JPS6020850B2 - dielectric porcelain material - Google Patents

Description

[Detailed description of the invention]

TECHNICAL FIELD The present invention relates to a composite berovskite-type electromagnetic porcelain material that can be obtained by tying in a non-oxidizing atmosphere and heat-treating it in an oxidizing atmosphere at a temperature lower than that for lump silk, and more specifically, The present invention relates to a dielectric ceramic material that is most suitable for a mirror layer ceramic capacitor having a structure in which a conductive paste containing nickel as a main component is applied to a dielectric green sheet and then sintered. Conventional technology Conventional multilayer ceramic capacitors are made by stacking and pressing a plurality of dielectric green sheets (green sheets) printed with guiding pastes of precious metals such as platinum and palladium, and firing them at high temperature in an oxidizing atmosphere. After that, it is manufactured by providing external extraction electrodes. However, since crab pole materials such as platinum and palladium are expensive, it has been impossible to provide inexpensive multilayer ceramic capacitors required by consumer devices. In order to solve this type of problem, it is conceivable to apply a conductive paste containing nickel as a main component to a green sheet and then bond it in a non-oxidizing atmosphere. However, even if it is formed in a non-oxidizing atmosphere, if the temperature at the side is high, for example 130 mm or higher, the nickel particles in the nickel guide fin paste will grow and agglomerate at the same time, causing nickel was distributed in a bead-like manner, making it difficult to form a high-quality electrode. In addition, some of the nickel may diffuse into the porcelain, degrading the insulation. For this reason, there is a need for a ceramic composition that can be solidified at low temperatures (for example, below 1250 qo) in a non-oxidizing atmosphere. OBJECTS OF THE INVENTION The objects of the present invention are to have a relatively high insulation resistance, which can be obtained by incubation at low temperatures in a non-oxidizing atmosphere, and which oxidizes under the above conditions; Dielectric loss (tan 6) is relatively small, and capacitance ×
An object of the present invention is to provide a dielectric ceramic material with which a capacitor having a relatively large resistance (CR) value can be obtained. Structure of the Invention The present invention to achieve the above object has the following features:
k is a numerical value in the range of 1 to 1.04);
10 parts by weight of the {(BaMCax)0}k(Ti,
-yZ★) 0.2 to 10.0 parts by weight of Li based on 02
20-MeO-SjQ glass (Me0 is Ba○, C
a0, and one or more metal oxides of Sr○), and the Li20-Me○-Si02 is Li2
In the triangular diagram showing the composition of 0, Me0, and SjO in mol%, the first point (1) indicates a composition of 0 mol% of Li20, 35 mol% of Me○, and 65 mol% of Si02.
, the Li20 is 0 mol%, and the Me○ is 40 mol%.
, the second point 'B where the Si02 has a composition of 60 mol%
}, and a third point showing a composition of 5 mol% of the Li20, 45 mol% of the Me○, and 50 mol% of the Si02 {
C}, a fourth point (3) showing a composition of 48 mol% of the Li20, 2 mol% of the Me0, and 50 mol% of the Si02, 23 mol% of the Li20, 2 mol% of the Me○, A fifth point where the Si02 shows a composition of 75 mol%

[
The present invention relates to a composite berovskite dielectric ceramic material characterized by having a composition within a region surrounded by five straight lines sequentially connecting E' and the first dot point. Effects According to the present invention, the following effects can be obtained. (2) By adding Li20-Me○-Si02 glass having a low melting point, it becomes possible to freeze at a low temperature (for example, 120 mm or less). 'B} Contains CaTi03 series, so
It has good oxidation performance at low temperatures, making it possible to perform oxidation heat treatment at a low temperature of 800°C, for example. Since low-temperature condensation is possible, almost perfect capacitor electrodes can be obtained even if base metal fin electrode materials such as nickel are simultaneously deposited. ■ For the reasons of W~'C) above, and because the sheath Ti03 included in the basic components contributes to obtaining a high relative permittivity, and contributes to improving the Z glass n8, the resistivity p
is 2.32 x 1 MQ/Suppressor or higher, MQ with CR value of 260
・rF or more, yen 6 is 1.5% or less, specific electric current is 2
It becomes possible to obtain a capacitor of 520 or more. EXAMPLES Next, examples of the present invention will be described. However, in order to clarify the present invention, examples outside the scope of the present invention are also included. Examples 1 to 78 (Tables 1 and 2) The ceramic capacitors of Examples 1 to 78 shown in Tables 1 and 2 were manufactured and their characteristics were measured in the following manner. First, (1-x), x, (1-y), y, and k of {(shelf, ★Cax)○}k(TiryZry)Q, which are the basic components of the fired product with a composite berovskite structure, are the first BaC with a purity of 99.0% or more in proportions that result in the values shown in the table.
