JPS6044904A - Conductive paste 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 Application of Industry-1- The present invention relates to a conductive paste composition used for, for example, internal electrodes or end electrodes of chip-shaped porcelain capacitors or integral formation of a conductive circuit with a thickness of 119 mm. relating to things.

Conventional laminated type double capacitors are made of fine grained dielectric ceramic material.
A raw dielectric porcelain sheet (unfired raw dielectric porcelain sheet) is produced by coating the dielectric porcelain paste as a component on the body surface 1- and drying it, and then applying it on top of this unfired 1E body porcelain sheet. A conductive paste M1 composition is coated on the substrate to form a conductive layer, and a plurality of sheets selected in this manner are sequentially laminated to produce a conductive layer.

1. When forming the q-electrolayer by printing, apply commercial paste 1M to a mesh template -I- such as a screen printing plate.
The electrodes or plates of the capacitor (are used) are formed by depositing a composite material and imprinting it in the desired shape. Coat with porcelain material and place /+1 in the middle of the intersection.The electrode layer existing on the intersection +7 is slightly protruded so as to be exposed on both ends of the laminate, and this is ?A: A laminated porcelain capacitor is formed by firing at a firing temperature similar to that of the resting device.Then, each electrode layer exposed at both ends of the fired capacitor is coated with silver or silver-palladium alloy haze].
1) Connect all of the exposed electrode layers on the lino side, and connect all of the exposed electrode layers on the other side, 11) The end electrode portions are formed by applying the following steps. Next, on the end electrode part where the burnout has finished,
For example, by joining the conductive wires by means such as 14111 attachment, a multilayer ceramic capacitor is completed.

The dielectric porcelain paste described in 111.
- A composition of a particulate dielectric porcelain material such as manguan oxide or strontium titanate, a temporary resinous organic binder, and a solvent for dissolving the resinous organic binder into a slurry.

The IO paste M1 composition, which is safe for electrode formation, has a composition in which finely divided metal particles or metal oxide particles are dispersed in a liquid substance. In this case, metal particles or metal oxide nets are selected based on cost and +1 ability. Performance 1 refers to the melting point below the sintering temperature of dielectric porcelain, An inert material must be selected that does not oxidize or react when it comes into contact with the dielectric ceramic during the process.As materials that satisfy this condition, conventionally, gold, platinum, palladium, or one 11t metals such as silver were used.Of these, gold and platinum have the advantage of being inert to oxidation during firing or reaction with dielectric porcelain, but they are 3 to 4 times more expensive than palladium. -2, there is a disadvantage that it is very expensive.

Silver and palladium have the advantage of being inexpensive compared to gold and platinum, making them preferred as metallizing components in conductive paste compositions. In particular, it is cost-effective to select more IRF containing inexpensive silver! It is advantageous. Palladium and silver form a complete system of solid solutions with liquidus and solidus levels that decrease stepwise from their respective melting points of 55,000 to 960°C. Therefore, by selecting a silver-palladium composition that does not melt at this firing temperature, depending on the firing temperature JB that is safe for sintering the Mzrjj body Ie vessel in the range below 1550°C, which is the melting point of palladium, the cost can be reduced. It is possible to form a 4-layer + 1 film that is economically advantageous and has economical performance.

Disadvantages of the Prior Art However, with the conventional silver-palladium composition, it was not possible to reduce the thickness of the JA Den 1 No. 1 coating to 3 gm or less. When the thickness of the conductive outer cover 11 is 3 gm or more,
After the composition of the electrode conductive skin 119, the w5 property is lost and 'I[
This is because problems such as f-cutting occur, resulting in lower quality and reliability. For this reason, the use of silver and palladium cannot be reduced to a certain amount of F, which limits the cost reduction.

L1 aspect of the present invention Therefore, the present invention provides a high-quality and high-4I reliable conductive film that is very thin, for example, about 2 gm in thickness, is dense, has low C/I and resistivity, and is applied to a ceramic base material. of,
It is an object of the present invention to provide an Imaichi P1 paste silk composition that can be formed at low cost.

In order to achieve objective 1-11 of the present invention, in 7, the invention is made by mixing a fine particulate gold component containing at least a small amount of χ)°L-containing silver with a liquid JRI body. The electrically conductive paste composition is characterized in that it contains one or more particulate precious metals selected from rhodium, platinum, and iris.

