JPH09312203A - Zinc oxide ceramic compsn., manufacture thereof and zinc oxide varistor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a high voltage zinc oxide varistor superior in electric characteristics and d-c load and surge reliability at a low sintering temp. of about 750-1050 deg.C and with high yield. SOLUTION: A mixture of at least one of B2 O3 , Cr2 O3 , GeO2 , La2 O3 , MgO, Nb2 O5 , Nd2 O3 , PbO, PrO, Sb2 O3 , SiO2 , SnO2 , Ta2 O5 , WO3 and Y2 O3 powders, with Bi2 O3 powder is heat treated at 400-700 deg.C and pulverized into a synthetic powder, this powder (0.5-20 parts wt.) and at least one of ferrous oxide powders of CoO, MnO2 and NiO (0.1-5.0 parts wt.) are added to zinc oxide powder (parts 100wt.), pulverized and sheeted with a binder, an Ag paste is applied to the surface of each of resultant sheets, fours of which are laminated and sintered at 840 deg.C in one body. The laminate zinc oxide varistor 20 is composed of an inner Ag electrode 21, an inner Ag counter electrode 22, an active layer 23, a reactive layer 24 and an outer Ag electrode 25.

Description

Detailed Description of the Invention

TECHNICAL FIELD The present invention relates to a zinc oxide porcelain composition and a method for producing the same. More specifically, the present invention relates to a zinc oxide porcelain composition for producing a zinc oxide varistor used for absorbing surges in an electric circuit and a method for producing the same.

2. Description of the Related Art Zinc oxide (ZnO) varistor is a zinc oxide raw material containing zinc oxide, basic additives of bismuth oxide, manganese dioxide and cobalt oxide, and various oxides added for further performance improvement. It is manufactured using a sintered body of a zinc oxide-based porcelain composition obtained by firing the powder. It is known that the rising voltage of the zinc oxide varistor increases almost in proportion to the number of grain boundaries existing between the electrodes. That is, the rise voltage of 3 to 4 volts per grain boundary rises. Therefore, in order to manufacture a zinc oxide varistor for high voltage, the average particle size is 4 to 40 μm.
It is necessary to produce a sintered body having ZnO particles having a small particle size of about m. Therefore, conventionally, in order to manufacture a zinc oxide varistor for high voltage, antimony oxide (Sb
_A method of suppressing the growth of ZnO particles by adding a ZnO particle growth suppressing material such as ₂ O ₃ ) has been used. The rising voltage refers to the voltage between both terminals when a current of 1 mA is applied to the varistor and is represented by V _1mA .
The voltage between the terminals when a current of 1 mA was applied to a sample with a thickness of 1 mm was defined as one of the constants of this material, and expressed as V _{1 mA / mm} . This means a rising voltage per 1 mm thickness of the sample.

However, high voltage
For obtaining high performance zinc oxide varistor
High sintering temperatures of ~ 1300 ° C were required. High sintering temperature
Not only power consumption but also intense flying such as bismuth oxide.
And the consequent consumption of furnace materials and containers, and the sintering temperature
There has been a demand for lower temperatures. Ie these higher
When fired at a temperature, steaming of bismuth oxide will occur even in the atmosphere.
The start is active. Also, bismuth oxide does not react with many substances.
It is easy to handle, and many ceramics such as furnace materials and containers
Easily corrodes substances. In addition, when the sample is placed in the furnace
Depending on the location, temperature, heating rate, Bi2O3 and Sb_TwoO_ThreeVapor pressure of
Difference occurs, it is difficult to keep them uniform, and
Cause Ki. Meanwhile, manufacture conventional zinc oxide varistors
A low firing temperature with a compounding composition of zinc oxide based porcelain composition for
If this is not done, sufficient sintering will not occur and the rising voltage will be too high.
It becomes extremely high, and the particle size of ZnO varies, causing non-linear resistance.
Anti-property is reduced. In addition, power load, pulse current load
Life is shortened. In the conventional manufacturing method,
For zinc oxide raw material powder, for example, bismuth oxide, anti-oxidant
Incorporate mon, chromium oxide, or boron oxide
Since all ingredients were mixed and baked as they were,
A rough reaction occurs, and antimony oxide and zinc oxide react first.
The corresponding part, bismuth oxide and antimony oxide react first
There will be parts to do. Also, boron oxide
It is used to lower the sintering temperature, but it is a heating process
And tend to form a liquid phase from the beginning and collect together.
It may cause uneven quality and uneven quality.
I'm sorry. In particular, antimony oxide easily sublimes into zinc oxide particles.
Prevents grain growth by covering the surface of the child and reacting with ZnO
Work. As a result, grain growth in the sintered body
The part that is not promoted and the part that is promoted may be mixed.
With the conventional manufacturing method,
Was difficult to manufacture. Therefore, uneven quality
And quality variations between lots are likely to occur. ZnO burr
Zinc oxide-bismuth oxide system which is the basic composition of porcelain
Has a eutectic composition with a eutectic temperature of 740 ° C.
The two of them react easily, but some of the additives have this reaction.
There are obstacles. The additives themselves are the above 2
When hindering contact with other people. Additive reacts with zinc oxide
It may form a chemically stable substance. As an example of the latter
And Zn_TwoSnO_Four, Zn_TwoSiO_Four , Zn_TwoTiO_Four , Zn _Two
GeO_Four , Cr_TwoZnO_Four, Mn_TwoZnO_Four, Zn_ThreeNb_TwoO₈ What
There is a throat. Furthermore, it can sufficiently control the abnormal grain growth of ZnO.
It was difficult to obtain it from one manufacturing lot.
Of electrical characteristics and reliability between zinc oxide varistors
There is a problem that the unevenness (variation within the lot) is large.
Was. In addition, zinc oxide burr obtained from different manufacturing lots
Variation in electrical characteristics and reliability between
There was a problem that it was also large. As mentioned above
In the method using the conventional porcelain composition, the electrical characteristics and
Stable zinc oxide varistor with low reliability and excellent reliability
Could not be manufactured. In addition, zinc oxide ballis
The excellent electrical characteristics of a battery means, for example, leakage current.
There is little flow, and the nonlinear resistance index described later_0.1mAα_1mAIs high
The reliability depends on the voltage applied for a long time.
In the case of high temperature, long time power load, pulse application
In some cases, there is no deterioration in electrical characteristics.
Is mentioned. The present invention solves the above-mentioned conventional problems.
Therefore, the low temperature sintering allows the electrical characteristics such as non-linear resistance characteristics and
Manufacturing highly reliable zinc oxide varistor with high yield
Provided are a zinc oxide-based porcelain composition and a method for producing the same.
The porpose is to do.