03, CaCQ, Ti02, and Zr02 were weighed as starting materials. Next, the weighed raw materials were warm mixed for 1 hour, pulverized, dried, and temporarily held in the air at about 1200 qC for 2 hours. This makes the starting material almost the basic component. next,{
(Stripe, ~Cax)○}k(Ti, -yZry)02 Li20-Me○- Si
02 glass powder was weighed, this glass powder was added to the basic component obtained by temporary scales, and at the same time 15 parts by weight of an organic/indredder consisting of an aqueous solution of acrylic acid ester polymer, glycerin, and condensed phosphate was added, Further, 5 parts by weight of water was added to the mixture, which was then placed in a ball mill, ground and mixed to produce a porcelain raw material slip. The composition of the Lj20-MeO-Si02 glass shown in Table 1 is as shown in Table 2, and Meo, which is a component of this glass, is one or more of Ba0, Ca0, and S. The contents (composition) are as shown in Table 2. That is, L et al 0-Me0- shown in mol% in Table 2
The content of Me0 in Si02 is at least one of Shigeru, Cao, and S, and the proportions of these are shown in the column of content of Me0 in mol%. In Table 2, L120-Me
○-The specific composition of SiQ is shown as a combination of two columns, but when shown together, for example, the glass composition of Example 1 is Li205 mol%, Ca045 mol%, Si0250 mol%, and the glass composition of Example 5 is Glass composition is Li2020
Mol%, Ba03mol%, Ca. 4 mol%, S^03 mol%, Si. It becomes 270 mol%. Next, after degassing the above-mentioned slip, a long green sheet is made from this slip by the doctor blade method, and after drying, the three green sheets 1 and 2 shown in FIG. , 3 were prepared. Next, on one main surface of the raw sheets 1 and 2, a guide fin paste containing nickel as a main component (Ni91wt%, Mh01M%
The conductive paste layers 4 and 5 shown in FIG. 2 are formed by printing a paste (Pb○-Ba○-Si02 glass blurred paste) to a thickness of about 6 Am, and then the conductive paste layers 4 and 5 shown in FIG. Three green sheets 1, 2, and 3 were stacked on top of each other in the order shown in Figure 3, and were bonded together by thermocompression. Next, the raw sheets 1, 2, and 3 were put into a heating furnace and heated from room temperature to 600 qC at a temperature increase rate of 100 qC/h.
Heated in air to combust the organic/inda. Thereafter, the atmosphere in the heating furnace was changed from air to a neutral or reducing non-oxidizing atmosphere. In Examples 1 to 60 and 65 to 78, the neutral or reducing non-oxidizing atmosphere was
2% by volume 10N298% by volume atmosphere, in Example 61 day 2
Zero volume % + main neck % atmosphere of N210, Example 62 was day 2
3 volume% + N295 volume% atmosphere, example scenario is day 21 main mirror % + N29 main mirror % atmosphere, example 64 is day 275
The atmosphere was 25% by volume + N2 by volume. Then, with the heating furnace in a non-oxidizing atmosphere as described above, the heat dissipation temperature of the raw sheet was changed from 60 pC to the firing temperature 1030 qo shown in Table 1.
~ 1 paper pi 0 at a rate of 100°C'h, and the firing temperature 1030 as shown in Table 1 in the above neutral or reducing atmosphere.
The raw sheet was fired by maintaining the oqo of qo ~ 1 spot for 3 hours. Next, while maintaining a neutral or reducing atmosphere, the temperature of the heating furnace was changed from a firing temperature of 103°C and 0 to 1 total oqo to 100°C and 0°C in Example 1, and to 800°C in Examples 2 to 78.
