or more kinds of metal elements and / or semi-metal elements excluding Pb and Cd as a resistor material, and the specific resistance of the resistor material. A ceramic resistor having a value of 70 kΩcm or more and having a resistance temperature characteristic of -1620 ppm / ° C or more. 6. The resistor material is a compound containing Mg and Si and / or a composite compound.
5. The ceramic resistor according to any one of 5 above. 7. Mg and Si, Ca, Zn, Sr, Ba
At least one selected from Sn, Al, Sb and G
Ceramics made of a compound and / or a composite compound containing at least one element selected from a, Cr, Mn and Ge and at least one element selected from Bi, Nb, Ta, V, W and Mo as a resistor. The ceramic resistor according to any one of claims 1 to 5, which is made of a material. 8. A ceramic obtained by using, as a starting material, a simple substance, a compound or a complex compound of four or more kinds of metals and / or semimetals excluding Pb and Cd, mixing the starting materials, and then molding and firing the mixture. In the method for manufacturing a ceramic resistor as a body material, the step of mixing depends on the means for causing the starting material to flow throughout the mixing container and the means for deaggregating the starting material in the mixing container. Characteristic ceramic resistor manufacturing method. 9. The method of manufacturing a ceramic resistor according to claim 8, wherein the means for deagglomerating the starting material is a high-speed rotating blade. 10. The method of manufacturing a ceramic resistor according to claim 8, wherein the mixing step is carried out under reduced pressure in the mixing container. 11. The mixing is performed without introducing water into the mixing container in the initial stage of the mixing process, and the water is introduced into the mixing container after a predetermined time and mixing is performed. A method of manufacturing a ceramic resistor according to any one of 1. 12. The flaky or clay-like starting material after the completion of the mixing process and before molding.
12. The method for manufacturing a ceramic resistor according to any one of 1 to 11. 13. Starting materials are Mg and Si, and Ca and Z.
at least one selected from n, Sr, and Ba, Sn,
Consists of a compound and / or a composite compound containing at least one element selected from Al, Sb, Ga, Cr, Mn, and Ge and at least one element selected from Bi, Nb, Ta, V, W, and Mo as a main component. 9. The method according to claim 8, wherein
13. The method for manufacturing a ceramic resistor according to any one of 12.