In order to achieve the above object,
Therefore, the zinc oxide porcelain composition of the present invention is a zinc oxide powder 1
Boron oxide (B_TwoO_Three), Chromium oxide
(Cr_TwoO_Three), Germanium oxide (GeO_Two), Lanthanum oxide
(La_TwoO_Three), Magnesium oxide (MgO), niobium oxide (Nb
_TwoO_Five), Neodymium oxide (Nd_TwoO_Three), Lead oxide (PbO), oxidation
Praseodymium (PrO), antimony oxide (Sb_TwoO_Three),acid
Silicon oxide (SiO_Two), Tin oxide (SnO_Two), Tantalum oxide (Ta_TwoO
_Five), Tungsten oxide (WO_Three), And yttrium oxide
(Y_TwoO_Three) At least one powder selected from
Suma (Bi_TwoO_Three) Mixture with powder at 400 ° C-700 ° C
Synthetic powder or mixture obtained by subjecting to range heat treatment and crushing
0.5-20 parts by weight of synthetic powder prepared from powder
And nickel oxide, cobalt oxide and manganese oxide
At least one iron group oxide powder selected is 0.1 to
It has a structure that 5.0 parts by weight is added.
is there. In the zinc oxide-based porcelain composition, zinc oxide
Is partly replaced by magnesium oxide.
And are preferred. In the zinc oxide porcelain composition,
Is the aluminum component in 100 parts by weight of zinc oxide powder.
On the other hand, it is 0.00062-0.
It is preferably contained in an amount of 372 parts by weight. Also the acid
In the zinc oxide-based porcelain composition, the aluminum component is
100 weight of mixed powder of zinc oxide powder and magnesium oxide
0.00062 in terms of aluminum oxide with respect to the parts
It is preferable that the content is from about 0.372 parts by weight. this
Beforehand, at least 100 parts by weight of zinc oxide
Boron oxide (B_TwoO_Three) And bismuth oxide (Bi_TwoO_Three)
Mixture with powder, chromium oxide (Cr_TwoO_Three) And bismuth oxide
(Bi_TwoO_Three) Mixture with powder, germanium oxide (GeO_Two)When
Bismuth oxide (Bi_TwoO_Three) Mixture with powder, lanthanum oxide (L
a_TwoO_Three) And bismuth oxide (Bi_TwoO_Three) Mixture with powder,
Gnesium (MgO) and bismuth oxide (Bi_TwoO_Three) Mixing with powder
Object, niobium oxide (Nb_TwoO_Five) And bismuth oxide (Bi_TwoO_Three) Powder and
A mixture of neodymium oxide (Nd_TwoO _Three) And bismuth oxide (Bi
_TwoO_Three) Mixture with powder Lead oxide (PbO) and bismuth oxide (Bi
_TwoO_Three) Mixture with powder, oxidation with praseodymium oxide (PrO)
Bismuth (Bi_TwoO_Three) Mixture with powder, antimony oxide (Sb_Two
O_Three) And bismuth oxide (Bi_TwoO_Three) Mixture with powder, silicon oxide
(SiO_Two) And bismuth oxide (Bi_TwoO_Three) Mixture with powder, oxidation
Tin (SnO_Two) And bismuth oxide powder (Bi_TwoO_Three) With a mixture of acids
Tantalum oxide (Ta_TwoO_Five) And bismuth oxide (Bi_TwoO_Three) Mixing with powder
Compound, tungsten oxide (WO_Three) And bismuth oxide (Bi_TwoO_Three)powder
Mixture with powder, and yttrium oxide (Y_TwoO_Three) And oxidation
Bismuth (Bi_TwoO_Three) 400 ° C for each mixture with powder
Heat treatment at ~ 700 ℃
Do not prepare at least one synthetic powder or mixed synthetic powder.
0.5-20 parts by weight of synthetic powder, nickel oxide, oxidation
At least one selected from cobalt and manganese oxide
0.1 to 5.0 parts by weight of the iron group oxide powder should be added.
When sintering zinc oxide-based porcelain composition,
Boron (B_TwoO_Three), Chromium oxide (Cr_TwoO_Three), Germanium oxide
Um (GeO_Two), Lanthanum oxide (La_TwoO_Three), Magnesium oxide
Um (MgO), niobium oxide (Nb_TwoO_Five), Neodymium oxide
(Nd_TwoO_Three), Lead oxide (PbO), praseodymium oxide (Pr
O), antimony oxide (Sb_TwoO_Three), Silicon oxide (SiO_Two),acid
Tin oxide (SnO_Two), Tantalum oxide (Ta_TwoO_Five), Oxidized tongue
Ten (WO_Three), And yttrium oxide (Y_TwoO_Three) Etc.
Sintering effect of zinc oxide powder is reduced and lower temperature
Even if it is fired at a certain temperature, sufficient sintering is possible and the particle size is even.
Can be made into a sintered body that has a non-linear resistance due to low temperature sintering.
Zinc oxide varis excellent in electrical characteristics such as characteristics and reliability
A zinc oxide-based porcelain composition that can be manufactured with a high yield is proposed.
Can be served. Further, the zinc oxide-based porcelain composition of the present invention
Is 100 parts by weight of zinc oxide powder
Parts, 0.00062 to aluminum oxide equivalent
A zinc oxide porcelain composition containing 0.372 parts by weight.
Preferably, there is. In this example, the added
The ruminium component forms a solid solution in the ZnO particles, and
Since it works as a rectifier, Z without compromising other electrical characteristics
to reduce the electrical resistance of nO to a desirable level.
Can improve the non-linear resistance characteristics of the varistor in the high current range.
A zinc oxide-based porcelain composition suitable for the above can be provided. Next book
The first method for producing a zinc oxide-based porcelain composition of the invention is
Boron oxide (B_TwoO_Three), Chromium oxide (Cr_TwoO_Three), Oxidized gel
Manium (GeO_Two), Lanthanum oxide (La_TwoO_Three), Oxide mug
Nesium (MgO), Niobium oxide (Nb_TwoO_Five), Neodymium oxide
Mu (Nd_TwoO_Three), Lead oxide (PbO), praseodymium oxide (Pr
O), antimony oxide (Sb_TwoO_Three), Silicon oxide (SiO_Two),acid
Tin oxide (SnO_Two), Tantalum oxide (Ta_TwoO_Five), Oxidized tongue
Ten (WO_Three), And yttrium oxide (Y_TwoO_Three)
At least one powder and bismuth oxide (Bi_TwoO_Three) Powder
The mixture with and is heat treated in the range of 400 ℃ ~ 700 ℃,
Pulverize to prepare synthetic powder or mixed synthetic powder, zinc oxide 10
0.5 to 20 parts by weight of the synthetic powder
Parts and nickel oxide, cobalt oxide and manganese oxide
0.1 at least one iron group oxide powder selected from
.About.5.0 parts by weight was added.
Things. Next, the second zinc oxide based porcelain set of the present invention
The manufacturing method of the product is to add magnesium oxide to zinc oxide.
To obtain a zinc oxide-magnesium oxide mixed powder
And boron oxide (B_TwoO_Three), Chromium oxide (Cr_TwoO_Three), Oxidation
Germanium (GeO_Two), Lanthanum oxide (La_TwoO_Three), Oxidation
Magnesium (MgO), Niobium oxide (Nb_TwoO_Five), Oxide neo
Dium (Nd_TwoO_Three), Lead oxide (PbO), praseodymium oxide
(PrO), antimony oxide (Sb_TwoO_Three), Silicon oxide (Si
O_Two), Tin oxide (SnO_Two), Tantalum oxide (Ta_TwoO_Five), Oxidation
Tungsten (WO_Three), And yttrium oxide (Y_TwoO_Three)
At least one powder selected from bismuth oxide (Bi_Two
O_Three) Heat treatment of the mixture with the powder in the range of 400 ° C to 700 ° C.
Process to adjust synthetic powder or mixed synthetic powder by grinding and crushing
And 100 weight of the zinc oxide-magnesium oxide mixed powder
0.5 to 20 parts by weight of the synthetic powder, and
Selected from nickel oxide, cobalt oxide and manganese oxide
0.1-5. At least one iron group oxide powder.
It has a structure including the process of adding 0 parts by weight.
is there. In the above method, the aluminum component is
100 parts by weight of lead powder or zinc oxide powder and magnesia oxide
Aluminum oxide against 100 parts by weight of mixed powder of aluminum
0.00062-0.372 parts by weight of aluminum
It is preferable to have the step of including with a solution of the aluminum salt.
Good. Next, the third zinc oxide-based porcelain composition of the present invention
The manufacturing method of is based on 100 parts by weight of zinc oxide powder,
Boron oxide, chromium oxide, germanium oxide, lanthanum oxide
Tan, magnesium oxide, niobium oxide, neodymium oxide
System, lead oxide, praseodymium oxide, antimony oxide, acid
Silicon oxide, tin oxide, tantalum oxide, tungsten oxide
And at least one selected from yttrium oxide
A mixture of oxide and bismuth oxide powder is 400 ° C to 7
Synthetic powder prepared by crushing by heat treatment at 00 ℃ is prepared.
0.5 to 20 parts by weight of synthetic powder, cobalt oxide and
And at least one iron group oxidation selected from manganese oxide
Composition of 0.1 to 5.0 parts by weight of the powder.
It is equipped with a success. Next, the fourth suboxide of the present invention
The production method of lead-based porcelain composition is based on boron oxide and black oxide.
Aluminum, germanium oxide, lanthanum oxide, magnesium oxide
Aluminum, niobium oxide, neodymium oxide, lead oxide, prase oxide
Odium, antimony oxide, silicon oxide, tin oxide, oxide
Tantalum, tungsten oxide and yttrium oxide?
At least one oxide and bismuth oxide powder selected from
The mixture with powder is heat-treated at 400 ℃ -700 ℃ and crushed.
And the process of making the adjusted synthetic powder, and zinc oxide powder
0.5-2 of the synthetic powder was added to 100 parts by weight of powder.
0 parts by weight, selected from cobalt oxide and manganese oxide
0.1 to 5.0 weight of at least one iron group oxide powder
It is provided with a structure including a step of adding a part.
In the above method, the aluminum component is zinc oxide powder.
0.0 based on 100 parts by weight of aluminum oxide
It is preferred to add 0062 to 0.372 parts by weight
Yes. In this example, the added aluminum component is
Acts as a semiconductor donor by forming a solid solution in ZnO particles
Then, the electrical resistance of ZnO can be improved without impairing other electrical characteristics.
It can be reduced to a desirable level, and
Suitable for improving non-linear resistance characteristics of varistor
A lead-based porcelain composition can be provided. Next, in the present invention,
The zinc oxide porcelain composition is a varistor.
It is a gift. In the varistor,
It is preferable that silver is integrally fired as the internal electrodes. Ma
In the varistor, the laminated type varistor and
At least one selected from disc type varistors
It is preferred that