Next, the atmosphere in the heating furnace was changed from a neutral or reducing atmosphere to an oxidizing atmosphere (air) to 1000°C in Example 1 and 80°C in Examples 2 to 78.
It was held at 0qo for 3 minutes and then cooled to room temperature (about 20°C) in an air atmosphere. As a result, as shown in FIG. 3, a first ceramic layer la corresponding to the raw sheet 1 and a second ceramic layer 2 corresponding to the raw sheet 2 are formed.
a and a third porcelain layer 3a corresponding to the raw sheet 3, between which electrodes 4a, corresponding to the paste layers 4, 5,
5a was obtained. The thickness of the porcelain layers la, 2a, and 3a in the dawn stripe body 6 is about 50 ridges, and the total thickness of the dawn stripe body 6 is the thickness of the fin poles 4a, 5.
It is approximately 160 meters including a, and its length and width are 6
column, and the electrodes 4a. The opposing area of 5a is 5 capes x 5 sides = 2
It's the 5th one. Next, the electrodes 4a and 5a emerge from the dawn formation 6.
A Zn paste consisting of Zn, a glass frit, and a vehicle was applied to the side surface of the electrode, dried, and then tested in the air at a temperature of 55 to 0. A Cu layer 8 was formed by depositing Cu by electroless plating, and a solder layer 9 was further formed by electroplating to form a pair of end electrodes 10 and 11. . Next, the electrical characteristics of the laminated ceramic capacitors of each example formed as described above, namely dielectric loss (n6), dielectric constant, resistivity p, static fin capacitance x resistance CR, were measured, and the results are shown in Table 2. The results shown are obtained. The capacitance was measured under the conditions of a specific porosity, a temperature of 25°C, a frequency lk ratio, and a voltage (effective value) of 0.5V. Electrodes 4a, 5
It was calculated from the thickness of 0.05 mm of the porcelain layer 2a between a.
Further, tan 6 was measured under the same conditions as the dielectric constant, and is shown in % in Table 2. That is, Table 2 shows the values of 10 orthogonal notes of the actual value of n6. Therefore, the actual value of tan 6 is 10-2 times the value in Table 2. Also, the resistivity p(
MQ/skin) was obtained by measuring the resistance value between electrodes 10 and 11 after applying DC 50V for 1 minute at a temperature of 25°C, and calculating from this measured value. Further, CR was determined by multiplying the measured capacitance value and resistance value. Table 1 Table 1 (Continued) Table 2 Table 2 (Continued) Examples 2 to 24 within the scope of the present invention in Tables 1 and 2
31~3〆 36~50 52~5mm Spotted ~ Mouse 70
~77, it is clear that the basic component {(&, -XC
x of aX)○}k(Ti, -yZry)02 is 0.02
~0.27, y is 0.01-0.26, k is 1-1.0
4, and 0.2 to 10 parts by weight of this basic component
Composite velopskite type crab porcelain containing Li20-Me0-Si02 glass in the range of 1 part by weight ranges from 1050 qo (Example 33) to 1160 qo (
It can be formed by competitive bonding at the temperature of Example 49) and then heat treatment in an oxidizing atmosphere of about 800 qo during the cooling process. And 0.5-1.4% of n8, 2520~
13060 p is 2.32 x 1 ~ 1.18 x 107M
It is possible to obtain a multilayer capacitor with a nickel electrode having a CR value of 2,600 to 318 plus Q and F characteristics.
However, the composition of the glass of Li20-Me0-Sj02 is
In the triangular diagram in Figure 5 showing this composition, sequentially place the first point ■, the second dot leg, the third point}, the fourth point ■, the fifth dot leg, and the first point ■. It must be within the area surrounded by the five connecting straight lines. Note that the first point ■ in the triangular diagram in FIG.
The composition is 0 mol%, Me035 mol%, Si0265 mol%, and the second point is the Li2 groove mol% of Example 21,
Showing the composition of Me040 mol% and Si0260 mol%,
The third point (C} is 205 mol% of Li in Example 22, Me
045 mol%, Si0250 mol%, and the fourth
The dot plate shows the composition of Example 23 with 2048 mol% Li, 2 mol% Me0, and 250 mol% Si0.
