JP2002047059A - Glass ceramic sintered compact and circuit board using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a glass ceramic sintered compact which can be colored except for white, and can reduce dielectric loss in a high frequency band; and a circuit board using the same. SOLUTION: A glass ceramic sintered compact contains a barium silica glass, with BaO of 30-60 weight %, in 50-70 volume % and a filler in 30-50 volume % in total. It also contains Cr oxide in 0.05-10 weight %, expressed in terms of Cr2O3 based on 100 parts by weight of the total of the glass and filler. It can be colored except for white, and has a property of dielectric loss with 10×10-4 or less at a 1 MH frequency. A circuit board A is manufactured by using this glass sintered compact as an insulation layer 1b.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for firing at a low temperature,
The present invention relates to a colored glass ceramic sintered body that can be simultaneously fired with Cu or Ag and is suitable as an insulating substrate in a wiring board or a package for housing semiconductor elements.

[0002]

2. Description of the Related Art Conventionally, as a ceramic multilayer wiring board,
An insulating substrate made of an alumina-based sintered body having a wiring layer made of a refractory metal such as tungsten or molybdenum formed on the surface or inside thereof is most widely used.

Further, recently, with the era of advanced information, the frequency band to be used is shifting to higher and higher frequencies. In such a high-frequency wiring board that requires transmission of a high-frequency signal, in order to transmit a high-frequency signal without loss, the resistance of the conductor forming the wiring layer is small, and the dielectric of the insulating substrate in the high-frequency region is low. Low loss is required.

However, conventional tungsten (W),
Refractory metals such as molybdenum (Mo) have high conductor resistance, have low signal propagation speeds, and have difficulty in signal propagation in the high-frequency region of 1 GHz or higher. It is necessary to use low resistance metals such as silver and gold. Since the wiring layer made of such a low-resistance metal has a low melting point and cannot be co-fired with alumina, recently, a so-called glass ceramic made of glass or a composite material of glass and ceramic has been insulated. Wiring boards used as substrates are being developed.

Recently, a glass ceramic obtained by adding a filler component such as quartz to barium silicate glass or the like has also been proposed as a glass ceramic having a high thermal expansion in order to reduce the thermal expansion difference with a printed circuit board on which a wiring board is mounted. Have been.

On the other hand, with respect to ceramics used as an insulating substrate, contrast can be added when optically detecting a bonding position at the time of wire bonding, or appearance defects due to taste or uneven color of a white insulating substrate occur. In order to prevent this and improve the yield, coloring is performed. Conventionally, as a coloring method, for example, alumina ceramics and the like are colored by adding a metal element such as W or Mo, and glass ceramics are also colored by W or Mo. It has been studied to add a coloring agent for coloring.

[0007]

However, when a glass ceramic mainly composed of barium silicate glass is used as the insulating substrate, there is a problem that a dielectric loss at a high frequency is larger than that of an alumina sintered body. Specifically, while the alumina-based sintered body was about 5 × 10 ⁻⁴ at a measurement frequency of 1 MHz, this glass-ceramic sintered body was as large as about 15 × 10 ⁻⁴ . Moreover, when the above-mentioned W or Mo is added as a coloring agent for the glass ceramic sintered body, the dielectric loss of the sintered body tends to increase.

Accordingly, the present invention provides a glass ceramic sintered body which can be simultaneously fired with a wiring layer of Cu or Ag, can be colored to a desired color, and can reduce dielectric loss. The purpose is to:

[0009]

The present inventors have repeatedly studied the composition of the glass ceramic sintered body with respect to the above problems, and as a result, have found that the glass ceramic sintered body containing barium silicate glass as a main component and containing a filler is used. To the glass-ceramic sintered body by adding Cr oxide, or a part thereof replaced with at least one selected from the group consisting of Cu, V, Fe, Ni, Mn and Co or a compound thereof. It has been found that a desired color can be obtained without impairing the characteristics, and the dielectric loss of the sintered body can be reduced.

