JPS60169102A - Voltage nonlinear resistor - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a voltage nonlinear resistor whose main component is zinc oxide.

BACKGROUND ART In general, this type of voltage nonlinear resistor has excellent nonlinearity and is therefore suitably used in surge absorbers of electrical equipment and the like. The production of this kind of voltage nonlinear resistor is
Zinc oxide (ZnO) as the main component K bismuth oxide (
It is carried out by mixing several types of additive components including BizO5) as subcomponents, molding the mixture, and then firing it. The reason why bismuth oxide is added here is that since it has a lower melting point than zinc oxide, it promotes the crystal growth of zinc oxide particles through liquid phase sintering, but conventionally For example, bismuth oxide was used in large amounts, for example, 0.3 mol% or more.

By the way, when manufacturing a voltage non-linear resistor, in order to improve the life characteristics of the resistor or to insulate the outer periphery of the resistor, it is necessary to heat the resistor at a temperature of 400 to 900°C after sintering.
The heat treatment step after sintering changes the crystal system of bismuth oxide. For this reason, the electrical characteristics of the voltage nonlinear resistor are greatly reduced, and the degree of this is greater as the heat treatment temperature is higher. As a result, in a certain current range (for example, 100 μA to IA), a conventional resistor has α (nonlinear index) of 9 or more and can obtain good % property, but in a region outside of that range, it is nonlinear. The index was extremely low. In addition to these problems, there is also the problem that the metal component B1 of Bi2O3, which is the main component of the additive, has a Clarke number of 2 x io and is a scarce resource.

Purpose of the Invention The present invention was made against this background.
The object of the present invention is to provide a voltage nonlinear resistor that can suppress the content of 81203 among additive components to a trace amount and improve various element properties such as nonlinear characteristics.

Summary of the Invention The first invention is characterized by containing zinc oxide (ZnO) as the main component, manganese oxide (MnO2), antimony oxide (Sb205), chromium oxide (Cr2O3), cobalt oxide (CO2O3), silicon oxide ( 5io2), bismuth oxide (RbO5) as an additive component, and lead oxide (pbo) and antimony oxide (Sb20).
3) Chromium oxide (CrzOs), zinc oxide (ZnO
), cobalt oxide (CO2O3) and manganese oxide (M
No. 4 second component obtained by mixing and calcining one or more of (n02) and sintering.

The second invention is characterized by containing znO as a main component,
MnO2, 5b203, Cr2O5, Co2O3, 8
102.

81z03, the first component containing aluminum oxide (AlzO3) as an additive component and the second component described above are mixed and sintered.

#! 3% mold of the invention is mainly composed of ZnO, MnO2, 5b203, Cr2O5, CO2O3
, 8102.

The first component containing 5t2o5 as an additive component, the second component described above, and zinc borosilicate glass are mixed and sintered.

The percentage mark of the fourth invention is based on znO as the main component,
MnO2, 5b203, Cr2O3, Co2O3,
5i02.

The first containing ai2o3 and At2o5 as additive components.
The above-mentioned second component and zinc borosilicate glass are mixed and sintered.

The fifth invention is characterized in that the main component is znOt, MnO2, 5b203, Cr2O5, Co2O3
, 5i02.

81203, ht2o5, nickel oxide (NiO
) as an added component, and the second Hy:, min.
The point is that the ingredients and zinc borosilicate glass are mixed and sintered.

EXAMPLES Hereinafter, examples of the present invention will be described, and characteristics of resistors of the examples will be explained with reference to the drawings.

The voltage nonlinear resistor according to the embodiment of the first invention is made of ZnO9
7,47% Le4, B12O30,03 mo/l/I,
Mn020.5 mol%, 5b2050.5 mol l, C
r2O30.5 mol%, Co2O30.5 mol%, 81
The first component obtained by weighing and mixing a predetermined amount to give 0.020.5 moles, and a mixed powder containing RbO, Cr2O3, and 5b203 at a molar ratio of 4:1:l, are calcined. This is obtained by mixing and sintering the second components such that the content ratio of the second components to the whole becomes a factor of 2 by weight.