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the functions of zinc oxide, which is the main component, and the additives that react with it are analyzed in detail. As a result, it was found that the raw materials for the zinc oxide sintered body were classified as follows. (1) Zinc oxide (ZnO) (2) Oxides (NiO, MgO, CoO, M) that easily dissolve in zinc oxide
(nO-a small amount, Al ₂ O ₃ -a small amount), (3) It is difficult to dissolve in zinc oxide and forms a liquid phase at high temperatures, which exists between ZnO particles and controls grain growth. . The zinc oxide of the above (1) is produced by evaporating and oxidizing metallic zinc in air, has a high purity, is fine, and is extremely reactive. Therefore, if possible, zinc oxide is preferably used as it is as a raw material without any modification. If the iron group oxide and magnesium oxide in (2) are fine particles, they react with ZnO particles at a temperature below 800 ° C
It forms a solid solution in O 2. On the other hand, a trace amount of Al ₂ O ₃ forms a solid solution with ZnO. That is, if the raw material of (2) is finely and uniformly mixed, it does not hinder the sintering. Therefore, the problem is various oxides belonging to (3). Originally, ZnO and Bi ₂ O ₃
There is a eutectic at about 740 ℃ in the Bi ₂ O ₃ -rich region between and, and both react easily. However, the presence of these additives (3) complicates the reaction and causes variations. Some of these additives (3) react with ZnO to form compounds. At the grain boundaries, it interferes with the grain growth of ZnO. Moreover, penetration into Bi ₂ O _3, promote liquid phase sintering at the grain boundaries to form a liquid phase with Bi ₂ O _3. Then, if they form a liquid phase at a high temperature, if they are reacted with Bi ₂ O ₃ in advance,
It is expected that there will be no choice in the reaction of the additive of (3) and the variation will be greatly reduced. Further, it does not interfere with the grain growth at the grain boundaries, and the sintering temperature can be lowered. Further, it is considered that the eutectic of bismuth oxide and zinc oxide has a small effect on the eutectic reaction even if a small amount of oxide is dissolved in bismuth oxide. When the zinc oxide-based porcelain composition of the present invention as described above is sintered, it is preferable to press-mold it into a predetermined shape and fire the molded body at about 750 to 1100 ° C. By firing at a temperature within this range, it becomes possible to manufacture a zinc oxide varistor having excellent electrical characteristics such as non-linear resistance characteristics and reliability with a high yield. Also,
This zinc oxide-based porcelain composition includes one that is sintered at a temperature of 900 ° C. or lower to form a sintered body having excellent electrical characteristics. A laminated varistor is obtained by molding these zinc oxide-based porcelain compositions into a sheet shape, alternately laminating it with an electrode material, sintering it, and connecting the electrodes by a predetermined connection method. At that time, in the conventional laminated type varistor, a firing temperature of 1200 ° C. or higher was required in order to obtain a good characteristic, but for that purpose, a noble metal such as platinum is used as an electrode material. However, when a zinc oxide-based ceramic composition that can be sintered at a temperature of 900 ° C. or lower is used, it becomes possible to use much cheaper silver as an electrode material, which will greatly contribute to the spread of varistor. One of the advantages of the present invention is that silver can be integrally fired as the internal electrodes of the varistor. It should be noted that ZnO varistor is often added with an aluminum salt in order to improve the non-linear resistance characteristic in a high current region, but the addition amount depends on the application of the varistor. In the examples, the amount of ZnO was uniformly set to 0.0013 g with respect to 1 mol. The amount of alumina added is increased to improve the non-linear resistance characteristics in the high current region, and is decreased to reduce the leakage current in the low current region. In addition, bismuth oxide (Bi ₂ O ₃ ) -manganese oxide (MnO) system, bismuth oxide (Bi ₂ O ₃ ) -cobalt oxide (CoO) system, bismuth oxide (Bi ₂ O ₃ ) -nickel oxide (N
The effect of addition of iO) was also examined, but no significant effect was observed compared to the case where manganese oxide (MnO), cobalt oxide (CoO), and nickel oxide (NiO) were added untreated, respectively. .