That is, the glass-ceramic sintered body of the present invention comprises 50 to 70% by volume of barium silicate glass containing 30 to 60% by weight of BaO, and 30 to 60% by weight of a filler.
The glass-ceramic sintered body contains 0.05% to 10% by weight of Cr oxide in terms of Cr ₂ O _{3 based on} 100 parts by weight of the total amount of the glass and the filler. % And a color other than white, and a dielectric loss of 10 × at a frequency of 1 MHz.
^10-4 Der where those characterized by or less, a part of the Cr compounds Cu, V, Fe, Ni, be substituted with at least one compound selected from the group consisting of Mn and Co desirable.

The filler contains at least quartz for the purpose of lowering the dielectric constant. For increasing the dielectric constant, it contains at least a titanate, especially at least one selected from the group consisting of lanthanum titanate, calcium titanate, strontium titanate, barium titanate, titania and magnesium titanate. It is desirable.

More specifically, a) lanthanum titanate, b) at least one selected from the group consisting of calcium titanate, strontium titanate, barium titanate, titania and magnesium titanate, and c) oxidation containing zirconium And at least one member selected from the group consisting of:
When the content of b) is represented by (1-x) and the weight ratio of both components is expressed, x is in the range of 0.2 ≦ x ≦ 0.8, the content of c) is y, and the content of a is a ) And b) are (1)
When y represents the weight ratio of both components, y is 0.0
It is desirable to be in the range of 5 ≦ y ≦ 0.3, and by using such a filler, the coefficient of thermal expansion at 40 to 400 ° C. is 8 × 10 ⁻⁶ / ° C. or more, and 1
It is desirable that the dielectric constant at MHz is 14 or more.

The wiring board of the present invention has at least one
Surface of an insulating substrate comprising a ceramic insulating layer and / or
Alternatively, a metallized wiring layer is provided inside, and the ceramic insulating layer includes any one of the glass ceramic sintered bodies described above.

Here, it is desirable that a plurality of the insulating layers are laminated, and that the dielectric constant of one of the insulating layers is different from the dielectric constant of another insulating layer.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The glass-ceramic sintered body of the present invention contains 50 to 70% by volume of barium silicate glass containing 30 to 60% by weight of BaO having an average particle size of 0.5 to 20 μm.
And a filler having an average particle size of 0.5 to 20 μm in a total amount of 30.
To 50% by volume.

In the present invention, barium silicate (BaO-
As SiO ₂ ) glass, BaO is 30 to 60% by weight.
Be one that a proportion of, as particularly preferred composition, the SiO ₂ 25 to 50 wt%, BaO or C
aO 30-60 wt%, the B ₂ O ₃ 5 to 15 wt%, A
contain each at a ratio of l ₂ O ₃ 1 to 10 wt%, _{further, ZnO, ZrO 2, MgO,} SrO, TiO 2, P 2
O at least one selected from the group of ₅ to desirably contains a proportion of 10 wt% or less.

Further, the sag point of the above glass is 400-400.
The temperature is desirably 800 ° C, particularly 400 to 700 ° C. This is because when molding a mixture consisting of glass and filler, a molding binder such as an organic resin is added, but this binder is efficiently removed, and the matching of the metallization and the firing conditions that are fired simultaneously with the insulating substrate is performed. If the yield point is lower than 400 ° C., the glass starts sintering at a low temperature. For example, simultaneous sintering with metallization at a sintering temperature of 600 to 800 ° C. for Ag, Cu, etc. This is because the binder cannot be decomposed and volatilized because the densification of the molded body starts at a low temperature, and the binder component remains, which results in affecting the properties. On the other hand, if the yield point is higher than 800 ° C., sintering becomes difficult unless the amount of glass is increased, and the use of relatively expensive glass increases, which hinders cost reduction.

The barium silicate glass may form an amorphous phase in the sintered body, reduce the dielectric loss of the sintered body, increase the strength, increase the thermal conductivity, and control the dielectric constant. After firing, for example, BaO.2SiO ₂ ,
A crystal phase such as BaAl ₂ Si ₂ O ₈ or BaB ₂ Si ₂ O ₈ may be deposited.