It shows the composition of i0275 mol%. Examples 2-2 in Table 2 31-3336-5052-5
458~Nejiji70~77 are 5 connecting the first to fifth points above.
Everything is contained within the area surrounded by the straight line of the book. Next, the reasons for limiting each component of the present invention will be described. As is clear from Example 1, which is outside the scope of the present invention, ``When x, that is, Ca, becomes zero, oxidation does not proceed sufficiently even if the oxidation heat treatment is performed at 1000 qo, and p becomes as low as 8.5 x 1 pi MQ. , tan 6 is also large at 15.6%.On the other hand, as is clear from Example 78, which is outside the scope of the present invention, x is 0.2%.
When it reaches 9, the value becomes as low as 860, and the CR value also becomes as low as 750. On the other hand, tan6, p, and CR of the embodiments within the range of the present invention in which x is 0.02 to 0.27 are values that are satisfactory as a capacitor. As is clear from Example 56, which is outside the bag range of the present invention, when y, that is, Zr becomes negative, n6 becomes large at 6.8, and g becomes low at 1030, and the CR value is also 7 times Q. It becomes low as rF. On the other hand, as is clear from "Example 57 outside the scope of the present invention", when y becomes 0.28, .
The CR value becomes as low as 80, and the CR value also becomes as low as 70. On the other hand, in embodiments within the scope of the present invention in which y is 0.01 to 0.26, electrical characteristics that can be satisfied as a capacitor are obtained. As is clear from Example 51, which is outside the scope of the present invention, k is 0. In the Nada, n6 increases to 7.2%, p decreases to 2.07×1piMQ・arc, and CR also decreases to 12. On the other hand, as is clear from Example 55, which is outside the scope of the present invention, when k is 1.05, it becomes difficult to form scale stripes, and a delicate cylindrical body cannot be obtained. On the other hand, if k is set in the range of 1 to 1.04, a satisfactory capacitor can be obtained.
As is clear from Example 34, which is outside the scope of the present invention, when the amount of glass added is IZ parts by weight, tan 8 becomes 3.8.
%, and the CR value is as low as 147 瓜Ke○・F. On the other hand, as is clear from Example 35, which is outside the scope of the present invention, when the amount of glass added is zero parts by weight, tan 6 becomes 5.
It gets worse at 6%. In contrast, embodiments within the scope of the invention in which 0.2 to 1 part by weight of glass is added to 10 parts by weight of the base component give satisfactory electrical properties.
As is clear from Examples 25 to 30 and 69, which are outside the scope of the present invention, when the composition ratio of Li20-Me0-Si02 glass is outside the range specified in FIG. The CR value is 18 plates M014F or less, and there are also cases where delicate scale bodies cannot be obtained as in Examples 30 and 69. On the other hand, in the embodiment where Li20-Me0-Si02 is within the region specified in FIG. 5, satisfactory electrical characteristics can be obtained. As is clear from Table 2, Me0 is Ba0,
Any combination of Ca0 and S may be used alone. Also, the mother 0 included in Me0, the mother of Ca0, Ca
is also included in the basic components, but the basic components include Ba and Ca.
This base was increased and a glass gunwale was added because it included
"It is impossible to reduce Cao. This is because Cao, which is the vitality of glass, exhibits an effect completely different from that of the basic components. The following effects can be obtained: [a] The condensation temperature in a non-oxidizing atmosphere can be made low (103 and 0 to 115 p0). [bl] It is possible to carry out oxidation heat treatment during the slow cooling process after freezing. 'C' day 2 in a non-oxidizing atmosphere consisting of 20 N2 Even if the ratio of 20 N2 x 100 (volume %) is changed from 2 to 75%, there is almost no change in the electrical characteristics, so a commonly used atmospheric furnace for mass production should be used. 'd} A capacitor with n 6 of 1.5% or less can be obtained. {e) Various dielectric constants in the range of 2520 to 13060 can be obtained. 'f' Resistivity p It is possible to make the resistivity p to be 2.32×1 and MQ×2 or more. It is possible to maintain a relatively large resistivity p in the temperature range of -35°C to 150q○. For example, the present invention The capacitor of Example 31, which does not contain glass, and the capacitor of Example 35, which does not include glass and is outside the scope of the present invention, were placed in a direct temperature bath.