EXAMPLES The present invention will be described more specifically with reference to the following examples.
explain. In the following examples, "weight" is
It may be displayed as "wt". (Example 1) Bismuth oxide (Bi_TwoO_Three) Powder and oxidation
Tin (SnO_Two) Powder (the particle size of each powder is an average
(A particle size of about 2 to 3 μm) is mixed in a weight ratio of 92: 8.
I combined. 5 hours at 600 ℃ this mixed powder in the atmosphere
After the heat treatment of
By pulverizing with a ball mill of Nomaron pot
To obtain synthetic powder (average particle size of about 0.5-1.5 μm)
Was. In the following, bismuth oxide and tin oxide were prepared in this way.
The produced synthetic powder is called bismuth oxide / tin oxide synthetic powder.
Bu Zinc oxide (ZnO) powder (average particle size 0.3 μm)
The bismuth oxide / tin oxide synthetic powder, and cobalt oxide
(CoO) powder (average particle size of about 0.5 to 1.5 μm)
And manganese dioxide (MnO_Two) Powder (average particle size of about 2
3 μm) and nickel oxide (NiO) powder (average particle size: approx.
0.5-1.5 μm) and the bismuth oxide / tin oxide
The weight ratio is 100: 0.1-2 while changing the amount of the synthetic powder.
0.0: 0.954: 0.414: 0.383
The powder blended with sea urchin
Mix and pulverize by a wet method for 18 hours using Abor, 32
It was crushed so as to pass through 5 mesh. The resulting blended powder
The powder was dried and pressed into a disk. Then you get
The temperature of the molded product in the air at a heating rate of 50 ° C / hour
Then, after holding at 900 ℃ for 17 hours, the temperature decrease rate is 50 ℃ /
The temperature was lowered over time to obtain a sintered body. The sample size of the sintered body is thick
The thickness was 1.2 mm and the diameter was 14 mm. Next, referring to FIG.
A method for manufacturing a zinc oxide varistor will be described with reference to FIG.
FIG. 1 was prepared using the zinc oxide porcelain composition of the present invention.
1 is a schematic perspective view of a disk type zinc oxide varistor 10.
is there. Aluminum is formed on both sides of the sintered body 11 obtained as described above.
An aluminum layer (illustrated
No) and then the aluminum formed on both sides.
Electrode 12 is formed by spraying copper on the um layer
did. After attaching the lead wire 13 to the electrode 12 with solder,
By coating the molded body other than the lead wire with epoxy resin
A zinc oxide varistor was obtained. The acid thus obtained
The electrical characteristics of the zinc oxide varistor were evaluated. Initial electrical characteristics
As the rising voltage V_{1mA / mm}(A current of 1 mA is applied.
Voltage for 1mm thickness between both terminals)
Line resistance index_0.1mAα_1mA(V_1mAAnd V_0.1mAFound using and
Value) was measured (in the following description, non-linear
Resistance index_{0.1 m A}α_1mAIs simply referred to as an α value. ) The greater the nonlinear resistance index, the greater the surge absorption capacity
Become. Moreover, the reliability with respect to a DC load was evaluated. 80
At a DC load of 0.2 watt for 500 hours in a high temperature environment of ℃
Applied to the varistor for a rising voltage V_1mARate of change ΔV
_1mA/ V_1mA(DC load change rate) was measured. Barista standing
Lift voltage V_1mARate of change ΔV_1mA/ V _1mAIs small
Thorough electrical characteristics of zinc oxide varistor are stable and reliable
It shows that the sex is good. In addition, confidence in surge
Reliability was evaluated. 8 × 20μsec, 0.5kA pulse
Varistor rising voltage V by applying 10 times_1mAchange of
Rate (surge change rate) ΔV_1mA/ V_1mA I asked. Table 1
Table 2 shows the composition of the sample, and Table 2 shows the evaluation results of the electrical characteristics. Sir
Electrical characteristics of zinc oxide varistors with smaller di-change rate
Is stable, and the rate of change is 5% or less
It's good. The evaluation results of electrical characteristics are shown.
Numerical values indicate the minimum and maximum values within the lot. But
Therefore, the smaller the difference between the minimum and maximum values in a lot, the more lot
It shows that there is little variation in quality.

[Table 1]

[Table 2] As can be seen from Table 1 and Table 2, the zinc oxide varistor using the zinc oxide based porcelain of the present example has a low bismuth oxide / tin oxide synthetic powder amount of 0.1 parts by weight of the sample (Sample No. #
Except for 001), the non-linear resistance characteristics are good, and the absolute value of the change rate (ΔV _1mA / V _1mA ) of the rising voltage V _1mA is 5% even for long-term DC load and surge. Below, the reliability was excellent. Further, as shown in Table 2, there was little variation in the electrical characteristics within the lot. Table 2
Although not shown in Table 1, when a zinc oxide varistor was prepared using the porcelain composition of this example, the variation in electrical characteristics between lots was as small as the variation within lots. For example, #
In the case of the composition of 005, specifically, the process capability index (one of the indices showing the product variation in the production factory) is set to ± 7% at the standard width of V _{1 mA} , and the conventional composition without heat treatment is used. In the sample used and baked at a high temperature of 1200 ° C., 1.0 was 1.333. As a result, the yield was 92% in the sample using the conventional composition without heat treatment, whereas it was 97% in this example, which was a remarkable improvement. If the added amount of Bi ₂ O ₃ / SnO ₂ synthetic powder exceeds 15 parts by weight, a plurality of compacts are stacked and fired at the time of firing. (Sticking), mass productivity of the varistor is lacking, and the samples stick to each other, so the electrical characteristics could not be measured (sample number # 008). Therefore, the addition amount of the synthetic powder is preferably 0.5 to 20 parts by weight with respect to 100 parts by weight of ZnO powder. (Example 2) A powder of bismuth oxide (Bi ₂ O ₃ ) and a powder of tin oxide (SnO ₂ ) (the particle size of each powder is about 2 to 3 μm) are used in a weight ratio of 92: 8. Mixed in. This mixed powder was subjected to heat treatment at 600 ° C. for 5 hours in an air atmosphere, and then finely pulverized with a ball mill of a monomaron pot using stabilized zirconia as a cobblestone to obtain a synthetic powder (particle size of about 0.5 to 1). 0.5 μm) was obtained. Hereinafter, bismuth oxide, tin oxide and the synthetic powder thus prepared are referred to as bismuth oxide / tin oxide synthetic powder. Zinc oxide (ZnO) powder (average particle size 0.3 μm), the bismuth oxide / tin oxide synthetic powder, cobalt oxide (CoO) powder (particle size about 0.5 to 1.5 μm), and manganese dioxide (MnO 2). ₂ ) Powder (particle size: about 2 to 3 μm) and nickel oxide (NiO) powder (particle size: about 0.5 to 1.5 μm)
The weight ratio of the bismuth oxide / tin oxide synthetic powder is 10%.
Powder blended so as to be 0: 3.0: 0.954: 0.414: 0.383 was mixed and pulverized by a wet method for 18 hours using a monomaron pot and a stabilized zirconia ball,
Grind to pass through 325 mesh. The obtained blended powder was dried and pressed into a disk shape. Then, the obtained molded body was heated in the atmosphere at a temperature rising rate of 50 ° C./hour and held at 750 ° C. to 1050 ° C. for 17 hours,
The temperature was decreased at a temperature decrease rate of 50 ° C./hour to obtain a sintered body. The sample size of the sintered body was 1.2 mm in thickness and 14 mm in diameter. Next, a zinc oxide varistor was obtained in the same manner as in Example 1. The electrical characteristics of the zinc oxide varistor thus obtained were evaluated in the same manner as in Example 1. Table 3 shows the composition of the sample and the firing temperature, and Table 4 shows the evaluation results of the electrical characteristics.
In the case of this composition, when the sintering temperature was 800 ° C. or lower, the sintering was insufficient and the electrical characteristics could not be measured. 110
At 0 ° C or higher, the sticking of the samples increased rapidly.