On the other hand, fillers such as quartz (quartz), cristobalite, tridymite, etc.
In addition to titanates such as O ₂ , titania, lanthanum titanate and calcium titanate, alumina, MgO, zirconia, forsterite (2MgO.SiO ₂ ), enstatite (MgO.SiO ₂ ), spinel (MgOA)
l ₂ O _3), wollastonite (CaO · SiO _2), Monty Celite _{(CaO · MgO · SiO 2)} , nepheline _{(Na 2 O · Al 2 O} 3, SiO2), lithium silicate (Li ₂ O · SiO ₂ ), Diopsite (CaO
・ MgO.2SiO ₂ ), melvinite (2CaO.M)
gO.2SiO ₂ ), Akermite (2CaO.MgO)
· 2SiO _2), Kanegiaito _{(Na 2 O · Al 2 O} 3 ·
2SiO ₂ ), magnesium borate (2MgO · B
₂ O ₃ ), Celsian (BaO.Al ₂ O ₃ .2Si)
O ₂ ), B ₂ O ₃ .2MgO.2SiO ₂ , garnite (Z
nO.Al ₂ O ₃ ), petalite (LiAlSi ₄ O ₁₀ )
Ceramics such as are used.

Among them, at least one kind of SiO ₂ -based compound selected from the group consisting of quartz, cristobalite and tridymite, particularly quartz, is required to achieve high thermal expansion and low dielectric constant of dielectric constant of 8 or less.
It is desirable that the content be at least volume%.

According to the present invention, in order to achieve a high thermal expansion property and a high dielectric constant exceeding a dielectric constant of 8, it is desirable to contain at least titanate. The titanate desirably contains at least 5% by volume of at least one selected from the group consisting of lanthanum titanate, calcium titanate, strontium titanate, barium titanate, titania, and magnesium titanate.

More preferably, a) Lanthanum titanate (α = 15 × 10 ⁻⁶ / ° C., ε = 4)
5) b) Calcium titanate (α = 13 × 10 ⁻⁶ / ° C., ε =
180), strontium titanate (α = 9 × 10 ⁻⁶ /
° C, ε = 300), barium titanate (α = 14 × 10
⁻⁶ / ° C., ε = 13000), titania (α = 9 × 10 ⁻⁶⁾
/ ° C, ε = 80), magnesium titanate (α = 10 ×
10 ⁻⁶ / ° C., ε = 20)
Species c) It is desirable that at least one of the zirconium-containing oxides is contained as an essential component.

According to these components, the component a) contributes to a high dielectric constant, a high thermal expansion, and an improvement in sinterability of the material. In addition, the component b) serves to compensate for the limitation in increasing the dielectric constant of the component a) alone, and to play a role in further improving the dielectric constant of the sintered body. Component c) plays a role in improving the sinterability of the material and increasing the dielectric constant.

The lanthanum titanate has the general formula La ₂
O ₃ .nTiO ₂ (n = integer of 2 to 5), specifically, La ₂ O ₃ .2TiO ₂ (α = 15 × 10 ⁻⁶ ) / ° C., ε =
45) La ₂ O ₃ .3TiO ₂ (α = 14 × 10 ⁻⁶ ) / ° C., ε =
47) La ₂ O ₃ .4TiO ₂ (α = 14 × 10 ⁻⁶ ) / ° C., ε =
51) La ₂ O ₃ .5TiO ₂ (α = 13 × 10 ⁻⁶ ) / ° C., ε =
55).

C) ZrO ₂ (α = 10 × 10 ⁻⁶ / ° C., ε = 30) MgZrO ₃ (α = 9.2 × 10 ⁻⁶ / ° C., ε = 32) CaZrO ₃ (α = 9.2 × 10 ⁻⁶ / ° C., ε = 32) SrZrO ₃ (α = 9.5 × 10 ⁻⁶ / ° C., ε = 30) BaZrO ₃ (α = 9.3 × 10 ⁻⁶⁾ / ℃, ε = 40 at least one selected from the group consisting of), ZrO ₂ is most desirable especially in view of improving and thermal expansion of the sinterability.

Further, according to the present invention, in a system containing a), b) and c), the content of a) is defined as x, and the content of b) is defined as (1-x), and the weight ratio of both components is represented by the following formula. In the case where x is 0.2 ≦ x ≦, a dense body having high thermal expansion characteristics and a desired high dielectric constant can be obtained at an appropriate firing temperature.
It is desirably in the range of 0.8.

