JPS60131708A - Nonreduced temperature compensating dielectric porcelain composition - 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 dielectric ceramic composition for temperature compensation, particularly (prior art) □ A dielectric ceramic composition for temperature compensation that has conventionally been used - titanium oxide. It was the main ingredient. Of these, small
When making a large-capacity temperature-compensating ceramic capacitor, the following procedure was carried out.

That is, electrodes are printed on a green sheet, and seven sheets are stacked so that the electrodes are alternately protruding from the end face and facing each other to form a laminate, and this laminate is bonded by thermocompression at °C. Fired in air at 1200-14001c'L
- (Product - Coredensor C was obtained. At this time, the electrode material C was fired in air at a high temperature of 1200 to 14001" [C] and the metal which did not react with the dielectric ceramic material and did not oxidize was C platinum, Conventionally, platinum-palladium alloys have been used.However, these electrode materials account for as much as 30 to 50 pieces of the product price, and it has become an important book in order to lower the cost of multilayer capacitors. na->'c'
It was.

As an alternative to these expensive electrode materials, there is a known method of using base metals such as low-density materials, but since they oxidize when fired in air, they must be fired in a reducing atmosphere. Gaatsumaru.

However, conventionally 4. When dielectric porcelain materials are fired in a reducing atmosphere, titanium oxide (101), rare earth elements, etc. are reduced, and the electrical properties such as L resistance, insulation resistance, and dielectric loss are significantly deteriorated. As a capacitor
There is also the problem of not being able to use C.

Assume that this problem has been resolved′ [,! Tokuko Sho 57-37
There is one disclosed in No. 081 and Japanese Patent Publication No. 57-39001. This traditional binding technique mainly uses calcium zirconate [(ori: '?: or return).

Even when fired in a natural atmosphere at °C, the resistance is less than 10Ω.

Above, one with a Q value of 6000 or more was obtained.
There is.

However, in this prior art, only a composition having a temperature characteristic of a dielectric constant of up to -120 ppm/C on the negative side can be obtained; is -100
It was not possible to obtain arbitrary temperature characteristics up to 0 pp+n/r. In addition, this conventional technology has poor sintering stability.
It was possible to fire only once in a narrow range from 1350°C to 1380r. (Purpose of the Invention) This Seimei was developed in view of these problems, and its purpose was to It is fired in a reductive atmosphere, and there is no deterioration in insulation resistance or dielectric loss.Furthermore, it is possible to arbitrarily obtain hot-seat characteristics that are three times smaller than those normally required for temperature-compensating porcelain capacitors. An object of the present invention is to provide a non-reducible temperature-compensating dielectric ceramic composition that can be fired in a wider temperature range.

(Explanation of actual circulation example)・ The present invention will be described below according to embodiments.

Fruit mi+11゜Preliminarily, calcium carbonate (CaCOj), carbonate ty7tiu A (SrC0,), titanium dioxide y (Tto
), zirconium oxide (Zr01), manganese oxide (MnO,), and silicon dioxide (StO,), etc., were prepared in an amount of 0.5 to 5.0 parts, and a porcelain composition having the composition ratio shown in Table 1 was prepared. This blended raw material was mixed for 16 hours to obtain a product.Then, it was dried.The mixture was heated in the air by grinding at a rate of 1/hour to 1,000~1000℃.
It was held at 1200°C for 2 hours and calcined at 1200°C. Add a binder to this calcined powder, add 4 parts by weight of C1 vinyl acetate, 4 parts of the calcined powder, and add 1 part of pure water.
Mixed for 60 minutes, then dehydrated and dried for 60 minutes.
．． Granulate to an extent that the mesh mesh is 4° (14,0
The molded body obtained in this manner was pressure-sensitive molded at a pressure of 750 KF/d to a size of uφXL2+gt.
The temperature is raised at a rate of 0t'/hour, held at 500υ5° for 2 hours, and the binder is combusted.
~ 58 volume CH), Nitrogen-1, Shun ratio carbon (0,1~5 volume CH))! The temperature was raised at a rate of 150t/hour (at 1350℃ for 2 hours, then allowed to cool naturally. When the temperature dropped to below 600℃, the charging was stopped and the porcelain element was taken out. did.