[Table 3]

[Table 4] (Example 3) Bismuth oxide powder (particle size: about 2 to 3 μm)
And niobium oxide powder (average particle size of about 2 to 3 μm) are mixed in a weight ratio of 1: 0.333, and heat-treated at 575 ° C. for 5 hours in an air atmosphere to obtain a stabilized zirconia ball. By using a wet milling in a Monomaron pot for 18 hours (bismuth oxide / niobium oxide)
Bi ₂ O ₃ / Nb ₂ O ₅ synthetic powder (2.33 /
0.333, average particle size of about 2-3 μm) was obtained. In the same manner, Bi ₂ O ₃ / B ₂ O ₃ synthetic powder (2.33 / 0.1
0, average particle size of about 2 to 3 μm), Bi ₂ O ₃ / Cr ₂ O ₃ synthetic powder (2.33 / 0.41, average particle size of about 2 to 3 μm)
m), Bi ₂ O ₃ / GeO ₂ synthetic powder (2.33 / 0.1
0, average particle size of about 2 to 3 μm), Bi ₂ O ₃ / La ₂ O ₃ synthetic powder (2.33 / 0.41, average particle size of about 2 to 3 μm)
m), Bi ₂ O ₃ / MgO synthetic powder (2.33 /, average particle size about 2-3 μm), Bi ₂ O ₃ / Nd ₂ O ₃ synthetic powder (2.33 / 0.50, average particle size about) 2-3 μm), Bi
₂ O ₃ / PbO ₂ synthetic powder (2.33 / 0.29, average particle size about 2 to 3 μm), Bi ₂ O ₃ / Pr ₆ O ₁₁ synthetic powder (2.33 / 0.64, average particle size about 2) ~ 3 μm), Bi
₂ O ₃ / Sb ₂ O ₃ synthetic powder (2.33 / 0.27, average particle size about 2-3 μm), Bi ₂ O ₃ / SiO ₂ synthetic powder (2.33 / 0.077, average particle size about) 2-3 μm), B
i ₂ O ₃ / SnO ₂ synthetic powder (2.33 / 0.19, average particle size of about 2 to 3 μm), Bi ₂ O ₃ / Ta ₂ O ₅ synthetic powder (2.33 / 0.66, average particle size) About 2-3 μm), Bi
₂ O ₃ / WO ₃ synthetic powder (2.33 / 0.29, average particle size of about 2 to 3 μm), Bi ₂ O ₃ / Y ₂ O ₃ synthetic powder (2.3
3 / 0.28, average particle size of about 2-3 μm) was obtained. Zinc oxide powder (average particle size 0.3 μm), Bi ₂ O ₃ / Nb ₂
O ₅ synthetic powder, cobalt oxide powder (particle size of about 0.5-
1.5 μm), manganese dioxide powder (particle size about 2-3 μm
m) and nickel oxide (particle size of about 0.5 to 1.5 μm)
In a weight ratio of 100: 2.5: 0.80: 0.40:
The powder blended so as to be 0.40 was wet-mixed and pulverized for 18 hours in a Monomeron pot using stabilized zirconia balls. The obtained powder is dried and the zinc oxide 10
Aluminum nitrate containing 0.0013 parts by weight of aluminum oxide in terms of Al ₂ O ₃ with respect to 0 parts by weight was added in the form of an aqueous solution to prepare a blended powder, and then the mixture was pressed into a disk shape. The obtained molded body was heated in an air atmosphere at a temperature rising rate of 150 ° C./hour, held at a temperature of 950 ° C. for 15 hours, and then cooled at a temperature lowering rate of 150 ° C./hour to obtain a sintered body. The sample size of the sintered body is 1.2 mm thick and the diameter is 1.
4 mm. A zinc oxide varistor was manufactured in the same manner as in Example 1 below. Further, in the same manner as in Example 1, the electrical characteristics of the obtained zinc oxide varistor were evaluated. Experiments similar to those for the Bi ₂ O ₃ / Nb ₂ O ₅ powder were performed on the other synthetic powders. Tables 5 to 6 show sample compositions, and Tables 7 to 8 show evaluation results of electric characteristics.

[Table 5]

[Table 6]

[Table 7]