The content of the component c) is defined as y, a) and b).
When the weight ratio of both components is expressed as the total amount of (1-y), y is 0 in that a dense body having high thermal expansion characteristics and a desired high dielectric constant can be obtained at an appropriate firing temperature. .
It is desirable to be in the range of 05 ≦ y ≦ 0.3.

As the filler component, a)
In addition to b) and c), the above-mentioned other filler components can be added to finely adjust the properties such as the coefficient of thermal expansion. Among other fillers, it is desirable to include quartz in order to achieve high thermal expansion and low dielectric constant.

Further, according to the present invention, 0.05 to 10 parts by weight, particularly preferably 0 to 10 parts by weight, in terms of Cr ₂ O ₃ , of Cr oxide is added to 100 parts by weight of the main component composition comprising the glass component and the filler component. It is a great feature that the sintered body is contained in a ratio of 2 to 6 parts by weight, whereby the sintered body can be colored to a color other than white and the dielectric loss of the sintered body in a high frequency band is reduced. can do. In the sintered body, the Cr oxide is desirably present as Cr ₂ O ₃ , and may be a non-stoichiometric oxide in which the valence of Cr changes depending on the firing atmosphere.

As the Cr compound, Cr ₂ O ₃ is most desirable, but carbonate, nitrate,
An acetate, a Cr-containing organic compound, or the like may be used, and even a carbide, nitride, or the like of Cr has a coloring effect and a dielectric loss reducing effect.

Although Cr can be added to the glass raw material, it is desirable to add Cr as a metal or ceramic powder from the viewpoint of adjusting the softening point of the glass and facilitating the production.

The reason why the content of the Cr oxide is set in the above range is that if the oxide equivalent is less than 0.05% by weight, the coloring is insufficient and the dielectric loss of the sintered body is reduced. On the other hand, if the content exceeds 10% by weight, sinterability is impaired, and the densification and strength of the sintered body are adversely affected. It should be noted that a green body-colored sintered body can be obtained by adding a Cr oxide to the sintered body.

Further, according to the present invention, a part of the Cr oxide can be replaced with at least one selected from the group consisting of Cu, V, Fe, Ni, Mn and Co, or a compound thereof. Also in this case, from the viewpoint of reducing the dielectric loss and coloring, it is desirable that the Cr oxide be contained in an amount of 0.05 part by weight or more in terms of Cr ₂ O _3.
It is contained so that the total of the oxides of the r oxide and the specific metal or the compound thereof in terms of oxide is 10 parts by weight or less.

By adding these specific metals or their compounds, the color of the sintered body can be changed from green to red, blue, yellow, and black without hindering the effect of adding the Cr compound. Can be changed to color.

Next, the glass-ceramic sintered body of the present invention comprises 50-70% by volume of barium silicate glass powder containing 30-60% by weight of BaO having an average particle size of 0.5-20 μm, The various fillers of 0.5 to 20 μm are weighed and mixed at a ratio of 30 to 50% by volume in total, and the Cr oxide is converted to 0.05 to 1 in terms of Cr ₂ O _3.
0 parts by weight, particularly 0.2 to 6 parts by weight. For a mixture containing the above-mentioned raw materials,
After adding an appropriate organic resin binder, molding into an arbitrary shape by desired molding means, for example, a mold press, a cold isostatic press, injection molding, extrusion molding, a doctor blade method, a calendar roll method, a rolling method, and the like. I do.

Next, in firing the above-mentioned molded body,
First, the binder component blended for molding is removed. The binder is removed in an air atmosphere at about 700 ° C., for example, when Cu is used as a wiring conductor, in a non-oxidizing atmosphere containing water vapor at 100 to 750 ° C. to prevent oxidation of Cu. It is desirable to be performed in. At this time, the shrinkage start temperature of the molded body is 700 to 85.
It is desirable to be about 0 ° C., and if the shrinkage onset temperature is lower than this, it is difficult to remove the binder. Therefore, it is desirable to control the properties of the crystallized glass in the molded body, particularly the yield point as described above. .

The firing is carried out at 850 to 1 which can be simultaneously fired with a metallized wiring layer containing a low-resistance conductor such as Cu or Ag.
It is performed in an oxidizing atmosphere or a non-oxidizing atmosphere at 050 ° C., particularly 850-950 ° C., so that the relative density is 90%.
It is refined to the above.