To describe a specific example of manufacturing such a resistor, first, a predetermined amount of each powder of PbO, Cr2O5, and 5b205 was weighed in the above proportions, and the weighed materials were thoroughly mixed in a centrifugal ball mill and then placed in an alumina pot. Calcination is performed at a temperature of 1000° C. for 4 hours, and the resulting calcined powder is pulverized in a centrifugal ball mill to obtain a reaction product, which is the second component. On the other hand, ZnO, 8
1205, Co2O3, 5i02゜MnO2, 5bz0
3. Weigh out a predetermined amount of each powder of Cr2O3 in the above ratio, add t-2 weight of the above reaction product to it, and then thoroughly mix in a rotating ball mill and form into a disk shape.

Next, the molded body was fired in air at a temperature of 1130° C. for 6 hours, and both end faces of the obtained sintered body were polished to form Vc.
An Ag electrode is applied and heat treated at a temperature of 590° C. for 1 hour, thereby obtaining a voltage nonlinear resistor. Here PbO, 5
b205. By calcining the Cr2O5 mixture, a reactant containing pyrochlore crystals as a main component can be obtained. In order to investigate this, the above calcined powder was subjected to X-ray diffraction, and the X-ray diffraction pattern was as shown in FIG. This shows that the main component of the reactant is pyrochlore crystals.

Next, we will discuss the results of comparing the device characteristics of the voltage nonlinear resistor actually manufactured as described above (this will be referred to as resistor A) and a conventional resistor whose main ingredient is 81203. Figure 2 is a graph showing current properties with current on the horizontal axis and voltage on the vertical axis, and Figure 3 shows the relationship between heat treatment temperature and rate of change in V1mA/s+m and α before and after heat treatment. The graph shows the heat treatment temperature on the horizontal axis and the amount of change on the vertical axis, and Figure 4 shows the temperature 1.
It shows the rate of increase in leakage current when a DC voltage of 85% of y imA/+ns+ is applied in a thermostatic oven at 30°C, with the horizontal axis representing the charging time and the vertical axis representing the rate of increase in leakage current. This is a graph. In FIGS. 2 to 4, 1 and 2 indicate the characteristics of the resistor A and the conventional resistor, respectively. Also, y l mA/sr is 1 mA for a resistor with the thickness of one fin.
α is the voltage across both ends when a current of ) is an exponent. K is a nonlinear resistance. Although α varies depending on the current value, a value obtained when a current in the range of 0.1 mA to 1 rnA is generally used is often used, and the value in this range will be adopted below.

First, looking at FIG. 2, the slope of curve 1 is smaller than that of curve 2 in the microcurrent region and the large current region. Here, α increases as the slope of the curve in Figure 2 decreases, so in the microcurrent region and large current region, the α of resistor A is larger than that of the conventional resistor, resulting in nonlinear characteristics. is understood to be superior. Also, looking at Figure 3, in the conventional resistor, V1
When the heat treatment temperature becomes higher than around 600°C, both mA/■ and α rapidly decrease as the temperature increases, and a deterioration in characteristics is observed. It can be seen that VlmA, z-, and α hardly change due to heat treatment, and the characteristics do not deteriorate. The curve indicated by 1' in FIG. 3 will be described later. Further, referring to FIG. 4, it can be seen that the resistor A of the embodiment has a smaller rate of increase in leakage current than the conventional resistor, and has good life characteristics.

FIG. 5 is a graph showing how α changes when the content ratio of s to2 is changed in this example, and B1 is the percentage curve.

Furthermore, the content ratios of other additive components are fixed. From this result, in order to obtain good characteristics, for 5io2, 0.
It is necessary that it be contained in a content ratio of 1 to 5 moles. Also MnO2, 5b203, Cr2O3, Co
Similar measurements were conducted for 2O3K, and it was found that in order to obtain good properties, it is necessary to contain each in a content ratio of 0.1 to 5 mol (relative to the first component). understood. Similar measurements were performed on the reaction products, and it was found that in order to obtain good properties, K must be contained at a content ratio of 0.2 to 20% by weight (relative to the whole). Ta.

Regarding the blending ratio of the above reaction products, pbo.

Any compound that forms pyrochlore crystals containing 5b2o5 may be used, and the compounding ratio is not limited to that shown in the examples. Also, regarding its composition, pbo.