[Table 8]As is clear from Tables 5 to 8, various types of (Bi_TwoO_Three/Money
As a result of firing ZnO using a synthetic oxide)
Zinc oxide varistor manufactured with the porcelain composition of the example,
It has a good non-linear resistance characteristic and is suitable for long-term DC loads.
Rise voltage V_1mA Strange
Conversion rate △ V_1mA/ V_1mAAbsolute value of 5% or less, excellent reliability
It was In addition, as shown in Tables 7 to 8,
The variation in electrical characteristics was also small. Shown in Tables 7-8
Not included in the porcelain composition of this example is a zinc oxide varistor.
By creating the
It was as small as the variation within. Specifically, conventional
In the method, the process capability index is_1mA± 5%
And 1.0 for the sample using the conventional composition without heat treatment.
Below was 1.33 or above. As a result,
In the case of the sample using the conventional composition whose yield is not heat-treated
While it was 90% or less, in this embodiment it was 95% or more.
Significantly improved. (Example 4) Bi_TwoO_Three, Sb_TwoO_Three, X three oxides
Mix, heat treat (650 ° C for 1 hour), crush and [Bi_Two
O_Three/ Sb_TwoO_Three/ X] (X = WO_Three, Y_TwoO_Three, SiO_Two, Nb_TwoO_Five, Nd
_TwoO_Three, Pr₆O ₁₁) Six kinds of synthetic powders (particle size about 2-3 μm)
I got In addition, cobalt oxide, manganese dioxide, nitric oxide
The powder of ice ax, CoO: MnO_Two: NiO = 0.954: 0.41
The mixture was mixed at a ratio of 4: 0.383. (This is CoO + MnO_Two
We call it + NiO mixed powder. ) Zinc oxide powder (average particle size 0.3 μm), the above [Bi_Two
O_Three/ Sb_TwoO_Three/ X] Synthetic powder, CoO + MnO_Two+ NiO mixture
Weigh the powder at a specified ratio and wet the zirconia balls.
Using a monolon pot for 18 hours wet mixing and crushing
Was. The obtained powder is dried and the zinc oxide 100 is added thereto.
Al to parts by weight_TwoO_ThreeConverted to 0.0013 parts by weight
Aqueous solution of aluminum nitrate containing aluminum oxide
Then, it was molded into a disk shape. The resulting molding
The body is heated in the atmosphere at a heating rate of 100 ° C./hour,
After holding at 950 ° C for 10 hours, the temperature decrease rate is 100 ° C / hour
The temperature was lowered in between to obtain a sintered body. The sample size of the sintered body is thickness
The diameter was 1.2 mm and the diameter was 14 mm. Example 1 below
Similarly, a zinc oxide varistor was produced. Also implemented
The electrical characteristics of the obtained zinc oxide varistor were measured in the same manner as in Example 1.
evaluated. That is, the reliability for DC load is evaluated.
Was. Apply a 0.5 watt DC load in a high temperature atmosphere of 80 ° C.
Applied for 500 hours, varistor rising voltage V_1mA Strange
Conversion rate △ V_1mA/ V_1mA(DC load change rate) was measured. Ba
Lister rising voltage V_{1m A} Rate of change ΔV_1mA/ V_1mABut
The smaller the value, the more stable the electrical characteristics of the zinc oxide varistor.
It shows that the reliability is good. Furthermore, to surge
The reliability was evaluated. 8 × 20μsec, 1.0kA
Rise voltage V by applying 10 times pulse of
_1mAChange rate (surge change rate) ΔV_1mA/ V_1mA Seeking
Was. The smaller the value of the surge change rate, the better the zinc oxide varistor
The electrical characteristics are stable, and the rate of change is 5% or less in both cases.
It shows that it is reliable. Table 9 shows the sample composition.
10 shows the evaluation results of electric characteristics.

[Table 9]

[Table 10] From Tables 9 and 10, the zinc oxide varistor using the porcelain composition of this example has a large α value, and the rate of change of the rising voltage V _1mA is Δ even with a long-term DC load and surge.
The absolute value of V _1mA / V _1mA was 5% or less, which was excellent in reliability. (Example 5) From the synthetic powder of [Bi ₂ O ₃ / metal oxide] produced in Example 3 (particle size of about 2 to 3 μm), two kinds of synthetic powder, [Bi ₂ O ₃ / X], were obtained. [Bi ₂ O ₃ / Y] was selected and mixed in a weight ratio as shown in the item of synthetic powder in Table 9 to prepare a synthetic powder. CoO: MnO ₂ : NiO = 0.95 with powders of cobalt oxide, manganese dioxide, and nickel oxide.
They were mixed in a ratio of 4: 0.414: 0.383 (weight ratio). (This is referred to as a CoO + MnO ₂ + NiO mixed powder.) Zinc oxide powder (average particle size 0.3 μm), the above [bismuth oxide / X], and [bismuth oxide / Y] synthetic powder, CoO
The + MnO ₂ + NiO mixed powder was weighed at a predetermined ratio and wet-mixed and pulverized for 18 hours in a Monomeron pot using zirconia balls in a wet process. The obtained powder was dried, and aluminum nitrate containing 0.0013 parts by weight of aluminum oxide in terms of Al ₂ O _{3 based} on 100 parts by weight of zinc oxide was added in the form of an aqueous solution to a disk. It was molded into a shape. The temperature rise rate of the obtained molded body is 100 in the atmosphere.
The temperature was raised at 900 ° C./hour, the temperature was kept at 900 ° C. for 10 hours, and then the temperature was lowered at a temperature decreasing rate of 100 ° C./hour to obtain a sintered body. The sample size of the sintered body was 1.2 mm in thickness and 14 mm in diameter. A zinc oxide varistor was manufactured in the same manner as in Example 1 below. Further, in the same manner as in Example 1, the electrical characteristics of the obtained zinc oxide varistor were evaluated. Tables 11 to 12 show the sample compositions, and Table 13 shows the evaluation results of the electrical characteristics.

[Table 11]

[Table 12]

[Table 13] From Tables 11 to 12 and Table 13, in the zinc oxide varistor using the porcelain composition of this example, when two synthetic powders of [Bi ₂ O ₃ / X] and [bismuth oxide / Y] were added, α
Large value, even for long-term DC load and surge,
The absolute value of the change rate ΔV _1mA / V _1mA of the rising voltage V _1mA was 5% or less, and the reliability was excellent. (Example 6) (Bi ₂ O ₃ + Sb ₂ O ₃ ), (Bi ₂ O ₃ + SnO ₂ ), (Bi ₂ O ₃ + Cr
₂ O ₃ ), each mixed powder is preheated at 475 ° C. for 5 hours, pulverized (Bi ₂ O ₃ / Sb ₂ O ₃ ), (Bi ₂ O ₃ / Sn
O ₂ ), (Bi ₂ O ₃ / Cr ₂ O ₃ ) synthetic powders were prepared.
Next, these synthetic powders were mixed with CoO + MnO ₂ + NiO powder (cobalt oxide, manganese dioxide, nickel oxide powder, CoO:
MnO ₂ : NiO = 0.954: 0.414: 0.383) and zinc oxide powder (average particle size 0.3 μm) were added and mixed and pulverized. Next, the mixed powder was sampled so as to be 50% by weight, and mainly butyral resin (5% by weight) and its plasticizer (2.5% by weight of D-n-butyl phthalate) were mixed with 2-butanol (7% by weight). 0.5 wt%) and butyl acetate solvent (35 wt%) were mixed with the mixed powder to form a sheet. Next, the sheet was cut, and a paste containing silver as a main component was applied to the surface of a part of the sheet by printing. Four sheets on which the silver paste was printed were laminated, unprinted sheets were laminated on the top and bottom, and silver external electrode paste was applied to both side surfaces. Then, the mixed powder and the silver electrode were integrally sintered at a temperature of 840 ° C. to manufacture a zinc chloride laminated chip varistor. A sectional view of the obtained laminated type varistor is shown in FIG. In FIG. 2, reference numeral 20 denotes a laminated type zinc oxide varistor, 2
Reference numeral 1 is an internal electrode made of silver, 22 is a counter internal electrode made of silver, 23 is an effective layer, 24 is an ineffective layer, and 25 is an external electrode made of silver. The thickness of the effective layer of the chip is 40 μm, the thickness of the ineffective layer is 200 μm, the thickness of the electrode is 5 to 6 μm, and the overall size of the laminated chip varistor is vertical: 3.2 mm,
It was a rectangular parallelepiped having a width of 1.6 mm and a thickness of 0.55 mm. After measuring the initial characteristics of these zinc oxide laminated chip varistors, an electrical load was applied to determine the reliability characteristics. The condition of the load is 0.02 watt × 500 hours, and the pulse application is 300 Amp. (8 × 20 μsec.) × 2 times. Table 14 shows the sample composition, and Table 15 shows the initial characteristics and load characteristics.