In the glass ceramic sintered body of the present invention thus produced, the crystal phase formed from the glass component, the crystal phase formed by the reaction between the glass component and the filler component, the filler component, or the filler component is decomposed. There is a case in which a crystal phase or the like generated by the above exists, and a glass phase exists in the grain boundary of these crystal phases. In addition, the coloring component exists in a form at the time of addition to the grain boundary of the crystal phase or in a vitrified form, and also as a reactant reacted with the glass raw material.

The above glass ceramic sintered body can be used publicly as an insulating substrate of a wiring board. Therefore, FIG.
FIG. 1 shows a schematic cross-sectional view of a multilayer wiring board as an example of a wiring board provided with an insulating layer made of the glass ceramic sintered body of the present invention.

According to FIG. 1, a multilayer wiring board 1 has a metallized wiring layer 2 on the surface and / or inside of an insulating substrate 1 in which insulating layers 1a, 1b and 1c made of a sintered glass ceramic are laminated in multiple layers. It is arranged. According to FIG. 1, at least one of the insulating layers 1a, 1b, and 1c 1b
However, as described above, for example, a glass ceramic sintered body having an average thermal expansion coefficient at 40 to 400 ° C. of 8 × 10 ⁻⁶ / ° C. or more, a high thermal expansion of more than 8, and a dielectric constant of more than 8, especially 14 or more, and even 20 or more Formed and other insulating layers 1
a, 1c is an average coefficient of thermal expansion at 40 to 400 ° C. of 8
High thermal expansion of × 10 ⁻⁶ / ° C. or more, dielectric constant of 8 or less, especially 7
An electrode layer 3-3 made of a conductor such as Cu is formed on the upper and lower sides of the insulating layer 1b and is formed of the following glass ceramic sintered body. By connecting, wiring layer 2
A predetermined capacitance can be taken out between -2.

Here, the insulating layer 1b is made of a glass ceramic sintered body containing titanate as a filler as described above. In addition, the insulating layers 1a and 1c having a high thermal expansion and a low dielectric constant laminated on the upper and lower surfaces of the insulating layer 1b easily contain a SiO ₂ -based filler as a filler as described above. Those having a reduced dielectric constant without impairing other characteristics such as dielectric loss can be suitably used.

At least one of the insulating layers 1a, 1b and 1c needs to be a glass ceramic sintered body obtained by adding and mixing a filler to barium silicate glass. Does not necessarily need to be barium silicate glass,
A combination of at least one selected from the group consisting of borosilicate glass, aluminosilicate glass, and alkali silicate glass, and a filler may be used. Also in this case, it is desirable that the insulating layer 1b and the insulating layers 1a and 1c have similar colors, dielectric loss, thermal expansion coefficient, firing temperature, and the like.

In order to manufacture the multilayer wiring board, a slurry is prepared by adding a suitable organic binder, a solvent and a plasticizer to the low dielectric glass ceramic composition comprising the above-mentioned glass powder and filler powder. The slurry is prepared and the slurry is formed into a green sheet by a known green sheet forming method using a doctor blade or the like.

Then, as a metallized wiring layer, a metal paste obtained by adding an organic binder, a solvent, and a plasticizer to a suitable metal powder is mixed and printed on the green sheet in a predetermined pattern by a known screen printing method. .
In some cases, the green sheet is appropriately punched to form a through hole, and the hole is filled with a metallizing paste.

On the other hand, a glass ceramic green sheet having a high thermal expansion and a high dielectric constant is formed by forming, punching, and printing an electrode layer in the same manner as described above.

Then, the above-mentioned low dielectric constant glass ceramic green sheet and high dielectric constant glass ceramic green sheet are laminated, and a green sheet laminate and metallization are simultaneously fired, so that an insulating layer functioning as a capacitor is built in. A multilayer wiring board can be obtained.

Since the wiring board of the present invention can be colored in a desired color, the production yield is improved and the wiring board has a good appearance. Further, since the dielectric loss in the high frequency band can be reduced, the transmission loss of the high frequency signal can be reduced and the signal can be transmitted well. In addition, since the coefficient of thermal expansion of the insulating substrate can be approximated to that of an external circuit board such as a printed circuit board containing an organic resin, when the wiring board is mounted on the external circuit board via ball-shaped solder terminals or solder. Even long-term reliability implementation for temperature cycling is possible.

