JP2001284816A - Multilayer circuit board and its manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a multilayer circuit board of high reliability, which has a silver based conductor pattern and little fluctuation in resistance of a thick film resistor. SOLUTION: This multilayer circuit board has an insulating layer provided with the silver based conductor pattern which has silver based conductor as a main body and contains inorganic additive component such as copper oxide and chromium oxide, and a thick film resistor of ruthenium oxide or the like. The insulating layer contains (A) silver and/or silver compound and (B) at least one kind of inorganic component (copper oxide or chromium oxide) which constitutes the inorganic additive component.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a multilayer circuit board having an insulating layer provided with a silver-based conductor pattern mainly composed of a silver-based conductor material and a thick-film resistor, and a method of manufacturing the same.

[0002]

2. Description of the Related Art In recent years, various electronic components such as personal computers and mobile communication terminals have been reduced in size and density by utilizing semiconductor integrated circuit elements such as ICs and LSIs. There is also an increasing demand for circuit boards used for hybrid ICs, packages, and the like on which the semiconductor integrated circuit element is mounted to be smaller and have higher densities.

In order to satisfy the demand for miniaturization and high density of these circuit boards, it is necessary to miniaturize a conductor pattern formed on the circuit board and to multiply the conductor pattern. Therefore, for a circuit board for a hybrid IC, for example, a multilayer circuit board has been developed in which a plurality of conductive patterns are arranged on a base substrate of alumina or the like via an insulating layer mainly composed of glass.

[0004]

Further, in a multi-layer circuit board such as a hybrid IC, there is a demand for high performance and high added value as well as miniaturization and high density. Therefore, a conductor pattern mainly composed of silver, copper, or the like having a small specific resistance is disposed on the inner layer or the surface layer of the multilayer circuit board, and a thick film resistor such as ruthenium oxide is formed on the inner layer or the surface layer. Attempts have been made.

Incidentally, a multilayer circuit board such as a hybrid IC is composed of, for example, (1) a silver powder as a main component and an inorganic additive component such as glass or copper oxide on an insulating base substrate made of alumina or the like. The silver-based conductor paste is screen-printed and fired at a predetermined temperature to form a silver-based conductor pattern. (2) An insulating paste mainly composed of amorphous glass or crystallized glass is applied and baked at a predetermined temperature to form an insulating layer (insulator). (3) A resistor paste is printed and baked to form a thick film resistor. (4) A silver-based conductor paste mainly containing silver powder or an inorganic additive component, or a copper-based conductor paste mainly containing copper powder or an inorganic additive component is screen-printed to form a conductor pattern that is electrically connected to the thick film resistor. Formed and fired at a predetermined temperature. (5) A protective film made of resin, glass, or the like is formed. It is formed through such a process.

However, when manufacturing a multilayer circuit board by the above-described thick film printing method, an insulating layer (insulator) is required.
When baking is performed, silver and inorganic additive components in the silver-based conductor pattern serving as the base may diffuse into the insulating layer. Further, when the thick film resistor is baked after the formation of the insulating layer, the silver and inorganic additive components in the silver-based conductor pattern, and further, the silver and inorganic additive components diffused into the insulating layer, are diffused into the thick film resistor. May spread to.

For example, when silver diffuses into a thick film resistor mainly composed of ruthenium oxide or the like or an inorganic additive component such as glass or copper oxide diffuses, the resistance value of the thick film resistor greatly varies. Thus, a desired resistance value cannot be obtained. In particular, when a multilayer circuit board is used, since a voltage is applied to the silver-based conductor pattern and the thick-film resistor, the resistance value is likely to fluctuate over time due to diffusion of silver or the like.

By the way, if the diffusion of silver and inorganic components contained in the silver-based conductor pattern into the insulating layer can be suppressed, the variation in the resistance value of the thick film resistor can be suppressed to some extent. However, the amount of diffusion of silver and inorganic additives into the thick-film resistor varies depending on the firing conditions of the thick-film resistor and the insulating layer, the area and position of the silver-based conductor pattern, the thickness and the material of the insulating layer, and the like. Therefore, it is very difficult to control the diffusion amount to be constant.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a multi-layer circuit board having an insulating layer provided with a silver-based conductor pattern and a thick-film resistor. It is an object of the present invention to provide a highly reliable multi-layer circuit board with little change in resistance value and a method for manufacturing such a multi-layer circuit board.

[0010]

That is, the present invention relates to a multilayer circuit board having an insulating layer provided with a silver-based conductor pattern containing a silver-based conductor and an inorganic additive component and a thick-film resistor. The present invention relates to a multilayer circuit board comprising (A) silver and / or a silver compound and (B) at least one inorganic component constituting the inorganic additive component.

In the multilayer circuit board according to the present invention, the insulating layer contains the silver and / or the silver compound in an amount of 0.001 to 5% by weight in terms of metallic silver.

Further, in the multilayer circuit board according to the present invention, the inorganic component may be contained in the insulating layer in an amount of 0.00 in terms of oxide.
It is characterized by containing 0.1 to 10% by weight.

Further, in the multilayer circuit board of the present invention, the inorganic component contains a glass component.

Further, in the multilayer circuit board of the present invention, the inorganic component contains at least one metal oxide, metal ion or metal colloid selected from the group consisting of copper, chromium, bismuth and cerium. And

Further, in the multilayer circuit board of the present invention,
The thick film resistor is provided so as to face the conductor pattern via the insulating layer.

Further, the present invention provides a step of forming a silver-based conductor pattern containing a silver-based conductor and an inorganic additive component on a substrate, and forming silver and / or a silver compound on the silver-based conductor pattern. Manufacturing a multilayer circuit board, comprising: a step of forming an insulating layer containing at least one inorganic component constituting an additive component; and a step of forming a thick-film resistor on the insulating layer. It provides a method.

In the method for manufacturing a multilayer circuit board according to the present invention, the silver and / or silver compound may be added to the insulating layer.
It is characterized by containing 0.001 to 5% by weight in terms of metallic silver.

In the method of manufacturing a multilayer circuit board according to the present invention, the insulating layer contains the inorganic component in an amount of 0.001 to 10% by weight in terms of oxide.

Further, in the method for manufacturing a multilayer circuit board of the present invention, the inorganic component contains a glass component.

In the method for manufacturing a multilayer circuit board according to the present invention, the inorganic component contains at least one metal oxide, metal ion or metal colloid selected from the group consisting of copper, chromium, bismuth and cerium. It is characterized by making it.

In the method of manufacturing a multilayer circuit board according to the present invention, the thick film resistor is formed so as to face the silver-based conductor pattern via the insulating layer.

In the method for manufacturing a multilayer circuit board according to the present invention, the silver and / or silver compound and the inorganic component are added to and mixed with the amorphous glass powder and / or the crystallized glass powder, respectively. After preparing the mixed powder, the mixed powder is vitrified, and thereafter, the insulating layer is formed by firing the paste composition or the slurry composition containing the obtained glass powder. .

In the method for manufacturing a multilayer circuit board of the present invention, the first mixed powder obtained by mixing the silver and / or silver compound with the inorganic component is subjected to a heat treatment, Amorphous glass powder and / or
Alternatively, the insulating layer is formed by mixing a crystallized glass powder to form a second mixed powder, and then firing the paste-like composition or the slurry-like composition containing the second mixed powder. It is characterized by the following.

In the method for producing a multilayer circuit board according to the present invention, the silver and / or silver compound and the inorganic component are added to and mixed with the amorphous glass powder and / or the crystallized glass powder. The insulating layer is formed by firing a paste-like composition or a slurry-like composition containing the obtained mixed powder.