The metallized component is finely divided into spheres or flakes sufficient for continuous screen printing operations and sintering.

For spherical powders, at least 90% have a maximum particle size of 2μ
In the case of flaky powder, at least 90% of the particle size should not exceed 30 m. Preferably, in the case of a 2L-shaped powder, all the particles are selected so that the IpLm is less than 1, and in the case of a scale-like powder, the maximum value of all the particles is selected so that the maximum value of all particles is 204tm or less. These metal flZ components are generally
Silver or a mixture or alloy of at least 30% silver and palladium oxide.

The relative strength of silver and palladium (i) is determined by the cost of eiJ and the firing temperature of the porcelain.・40-75% due to the need to ensure
A range of 1 sho, Ql, or preferably 45 to 65% is appropriate.

In the present invention, the addition of one or more fine-grained precious metals selected from the group consisting of rhodium, platinum, and iridium is woody in the present invention. The addition of this fine particulate noble metal is at a rate of 0.01 to 5 mass%, preferably 0.03 to 5%+t%, based on the heavy dissolution of the metallized component, or the cost is reduced. If selected in advance, 0.03 to 1 ton (%) is the optimum addition silicon.This fine particulate precious metal is
It is desirable to add and disperse it in the form of

The liquid mixture in which the layering component and the noble metal are dispersed must contain a temporary organic binder for the particulate metallization component. This binder is punctured out during the sintering process. As such an organic binder, cellulose resin, butyral resin, acrylic resin, etc. are suitable, and one or two of these resins are contained. The temporary organic binder is also sufficiently sensitive to effectively bind the particulate metallization component to ensure adhesion of said metallization component to the dielectric porcelain sheet. It is necessary to make it exist in the liquid JL1 body. Generally, 2 to 50% of the total weight of the liquid carrier is effective, but 3 to 3% of the total weight of the liquid carrier is effective.
~20% is preferred.

The tetraelectric paste composition of Unfired No. 1 according to the composition described above was prepared according to unfired ceramic according to more well-known means.

Shoes are coated with FI7 on the material, and then fired in the same manner as the ceramic material.
A -q'+lj film is formed on the base material 1. However, pre-fired ceramic shoes (Murakami) can also be printed and used.

When a conductive base composition having such a composition is used, the thickness of the conductive film formed on the ceramic/substrate 1- can be made significantly thinner than before, and the use of silver or palladium can be made much thinner than before. In order to reduce the energy consumption and achieve cost reduction, we also made the IE film composition 1 more dense, and 1) increased the capacity of the capacitor and lowered the 4-power loss coefficient. I found out that it can be done. In this way, the slight addition of rhodium, platinum, and ilium to silver and palladium-based metallization components results in a conductive film composition that is 119 thinner and denser than the case without addition. It is truly amazing that it can be formed. Next, the contents of the present invention will be explained more fundamentally by referring to specific embodiments.

Example Figure 1 shows the sheet resistivity of a fired conductive film formed on a ceramic base material using the conductive paste I-composition according to the present invention, compared to that of a conventional silver-based electroconductive paste composition. FIG. 3 is a diagram showing a comparison of the sheet resistivity of the firing conductivity and the sheet resistivity of the material. tFS 1 The vertical axis of the diagram shows the sheet resistance -i8LΩ-CII+, and the horizontal axis shows the sheet resistance -tt
Take that. Curve AI in FIG. 1 is the 4Y property when a conventional conductive paste composition is used, and curves B1-B5 are the properties when the conductive paste composition according to the present invention is used. Among curves Bl-, 33, curve B1 is the characteristic when 0.12% by weight of Iridium J is added to the heavy weight sum of silver and palladium, and curve B2 is the characteristic when 0.2% by weight of platinum is also added. Special +IL in case of near, curve B3 should be turned
When 0.09% Rosiu 1 is added! The conventional conductive paste I composition of 6 curves AI is 332≦Ag-22%Pd-45% liquid carrier composition (Tonhaya ratio), and curve B1 In the -B5 conductivity +1〆-X1・M1 composition according to the present invention, the Ag and liquid carrier remain I as in the conventional case, and the weight of Ag and Pd is +11
Iridium, platinum or rhodium is
The weight ratio of Pd was determined to be the ratio of i and ij.