Further, by controlling the composition and the like of the glass ceramic sintered body, it is possible to produce a high dielectric constant type or low dielectric constant type glass ceramic sintered body.
A multilayer wiring board having a built-in capacitor can also be manufactured, and a capacitor conventionally mounted on an external circuit board is not required. Therefore, the external circuit board can be reduced in size and mounting cost can be reduced.

[0049]

[Example] The following two types of glass were prepared as glass powder.
did. A: SiO_Two: 41% by weight-BaO: 37% by weight-B_TwoO
_Three: 10% by weight-Al_TwoO_Three: 7% by weight-CaO: 5% by weight
% (Yield point 700 ° C, coefficient of thermal expansion 6.5 × 10^-6/ ℃, P
b: 50 ppm or less) B: SiO_Two: 29% by weight-BaO: 55% by weight-B_TwoO
_Three: 7% by weight-Al_TwoO_Three: 2% by weight-ZnO: 7% by weight (Yield point: 657 ° C, coefficient of thermal expansion: 10.8 × 10^-6/ ℃,
(Pb content 50 ppm or less) La is used as a filler with respect to these glasses A and B.
_TwoTi_TwoO₇, CaTiO_Three, ZrO_TwoAnd Cr_TwoO_ThreeQuasi
These were mixed in the ratios shown in Table 1. The ratio in Table 1 is
La in weight ratio_TwoTi_TwoO₇X, CaTiO_ThreeIncluding
Let the amount be (1-x), ZrO_TwoThe content of y, La_TwoT
i_TwoO₇And CaTiO_ThreeIs the total amount of (1-y)
is there. For glass A, quartz (SiO_Two),Aluminum
(Al_TwoO_Three), Titania (TiO_Two), Calcium titanate
Cium (CaTiO_Three) And forsterite in Table 2
At a rate of 100 parts by weight of the mixture and Cr_TwoO_Three
Were mixed in the ratios shown in Table 2. La as a filler for glass A_TwoTi_TwoO
₇, CaTiO_Three, ZrO _TwoUsing La_TwoTi_TwoO₇Including
X, CaTiO_ThreeWith the content of (1-x)
= 0.4 and ZrO_TwoThe content of y, La_TwoTi_TwoO₇When
CaTiO_ThreeIs set to (1-y), y = 0.1.
And weighed to mix. And for this mixture:
Cr_TwoO_ThreeAnd oxides of various transition metals shown in Table 3
And mixed.

A solvent is added to each of the above mixed powders, and the mixture is pulverized and mixed using a ball mill. Then, an organic binder and a plasticizer are added and mixed sufficiently to prepare a slurry, and a green sheet having a thickness of 500 μm is prepared by a doctor blade method. did. From the obtained green sheet, 60 mm x 6
A 0-mm sample was prepared, and after removing the binder at 750 ° C. in a nitrogen atmosphere containing water vapor, sintering was performed at the temperatures shown in the table.

Next, the sintered body obtained as described above was measured with an impedance analyzer at a measuring frequency of 1M.
The dielectric constant at Hz, the dielectric loss, and the average thermal expansion coefficient at 40 to 400 ° C. were measured. Further, the color tone of the sintered body was confirmed.

[0052]

[Table 1]

[0053]

[Table 2]

[0054]

[Table 3]

As is clear from Tables 1 to 3, Sample No. 1 having a glass content of less than 50% by volume was used. In 11, 26 and 45, the sintered body could not be densified by firing at 1000 ° C. Further, the sample No. having a glass content of more than 70% by volume. Regarding Examples 19 and 29, sintering of the sintered body progressed excessively by sintering at 800 ° C., resulting in an increase in dielectric loss.
Simultaneous firing with metallization was not possible.