Further, the present invention provides an electronic component characterized by mounting components on at least one principal surface of the multilayer circuit board of the present invention, and a multilayer circuit board of the present invention or an electronic component of the present invention. The present invention provides an electronic device provided with the electronic device.

According to the multilayer circuit board of the present invention, in a multilayer circuit board having an insulating layer provided with a silver-based conductor pattern including a silver-based conductor and an inorganic additive component and a thick-film resistor, the insulating layer includes: Since silver and / or a silver compound and at least one inorganic component constituting the inorganic additive component are respectively contained, the fluctuation range of the content of silver and the inorganic additive component in the insulating layer can be minimized. Thus, the fluctuation rate of the diffusion amount of silver or the inorganic additive component into the thick film resistor can be suppressed to a minimum. Therefore, regardless of the area and position of the silver-based conductor pattern, the thickness and the material of the insulating layer, the variation of the resistance value over time due to the diffusion of the silver-based conductor and the inorganic additive component is suppressed, and the variation in the resistance value is small and the precision is high And a highly reliable multilayer circuit board provided with the thick film resistor.

Here, the inorganic additive component is a component other than the silver-based conductor added to improve various characteristics such as the adhesive strength and the temperature characteristics of the silver-based conductor pattern, and is, for example, glass, oxide, or the like. It is composed of inorganic components such as copper and chromium oxide.

Further, according to the method for manufacturing a multilayer circuit board of the present invention, a step of forming a conductor pattern containing a silver-based conductor and an inorganic additive component on a substrate, and forming silver and / or silver on the conductor pattern A step of forming an insulating layer containing a compound and at least one inorganic component constituting the inorganic additive component, and a step of forming a thick-film resistor on the insulating layer; A highly reliable multilayer circuit board having a thick film resistor can be manufactured with good reproducibility.

Further, according to the electronic component of the present invention, since at least one principal surface of the multilayer circuit board of the present invention is mounted with a chip capacitor, a chip inductor, and a mounting component such as an IC or an LSI, reliability is improved. It is an electronic component that has high performance and achieves miniaturization and high density. Further, according to the electronic device of the present invention, since the electronic device of the present invention includes the multilayer circuit board of the present invention and the electronic component of the present invention, the electronic device has high reliability and is downsized, such as a mobile communication device.

[0030]

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to Ag, Ag-Pt, A
silver-based conductor such as g-Pd as a main component, glass, copper oxide,
In a multilayer circuit board having an insulating layer including a silver-based conductor pattern containing an inorganic additive component such as chromium oxide, and a thick-film resistor mainly containing ruthenium oxide or the like, the insulating layer includes silver in advance. And / or a multilayer circuit board containing a silver compound and at least one inorganic component constituting an inorganic additive component, and a method for producing the same.

In the present invention, the silver and / or silver compound is contained in the insulating layer in an amount of 0.001 in terms of metallic silver.
-5% by weight is desirable. That is,
When the content of silver and / or silver compound in the insulating layer is 0.001 to 5% by weight, the diffusion amount of silver (including silver ions and silver colloid) in the insulating layer while maintaining high insulating properties of the insulating layer Of the thick film resistor can be sufficiently suppressed.

However, when the content of silver or silver compound in the insulating layer is less than 0.001% by weight in terms of metallic silver, the variation rate of the diffusion amount of silver in the insulating layer becomes large, and the thickness of the thick film resistor becomes large. The resistance value tends to fluctuate. On the other hand, when the content of silver or a silver compound in the insulating layer exceeds 5% by weight in terms of metallic silver, the insulating property of the insulating layer is reduced, and the reliability of the multilayer circuit board may be impaired.

The silver and / or silver compound content in the insulating layer is more desirably 0.1 to 2% by weight in terms of metallic silver. Examples of the silver compound include silver oxide, silver nitrate, and silver carbonate.

It is preferable that the insulating layer contains the inorganic component in an amount of 0.001 to 10% by weight in terms of oxide. That is, when the content of the inorganic component in the insulating layer is 0.001 to 10% by weight in terms of oxide, it is possible to minimize the variation ratio of the diffusion amount of the inorganic component in the insulating layer while maintaining high insulating properties. Accordingly, the variation of the resistance value of the thick film resistor over time can be sufficiently suppressed.

However, when the content of the inorganic component in the insulating layer is less than 0.001% by weight in terms of oxide, the variation rate of the diffusion amount of the inorganic component in the insulating layer becomes large, and the resistance of the thick film resistor becomes large. Values fluctuate easily. On the other hand, when the content of the inorganic component in the insulating layer exceeds 10% by weight in terms of oxide, the dielectric constant of the insulating layer may be increased, or interaction with the thick film resistor may occur. May cause the resistance value to fluctuate.

The content of the inorganic component in the insulating layer is more preferably 0.1 to 5% by weight in terms of oxide. Examples of the inorganic component include a glass component, copper oxide, chromium oxide, bismuth oxide, cerium oxide, lead oxide, nickel oxide, and manganese oxide.

Further, in order to sufficiently suppress the variation in the amount of diffusion of silver in the insulating layer and the variation in the amount of diffusion of the inorganic component, the content of silver and / or a silver compound contained in the insulating layer must be reduced by metallic silver. 0.001 to 5% by weight in terms of conversion, and the content of the inorganic component is 0.001 to 5% in terms of oxide.
Desirably, it is 10% by weight.

Further, in the present invention, the insulating layer
As the inorganic component, a glass component may be contained.
desirable. This glass component is, for example, SiO 2_Two-B_TwoO
_Three-PbO-based, SiO_Two-B_TwoO_Three-Bi_TwoO_ThreeSystem, SiO_Two
-B_TwoO_Three-ZnO-based, SiO _Two-B_TwoO_Three-Alkali metal
Oxide-based, etc., amorphous glass, crystallized glass
Regardless. Thus, the insulating layer mainly contains the glass component.
If it is a body, the above-mentioned silver easily diffuses over time.
However, according to the present invention, the diffusion is sufficiently suppressed.
be able to.

Further, the inorganic component in the insulating layer may include at least one metal oxide, metal ion or metal colloid selected from the group consisting of copper, chromium, bismuth and cerium. For example, copper oxide may be contained in the conductor pattern as an inorganic additive component capable of improving the adhesive strength, but copper ions and copper colloid by the copper oxide react with the glass component in the insulating layer. In addition, the resistance value of the thick film resistor tends to fluctuate.
On the other hand, according to the present invention, since the insulating layer contains a predetermined amount of at least one inorganic component constituting the inorganic additive component in advance, the resistance value of the thick film resistor over time is reduced. Variations can be sufficiently suppressed, and a highly accurate multilayer circuit board can be formed.

In the present invention, the thick film resistor may be provided so as to face the silver-based conductor pattern via the insulating layer. That is, when the silver-based conductor pattern and the thick-film resistor are arranged to face each other with the insulating layer interposed therebetween, silver and the like in the silver-based conductor pattern are easily diffused into the adjacent thick-film resistor. Resistance value variation tends to increase. In contrast, according to the present invention, since a predetermined amount of silver and an inorganic additive component are contained in the insulating layer in advance, even if silver or the like in the silver-based conductor pattern diffuses into the insulating layer, The variation ratio of the component amount of the insulating layer is minimized, so that a thick film resistor having a stable and highly accurate resistance value can be obtained, and the insulation reliability of the insulating layer can be sufficiently ensured.

