JPH01175218A - Manufacture of ceramic electronic component - Google Patents

Abstract

PURPOSE:To simplify a manufacturing process sharply by coating an electrode paste on a dielectric porcelain composition molded body to which PbO.GeO2- based, PbO.B2O3.SiO2-based or Na2O.B2O3.SiO2-based glass has been added as an auxiliary component so that this paste can be baked collectively and simultaneously. CONSTITUTION:xPbO.yGeO2 (where x=1-6 and y=1-3), in a range of 0.01-30wt.% of a main component, which is PbO.GeO2-based, PbO.B2O3.SiO2- based or Na2O.B2O3.SiO2-based glass having a property to behave ferroelectrically and a low melting point, is added to a dielectric porcelain composition as the main component; a hetero-phase ceramic bulk is generated by a liquid sintering operation, and is sintered at a low temperature of 850-1000 deg.C without lowering a characteristic inherent in a dielectric porcelain. By this setup, an electrode paste can be baked simultaneously and collectively, which was impossible by a conventional method. An arbitrary electrode paste for baking use which contains a conductive powder such as Ag, Cu or the like can be used as the electrode paste.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for manufacturing ceramic electronic components using a dielectric ceramic composition that can be sintered at low temperatures, and particularly relates to a method for manufacturing ceramic electronic components using a dielectric ceramic composition that can be sintered at low temperatures. It relates to something that is characterized by being fired.

[Conventional technology]

Dielectric ceramic materials are used in various electronic components such as piezoelectric components, capacitors, and pyroelectric elements. As this type of dielectric ceramic composition, those exhibiting piezoelectricity, pyroelectricity, and ferroelectricity, such as lead titanate-based, lead zirconate titanate-based, and barium titanate-based compositions, are used.

To obtain the above-mentioned electronic components, a dielectric porcelain composition is molded to obtain a molded body, and this molded body is fired to create a dielectric porcelain. After printing the paste, the electrode paste is baked to form an electrode.

[Problems to be Solved by the Invention] The sintering temperature of dielectric porcelain is as high as approximately 1100"C, and the firing temperature of the electrode paste is quite different from that of the sintering temperature, so it is necessary to perform the firing twice as described above. However, it was not possible to obtain electronic components or electronic component elements.

Therefore, an object of the present invention is to provide a method for obtaining a ceramic electronic component in which electrodes are formed on dielectric ceramic by one firing.

[Means for solving problems]

The present invention has a dielectric ceramic composition as a main component, and P b O-G e Os system, Pb0-B, Os
・5lox series or Na, 0-BI Os '310
A step of molding a dielectric ceramic composition formed by adding 8 series glass to obtain a molded object, a step of applying an electrode paste to the obtained molded object, and a step of co-firing the molded object and the electrode paste. It is characterized by having

Examples of dielectric ceramic compositions that are main components include lead titanate, lead zirconate titanate, barium titanate, strontium titanate, and magnesium titanate. It is not limited.

Barium titanate-based compositions include true and modified barium titanate-based porcelain compositions.

Lead titanate-based compositions refer to genuine and modified lead titanate-based porcelain compositions, and modified lead titanate-based porcelain compositions include simple oxides such as Cry's, Nbi Os, T
ag Os, Bit Os, MnO3 and other transition element oxides, Pb sites are replaced with Mg, Ca, Sr.
, alkaline earth metals such as Ba, Law o3, Ndx
Those substituted with rare earth elements such as Os, YtOs, and a part of PbTiOs are substituted with general formulas (1) to (V[) described below.
It includes two-component ceramic compositions, three-component ceramic compositions, and other multi-component ceramic compositions substituted with at least one kind of composite perovskite compound represented by the above formula, or a combination thereof.

Furthermore, the lead zirconate titanate-based composition refers to both genuine and modified lead zirconate titanate-based porcelain compositions, and the modified lead zirconate titanate-based porcelain composition includes Pb (TI
, Zr) Os to CrgO,, Lag Os, Nbi
Os, Bit Os, MnOx, etc., with addition of metal oxides, pb site with alkaline earth metals such as Mg, Ca, Sr, Ba, Lamo$, Ndl Os
, those substituted with rare earth elements such as YtOs, and Pb
A part of (TiZr)Ox is expressed by the following general formulas (1) to (Vl
) 3-component, 4-component and other multi-component ceramic compositions substituted with one kind of composite perovskite compound, or a combination thereof.