In addition to the combination of 5b205 and Cr2O3, pbo
and 5b2o, and Cr2O5, ZnO, Co2O3,
A similar effect can be obtained if it is combined with at least one type of MnO2. The calcination temperature and calcination time in the calcination step for obtaining the above reaction product are preferably in the range of 800 to 11,000 c and 1 to 10 hours, respectively. The reason for this is that if the calcination temperature is lower than 800°C or the calcination time is shorter than 1 hour, the reaction will not occur sufficiently, and if the calcination temperature is higher than 1100°C or the calcination time is It's about 10 hours long.

This is because the greater the degree of volatilization, the worse the nonlinear characteristics will be.

The aX temperature and firing time in the firing step after mixing the first component and the second component are preferably 950 to 1350°C and 1 to 20 hours, respectively. The reason is that the firing temperature is 95
If the temperature is lower than 0℃ or the firing time is shorter than 1 hour, it will not be possible to obtain a dense and uniform sintered body, and the firing temperature will be too low.
This is because if the temperature is higher than 50° C. or the firing time is longer than daylight saving time, the degree of volatilization of pbo and 81203 near the surface increases, resulting in poor nonlinear characteristics.

Here, to describe the role of 5i2o5, the relationship between the firing temperature in the firing process after mixing the first component and the second component, and α and V1mA/1m is 5i2o5.
The solid lines 3 and 4 show the results of the investigation with and without the addition of 5i2, respectively.
The solid line 5.6 shows the change in VlmAy' and the change in α for the case where 5i2o5 is added, and the solid line 5.6 shows the change in V1m4- and the change in α for the case where 5i2o5 is not added. In this case, the other additive components of the resistor are resistor A
is the same as As is clear from the figure, a trace amount of 8120
By adding 3, the optimum firing temperature range can be expanded. In order to obtain the effect of expanding the optimum firing temperature, the content ratio of 5i2o5 is O, OI
It needs to be 1 or more. The reason for this effect is thought to be that Bi2O3 and the reaction product are added in combination. - As the content of 1,5,5i2o5 increases, the decrease in α after heat treatment increases.The higher the heat treatment temperature, the greater the degree of decrease. Third
The solid line 1' in the figure shows the rate of change in α when 5t2o3 is added in a 0.1 molar proportion. Comparing this solid line 1' with the solid line 1 in the same figure (BlzO50,o 3 molar addition), it is found that B12O3 is The one with 0.1 molar addition is 812
The rate of decrease in α is greater than that of the one in which 0.03 mole of 03 was added. From the comparison between solid line 1' and solid line 2 (conventional resistor), the one with 0.1 molar addition of B12O3 is:
Although good characteristics can be obtained with conventional resistors, Bi2O
If the content of 3 exceeds 0.1 mole, the properties will approach those of conventional products and the effect will be lost. Therefore, the content of 512o5 needs to be in the range of o, oi to more than 0.1 mole.

In addition, the heat treatment temperature of the sintered body is preferably 500 to 850°C, and if it is lower than 500°C, the life characteristics will be poor;
If the value is also high, the nonlinear characteristics will deteriorate.

In the above embodiments, a centrifugal ball mill and an aluminium crucible were used to manufacture the resistor, but the type of equipment may be any suitable for the purpose and is not limited to these.

Next, describing the second invention, the voltage nonlinear resistor according to the embodiment of the second invention contains Zn097.467 mol or more, B
i2O50.03 mol%, MnO2o, 5-el%,
5b2050.5 mon, %, Cr2O30.5 mole era, co2050.5% le%, 81020.5
PbO
r Cr205r 5b203 t-molar ratio Te4:l
: The second component obtained by calcining a mixed powder containing a ratio of 1:1 is obtained by mixing the second component in a weight ratio of 2 with respect to the entire second component and sintering the mixture.

To describe a specific example of manufacturing such a resistor, first, a reaction product as the second component was obtained in the same manner as in the embodiment of the first invention, and on the other hand, ZnO, B12O3 + MnO2, 8b2
05. Cres5. Coz05. Sing,
Weigh a predetermined amount of each powder of At205 at the above ratio,
Two weights of the above reaction product are added to this, and then a voltage nonlinear resistor is obtained in the same manner as in the embodiment of the first invention.