In the method of manufacturing a multilayer circuit board according to the present invention, it is preferable that the insulating layer is formed by any one of the following methods (1) to (3). (1) After adding and mixing the silver and / or the silver compound and the inorganic component to the amorphous glass powder and / or the crystallized glass powder, a mixed powder is produced, and then the mixed powder is vitrified. Thereafter, the paste composition or the slurry composition containing the obtained glass powder is fired. (2) After subjecting a first mixed powder obtained by mixing the silver and / or silver compound and the inorganic component to a heat treatment, the first mixed powder is mixed with an amorphous glass powder and / or crystallized. Mixing the glass powder to produce a second mixed powder,
Thereafter, the paste-like composition or the slurry-like composition containing the second mixed powder is fired. (3) After adding and mixing the silver and / or the silver compound and the inorganic component to the amorphous glass powder and / or the crystallized glass powder, a paste composition or a slurry composition containing the obtained mixed powder. The object is fired.

The insulating layer can be manufactured by various methods as described above. However, the method shown in the above (2) is preferable because the variation in resistance can be reduced efficiently.

Next, the present invention will be described based on embodiments.

<First Embodiment: Multilayer Circuit Board and Electronic Component by Green Sheet Laminating Method> The electronic component 1 shown in FIG. 1 has insulating layers 2a, 2b, 2c, 2d, 2e, 2f,
2g and 2h are sequentially laminated, and inside thereof, silver-based inner conductor patterns 3a, 3b, 3c and 3d, thick film resistors 4a and 4b mainly containing ruthenium oxide or the like.
A mounting component such as a chip capacitor 7 and a semiconductor IC 8 is mounted on a multilayer circuit board 2 having

On one main surface of the multilayer circuit board 2,
A surface layer conductor pattern such as an electrode pad and a surface wiring is formed, and surface mount components such as a chip capacitor 7 and a semiconductor IC 8 are mounted. The surface mount components such as the chip capacitor 7 and the semiconductor IC 8 are formed on the multilayer circuit board 2.
, The via conductors 5, the inner conductor patterns 3a and 3d, and the like.

The insulating layers 2a, 2b, 2c, 2d, 2e, 2f, 2g and 2h constituting the multilayer circuit board 2
Is formed mainly of a crystallized glass material and an amorphous glass material, and further has an inorganic component such as silver and / or a silver compound, copper oxide, and chromium oxide based on the characteristic structure of the present invention. Each is contained in a predetermined amount.

Next, an example of a method for manufacturing the multilayer circuit board 2 shown in FIG. 1 will be described.

First, as a material of the insulating layers 2a to 2h, for example, alumina ceramic powder and CaO--Al ₂ O _3-
After preparing a glass powder mainly composed of SiO ₂ , 20 to 30 parts by weight of the glass powder is added to 100 parts by weight of the alumina ceramic powder and mixed. And
After adding a predetermined amount of silver and / or a silver compound and an inorganic component to the obtained mixed powder, an appropriate amount of an organic binder, a dispersant, a plasticizer, an organic solvent and the like are added, and these are mixed to form an insulator layer. Prepare ceramic slurry for use. Thereafter, the ceramic slurry for the insulating layer is formed into a sheet shape by a doctor blade method or the like to obtain a ceramic green sheet for the insulating layer.

The ceramic green sheet for an insulating layer thus obtained is provided with holes for via holes as necessary, and the holes are filled with a silver-based conductor paste or silver-based conductor powder to form via holes. A silver-based conductor pattern is formed as needed. A thick film resistor made of ruthenium oxide or the like is printed on a predetermined ceramic green sheet for an insulating layer. Then, a predetermined number of the obtained ceramic green sheets for an insulator layer are stacked in a predetermined order.

Thereafter, the stacked ceramic green sheets are pressed to form a laminate block. If necessary, the produced block may be cut into an appropriate size or a groove may be formed. Then, by firing this block at 1000 ° C. or lower, a multilayer circuit board 2 including the thick film resistors 4a and 4b and the like is obtained as shown in FIG. Then, the electronic component 1 is completed by mounting the chip capacitor 7 and the semiconductor IC 8 and printing the thick film resistor 9.

That is, in the multilayer circuit board 2, silver or an inorganic additive component due to a silver-based inner conductor pattern, a silver-based surface conductor pattern, or the like is added to the insulating layers 2 a, 2 b, 2 c, 2 d, 2.
e, 2f, 2g, and 2h, even if they diffuse into the insulating layers, since these insulating layers contain the above-mentioned predetermined amount of silver and inorganic components, the amount of silver components in the insulating layers, The variation width of the amount of the inorganic component can be reduced.

Then, the fluctuation width of the silver diffusion amount and the fluctuation width of the inorganic component diffusion amount into the thick film resistors 4a, 4b and 9 provided adjacent to the insulating layer can be suppressed to a minimum.
Regardless of the variation in the amount of diffusion due to the firing conditions, the area of the silver-based conductor pattern and its formation position, the thickness of the insulator layer, etc. High-precision thick film resistors 4a, 4b and 9 can be formed.

Further, like the multilayer circuit board 2 according to the present embodiment, the thick film resistor 4a may be provided to face the silver-based conductor pattern 3a with the insulating layer 2b interposed therebetween. When the silver-based conductor pattern and the thick-film resistor are disposed to face each other with the insulating layer interposed therebetween, the rate of change in the resistance of the thick-film resistor due to component diffusion in the silver-based conductor pattern tends to be particularly large. However, according to the present embodiment, since the insulating layer 2b contains the above-described amounts of silver and the inorganic additive component, silver and other components in the silver-based conductor pattern 3a are not included in the insulating layer 2b.
Even if it diffuses into the insulating layer 2b, it is possible to obtain a thick-film resistor having a stable and high-precision resistance value while minimizing the variation ratio of the component amount of the insulating layer 2b, and at the same time, to improve the insulation reliability of the insulating layer. Nature can be sufficiently secured.

The insulating layer 2 forming the multilayer circuit board 2
a, 2b, 2c, 2d, 2e, 2f, 2g and 2h
May be a glass-ceramic layer mainly composed of amorphous glass or crystallized glass. That is, the diffusion rate of silver or the like is high in the glass ceramic layer, and therefore, the resistance value of the thick film resistor is particularly likely to vary. However, even in such a case, when the glass ceramic layer contains the silver and / or silver compound and the inorganic component in the above-described amounts, respectively, the thick film resistor having a stable and highly accurate resistance value. And at the same time,
The insulating property of the glass ceramic layer can be sufficiently ensured.

The silver-based inner conductor pattern or surface pattern may be a conductor pattern mainly composed of Ag alone, but is a conductor pattern mainly composed of Ag-Pd, Ag-Pt or the like. Is also good. In such a case,
This is because a change in the resistance value of the thick film resistor due to diffusion of silver or the like is recognized. Further, the silver-based conductor pattern can be formed by, for example, printing and firing a silver-based conductor paste,
The silver-based conductor paste may contain a glass frit, a ceramic filler, and the like, in addition to a conductor material such as Ag, Ag-Pd, and Ag-Pt, an organic binder and an organic solvent.

Then, as described above, the multilayer circuit board 2
Insulation of each insulating layer can be improved, and the fluctuation of the resistance value of each thick film resistor can be suppressed. An excellent, compact and high-density electronic component 1 can be achieved.

In the present embodiment, it is not necessary for all the insulating layers constituting the multilayer circuit board to contain the above-mentioned amount of silver or inorganic component. Layer (here, insulating layer 2
b, 2c, 2f and 2g) may contain the above-mentioned amount of silver and the above-mentioned amount of inorganic component.

<Second Embodiment: Multilayer Circuit Board and Electronic Component by Thick Film Printing> Electronic component 21 shown in FIG.
A base substrate 11 made of alumina or the like, first insulating layers 14a and 14b made of amorphous glass, crystallized glass or the like provided on both upper and lower main surfaces thereof, and a first insulating layer 14a
And 14b, the second insulating layers 18a and 18b provided on the multilayer circuit board 22, respectively.
A mounting component 20 such as a capacitor, a coil, and a semiconductor IC is mounted thereon.