Typical examples of the composite perovskite compound include the general formula (1): A"(B+zs"Bl/S")O
Compounds represented by s, for example, Ba(ZnwsNbzs)Os, Ba(Cd+
zi Nbmzs ) 0ssBa(Mg+zs Nb
mzs ) Os , Sr (Cd+zs Nbmzs )
Os, Pb(Mg+zs Nbmzs) Os, P
b(Ni+z*Nbmzs) Os, PR(Mll
tzs Nbmzs )Os , Pb(FILzs T
ays) Os, Pb(Ni+/*rag/3)
Os, Pb(Cd+/sNbmzs) Os;
General formula (If): A” (B+zt” Bl/!”)
Compounds represented by O, for example, Ha(Fe171Nb+zs)Os, Ba(SC
I/l Nb+zm) Os, Ca(Cr+yt N
b+z*)Os, Pb(Fe1zl NbIyz
)Os, Pb(Fe+z*τal/l)Os,
Pb(Sc, zl NbI/z) Os, Pb(SC
I/l rat/1 )Os 5Pb(Yb+z*N
b+z*) Ox, Pb (Yb+z* ta+/ meaning)
Os, Pb(LLII/l Nbl/l) Os,
Pb (In+/Nb+z寥)Os i general formula (II
I): Compounds represented by A""(Bu/z'B+zt")Os, for example, Pb(Cd+i*Wl/I)Os, Pb(Mn+
7m W+/l) Os, Pb(Zn+/* w,,
, )ox, Pb(Mg+zgVhyt)Os
, Pb(CO+zx w+, /*)Os , Pb(N
i+zt W+yx ) Os, Pb(MLzt te
l/g ) Os , Pb (Mn+zt Te+zz )
Os, Pb(Cotzt Te+z*)os;
General formula (iV): A grass (B t/1”°Bl/3”
)Os, for example, Pb(Feys W
+/5) General formula (V): A” (B+/l”
B/! ”)Os, for example, Pb(Sn+z*sbl/l)Os, La(Mg
+zg Titzs )Os, Nd(Mg+zx Ti
tzs )Os ; and general formula (VI) + (
Compounds represented by Al/l"A+z*")B"Os, for example, (Natzt La+zm)TIOs, (K+/l
La+zm)TIOs, (1ial/l Ce+
zt ) Ties, (Natzt Natzt )T
ies, (Nd Gi/Wealth Bi,, Mushroom) TiOko・
(K1/Tomi Bi I/Yuki) Ties etc.

Other examples include non-reducible dielectric ceramic compositions.

[Effect]

In the present invention, PbO/GeOx, which has a property of exhibiting ferroelectric behavior at a low melting point, is added to the dielectric ceramic composition as the main component.
system, Pbo ・Bm Os ・S Lot system or N
ag O・Bx 03 ・S Lot glass is added to produce a different phase ceramic bulk through liquid phase sintering, thereby significantly reducing the inherent properties of dielectric ceramics, such as the electromechanical coupling coefficient. This makes it possible to sinter the electrode paste at a low temperature of 850 to 1000° C., thereby making it possible to simultaneously and integrally bake the electrode paste, which was previously impossible.

For molding the dielectric ceramic composition in the present invention, any molding method such as a press molding method, an extrusion molding method, a sheet molding method, a hot pressing method, etc. can be used.

Further, as the electrode paste, any baking electrode paste containing conductive powder such as Ag or Cu can be used.

Furthermore, printing or other methods can be used to apply the electrode paste to the molded body.

The above-mentioned glass, which is a subcomponent, lowers the sintering temperature of the dielectric ceramic composition, and its content is preferably in the range of 0.01 to 30% by weight of the main component. 0.01% by weight
If the amount is less than 30% by weight, the effect of lowering the sintering temperature cannot be expected to be significant. On the other hand, if the amount is less than 30% by weight, the sintering temperature will be lowered, but the decrease in electrical properties, such as the electromechanical coupling coefficient, will be noticeable. be.

Particularly preferably, the glass is xPbo-yGe O*
If (X −1 to 6, V = 1 to 3) is used, deterioration of the electrical characteristics of the dielectric ceramic can be effectively prevented, as is clear from the examples described later. The values of x and y are set to x-1 to 6.7-1 to 3 because it can be vitrified by melting at a low temperature, and it also has strong properties when this glass is heat-treated and recrystallized. This is because dielectric properties can be obtained.

[Explanation of Examples]

As shown in Table 1, as a dielectric ceramic composition, P b
T io, *Z re, 5gOs 1. 0% by weight Nb.

Four types of molded bodies were created using a raw material obtained by adding xPbo/yGeot glass powder as a subcomponent. An electrode paste for baking, which is made by kneading Ag powder and an organic vehicle in which a binder made of ethyl cellulose is dissolved in butyl acetate as a solvent, is printed on each of the obtained molded bodies, and the molded bodies and the electrode paste are printed. A ceramic electronic component using dielectric porcelain was obtained by integral firing. The characteristics of the ceramic electronic component obtained in this way were
It is also shown in the table.