Next, we will discuss the results of comparing the device characteristics of the voltage nonlinear resistor actually manufactured as described above (this will be referred to as resistor B) and a conventional resistor whose main additive is Bi2O3. Figure 7 is a graph showing the voltage-current characteristics with the horizontal axis representing voltage and the vertical axis representing voltage, and Figure 8 represents temperature 1.
This is a graph showing the rate of increase in leakage current when a DC voltage of 85V of V1m year is applied in a constant temperature oven at 30℃, with the horizontal axis representing the application time and the vertical axis representing the rate of increase in leakage current. It is. In FIGS. 7 and 8, 7 and 2 are resistors 8, respectively.
and the characteristics of conventional resistors, 8 is Az2o
The characteristics of a resistor manufactured in the same manner as in the example except that the content ratio of 5 was changed to 20/1000 mol are shown below.

As can be seen from FIG. 7, the resistor B according to the first embodiment has a larger α than the conventional resistor in the micro current region and the large current region, and as can be seen from FIG. The increase rate of leakage current is small and the life characteristics are good.

Figure 9 shows Co2O3 or 5to2 or Al2O3
It is a graph examining how α changes when the content ratio (content ratio with respect to the first component) is changed.

However, B 2 to 13 are respectively Co2O3,5102+
In addition, when changing the content ratio of each component, the composition of the added components other than the changed component is the same as in the example. Regarding kt205, Co2o from the example
5, 5io2 '1 has been removed from the experiment. From this result, in order to obtain good characteristics, Co2
About O3 BO, 1~5 Mo/I/ 4.5120
It is necessary that each of s be contained in a content ratio of 0.1 to 5 mol%. In addition, Az2o3 plays a role of increasing α in the large current region as described above, so 0.2/
It is necessary that it contains 1000 moles or more,
If it exceeds 2,071,000 molar ratio, α will become smaller, so it is necessary to contain 0.271,000 to 20/1000 molar ratio.

Similar measurements were also performed on MnO2, 5b203 r Cr2O5, and it was found that in order to obtain good properties, the content ratio of each should be 0.1 to 5 mol% (relative to component I).
It was found that it was necessary to include Similar measurements were conducted for the reaction products, and it was found that in order to obtain good properties, it is necessary to contain the reaction products at a content ratio of 0.2 to 20% by weight (relative to the whole). Ta.

Next, the third invention will be described. The voltage nonlinear resistor according to the embodiment of the third invention contains Zn097.47 mol%, Mn
O20, 5 mol%, 5b2050.5 mol%, Cr20
50.5 mol%, Co2O30.5 mols, 5t2
A first component consisting of O50.5 mol% and BizO50.03 mol%, and a second component obtained by calcining a mixed powder containing PbO, Cr2O5, 5b203 in a molar ratio of 4:1: , the content ratio of the second component is 2% by weight, and the content ratio of the borosilicate zinc glass is 0.2%.
It was obtained by mixing and sintering so that the balance by weight was the first component.

To describe a specific example of manufacturing such a resistor, first, a reaction product as the second component was obtained in the same manner as in the embodiment of the first invention, and on the other hand, ZnO, Bi2O3rMn02, 5b
zQ3, Cr2O3, Co2O3+ 5I02 <
) Weigh out a predetermined amount of each powder in the above ratio, add 2 parts by weight and 0.2 parts by weight of the above reaction product and zinc borosilicate glass, respectively, and then proceed in the same manner as in the example of the first invention. Obtain a voltage nonlinear resistor.

Next, we will discuss the results of comparing the device characteristics of the voltage nonlinear resistor actually manufactured as described above (this will be referred to as resistor C) and a conventional resistor whose main additive is BizO5. Figure 10 is a graph showing the voltage-current characteristics with current on the horizontal axis and voltage on the vertical axis, and Figure 11 shows when a DC voltage of 85 Yus of V1m yr is applied in a thermostatic oven at a temperature of 130°C. This graph shows the rate of increase in leakage current, with the horizontal axis representing the energization time and the vertical axis representing the rate of increase in leakage current. In FIGS. 10 and 11, 9 and 2 indicate the characteristics of the resistor C and the conventional resistor, respectively.

As can be seen from FIG. 10, the resistor C according to the embodiment has a larger α than the conventional resistor in the small current region and the large current region, and as can be seen from FIG. Compared to conventional products, the increase rate of leakage current is smaller and the life characteristics are better.