A nickel paste containing 20 to 30 ffice of alkali and a low point glass frit that does not contain alkali is applied to both sides of the porcelain body prepared in this way, and heated to 800 to 1000 ffice in a neutral or reducing atmosphere. Baking at 20°C [use as an electrode, measure the electrical characteristics,
Table, 644), ゛, [shown.

Temperature of permittivity in Table 1 - P! 1Fti and Q value are i
Value at Vrms/1MHg, 500 V/
uDc voltage, charging time 2 minutes diameter? The measured values are shown respectively.

Furthermore, the dielectric constant! The temperature characteristics were calculated from the following formula.

' (ppm/C) C: Dielectric constant at 85t' CzsH Dielectric constant at 25°C Note that the items marked with * on the front page are outside the scope of my invention.
Everything else is within the scope of the invention. The reason for setting the Cff1 formation range to one slope in this invention is as follows.
I stuttered the next word and got nine. In other words, when at least 10,000 of X and y are 0.6 or more, the temperature characteristic
This is because r: is larger than or equal to C, and the Q value is 1500 or less. Furthermore, if m is less than 0.85, the Q value will decrease significantly, and if m is more than 1.30, sufficient sintering will not occur. Also, M n O! (=z) from (Ca□-
rX) m(z r 17T i y) o @1
This is because when the iji is 1.00, the Q value decreases when it is less than 'C11,005, and when it is more than 0.08, the specific resistance becomes less than 1010 Ωtm.

As can be seen from this implementation sequence, according to the present invention, +
Any temperature profile between 15 ppm/c and 1 UOOppm/r can be obtained.

Example 2゜Porcelain composition with the same composition ratio as sample number 15 (within the invention range) of Example 1, i.e. (Ca, , Sro, o2)
,,,,(Zr11..8”'o,ox)t-)s
+Mn0. t), and the raw materials for preparation of C were prepared in the same manner as in Example 1 so as to obtain 02jit parts. These mixed raw materials were treated in the same manner as in Example 1, and then fired at two firing temperatures of 1300 t' and 1400 t'' to obtain two samples (sample numbers 13-1.13-2).

Example 1 to the magnetic element of each sample obtained
Electrodes were provided in the same manner as in Example 1, and the electrical characteristics were measured in the same manner as in Example 1. The results are shown in Table 2.

In addition, for reference °[, conventional porcelain compositions (Ba, □C
a) Zr0s+Mn01 Table 3 shows the changes in properties when the firing temperature of Q and Q5 parts by weight was changed by 0.9.

s2 table (”0.Ill Sr0.0!) 1jli (zr
(1,1111TlG, 0!) 0s+Mn0ffi
0.02 Test number 3 3 Table 5 (Bao, tc aOJ) zro z + u”s
0-05 parts by weight As is clear from this example series, the present invention has good sintering stability and can be fired in a wide temperature range from 1300r to 140(l).In contrast, the conventional porcelain composition However, sintering can only be carried out within a narrow temperature range of 1350 to 1680''C, and outside this range, sintering may not occur or the resistivity may decrease.

As described above, according to this firing method, a resistivity of 101 Ω or more and a q value of 3000 or more can be obtained even when fired in a neutral or reducing atmosphere. In addition, the dielectric constant shows a value of 2B to 108, and its temperature characteristic is +15 ppm/
C can be obtained in a wide range of 100 ppm/7 ct. Moreover, from 1300C to 1400
Firing is possible over a wide temperature range of t'. Furthermore, a low-grade base metal material such as nickel can be used as the electrode, and an inexpensive temperature-compensating magnetic capacitor can be obtained.

patent applicant Murata Manufacturing Co., Ltd.

Claims (1)

[Claims] (Ca8r)(ZrTi)Os and MflO, general formula (Ca, -X8rX), (ZrX-, Ti,)
Os+'ZMnO. When expressed as (C' * - x 8 rx ) m
(Z r 1-y 'T Ly) 0, X + 'I
If e m is in the range shown below, and ((a,, srx
)m(Zr,-,Ti,)J, for the weight of 1lLOOK,
A non-reducible temperature-compensating dielectric ceramic composition comprising MnO, (=Z) in the following weight ratio. 0≦X<0.6'0≦y<0.60.85<m<1.30' 0.00 s<z<o, o 8 (weight ratio) However, "
-Except when both 7 become 0.