As is clear from the comparison between the characteristics A1 and 4+IBI~B3 in FIG. 1, when the conductive paste composition according to the present invention is used, the resistivity can be significantly reduced by -1 compared to the conventional one. In particular, in the case of adding 1\1, the thickness of 11 is 5 m.
[Sheet] 1 (Resistivity could be reduced to 40% or less of the conventional value. Therefore, according to the present invention, the required conductive film quality can be ensured while reducing the film thickness, and In addition, the capacitor manufactured using the conductive paste composition according to the present invention has a lower cost compared to the conventional system without the addition of rhodium 1, I. The capacity j4 is large and the loss is small.

FIG. 2 shows the case where a conventional conductive paste composition is used, and FIGS. 3 to 5 show the case where the conductive paste composition according to the present invention is used.
- Each electron microscope photograph of the ceramic firing surface when using the composition is shown.

No. 31 Δ is the case when 0.12 weight h (%) of iridium is added to make the film thickness 34 m, and Fig. 4 shows a 0.2 ton product.

% of platinum was added to make the film thickness 3.2 gm, and Figure 5 shows the thickness of each layer when 0.09% of rhodium was added to make the film thickness 2.1 μm. w4 microscopic photo,
1 (doing)

As is clear from the comparison between Fig. 214 and Figs. 3 to 5, when the conductive paste composition according to the present invention is used,
A conductive film with a smaller structure than conventional ones can be formed. In particular, in the case of rhodium powder, an extremely dense conductive film is formed.

Effects of the present invention As described above, the present invention provides a conductive paste M1 composition formed by mixing a finely divided metallization component containing at least finely divided silver with a liquid 431 body.
Because it is characterized by containing fine particulate precious metals derived from 4゛C of platinum and iridium, it is very thin, for example, about 2 meters thick, compared to the ceramic base material. It is possible to provide a conductive paste composition capable of forming a conductive film of high quality and high reliability with a small sheet thickness of 11ξ 10 at a low cost.

[Brief explanation of the drawing]

FIG. 1 shows a sheet 1 of a fired conductive film formed on a ceramic substrate using a conductive heavy paste composition according to the present invention.
The sheet resistance of the fired conductive film with the conventional silver-palladium conductive +1 Pace I composition is compared with that of the conventional silver-palladium conductive +1 Pace I composition. )・F33-FIG. 5 show the results of each 'Tunr-Microscope' on the four sides of the ceramic firing when using the '4' City+1 Paste M+ composition' according to the present invention. I.J.
I've left a page out. -r-Itodata Neichi -1-13 Book 1980 12J15 II IIl+1Japanese 58 Year 614'l Application No. 151419 2 Name of Invention Conductive Pace)・M1 Product 3,? +fi '+-E Representative Nagisa Hiroshi Okura 4 Representative 125 1ELO3 (600) 5090
Address 1-1 Toganemachi, Katsushika-ku, Tokyo] '1137-2'+5
Supplement + E Order 1-1 November 8, 1982 [16, Number of Inventions Increased by Supplement II 07, Pair of Sleeve Stops
Elephant details! ) from page 13, line 4 to line 8 of the amended description of the drawings, the statement ``Figure 2 shows the conventional 010. Figure 2 is an electron micrograph showing the metal composition of a conductive film formed using a conventional conductive paste composition, and Figures 3 to 5 are photographs using a conductive paste composition according to the present invention. This is an electronic W4 microphotograph showing the metal composition of the conductive film formed by the process.

Claims (1)

[Claims] (1,) A conductive +1 paste composition comprising 6 g of a liquid 11 substance and a finely oxidized metallization component containing at least slightly ionized silver. A conductive paste composition characterized in that it contains one or more fine particulate precious metals selected from rhodium 11, platinum, and iridium. Claim 1, characterized in that it consists of a mixture of 1% silver and palladium oxide.
The conductive paste composition described in . (3) The metallization component is silver or at least 30I
Claim 1si characterized in that it consists of an alloy of silver and palladium palladium oxide of rI'IiV%.
The conductive paste composition according to r. (4) The fine particulate noble metal is contained in a proportion of 0.01 to 5 tons-1% of the metallization component, 4. Conductive paste I/composition according to item 4. (5) Claim 61, characterized in that the fine particulate noble metal is in the form of organic salts,
The conductive paste composition according to the third item or the fourth item.