Figure 12 shows zinc borosilicate glass or CO20! ! Or, if you change the content ratio of 5102, here is a graph that shows how α changes, solid lines B5 to B7
1 and 2 show characteristics with varying content ratios of zinc borosilicate glass and Co205.5i2o5, respectively. However, the added components other than those whose content ratios were changed are fixed as in the examples. Regarding changing the content ratio of zinc borosilicate glass, the amount of the first component having the same composition as in the example was changed. The content ratio of zinc borosilicate glass is the content ratio relative to the whole, and the content ratio of Co2O3 and 8102 is the content ratio relative to the first component. From this result, in order to obtain good properties, the content should be 0.01 to 5% by weight for zinc borosilicate glass, 0.1 to 5 mol% for CO2O3, and 0.1 to 5 mol% for 5i02. It is necessary that each of these be included.

Similar measurements were also performed on MnO2, 5b203, and Cr2O5, and it was found that in order to obtain good characteristics, the content ratio of each of them should be 0.1 to 5 mol% (relative to the first component).
It was found that it was necessary to include Similar measurements were conducted on the reaction products, and it was found that in order to obtain good properties, it is necessary to contain them at a content ratio of 0.2 to 20% by weight (based on the whole). Ta.

Next, the fourth invention will be described. The voltage nonlinear resistor according to the embodiment of the fourth invention contains Zn097.467 mol or more, M
nO20.5 mol elb, 5bz050.5 mol%, C
r2O50,5 mo/I/%, CO2O30,5 mole%, 81020.5 mole%, At20.3/1000 mole, Bi2O30,03-vnyl% J:D, pbo, cr2o5, 5b2o3 A second component obtained by calcining a mixed powder containing the following in a molar ratio of 4:1:l and zinc borosilicate glass, the content of the second component being 2% by weight, zinc borosilicate glass. The content ratio is 0.2
It was obtained by mixing and sintering so that the balance was the first component.

To describe a specific example of manufacturing such a resistor, first, a reaction product as the second component was obtained in the same manner as in the example of the first invention, and -10,000 Zn0, 81203 was obtained.

MnO2r 5b203, Cr2O3, Co2O3
, SiO2, and AA203 in the above proportions, and to this, 2! each of the above reaction product and zinc borosilicate glass were weighed. Add weight weight and 0.2 weight weight, then 1st
A voltage nonlinear resistor is obtained in the same manner as in the embodiment of the invention.

Next, we compared the device characteristics of the voltage nonlinear resistor actually manufactured as described above (this will be referred to as a resistor) and a conventional resistor whose main additive is B i go 3. Regarding the results, in Figure 13, the horizontal axis shows the current;
Graph showing voltage-current characteristics with voltage on the vertical axis, 1st
Figure 4 shows 85% of V1mA'- in a thermostat at 130°C.
This is a graph showing the rate of increase in leakage current when a DC voltage of 1 is applied, with the horizontal axis representing the voltage application time and the vertical axis representing the rate of increase in leakage current. 10 in Figures 13 and 14
and 2 show the characteristics of a resistor and a conventional resistor, respectively, and 11 shows the content ratio of Al2O3 at 20/1000.
The characteristics of a resistor manufactured in the same manner as in the example are shown except that the molar ratio is used.

As can be seen from FIG. 13, the resistor according to the example has a larger α than the conventional resistor in the micro current region and the large tlt flow region, and in particular, because it contains Az2O5, the α in the large current region is large. Furthermore, as can be seen from FIG. 14, the resistor element has a smaller leakage current increase rate and better life characteristics than the conventional resistor element.

FIG. 15 is a graph showing the relationship between the content ratio of zinc borosilicate glass and α, and FIG. 16 is a graph showing the relationship between the content ratio of Co2O3 or 5102 and α. solid line as-s
1o is zinc borosilicate glass, CO2O3 and 5io2 respectively
The characteristics are shown by changing the content ratio of . However, the components other than those whose content ratios were changed are fixed as in the examples. Regarding the content ratio of borosilicate zinc glass, the content ratio is shown based on the total content, and Co2O3, 5102
The content ratio is the content ratio with respect to the expanded first component. From this result, in order to obtain good properties, the weight should be 0.01 to 5 for zinc borosilicate glass, and 0.1 to 6 mol for -CO2O3, and 0.1 to 6 for 4.5iOz.
It is necessary that each of them be contained in a content ratio of 5 molar width.

Also, Az2o3 is 0.2/1 for the same reason as mentioned above.
It is necessary that it be contained in an amount of 000 to 2071000 mol%.