After applying DC 50V for 1 minute at each temperature of 0 and 15 0, the resistance was measured and the resistivity p was calculated, and it was found that the capacitor of Example 31 according to the present invention had the curve R shown in FIG.
, and the capacitor of Example 35, which does not fall within the scope of the present invention, had the results shown by curve R2 in FIG. As is clear from this result, by adding glass, p is relatively high even at temperatures of 15 to 10 degrees. Therefore, glass not only has the effect of lowering the competitive temperature, but also
The resistivity characteristics are also significantly improved. (en) According to the present invention,
It is possible to improve the DC bias characteristics by adding glass. For example, using the capacitors of Examples 19 and 31 according to the present invention in which glass is added, and the capacitor of Example 35 which is outside the scope of the present invention and in which no glass is added, a DC bias turtle pressure of 10 to 80 y is applied to 25 hills. With the applied condition, the AC measurement voltage was 0. When the capacitance was measured under the conditions of 25 qo (effective value), lk, and 25 qo, and the ratio of protection forces was calculated, the results shown in Fig. 7 were obtained. In Figure 7, curve E,
Curve E2 shows the capacitor of Example 19, curve E3 shows the capacitor of Example 35, which is outside the scope of the present invention, at each DC voltage. As is clear from this result, the addition of glass can dramatically improve the direct current bias characteristics, that is, the effective load characteristics. Examples 79 to 82 (Table 3) As shown in Table 3, in Examples 79 to 82, green sheets having the same porcelain composition as Examples 11, 1932, and 58 were made by method. Next, a raw sheet with a thickness of 60 mm was punched into a rectangular shape using a press, and rectangular raw sheets of 2 materials were prepared in each of Examples 79 to 82. The same nickel paste as in Examples 1 to 78 was printed on the raw sheet in the same state as shown in FIG. 2 using the same method, and the two raw sheets were stacked and bonded together by thermocompression. Next, this integrated product is heated in air to 50,000 to combust the organic/indredder, and then the ratio is 2% by volume + N29 contact volume%.
The atmosphere was changed to 1, and the temperature was raised to the firing temperature shown in Table 3 at a rate of 1000 C/h, and this firing temperature was maintained for 2 hours. Next, it was cooled to 800° C. at a rate of 100 qC/h, switched to an oxidizing atmosphere (air), subjected to oxidation heat treatment at 800 qo for 30 minutes, and then allowed to cool. As a result, as shown in FIG. 8, the ceramic layers 12a, 12b,
A scale body having 27 porcelain layers such as 12c, 12d and 12e and 26 electrodes such as electrodes 13a, 13b, 13c and 13d was obtained. The width of this composite body is 2.5 feet, the length is 3.2 feet, and the thickness is 1.0 feet. Next, as shown in FIG. 8, end electrodes 10 and 11 were formed on both exposed end surfaces of the sintered body using the same material and method as in Examples 1 to 78, and tan 6 was formed in the same manner as in Examples 1 to 78. (%), capacitance C (mountain F), insulation resistance I
When R (×1 and MQ) was measured, the results shown in the initial electrical characteristics column of Table 3 were obtained. Next, the capacitor whose initial value was measured was fixed on the electrode of the alumina board with solder, and a high-temperature load life test was performed by maintaining the applied state of temperature 8 0 and DC voltage 50 V], 25 m hours, 50 hours. , 100q hours, and 200 feeding hours. As a result, it was found that even after 200 field hours, it had sufficient properties for use in hollyhocks. Table 3 Table 3 (continued) Examples 83 to 90 (Table 4) Comparison of equivalent series resistance (ESR) when glass is added according to the present invention and when no glass is added outside the scope of the present invention In order to do this, capacitors were made in the same manner as Examples 1 to 78 for Examples 86 to 86 in Table 4, and in the same manner as Examples 79 to 82 for Examples 87 to 90, and the capacitance C, When the equivalent series resistance (ESR) was measured, the results shown in Table 4 were obtained.The composition and manufacturing conditions of the porcelains of Examples 87 and 89 were the same as those of Example 19 according to the present invention. , Example 84
The composition and manufacturing conditions of porcelain 808 & 90 are the same as Example 35, which is outside the scope of the present invention. In addition, the number of laminated layers in Table 4 indicates the number of composite layers that act as a capacitor, that is, the number of porcelain layers having opposing electrodes, and the thickness of one layer and the effective electrode area of one layer represent the number of composite layers that function as a capacitor. The thickness of the layer and the effective area of the electrode here are shown. The equivalent series resistance (ESR) of each of the capacitors of each example was set at 25° C. and measured at the resonance point. As is clear from the results in Table 4, adding glass according to the present invention lowers the equivalent series resistance at the same capacitance C. In tuner circuits, chip-shaped ceramic capacitors with an ESR of 1000 to 220 F are often used, and capacitors with an ESR of, for example, 250
Although the following is desired, according to the present invention, it is possible to provide a capacitor that satisfies this demand. Modification Examples The embodiments of the present invention have been described above, but the present invention is not limited thereto and can be further modified. For example, the starting materials for obtaining the basic components were
Other than those shown in 78, compounds containing Ca, TLZr, for example, oxides or hydroxides of Ca0, Ti02, Tn02, etc. may be used. In addition, the oxidation temperature should be set to 750 to 1000 qo other than 80 qo (preferably 80 qo).