The base substrate 11 is provided with via holes 12 in which through-holes for via holes are filled with a conductive material containing a silver-based conductor as a main component. First containing conductor and inorganic additive component
Conductor patterns 13a and 13b are provided respectively.

The first insulating layers 14a and 14b are provided with through holes for via holes in advance.
Via holes 15a and 15b filled with a conductor material mainly composed of a silver-based conductor are provided in the through holes for via holes, and the first insulating layers 14a and 14b are further provided.
b, the thick film resistors 16a and 16b made of, for example, ruthenium oxide and the like, and the thick film resistors 16a
Second conductor patterns 17a and 17b, which are electrically connected to the first and second conductor patterns 16b and 16b, respectively, are provided.

In this multi-layer circuit board 22, a mounting component 20 such as a capacitor, a coil, and a semiconductor IC is mounted on the surface of the second insulating layer 18a. Through the second conductor pattern.

Next, an example of a method for manufacturing the multilayer circuit board 22 shown in FIG. 2 will be described.

First, the base substrate 11 is prepared. As the base substrate 11, for example, an alumina fired plate or a low-temperature fired ceramic plate having a thickness of about 0.5 mm can be used. Next, after a through hole for a via hole is formed in the base substrate 11 by punching, laser processing, or the like, the through hole for the via hole is filled with a conductor material mainly composed of a silver-based conductor, and fired in air at about 850 ° C. By doing so, a via hole 12 is formed.

Next, a conductor paste containing a silver-based conductor and an inorganic additive component is screen-printed on the upper and lower main surfaces of the base substrate 11 and is similarly baked at about 850 ° C. in the air to form the first paste. Conductor patterns 13a and 1
3b is formed.

Next, on both main surfaces of the base substrate 11 on which the first conductor patterns 13a and 13b are formed, silver, a silver compound, and other inorganic components are mainly composed of crystallized glass or amorphous glass. The first insulating layers 14a and 14b having through holes for via holes are provided by screen-printing the containing insulating paste, and the through holes for via holes are further filled with a conductive material mainly containing a silver-based conductor,
This is baked at about 850 ° C. in the air to form a first insulating layer 14 having via holes 15a and 15b.
a and 14b are formed.

Next, the first insulating layers 14a and 14b
A thick paste resistor 16a and 16b is formed by screen-printing a resistor paste mainly containing ruthenium oxide or the like on the surface of the substrate and baking it at about 850 ° C. in the air. Further, the first insulating layer 14
The second conductor patterns 17a and 17b are formed on the surfaces of the conductor patterns a and 14b by screen-printing a conductor paste containing a silver-based conductor and an inorganic additive component, followed by firing at about 750 ° C. in air. Furthermore, the first
The surface of the insulating layers 14a and 14b is screen printed with an insulating paste mainly composed of amorphous glass or crystallized glass to form the thick film resistor 16a formed earlier.
And 16b, second conductor patterns 17a and 17b
Insulating layers (protective films) 18a and 18b for protecting
Is formed, and a multilayer circuit board 22 is manufactured.

Then, after the solder (for example, cream solder) is arranged at a predetermined position on the second insulating layer 18a, the mounted component 20 is mounted, and the mounted component 20 is reflowed. And the second conductor pattern 1
7a to complete the electronic component 21 shown in FIG.

That is, in the multilayer circuit board 22 according to the present embodiment, even when silver or an inorganic additive component due to the silver-based inner conductor pattern or the silver-based surface conductor pattern diffuses into the insulating layers 14a and 14b. Since these insulating layers contain the above-mentioned predetermined amounts of silver and inorganic components, it is possible to reduce the fluctuation range of the amounts of silver components and inorganic components in the insulating layers.

That is, the fluctuation width of the silver diffusion amount and the fluctuation width of the inorganic component diffusion amount into the thick film resistors 16a and 16b provided adjacent to the insulating layers 14a and 14b can be suppressed to a minimum. , Regardless of the diffusion amount variation due to the firing conditions, the area of the silver-based conductor pattern and its formation position, the thickness of the insulator layer, and the like, and further, regardless of the diffusion amount variation over time during use. It is possible to form the high-precision thick film resistors 16a and 16b having the following.

The multilayer circuit board 21 according to the present embodiment
In, the thick film resistor 16a is provided to face the silver-based conductor pattern 13a with the insulating layer 14a interposed therebetween.
Since a predetermined amount of silver and an inorganic component are contained in the insulating layer 14a, even if silver and other components in the silver-based conductor pattern 13a diffuse into the insulating layer 14a, the insulating layer 14a
And the thick film resistor 16a having a stable and highly accurate resistance value can be obtained, and the insulation reliability of the insulating layer 14a can be sufficiently ensured.

Then, as described above, the multilayer circuit board 2
2 can improve the insulating properties of each insulating layer and suppress the fluctuation of the resistance value of each thick film resistor, so that it can sufficiently cope with the thinning of the insulating layer and the high density of the conductor pattern, And a small and high-density electronic component 21 can be achieved.

In the present embodiment, the above-mentioned amounts of silver and inorganic components may be contained in the insulating layers 18a and 18b of the multilayer circuit board 22.

While the present invention has been described based on specific multilayer circuit boards and electronic components, the present invention is limited to the electronic component 1 formed by the above-described green sheet lamination method and the electronic component 21 formed by the thick film printing method. It is not something to be done. The electronic components of the present invention include, for example, high-frequency circuit electronic components such as chip capacitors and chip LC filters, as well as VCOs (Volt
age Controlled Oscillator) and PLL (Phase Locked)
Electronic components such as a high-frequency module such as a loop), a substrate for a multichip module, and a substrate for an IC package. Further, the insulating layer in the multilayer circuit board is not limited to the insulating layer made of ceramic, but may be an insulating layer made of resin.

[0074]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below with reference to specific embodiments.

Example 1 Multilayer Circuit Board by Thick Film Printing <Conductor Paste> SiO ₂ , H ₃ BO ₃ , ZnO, Bi as starting materials for glass powder to be added to the conductor paste
_After preparing ₂ O ₃ and PbO, respectively, and mixing them so as to have the composition shown in Table 1 below, the obtained mixture was mixed with 1100
It was melted at a temperature of ° C to produce a molten glass. And
This molten glass was put into pure water, rapidly cooled, and then pulverized to obtain glass powders represented by glass numbers 1-2 in Table 1 below.

[0076]

[Table 1]

Next, Cu powder, Cr ₂ O ₃ powder, Bi ₂ O ₃ powder and C ₂ O ₃ powder were added to the glass powders of glass numbers 1 and 2 and the Ag powder so that the compositions shown in Table 2 below were obtained.
adding an inorganic powder consisting of eO ₂ powder, it was mixed to prepare a conductor composition represented by the conductor composition numbers 1-2. Then, to 85 parts by weight of the obtained conductor composition, 15 parts by weight of an organic vehicle obtained by dissolving an ethylcellulose-based resin in α-terpineol was added and kneaded to prepare an Ag-based conductor paste.

[0078]

[Table 2]

<Insulating Paste> SiO ₂ , MgCO ₃ , CaCO ₃ , H ₃ B are used as starting materials for insulating paste glass.
O ₃ and K ₂ CO ₃ were prepared and mixed to obtain the composition shown in Table 3 below.
Melting was performed at a temperature of 0 ° C. to produce a molten glass. Then, the molten glass was put into pure water, rapidly cooled, and then pulverized to obtain a glass powder represented by glass number 3 in Table 3 below.