Similar measurements were also performed on MnO2+ 5b205 + Cr2O3, and it was found that each must be contained in a content ratio of 0.1 to 5 molar range (relative to the first component) in order to obtain good characteristics. It turned out to be. Similar measurements were conducted on reaction products, and it was found that in order to obtain good properties, it is necessary to contain the reaction products at a content ratio (relative to the whole) of 0.2 to weight factor. Ta.

Next, describing the fifth invention, the voltage nonlinear resistor according to the embodiment of the fifth invention contains Zn096.967 mol%, M
nO20.5mol96.8b2050.5mol%, Cr
2O5o, 5 moles 9b, Co2O30, 5 moles f6.
81020.5 mol%, NIO 0.5 mol%, AZ20
A first component consisting of 53/1000 mol%, 8120, 0.03 mol%, and pbo.

C'205 r 5b203 in mo/l, ratio 4:l:1
A second component obtained by calcining a mixed powder containing a proportion of 2% by weight of the second component and 0.2% by weight of zinc borosilicate glass. , the remainder being the first component and sintering.

To describe a specific example of manufacturing such a resistor, first, a reaction product as the second component was obtained in the same manner as in the embodiment of the first invention, and -10,000 ZnO, Bi2O5.

MnO2r 5b2o51 Cr2O3+ Co2O3
A predetermined amount of each powder of T S 102 + NIOTAz2o3 in the above ratio was weighed, and to this was added the above reaction product and zinc borosilicate glass in an amount of 2% by weight and 2% by weight, respectively, and then the powder of the first invention was added. A voltage nonlinear resistor is obtained in the same manner as in the example.

Next, we will discuss the results of comparing the device characteristics of the voltage nonlinear resistor actually manufactured as described above (this will be referred to as resistor E) and a conventional resistor whose main component is an at2o3k additive. In Fig. 17, 11. is plotted on the horizontal axis. Flow,
Graph showing voltage-current characteristics with voltage on the vertical axis, 1st
Figure 8 shows the rate of increase in leakage current when a DC voltage of 85 of VlmAz- is applied in a thermostatic chamber at a temperature of 130°C, with the horizontal axis representing the application time and the vertical axis representing the rate of increase in leakage current. It's a huge graph. Furthermore, Fig. 19 shows the voltage change (ΔV l mA /V 1 m
It is a graph showing the relationship between A) and the pulse current value.

17 to 19, 12 and 2 are resistors E, respectively.
and % for conventional resistors, 13 is Al2
A custom made resistor was manufactured in the same manner as in the example except that the content ratio of O3 was changed to 20/100 molar.
14 shows the characteristics of the resistor E excluding N10.

As can be seen from FIG. 17, the resistor E according to the example has a larger α than the conventional resistor in the small '#L flow edge region and the large current region, and especially in the large current region because Al2O3 is added. α is large. Furthermore, as can be seen from FIG. 18, the resistor E has a smaller leakage ilF and a smaller current increase rate than the conventional one, and has good life characteristics. As can be seen from Figure 19, the history contains NiO! For those without NiO, the amount of voltage change decreases to a large degree with respect to an increase in pulse current, but for the resistor E, the degree of decrease is smaller than that for the resistor E that does not include NiO. By adding NiO in this way, it is possible to suppress the degree of decrease in the voltage change rate with respect to an increase in pulse current.

Fig. 20 is a graph showing the relationship between the content ratio of NiO and α, and Fig. 21 is a graph showing the relationship between the content ratio of borosilicate zinc glass and α? The graph shown in Figure η is a graph showing the relationship between the content ratio of CO2O3 or 5i02 and α. Solid line all-
Bl'i is N10. Zinc borosilicate glass, CO2O3
The characteristics obtained by changing the content ratio of 5102 and 5102 are shown. However, the fractions other than those whose content ratios are varied are fixed as in the examples.

The content ratio of f#JNiO is the content allocation for the first component, and the content ratios of other fractions are the same as those described above.

From this result, in order to obtain a good percentage, NiO should be 0.1 to 5 mol %, and zinc borosilicate glass should be 0.1 to 5 mol %.
Ol ~5 weight sound, CO2O3 weight is 0.1~5
It is necessary that the content of the 81Dz frame is 0.1 to 5 mol%, respectively.