The temperature may range from 0 to 900 qo. That is, it is possible to make changes taking into account the electrodes made of nickel or the like and the oxidation of the ceramic. Furthermore, the firing temperature in a non-oxidizing atmosphere can also be determined taking into consideration the Kame electrode material. Further, other substances may be further added within a range that does not impede the object of the present invention. For example, for the porcelain of the present invention, MN02 is 0.05 to 0.
．． It may be added in an amount of 1% by weight. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a perspective view showing green sheets according to Examples 1 to 78;
Figure 2 is a perspective view showing the raw sheet shown in Figure 1 printed with nickel paste, Figure 3 is a cross-sectional view showing the raw sheet shown in Figure 2 integrated and married, and Figure 4 is the raw sheet shown in Figure 2. FIG. 4 is a cross-sectional view showing a state in which end electrodes are provided on the sintered body of FIG. 3; FIG. 5 is a triangular diagram showing the composition of glasses in Examples 1 to 78. FIG. 6 is a characteristic diagram showing the relationship between temperature and resistivity of the capacitors of Examples 19 and 35. FIG. 7 is a characteristic diagram showing the relationship between the DC bias voltage and the yield rate of Examples 19, 31, and 35. FIG. 8 is a sectional view showing a part of the laminated ceramic capacitors of Examples 79 to 82. 1, 2, 3...raw sheet, la, lb, lc...・
... Porcelain layer, 4, 5... Paste layer, 4a, 4b...
...Fin pole, 6... Composite body, 10, 11... End face electrode. Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 7 Figure 8 Figure 6

Claims (1)

[Claims] 1 {(Ba_1_−_xCa_x)O}_k(Ti_
1_-_yZr_y)O_2 (however, x is 0.02 to 0.
27, y is a numerical value in the range of 0.01 to 0.26, k is a numerical value in the range of 1 to 1.04), and 100 parts by weight of the above {(Ba_1_−_xCa_x)O}_k(Ti_1_
-_yZr_y) 0.2 to 10.0 parts by weight of Li_2O-MeO-SiO_2 glass (however, Me
O contains one or more metal oxides of BaO, CaO, and SrO, and the Li_2O-MeO-S
iO_2 is the first point in the triangular diagram showing the composition of Li_2O, MeO, and SiO in mol%, where the Li_2O is 0 mol%, the MeO is 35 mol%, and the SiO_2 is 65 mol%. (A) and the Li_2O
is 0 mol%, the MeO is 40 mol%, the SiO_2
a second point (B) showing a composition of 60 mol%;
i_2O is 5 mol%, the MeO is 45 mol%, the S
A third point (C) showing a composition of 50 mol% iO_2,
The Li_2O is 48 mol%, and the MeO is 2 mol%.
, the fourth point where the SiO_2 has a composition of 50 mol% (
D), the fifth point (E) showing a composition of 23 mol% of the Li_2O, 2 mol% of the MeO, and 75 mol% of the SiO_2, and the first point (A), in sequence. A composite perovskide dielectric ceramic material characterized by having a composition within a region surrounded by five connecting straight lines.