[0080]

[Table 3]

On the other hand, glass numbers 1 to 3 shown in Tables 2 to 3
Glass powder, Ag powder, CuO powder, Cr ₂ O ₃ powder,
A Bi ₂ O ₃ powder and a CeO ₂ powder were prepared, respectively, and were mixed so as to have the composition shown in Table 4 below. Then, the obtained mixture was melted at a temperature of 1600 ° C. to produce a molten glass. Next, the molten glass was put into pure water, rapidly cooled, and then pulverized to obtain a glass number 4 to 17 in Table 4 below.
Was prepared.

[0082]

[Table 4]

Further, glass powders of glass numbers 1 and 2 shown in Table 2, Ag powder, CuO powder, Cr ₂ O ₃ powder,
After preparing i ₂ O ₃ powder and CeO ₂ powder, respectively, and mixing them so as to have the composition shown in Table 5 below, the resulting mixture was heat-treated at a temperature of 1000 ° C., and pulverized. Inorganic powders having the compositions indicated by No. 1 and No. 2 were prepared.

[0084]

[Table 5]

Then, glass powders having glass numbers 3 to 17, inorganic powders having inorganic powder numbers 1 and 2, metal Ag powder, C
The uO powder, the Cr ₂ O ₃ powder, the Bi ₂ O ₃ powder, and the CeO ₂ powder are mixed so as to have the compositions shown in Tables 6 to 7 below, thereby producing insulating compositions represented by insulating composition numbers 1 to 31. did. Then, to 60 parts by weight of the obtained insulating composition, 40 parts by weight of an organic vehicle obtained by dissolving an ethylcellulose-based resin in α-terpineol was added and kneaded to prepare an insulating paste.

The “addition forms of additives” in Tables 6 and 7 below indicate that an insulating paste (insulating composition No. 1) made of only glass No. 3 without Ag powder or other inorganic powders was used. ) Is a glass powder obtained by adding Ag powder or other inorganic powder to glass powder of glass No. 3 and melting and vitrifying them.
17) (insulating composition numbers 2-1)
3, 27-28) is to add and mix glass powder of glass No. 3 with glass powder of glass No. 1-2, Ag powder, and inorganic powder obtained by heat-treating other inorganic powder (inorganic powder No. 1-2). An insulating paste (insulating composition Nos. 14, 29) using this as an insulating composition is obtained by adding and mixing Ag powder or other inorganic powder to glass powder of glass No. 3, Means insulating pastes (insulating composition numbers 14 to 26, 30 to 31), respectively.

[0087]

[Table 6]

[0088]

[Table 7]

Next, an Ag-based conductor paste containing the conductor compositions of the conductor composition numbers 1 and 2 as a main component and an insulating glass paste containing the insulation composition of the insulation composition numbers 1 to 31 as a main component were used. By printing and firing in the combinations shown in Table 9 below, the multilayer circuit boards A to E having the configurations shown in FIGS.
Was prepared. Hereinafter, the multilayer circuit boards A to E will be described with reference to FIGS.

(1) Multilayer circuit board A First, an alumina substrate having a thickness of 0.635 mm is prepared as the insulating substrate 31a, and the insulating glass paste prepared above is screen-printed thereon, and then is heated at 850 ° C. in air.
To form an insulating layer 32a. Next, after the Ag-based conductor paste prepared above was screen-printed, it was baked at 850 ° C. in air to form an upper-layer conductor pattern 33a. Here, the upper conductor pattern 33a is a terminal electrode with a spacing of 1 mm for forming a thick film resistor.

Then, a resistor paste is applied so as to overlap with 0.5 mm on both sides of the upper conductor pattern 33a, and then fired to form a 1 mm square thick film resistor 34a.
Was formed to produce a multilayer circuit board A shown in FIG. As the resistor paste, a Ru-based resistor paste having a nominal sheet resistance value of 100Ω / □ and 10KΩ / □ was used.

(2) Multilayer Circuit Board B First, an alumina substrate having a thickness of 0.635 mm is prepared as the insulating substrate 31b, and an Ag-based conductor paste is screen-printed thereon, and then fired at 850 ° C. in air. The lower conductor pattern 35b was formed. Here, the lower conductor pattern 35b was a 10 mm square electrode. Thereafter, the insulating glass paste prepared above was screen-printed on the lower conductive pattern 35b, and fired at 850 ° C. in air to form the insulating layer 32b. Next, after the Ag-based conductor paste is screen-printed, it is baked at 850 ° C. in air,
Similarly, an Ag-based upper conductor pattern 33b was formed. Here, the upper conductor pattern 33b is a terminal electrode with a spacing of 1 mm for forming a thick film resistor.

Then, after a resistor paste is applied so as to overlap 0.5 mm on both sides of the upper conductor pattern 33b, it is baked and baked to form a 1 mm square thick film resistor 34b.
Was formed to produce a multilayer circuit board B shown in FIG. As the resistor paste, the same Ru-based resistor paste as described above was used.

(3) Multilayer Circuit Board C First, an alumina substrate having a thickness of 0.635 mm is prepared as the insulating substrate 31c, and an Ag-based conductor paste is screen-printed thereon, and then fired at 850 ° C. in air. The lower conductor pattern 35c was formed. Here, the lower conductor pattern 35c was a line of 100 μm width at an interval of 150 μm. After that, the insulating glass paste prepared above is screen-printed on the lower conductor pattern 35c, and the screen is printed in air.
By baking at 0 ° C., an insulating layer 32c was formed. Then Ag
After screen printing the system conductor paste, in air, 85
The upper conductor pattern 33c was formed by firing at 0 ° C.
Here, the upper conductor pattern 33c is a terminal electrode with an interval of 1 mm for forming a thick film resistor.

Then, after a resistor paste is applied so as to overlap 0.5 mm on both sides of the upper conductor pattern 33c, it is baked, and is fired to form a 1 mm square thick film resistor 34c.
Was formed to produce a multilayer circuit board C shown in FIG. As the resistor paste, the same Ru-based resistor paste as described above was used.

(4) Multilayer Circuit Board D First, an alumina substrate having a thickness of 0.635 mm was prepared as the insulating substrate 31d. Next, the insulating glass paste prepared earlier is screen-printed on the insulating substrate 31d,
The resultant was fired at 850 ° C. in the air to form an insulating layer 32d.
Next, after screen printing the Ag-based conductor paste,
The upper conductor pattern 35d was formed by firing at 850 ° C. in the air. Here, the lower conductor pattern 35d is 1 m apart.
m terminal electrode and a 500 μm wide line electrode formed at a distance of 200 μm in parallel with the terminal electrode.

Subsequently, a paste for resistor was applied so as to overlap 0.5 mm on both sides of the upper conductor pattern 33d, and then baked to obtain a thick film resistor 3 of 1 mm square.
4D was formed to produce a multilayer circuit board D shown in FIG. As the resistor paste, the same Ru-based resistor paste as described above was used.

(5) Multilayer Circuit Board E First, an alumina substrate having a thickness of 0.635 mm is prepared as the insulating substrate 31e, and an Ag-based conductor paste is screen-printed thereon, and then fired at 850 ° C. in air. A lower conductor pattern 35e was formed. The lower conductor pattern 35e has a diameter of 8 for one electrode of the capacitor.
mm disk-shaped electrode. Next, the conductor pattern 35e
The above-prepared insulating glass paste was screen-printed thereon and fired at 850 ° C. in air to form an insulating layer 32e. Next, after the Ag-based conductor paste was screen-printed, it was baked at 850 ° C. in air to form an Ag-based upper layer conductor pattern 33e, thereby producing a multilayer circuit board E shown in FIG. Here, the conductor pattern 33e has a guard electrode 3 around 500 μm as the other electrode of the capacitor.
6 is a disk-shaped electrode with a diameter of 4 mm.