Also, ht2o 5 is 0.2/ for the same reason as mentioned above.
It is necessary to contain 1000 to 20/1000 moles.

Similar measurements were also conducted for MnO2, 5b205, and Cr2O3, and it was found that in order to obtain a good custom order, the content ratio of each must be 0.1 to 5 mol% (relative to the first component).
It was found that it was necessary to include A similar measurement was conducted for the reaction product, and it was found that in order to obtain a good percentage, it is necessary to contain it at a content ratio of 0.2 to 20% by weight (relative to the whole). understood.

Here, regarding the resistors B to E which are the embodiments of the second to fifth inventions, the relationship between V1m/9- and α before and after heat treatment (heat treatment performed for the purpose of improving life characteristics, etc.) ft Upon investigation, it was found that resistor A is an embodiment of the m1 invention.
As in the case of , no change in % sex ratio was observed.

Further, in the second to fifth inventions, at2o3 plays the role of obtaining a wide optimum firing R temperature, just as in the case of the first invention, and its content ratio is o, oi for the same reason. ~o1 mole is required.

tji1 Regarding the reaction product which is the second component, the compounding ratio, combination of components, calcination conditions, etc. are exactly the same as in the case of the first invention. The conditions and the heat treatment conditions after sintering are also exactly the same as in the case of the first invention.

Effects of the Invention As described above, according to the present invention, instead of using a large amount of ai2o3 as the main component of the additive, pbo, 5b20
Reaction products mainly composed of pyrochlore crystals containing 3, MnO2, 5b203, Cr2O5, Co2O3
, 5i02, etc. as additive components, Bi2
Good characteristics can be obtained while suppressing O5 to a trace amount.

Moreover, its percentage properties are better than those of conventional resistors which have ai2o3 t-additive as the main component. That is, compared to the conventional voltage non-linear resistor in which a large amount of 81205F is added, the decrease in the resistance due to heat treatment after sintering is smaller, and the heat treatment can be performed in the normal temperature range (400°C to 900°C) in the heat treatment process. Depending on the condition, the electrical % property will hardly decrease. As a result, the non-@ line index in the minute wL flow region is larger than that of the conventional one, and since the non-linear index in the minute current region is large, the leakage current during energization is low. Moreover, leakage due to M charging
A Bouzi absorption element with a long life and a small increase in IL current can be obtained.

and the reaction product as the second component and 8120. By adding all of these in combination, it is possible to widen the optimum firing temperature range and facilitate control in the F)H manufacturing process. Also, Bi205 (Clark number 2x lo-' of Bl
) *It is more advantageous in terms of resources than when used in large quantities. The reason is that among the metal components used as additive components,
The one with a small Clark number is Co (Clark number 1ixtO
), pb (Clarke number 1.5 x 3 1O), and Sb (Ri 2 - Ri number 5 This is due to h, which is similarly small in abundance but has a high content ratio like 81 in the conventional case. In addition to the above effects, υP can be increased by using a reaction product containing pbo2 in combination with a trace amount of Bi2O5.
There is almost no volatilization of bO and 5i2o3, which is advantageous in terms of occupational health and environment.

[Brief explanation of the drawing]

Figure 1 is an X-ray diffraction diagram of an example of the reaction product used in the present invention, Figure 2 is a voltage-current characteristic diagram of a voltage nonlinear resistor, and Figure 3 is a diagram of voltage-current characteristics of a voltage nonlinear resistor.
The figure is a graph showing the change in V1m year and α with respect to the heat treatment temperature of the voltage non-linear resistor. Figure 4 is a graph showing the leakage current increase rate with respect to the energization time of the voltage valve @ wire resistor.
The figure is a graph showing the non-linear %'tl k with respect to the content ratio of the additive component of the voltage valve @ wire resistor. Figure 7~#! Figure 9 shows a voltage-current characteristic diagram of the voltage non-linear resistor, a graph showing the leakage current increase rate with respect to the energization time, and a graph showing the non-linear characteristics with respect to the content ratio of additive components, and Figures 10 to 10 respectively. Figure 13 shows a voltage-current characteristic diagram of a voltage non-linear resistor, a graph showing the rate of increase in leakage current with respect to energization time, a graph showing non-linear characteristics with respect to the content ratio of additives, respectively. Figure, 14th
The figures are a voltage-wL current characteristic diagram of a voltage non-linear resistor and a graph showing an increase in leakage current a [- with respect to energization time, the first
Figure 5. Figure 16 is a graph showing the non-linearity with respect to the content ratio of each additive component, Figures 17 to 19 are voltage-tortoise current characteristic diagrams of a voltage non-linear resistor, and leakage current with respect to energization time, respectively. A graph showing the increase rate, a graph showing the relationship between the voltage change rate after impulse application and the pulse flow value, and Figures A to 4 are graphs showing non-linearity with respect to the content ratio of additive components. It is.