In addition, the characteristics of electronic components obtained using the same dielectric ceramic material and glass powder as above and using the conventional method, that is, the method of baking the electrodes in a separate process, are also listed as Conventional Examples 1 to 5, and the characteristics are shown in Table 1. Also shown.

As shown in Table 1 and Table 2, as a dielectric ceramic composition, 0.0
5Pb (Sn+z* Sb+zt)Os O,4
7PbT10.0.48PbZrosO, 7% by weight
Ceramic electronic components (numbers 5 to 8) were obtained in the same manner as in Example I using M n Ox. The difference is that in addition to the dielectric ceramic material mentioned above, the molding was performed by sheet molding instead of press molding.

The electrical properties of the obtained ceramic electronic component are also shown in Table 2.

Table 2 also shows the compositions and characteristics of ceramic electronic components obtained by conventional methods as Conventional Examples 6 to 10.

(Left below) As shown in Table 2 and Table 3, as a dielectric porcelain material, 0.05
Pb(Mn+zsNbtz,)Os 0.45PbT
Using iOsO,50Pbzno3, a molded body was fired in the same manner as in Example 2 to obtain a ceramic electronic component (
Nos. 9 to 13), the electrical properties of the obtained ceramic electronic components are also shown in Table 3.

Table 3 also shows the compositions and characteristics of ceramic electronic components constructed using the same materials using conventional methods.

As shown in Table 3 and Table 4, P b@
1sL as1*T i Os -0.7% by weight MnO
Ceramic electronic parts (Nos. 14 to 17) were obtained in the same manner as in Example (1) using No. 3. However, in this example, the molding was performed by extrusion molding. The electrical properties of the obtained ceramic electronic component are also shown in Table 4.

Table 4 also shows the compositions and characteristics of ceramic electronic components made of the same material using the conventional method.

(Left space below) Table 4 Dielectric ceramic composition using the four materials shown in Table 5, and Pb-B-3t glass or Na as a subcomponent.
A ceramic electronic component was obtained by molding and sintering in the same manner as in Example I using -B-3i glass mixed in the proportions shown in Table 5. The electrical characteristics of the obtained ceramic electronic component are also shown.

Table 6 also shows the composition and electrical properties of ceramic electronic components obtained using the same materials by the conventional method.

Table 5 (blank below) Table 6 In Tables 5 and 6, in the dielectric porcelain composition, ■■■■
represents the following composition:

■; P bT is, 4sZ re, 5xos −1
,0wt%b2O3 ■i 0.05Pb (Sn+zx sbl/1)O
s-0,47PbTiOs O,48PbZro,-
0.7% by weight M n Ox ■; 0. 05 P b (Mn+zs N bgz
3) Os-'3゛9 0, 45PbTiOi O,5PbZrOs■i
P bo, ssL ae, +oT i Os O,
7% by weight M n Os Also, in Tables 5 and 6, *1 and *2 indicate the following compositions.

*1; Pb-B-3i is 68 mol% PbO21
5 mol% B, Ogo, 4 mol% Stow, and 13 mol% A1. ox, an alkali metal oxide or an alkaline earth oxide.

*2; Na.B-3i is 11 mol% Na, 0112 mol% BxOs, 72 mol% Sin.

, and 5 mol % of AItxOs, an alkali metal oxide or an alkaline earth oxide.

〔Effect of the invention〕

As described above, according to the present invention, P b as a subcomponent
O・G e O system, 'PbO・Bt Os ・5t
By applying electrode paste to a dielectric ceramic composition molded body to which O1-based or Na, O・Bt O,・Slow-based glass is added and the sintering temperature is lowered, the electrode paste and the ceramic composition molded object are produced. Ceramic electronic components with electrodes can be obtained by simply co-firing them together. Therefore, unlike the conventional example, there is no need to carry out a separate step of baking the electrode after baking the dielectric ceramic composition molded body, so the manufacturing process of the electronic component can be greatly simplified.

The manufacturing method of the present invention can be used to manufacture various electronic components such as single-plate capacitors, multilayer capacitors, piezoelectric buzzers, piezoelectric filters, multilayer piezoelectric elements, and pyroelectric elements.

Claims (2)

[Claims] (1) The main component is a dielectric ceramic composition, and the subcomponent is P.
bO・GeO_2 series, PbO・B_2O_3・SiO_
A step of molding a dielectric ceramic composition formed by adding 2-based or Na_2O・B_2O_3・SiO_2-based glass to obtain a molded body; a step of applying an electrode paste to the molded body; and a step of applying an electrode paste to the molded body and the electrode paste. A method for manufacturing a ceramic electronic component, comprising a step of simultaneous firing. (2) As the subcomponent glass, the general formula xPbO-yG
Using eO_2 (where x = 1 to 6, y = 1 to 3), adding 0.01 to 30% by weight of the main component,
A method for manufacturing a ceramic electronic component according to claim 1.