As described above, five types of multilayer circuit boards were completed by the thick film printing method. In addition, the multilayer circuit boards A to
D is a multilayer circuit board for evaluating a resistance value, and multilayer circuit board E is a multilayer circuit board for evaluating insulation resistance and relative permittivity.

Next, the resistance change rates of the thick film resistors 34a to 34d of the multilayer circuit boards A to D were measured. Here, the upper-layer conductor patterns 33a to 33d are measured with a tester, so that the thick-film resistor 3 of the multilayer circuit board A is measured.
Multilayer circuit boards B and C when resistance value of 4a is used as a reference value
Thick film resistors 34b, 34c and 34 in FIGS.
The rate of change in resistance value of d was determined.

On the other hand, with respect to the multilayer circuit board E, the insulating layer 3
The insulation reliability of 2e was measured. Here, the guard electrode 3
The guard is taken at 6 and 100 ° C between the conductor pattern 35e and the conductor pattern 33e under the condition of 85 ° C. and 85% RH.
After applying a voltage of 1000 V for 1000 hours,
After applying for one minute, the insulation resistance (LogIR) was measured.

Further, with respect to the multilayer circuit board E, the capacitance value and the film thickness of the insulating layer 32e were measured and converted into a relative dielectric constant.
Here, a guard is provided by the guard electrode 36, and the temperature is 25 ° C.
Under the condition of MHz, the capacitance value was measured between the conductor pattern 35e and the conductor pattern 33e using an LCR meter. The thickness of the insulating layer 32e provided between the conductor pattern 35e and the conductor pattern 33e was measured by using a metal microscope from a cross section of the insulation layer 32e. Then, the relative dielectric constant was determined from the capacitance value, the film thickness, and the electrode area.

Table 8 below shows the measurement results of the resistance change rates of the multilayer circuit boards A to D, the insulation reliability of the multilayer circuit board E, and the relative dielectric constant using the insulating compositions of the insulating composition numbers 1 to 31.
(Examples 1 to 32).

[0104]

[Table 8]

From Table 8, Examples 4 to 10, Example 14, and Examples 17 to
23, as in Examples 28 to 32, the insulating layer provided with the Ag-based conductor pattern and the thick-film resistor contains 0.001 to 5% by weight of Ag powder in terms of the amount of metallic Ag, and A multilayer circuit board containing at least one or more inorganic powders other than Ag in the conductor paste, the total of which is 0.001 to 10% by weight in terms of oxide, has a high insulation resistance of the insulating layer, and It was found that the dielectric constant was low and the rate of change in resistance of the thick film resistor was small. That is, in a multilayer circuit board having an Ag-based conductor pattern, a stable and highly accurate resistor can be formed without impairing the insulation reliability of the insulating layer and without significantly increasing the relative permittivity. Was.

Further, when Examples 6, 14, 19, and 29 to 30 in which the addition form of the additive was changed were compared,
When adding inorganic powders other than Ag in the g powder and the conductor paste, these additives were heat-treated in advance, and the insulating composition obtained by adding the additives to the glass powder was able to suppress the rate of change of the resistance value extremely efficiently. I understand.

On the other hand, Examples 1 to 3, Examples 15 to 16,
As in Example 27, the amount of Ag powder in the insulating layer was less than 0.001% by weight in terms of the amount of metallic Ag, or the total amount of inorganic powders other than Ag in the conductive paste was 0.001% in terms of oxide. When the content is less than 10% by weight, the insulation resistance is excellent and a low dielectric constant can be obtained, but the resistance value of the thick film resistor changes, and the obtained resistance value varies.

When the amount of Ag powder in the insulating layer exceeds 5% by weight as in Examples 11, 13, 24 and 26, the rate of change in the resistance of the thick film resistor can be suppressed, but the insulation resistance is reduced. As a result, the insulation reliability was reduced. Also, as in Examples 12 and 25, when the inorganic component other than Ag in the conductor paste exceeded 10% by weight in terms of oxide, the relative dielectric constant of the insulating layer exceeded 10.

Example 2: Multi-layering by a green sheet laminating method
Layer Circuit Board <Conductor Paste> First, in the same manner as in Example 1, the glass powders (glass numbers 1 and 2) shown in Table 1 described above were obtained.
In the same manner as in Example 1, a conductor paste containing the conductor compositions (conductor composition numbers 1 and 2) shown in Table 2 as main components was prepared.

<Ceramic Green Sheet> First, in the same manner as in Example 1, the above-mentioned glass powders (glass numbers 3 to 17) shown in Tables 3 and 4 were obtained. Further, in the same manner as in Example 1, the above-mentioned inorganic powders (inorganic powder numbers 1-2) shown in Table 5 were obtained.

Next, glass powders of glass numbers 3 to 17, inorganic powders of inorganic powder numbers 1 and 2, metal Ag powder, C
The uO powder, the Cr ₂ O ₃ powder, the Bi ₂ O ₃ powder, and the CeO ₂ powder are mixed so as to have the compositions shown in Tables 6 to 7 above to form insulating compositions represented by Sample Nos. 1 to 31. did. Further, a predetermined amount of an organic binder and a solvent (toluene) were added to the obtained insulating composition, mixed and kneaded sufficiently with a ball mill,
After uniformly dispersing, defoaming was performed under reduced pressure to prepare a green sheet slurry.

Then, the obtained green sheet slurry was applied to a thickness of 0.1 mm on a carrier film by a casting method using a doctor blade, dried, and then peeled off from the carrier film. A 100 μm ceramic green sheet was produced.

The Ag-based conductor patterns of the conductor paste numbers 1 and 2 were placed on ceramic green sheets made of the insulation compositions of the insulation composition numbers 1 to 31, respectively, as shown in Tables 9-1 below.
0 was printed. Thereafter, a plurality of ceramic green sheets having an Ag-based conductor pattern are laminated,
The multi-layer circuit boards a to e shown in FIGS. Hereinafter, the configurations of the multilayer circuit boards a to e will be described with reference to FIGS.

(1) Multilayer Circuit Board a An Ag-based conductor paste was screen-printed on the ceramic green sheet prepared above, and further a resistor paste was printed. Next, after these are pressed, 500
The mixture was degreased for 1 hour at a temperature of 50 ° C./min, and then baked at 850 ° C. for 10 minutes.

Then, as shown in FIG. 5A, an insulating layer 41a formed by firing a ceramic green sheet is placed on the insulating layer 41a.
A multilayer circuit board a having a conductor pattern 42a made of an Ag-based conductor paste and a thick film resistor 44a made of a resistor paste was obtained.

Note that the conductor pattern 42a is a terminal electrode with a spacing of 1 mm for forming a thick film resistor. The thick film resistor 44a is a 1 mm square thick film resistor formed so as to overlap 0.5 mm on both sides of the conductor pattern 42a, and has a nominal sheet resistance of 100Ω / □,
It was formed by using a Ru-based resistor paste of 0 KΩ / □.

(2) Multilayer circuit board b First, A was placed on the previously prepared ceramic green sheet.
After screen printing the g-based conductor paste, similar ceramic green sheets were stacked. Next, A
After screen printing of the g-based conductor paste, the resistor paste was printed. Then, after crimping these,
Degreasing treatment was performed at 500 ° C. for 1 hour, and the temperature was increased at 50 ° C./min.

Then, as shown in FIG. 5B, the insulating layer 41b formed by firing the ceramic green sheets is
A multilayer circuit board b having a lower conductor pattern 43b made of an Ag-based conductor paste and having an upper conductor pattern 42b made of an Ag-based conductor paste and a thick film resistor 44b made of a resistor paste is formed on the insulating layer 41b. Was.

The lower conductor pattern 43b has a thickness of 10 mm.
The upper conductor pattern 42b is a square-shaped electrode, and is a terminal electrode with an interval of 1 mm for forming a thick-film resistor. The thick-film resistor 44b is a 1-mm square thick-film resistor formed so as to overlap 0.5 mm on both sides of the conductor pattern 42b, and is formed using the same resistor paste as described above.