Claims (1)

[Claims] (1) Mancan oxide 01 to 5 moles, antimony oxide 0
．． 1 to 5 mol%, chromium oxide 0.1 to 5 mol%, cobal oxide) (1,1 to 5 mol%, silicon oxide 0.1 to 5 mol 1, bismuth oxide 0.01 to 0.1 mol, A second component obtained by calcining a mixture of one or more of chromium oxide, zinc oxide, cobalt oxide and manganese oxide, and lead oxide and antimony oxide to the first component, the balance of which is zinc oxide; The content ratio of m2 component to the whole is 0.2~
A voltage P linear resistor characterized in that it is made by mixing and sintering the mixture so that it is 20% by weight. (2) Manganese oxide 0.1-5 mol %, antimony oxide O 1-5 mol, chromium oxide 0.1-5 mol %, copal oxide) 0.1-5 mol %, silicon oxide 0.1-5 mol % 5 mol%, aluminum oxide 0.2/1000~20/
1,000 moles of bismuth oxide, 0.01 to 0.1 moles of bismuth oxide, residual S zinc oxide, and one or more of chromium oxide, zinc oxide, cobalt oxide, and manganese oxide, and lead oxide and oxide. It is characterized by being made by mixing and sintering a second component obtained by calcining a mixture consisting of antimony and other ingredients such that the content of the second component is 0.2 to 20% by weight based on the total amount of the second component. Voltage nonlinear resistor. (3) Manganese oxide 0.1-5 mol%, antimony oxide 0.1-5 mol%, chromium oxide 0.1-5 mol%, copal oxide) 0.1-5 mol%, silicon oxide 0.1-5 mol% 5 mol 4, ]tr bismuth 0.01-0.1 mol", '1Ai
n A first component consisting of zinc oxide, and a second component obtained by calcining a mixture consisting of one or more of chromium oxide, zinc oxide, cobalt oxide and manganese oxide, and lead oxide and antimony oxide. , mixed with zinc borosilicate glass and sintered, the content of the second component is 0.2 to 20% by weight, the content of zinc borosilicate glass is 0.01 to 5% by weight, and the balance is the second component. A voltage nonlinear resistor whose % characteristic is that it is one component. +41 Manganese oxide 0.1-5 mol%, antimony oxide 0.1-5 mol', chromium oxide 0.1-5 mol%, cobal oxide) O, 1-5 mol range, silicon oxide 0.1-5 mol %, aluminum oxide 0.2/1000-20/1
000 mol%, hismuth oxide o, o i ~ 0.1 mol%, the balance consisting of zinc oxide, and chromium oxide,
A second component obtained by calcining a mixture of one or more of zinc oxide, cobalt oxide and manganese oxide, lead oxide and antimony oxide, and zinc borosilicate glass are mixed and sintered. B. A voltage non-linear resistor characterized in that the content of the second component is 0.2 to 20% by weight, the content of zinc borosilicate glass is 0.01 to 5% by weight, and the balance is the first component. . (5) Manganese oxide 0.1-5 mol%, antimony oxide 0.1-5 mol%, chromium oxide 0.1-5 mol%, cobalt oxide 0.1-5 mol%, silicon oxide, 1-5 Aluminum oxide=UA 0.2/1000-20/
1000 mol%, a first component consisting of nickel oxide 0.1-5 mol%, bismuth oxide 0.01-0.1 mol%, the balance zinc oxide, and chromium oxide, zinc oxide, cobalt oxide and manganese oxide. A second component obtained by calcining a mixture of one or more of lead oxide and antimony oxide, and zinc borosilicate glass are mixed and sintered to produce Jilt, a second component.
A voltage nonlinear resistor characterized in that the content ratio of the components is 0.2 to 5% by weight, the content ratio of zinc borosilicate glass is 0.01 to 5% by weight, and the remainder is the first component.