[Table 14]

[Table 15] From Table 14 and Table 15, the zinc oxide varistor using the porcelain composition of this example could be sintered at an extremely low temperature. In addition, it showed good characteristics despite being a small varistor. (Example 7) Mixed powder Z of zinc oxide and magnesium oxide
nO + MgO (ZnO: MgO = 92: 8 wt ratio) was made. Next, (Bi
₂ O ₃ + Sb ₂ O ₃ ), (Bi ₂ O ₃ + Cr ₂ O ₃ ), (Bi ₂ O ₃ + B ₂ O ₃ ), (Bi ₂ O ₃ + S
nO ₂ ) mixed powder is preheated at 500 ° C. for 2 hours,
Four kinds of synthetic powder, namely (1) Bi ₂ O ₃ / Sb ₂ O ₃ (Bi
₂ O ₃ : Sb ₂ O ₃ = 1.30: 0.20 wt ratio), (2) Bi ₂ O ₃ / Cr ₂ O
₃ (Bi ₂ O ₃ : Cr ₂ O ₃ = 0.18: 0.006 wt ratio,) (3) Bi ₂
O ₃ / B ₂ O ₃ (Bi ₂ O ₃ : B ₂ O ₃ = 0.23: 0.002 wt ratio), and (4) Bi ₂ O ₃ / SnO ₂ (Bi ₂ O ₃ : SnO ₂ = 0.18: 0.006 wt)
Ratio) was obtained. Next, the synthetic powder (Bi ₂ O ₃ / Sb ₂ O ₃ ) :( Bi ₂ O ₃ / C
r ₂ O ₃ ) :( Bi ₂ O ₃ / B ₂ O ₃ ) :( Bi ₂ O ₃ / SnO ₂ ) = 1.5: 0.24: 0.25:
Mixed at a ratio of 1.0 wt to prepare a synthetic powder (Bi ₂ O ₃ / Sb ₂ O ₃ + Bi ₂ O ₃ / Cr _{2
O 3 + Bi 2 O 3 /} B 2 O 3 + Bi 2 O 3 / SnO 2) was obtained. Based on 100 wt parts of the (ZnO + MgO) mixed powder, the above (Bi ₂ O ₃ / Sb ₂ O ₃ + Bi ₂ O ₃ / Cr ₂
O ₃ + Bi ₂ O ₃ / B ₂ O ₃ + Bi ₂ O ₃ / SnO ₂ ) Synthetic powder 2.99 wt parts,
(CoO + MnO ₂ + NiO) mixed powder 1.751 wt part was added, and 0.0013 wt part of aluminum oxide was added with a solution of aluminum nitrate, mixed, pulverized, dried, and pressure-molded.
It was baked at 0 ° C. for 10 hours to produce a zinc oxide varistor.
In a similar manner, (Bi ₂ O ₃ / Sb ₂ O ₃ + Bi ₂ O ₃ / Cr ₂ O ₃ + Bi ₂ O ₃ / B ₂ O ₃ + Bi ₂ O ₃ / SiO ₂ ) synthetic powder (Bi ₂ O 3 ₃ / Sb ₂ O ₃ + Bi ₂ O ₃ / Cr ₂ O ₃ + Bi ₂ O ₃ / B ₂ O ₃ + Bi ₂ O ₃ / Nb ₂ O ₅ ) Synthetic powder (Bi ₂ O ₃ / Sb ₂ O ₃ + Bi ₂ O ₃ / Cr ₂ O ₃ + Bi ₂ O ₃ / B ₂ O ₃ + Bi ₂ O ₃ / PbO) synthetic powder was prepared, a ZnO varistor was prepared, and the electrical characteristics were measured. That is, the reliability against a DC load was evaluated. A DC load of 0.5 watt was applied for 500 hours in a high temperature atmosphere of 80 ° C., and a change rate ΔV _1mA / V _1mA (DC load change rate) of the varistor rising voltage V _1mA was measured. As the rate of change △ V _1mA / V _1mA of the varistor threshold voltage V _{1 m A} is smaller, the electric characteristics of the zinc oxide varistor is stable, indicating that good reliability. Furthermore, the reliability against surge was evaluated. 8 × 20μsec, 1.0kA
Rise voltage V by applying 10 times pulse of
The change rate of _{1 mA} (surge change rate) ΔV _1mA / V _1mA was obtained. Table 16 shows the composition of the sample, and Table 17 shows the evaluation results of the electrical characteristics. The smaller the surge rate of change, the more stable the electrical characteristics of the zinc oxide varistor, and the rate of change is 5% in both cases.
The following shows that the reliability is good.

[Table 16]

[Table 17]

As described above, according to the present invention, a zinc oxide varistor capable of producing a zinc oxide varistor excellent in electrical characteristics such as non-linear resistance characteristics and reliability by low temperature sintering at a high yield is provided. A porcelain composition can be provided. The zinc oxide-based ceramic composition of the present invention can uniformly promote the growth of zinc oxide particles even when the firing temperature is lowered to a low temperature of 750 ° C. to 1050 ° C. when producing the sintered body. Then, a sintered body of zinc oxide particles having a narrow particle size distribution is obtained. As a result, a zinc oxide varistor having excellent electrical characteristics and reliability can be manufactured with a high yield. Further, since the zinc oxide-based porcelain composition of the present invention can be sintered at a low temperature, power consumption during sintering is reduced, consumption of the furnace material / container of the electric furnace used for sintering is reduced, and energy saving is achieved. -It can also contribute greatly to resource saving. Furthermore, it was found that an electrode composed mainly of silver could be formed at the same time when firing porcelain.
It was successfully formed inside ZnO porcelain. Then, a stacked ZnO varistor using silver as an internal electrode has become possible. In addition, the method for producing a zinc oxide-based ceramic composition of the present invention can provide a method for efficiently and rationally producing a zinc oxide-based ceramic composition that can achieve the above excellent effects.

[Brief description of drawings]

FIG. 1 is a schematic perspective view of a disk type zinc oxide varistor formed by using the zinc oxide ceramic composition of Example 1 of the present invention.

FIG. 2 is a cross-sectional view of a laminated type zinc oxide varistor formed by using the zinc oxide based ceramic composition of Example 6 of the present invention.