(3) Multilayer circuit board c First, A was placed on the previously prepared ceramic green sheet.
After screen printing the g-based conductor paste, similar ceramic green sheets were stacked. Next, A
After screen printing of the g-based conductor paste, the resistor paste was printed. Then, after crimping these,
Degreasing treatment was performed at 500 ° C. for 1 hour, and the temperature was increased at 50 ° C./min.

Then, as shown in FIG. 5C, the insulating layer 41c formed by firing the ceramic green sheet is placed inside the insulating layer 41c.
The multilayer circuit board c has a lower conductor pattern 43c made of an Ag-based conductor paste, and has an upper conductor pattern 42c made of an Ag-based conductor paste and a thick film resistor 44c made of a resistor paste on the insulating layer 41c. .

The lower conductor pattern 43c has a size of 150 μm.
It is a line electrode having an interval of m and a width of 100 μm, and the upper conductor pattern 42c has an interval of 1 mm for forming a thick film resistor.
Terminal electrode. The thick film resistor 44c is
It is a 1 mm square thick film resistor formed so as to overlap 0.5 mm on both sides of the conductor pattern 42c, and was formed using the same resistor paste as described above.

(4) Multilayer circuit board d First, A was placed on the previously prepared ceramic green sheet.
The g-based conductor paste was screen-printed, and further a resistor paste was printed. Subsequently, after they were pressed, they were degreased at 500 ° C. for 1 hour, and were further heated at 50 ° C./minute and baked at 850 ° C. for 10 minutes.

Then, as shown in FIG. 5D, an insulating layer 41d obtained by firing a ceramic green sheet is placed on the insulating layer 41d.
A multilayer circuit board d including an upper conductor pattern 42d made of an Ag-based conductor paste and a thick film resistor 44d made of a resistor paste was obtained.

The conductor pattern 42d is a terminal electrode having a spacing of 1 mm and a line electrode having a width of 500 μm formed in parallel with the terminal electrode at a spacing of 200 μm. The thick-film resistor 44d is connected to the conductor pattern 42d.
Is a 1 mm square thick film resistor superimposed on both sides of 0.5 mm, and formed using the same resistor paste as described above.

(5) Multilayer circuit board e First, A was placed on the ceramic green sheet prepared earlier.
After screen printing the g-based conductor paste, similar ceramic green sheets were stacked. Next, A
After screen printing of the g-based conductor paste, the resistor paste was printed. Furthermore, on top of this, SiO ₂ —B ₂ O
An insulating paste containing ₃ -alkali metal oxide-based glass as a main component was printed. Then, after crimping these, 50
After degreasing at 0 ° C. for 1 hour, the temperature was raised at 50 ° C./min, and calcination was performed at 850 ° C. for 10 minutes.

Then, as shown in FIG. 5 (E), the insulating layer 41e formed by firing the ceramic green sheet is placed inside the insulating layer 41e.
It has a lower conductor pattern 43e made of an Ag-based conductor paste, and an upper conductor pattern 42e made of an Ag-based conductor paste, a thick film resistor 44e made of a resistor paste, and an insulating layer made of an insulating paste are formed on the insulating layer 41e. 45 is a multilayer circuit board e including

The lower conductor pattern 43e is 10 mm
The upper layer conductor pattern 42e is a terminal electrode with a 1 mm interval for forming a thick film resistor. The thick-film resistor 44e is a 1-mm square thick-film resistor superimposed on 0.5 mm on both sides of the conductor pattern 42e, and is formed using the same resistor paste as described above.

(6) Multilayer circuit board f First, A was placed on the previously prepared ceramic green sheet.
After the g-based conductor paste was screen-printed, the same ceramic green sheets were stacked thereon, and the Ag-based conductor paste was also screen-printed. Subsequently, after they were pressed, they were degreased at 500 ° C. for 1 hour, and were further heated at 50 ° C./minute and baked at 850 ° C. for 10 minutes.

Then, as shown in FIG. 6, a conductor pattern 4 having a diameter of 8 mm for one electrode of a capacitor is formed on an insulating layer 46f formed by firing a ceramic green sheet.
3f, an insulating layer 41f of a ceramic green sheet,
This is a multilayer circuit board f provided with a conductor pattern 22f having a diameter of 4 mm and having a guard electrode 47 around 500 μm as the other electrode of the capacitor.

As described above, six types of multilayer circuit boards were completed by the green sheet laminating method. The multilayer circuit boards a to e are multilayer circuit boards for evaluating a resistance value, and the multilayer circuit board f is a multilayer circuit board for evaluating an insulation resistance and a relative dielectric constant.

Next, the resistance change rates of the thick film resistors 44a to 44e were measured for the multilayer circuit boards a to e. Here, the upper-layer conductor patterns 42a to 42e are measured by a tester, so that the thick-film resistor 4 of the multilayer circuit board a is measured.
A multilayer circuit board b using the resistance value of 4a as a reference value,
Thick film resistors 44b, 44c, 4 in c, d and e
The resistance change rates of 4d and 44e were determined.

On the other hand, for the multilayer circuit board f, the insulating layer 4
The insulation reliability of 1f was measured. Here, the guard electrode 4
7, a guard is provided between the conductor pattern 43f and the conductor pattern 42f under the conditions of 85 ° C. and 85% RH.
After applying a voltage of 1000 V for 1000 hours,
After applying for one minute, the insulation resistance (LogIR) was measured.

Further, with respect to the multilayer circuit board f, the capacitance value and the film thickness of the insulating layer 41f were measured and converted into the relative permittivity.
Here, a guard is provided by a guard electrode 47, and the temperature is controlled at 25 ° C., 1
Under the condition of MHz, the capacitance value was measured between the conductor pattern 43f and the conductor pattern 42f using an LCR meter. The thickness of the insulating layer 41f provided between the conductor pattern 43f and the conductor pattern 24f was measured by breaking it and measuring its cross section with a metallographic microscope. Then, the relative dielectric constant was determined from the capacitance value, the film thickness, and the electrode area.

The following table shows the measurement results of the resistance change rate of various multilayer circuit boards using the insulating compositions represented by the insulating composition numbers 1 to 31, the insulation reliability of the multilayer circuit board f, and the relative dielectric constant. 9 to 10 (Examples 33 to 64).

[0136]

[Table 9]

[0137]

[Table 10]

From Tables 9 to 10, Examples 36 to 42, Example 46,
As in Examples 49 to 55 and Examples 60 to 64, the insulating layer provided with the Ag-based conductor pattern and the thick film resistor contains 0.001 to 5% by weight of Ag powder in terms of the amount of metal Ag. The multilayer circuit board in which the total amount of inorganic powders other than Ag in the conductor pattern is 0.001 to 10% by weight in terms of oxide has a high insulation resistance of the insulating layer and a low insulation resistance. It was found that it was a dielectric constant and the rate of change in resistance of the thick film resistor was small. That is, in a multilayer circuit board having an Ag-based conductor pattern, a stable and highly accurate resistor can be formed without impairing the insulation reliability of the insulating layer and without significantly increasing the relative permittivity. Was.

Further, Example 38 in which the addition form of the additive was changed,
Comparing Example 46, Example 51, and Example 61 to Example 62, when Ag powder and other inorganic powders are added, it is more efficient to add these inorganic powders which have been heat-treated in advance to the glass powder, more efficiently. It can be seen that the rate of change of was able to be suppressed.

On the other hand, Examples 33 to 35 and Examples 47 to 4
8. As in Example 59, the amount of Ag powder in the insulating layer is less than 0.001% by weight in terms of the amount of metallic Ag, or the total of inorganic powders other than Ag in the conductive paste is 0.
When the content is less than 001% by weight, the insulation resistance is excellent and a low dielectric constant can be obtained, but the resistance value of the thick film resistor changes, and the obtained resistance value largely varies.

When the amount of Ag powder in the insulating layer exceeds 5% by weight as in Examples 43, 45, 56 and 58, the rate of change in the resistance of the thick film resistor can be suppressed, but the insulation resistance is reduced. As a result, the insulation reliability was reduced. Also, as in Examples 44 and 57, when the amount of inorganic powder other than Ag in the conductor paste in the insulating layer exceeds 10% by weight in terms of oxide, the relative dielectric constant of the insulating layer exceeds 10. Was.

As is clear from Tables 8 to 10, in particular, the insulating layer contains 0.001 to 5% by weight of Ag powder in terms of the amount of metallic Ag, The total amount of inorganic powders other than Ag is 0.
001 to 10% by weight, the thick film printing method and the green sheet laminating method do not impair the insulation reliability of the insulating layer and increase the relative dielectric constant to 10 or more. Thus, a thick film resistor having a stable resistance value within a change rate of ± 10% was able to be formed.

That is, when a thick film resistor is formed on a multilayer circuit board having an Ag-based conductor pattern, the precision is high regardless of the diffusion amount of the Ag electrode component due to the area and position of the conductor pattern and the thickness of the insulating layer. A thick film resistor having a resistance value could be formed.

[0144]

According to the multilayer circuit board of the present invention, in a multilayer circuit board having an insulating layer provided with a conductor pattern containing a silver-based conductor and an inorganic additive component and a thick film resistor, (A) silver and / or a silver compound, (B)
Since at least one inorganic component constituting the inorganic additive component is contained, variation in the content of silver and the inorganic additive component in the insulating layer is minimized, and silver and inorganic components in the thick film resistor are minimized. The fluctuation rate of the diffusion amount of the additive component can be suppressed to the minimum. Therefore, regardless of the area and formation position of the silver-based conductor pattern, the thickness and the material of the insulating layer, the variation of the resistance value over time due to the diffusion of the silver-based conductor and the inorganic additive component is suppressed, and a high-precision thick film resistor is formed. A highly reliable multi-layer circuit board having the same can be obtained.

According to the method for manufacturing a multilayer circuit board of the present invention, a step of forming a conductor pattern containing a silver-based conductor and an inorganic additive component on a substrate, and a step of forming a silver and / or silver compound on the conductor pattern A step of forming an insulating layer containing at least one inorganic component constituting the inorganic additive component, and a step of forming a thick-film resistor on the insulating layer, so that a high-precision thick film A highly reliable multilayer circuit board having a resistor can be manufactured with good reproducibility.

According to the electronic component of the present invention, since at least one principal surface of the multilayer circuit board of the present invention has mounted thereon a chip capacitor, a chip inductor, and a mounted component such as an IC or LSI, the reliability is improved. It is an electronic component that is high and has achieved miniaturization and high density. Further, according to the electronic device of the present invention, since the electronic device of the present invention includes the multilayer circuit board of the present invention and the electronic component of the present invention, the electronic device has high reliability and is downsized, such as a mobile communication device.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view of a multilayer circuit board (green sheet laminating method) according to a first embodiment of the present invention.

FIG. 2 is a schematic sectional view of a multilayer circuit board (thick film printing) according to a second embodiment of the present invention.

FIG. 3 is a schematic cross-sectional view of a multilayer circuit board (thick film printing method) for evaluating a resistance value.

FIG. 4 is a schematic sectional view of a multilayer circuit board (thick film printing method) for evaluating insulation reliability and relative permittivity.

FIG. 5 is a schematic sectional view of a multilayer circuit board for evaluating a resistance value (green sheet laminating method).

FIG. 6 is a schematic sectional view of a multilayer circuit board (green sheet laminating method) for evaluating insulation reliability and relative permittivity.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Electronic component 2 ... Multilayer circuit board 2a, 2b, 2c, 2d, 2e, 2f, 2g, 2h ... Insulating layer 3a, 3b, 3c, 3d ... Inner-layer conductor pattern 4a, 4b, 9 ... Thick film resistor

Claims (17)

[Claims] 1. A multilayer circuit board having an insulating layer provided with a silver-based conductor pattern containing a silver-based conductor and an inorganic additive component and a thick film resistor, wherein the insulating layer comprises: (A) silver and / or silver Compound (B) A multilayer circuit board comprising at least one inorganic component constituting the inorganic additive component. 2. The multilayer circuit according to claim 1, wherein the insulating layer contains the silver and / or the silver compound in an amount of 0.001 to 5% by weight in terms of metallic silver. substrate. 3. The multilayer circuit board according to claim 1, wherein the insulating layer contains the inorganic component in an amount of 0.001 to 10% by weight in terms of oxide. 4. The multilayer circuit board according to claim 1, wherein said inorganic component contains a glass component. 5. The method according to claim 1, wherein the inorganic component contains at least one metal oxide, metal ion or metal colloid selected from the group consisting of copper, chromium, bismuth and cerium. The multilayer circuit board according to any one of the above. 6. The multilayer circuit board according to claim 1, wherein said thick-film resistor is provided to face said conductor pattern with said insulating layer interposed therebetween. 7. A step of forming a silver-based conductor pattern containing a silver-based conductor and an inorganic additive component on a substrate; and silver and / or a silver compound on the conductor pattern.
A step of forming an insulating layer containing at least one inorganic component constituting the inorganic additive component; and a step of forming a thick-film resistor on the insulating layer. Substrate manufacturing method. 8. The multilayer circuit board according to claim 7, wherein said insulating layer contains said silver and / or silver compound in an amount of 0.001 to 5% by weight in terms of metallic silver. Method. 9. The method according to claim 7, wherein the insulating layer contains the inorganic component in an amount of 0.001 to 10% by weight in terms of oxide. 10. The method for manufacturing a multilayer circuit board according to claim 7, wherein a glass component is contained in the inorganic component. 11. The method according to claim 1, wherein the inorganic component is at least one selected from the group consisting of copper, chromium, bismuth and cerium.
The method for producing a multilayer circuit board according to any one of claims 7 to 10, further comprising a metal oxide, a metal ion, or a metal colloid. 12. The multilayer circuit board according to claim 7, wherein said thick-film resistor is formed so as to face said silver-based conductor pattern via said insulating layer. Production method. 13. A mixed powder is prepared by adding and mixing said silver and / or silver compound and said inorganic component to an amorphous glass powder and / or a crystallized glass powder, respectively. And then
The method of manufacturing a multilayer circuit board according to claim 7, wherein the insulating layer is formed by firing the paste-like composition or the slurry-like composition containing the obtained glass powder. Method. 14. After subjecting a first mixed powder obtained by mixing the silver and / or silver compound and the inorganic component to a heat treatment, the first mixed powder is mixed with an amorphous glass powder and / or Forming a second mixed powder by mixing the crystallized glass powder and then baking the paste-like composition or the slurry-like composition containing the second mixed powder to form the insulating layer; The method for manufacturing a multilayer circuit board according to any one of claims 7 to 12, wherein: 15. A paste-like composition or slurry containing the mixed powder obtained after adding and mixing the silver and / or silver compound and the inorganic component to the amorphous glass powder and / or the crystallized glass powder. Forming the insulating layer by firing the composition.
A method for manufacturing a multilayer circuit board according to claim 7. 16. An electronic component, wherein a mounting component is mounted on at least one main surface of the multilayer circuit board according to claim 1. 17. An electronic device comprising the multilayer circuit board according to claim 1 or the electronic component according to claim 16.