[Explanation of symbols]

 10 Disk Type Zinc Oxide Varistor 11 Zinc Oxide Sintered Body 12 Electrode 13 Lead Wire 20 Laminated Type Zinc Oxide Varistor 21 Internal Electrode 22 Opposed Internal Electrode 23 Effective Layer 24 Ineffective Layer 25 External Electrode

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kazushige Koyama 1006 Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd.

Claims (12)

[Claims] 1. Boron oxide (B ₂ O ₃ ), chromium oxide (Cr ₂ O ₃ ), germanium oxide (GeO ₂ ), lanthanum oxide (La ₂ O ₃ ), 100 parts by weight of zinc oxide powder, Magnesium oxide (MgO), niobium oxide (Nb ₂ O ₅ ), neodymium oxide (Nd ₂ O ₃ ), lead oxide (PbO), praseodymium oxide (Pr)
O), antimony oxide (Sb ₂ O ₃ ), silicon oxide (SiO ₂ ), tin oxide (SnO ₂ ), tantalum oxide (Ta ₂ O ₅ ), tungsten oxide (WO ₃ ), and yttrium oxide (Y ₂ O _3). A mixture of at least one powder selected from the following) and bismuth oxide (Bi ₂ O ₃ ) powder is subjected to heat treatment in the range of 400 ° C. to 700 ° C. and pulverized, or a synthetic powder prepared from a mixed synthetic powder. 0.5-20 parts by weight of powder and 0.1-5.0 of at least one iron group oxide powder selected from nickel oxide, cobalt oxide and manganese oxide.
A zinc oxide-based porcelain composition which is added by weight. 2. The zinc oxide-based porcelain composition according to claim 1, wherein a part of zinc oxide is replaced by magnesium oxide. 3. An aluminum component is zinc oxide powder 10
0.000 in terms of aluminum oxide with respect to 0 part by weight
The zinc oxide porcelain composition according to claim 1, wherein the zinc oxide porcelain composition is contained in an amount of 62 to 0.372 parts by weight. 4. The oxidation according to claim 1, wherein the aluminum component is contained in an amount of 0.00062 to 0.372 parts by weight in terms of aluminum oxide based on 100 parts by weight of a mixed powder of zinc oxide powder and magnesium oxide. Zinc-based porcelain composition. 5. Boron oxide (B ₂ O ₃ ), chromium oxide (Cr ₂ O 3
₃ ), germanium oxide (GeO ₂ ), lanthanum oxide (La
₂ O ₃ ), magnesium oxide (MgO), niobium oxide (Nb
₂ O ₅ ), neodymium oxide (Nd ₂ O ₃ ), lead oxide (PbO), praseodymium oxide (PrO), antimony oxide (Sb ₂ O ₃ ), silicon oxide (SiO ₂ ), tin oxide (SnO ₂ ), oxidation Tantalum (Ta ₂ O
₅ ), a mixture of at least one powder selected from tungsten oxide (WO ₃ ) and yttrium oxide (Y ₂ O ₃ ) and a bismuth oxide (Bi ₂ O ₃ ) powder is heat treated in the range of 400 to 700 ° C. Then, the synthetic powder or the mixed synthetic powder is pulverized to prepare 100 parts by weight of zinc oxide.
5-20 parts by weight, and a method for producing a zinc oxide-based porcelain composition including the step of adding 0.1 to 5.0 parts by weight of at least one iron group oxide powder selected from nickel oxide, cobalt oxide and manganese oxide. . 6. Addition of magnesium oxide to zinc oxide,
A step of obtaining a zinc oxide-magnesium oxide mixed powder, boron oxide (B ₂ O ₃ ), chromium oxide (Cr ₂ O ₃ ), germanium oxide (GeO ₂ ), lanthanum oxide (La ₂ O ₃ ), magnesium oxide ( MgO), niobium oxide (Nb ₂ O ₅ ), neodymium oxide (Nd ₂ O ₃ ), lead oxide (PbO), praseodymium oxide (Pr)
O), antimony oxide (Sb ₂ O ₃ ), silicon oxide (SiO ₂ ), tin oxide (SnO ₂ ), tantalum oxide (Ta ₂ O ₅ ), tungsten oxide (WO ₃ ), and yttrium oxide (Y ₂ O _3). A heat treatment of a mixture of at least one powder selected from the above) and bismuth oxide (Bi ₂ O ₃ ) powder in the range of 400 ° C. to 700 ° C., and pulverizing to prepare a synthetic powder or a mixed synthetic powder, and 0.5 to 20 parts by weight of the synthetic powder and 0.1 to 5 parts by weight of at least one iron group oxide powder selected from nickel oxide, cobalt oxide and manganese oxide based on 100 parts by weight of the zinc oxide-magnesium oxide mixed powder. A method for producing a zinc oxide-based porcelain composition, which comprises the step of adding 0 part by weight. 7. An aluminum component is zinc oxide powder 100.
6. The method further comprises the step of adding a solution of an aluminum salt in an amount of 0.00062 to 0.372 parts by weight in terms of aluminum oxide to 100 parts by weight of a mixed powder of zinc oxide powder and magnesium oxide. 7. The method for producing a zinc oxide-based porcelain composition according to any of 6. 8. Boron oxide, chromium oxide, germanium oxide, lanthanum oxide, magnesium oxide, niobium oxide, neodymium oxide, lead oxide, praseodymium oxide, antimony oxide, silicon oxide, tin oxide, relative to 100 parts by weight of zinc oxide powder. A mixture of at least one oxide selected from, tantalum oxide, tungsten oxide and yttrium oxide and bismuth oxide powder at 400 ° C to 7 ° C.
0.5 to 20 parts by weight of a synthetic powder prepared by preparing a synthetic powder obtained by crushing by heat treatment at 00 ° C., and 0.1 to at least one iron group oxide powder selected from cobalt oxide and manganese oxide. A zinc oxide porcelain composition containing 5.0 parts by weight. 9. Boron oxide, chromium oxide, germanium oxide, lanthanum oxide, magnesium oxide, niobium oxide,
4 in a mixture of bismuth oxide powder with at least one oxide selected from neodymium oxide, lead oxide, praseodymium oxide, antimony oxide, silicon oxide, tin oxide, tantalum oxide, tungsten oxide and yttrium oxide.
A step of producing a synthetic powder prepared by subjecting to a heat treatment at 00 ° C. to 700 ° C. and crushing, and 0.5 to 20 parts by weight of the synthetic powder, relative to 100 parts by weight of zinc oxide powder, cobalt oxide and manganese oxide. A method for producing a zinc oxide-based porcelain composition, which comprises the step of adding 0.1 to 5.0 parts by weight of at least one iron group oxide powder. 10. A zinc oxide powder 10 having an aluminum component.
0.000 in terms of aluminum oxide with respect to 0 part by weight
62-0.372 weight part is added, The manufacturing method of the zinc oxide ceramic composition of Claim 9. 11. The zinc oxide based varistor according to claim 1, wherein the zinc oxide based ceramic composition is a varistor. 12. The zinc oxide based varistor according to claim 11, wherein silver is integrally fired as an internal electrode of the varistor.