In the case of Sample No. to which Cr ₂ O ₃ was not added. 1
In the sample No., which could not be colored, did not add Cr ₂ O _3, and added another specific transition metal. 42, 5
Sample No. 2 to which WO ₃ or MoO ₃ was added 6
Also in 2, 63, the dielectric loss increased. Sample No. _{3 in which the} amount of Cr ₂ O ₃ was less than 0.05% by weight was used. 2, 20, 34
Had a high dielectric loss. Further, the sample content of Cr ₂ O ₃ amount or Cr ₂ O _3, and the specific metal exceeds 10% by weight in total No. 10, 25, 45, 48, 51,
In Nos. 55, 58, and 61, many pores were observed inside, and a good dense body was not obtained, and the dielectric loss increased.

In contrast, the sample N according to the present invention
o. 3-9, 12-18, 21-24, 27, 28, 3
1-33, 35-41, 43, 44, 46, 47, 4
In 9, 50, 53, 54, 56, 57, 59, 60,
Any of them could be colored, and the dielectric loss was 10 × 10 ⁻⁴ or less, and simultaneous firing with Cu metallization was possible.

[0058]

As described above in detail, the glass-ceramic sintered body of the present invention has a Cr oxide in addition to a barium silicate glass and a filler, and further includes a part of Cu, V, F
By substituting at least one selected from the group consisting of e, Ni, Mn and Co or a compound thereof, it is possible to produce a glass ceramic sintered body having a good appearance and high productivity by being colored to a color other than white. In addition, dielectric loss in a high frequency band can be reduced. As a filler, various combinations of low dielectric constant and high dielectric constant glass-ceramic sintered bodies can be produced by various combinations. For example, a high dielectric constant sintered body is used as an insulating layer to form electrode bodies on both surfaces thereof. By forming the insulating layer, the insulating layer can function as a capacitor, and by laminating the insulating layer on the insulating substrate, a wiring board having a built-in capacitor can be formed. Can be reduced.

Further, since the glass-ceramic sintered body of the present invention has a high coefficient of thermal expansion, even if the wiring board is mounted on the surface of the external circuit board by using a ball or solder, it is mounted for a long period of time. Reliability can be improved.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing an example of a multilayer wiring board using a glass ceramic sintered body of the present invention as an insulating layer.

[Description of Signs] A Multi-layer wiring board 1 Insulating board 1a-1c Insulating layer 2 Metallized wiring layer 3 Electrode body 4 Through-hole conductor

 ──────────────────────────────────────────────────の Continued on the front page (72) Inventor Yasuhide Minami 1-4 Yamashita-cho, Kokubu-shi, Kagoshima Inside the Kyocera Research Institute (72) Inventor Masaya Kokubu 1-4-Yamashita-cho, Kokubu-shi, Kagoshima No. F-term in Kyocera Research Institute (Reference) 4G030 AA07 AA08 AA09 AA10 AA13 AA16 AA17 AA19 AA22 AA25 AA27 AA28 AA29 AA31 AA37 5G303 AA01 AA05 AB07 AB15 BA09 CA03 CB03 CB09 CB13 CB13 CB13 CB13 CB13 CB13 CB13 CB13

Claims (11)

[Claims] 1. A glass-ceramic sintered body containing 50 to 70% by volume of barium silicate glass containing 30 to 60% by weight of BaO and 30 to 50% by volume in total of a filler. The ceramic sintered body is Cr based on the total amount of 100 parts by weight of the glass and the filler.
Oxide is contained in a proportion of 0.05 to 10 parts by weight in terms of Cr ₂ O ₃ , exhibits a color other than white, and has a frequency of 1 MHz.
A glass ceramic sintered body characterized in that the dielectric loss at z is 10 × 10 ⁻⁴ or less. 2. The method according to claim 1, wherein a part of the Cr compound is Cu, V, Fe,
2. The glass ceramic sintered body according to claim 1, wherein said sintered body is substituted by at least one compound selected from the group consisting of Ni, Mn and Co. 3. The glass-ceramic sintered body according to claim 1, wherein the filler contains at least quartz and has a dielectric constant of 8 or less. 4. The glass-ceramic sintered body according to claim 1, wherein the filler contains at least titanate and has a dielectric constant of more than 8. 5. The glass-ceramic firing according to claim 4, wherein the titanate is at least one selected from the group consisting of lanthanum titanate, calcium titanate, strontium titanate, barium titanate, titania, and magnesium titanate. Union. 6. As the filler, at least a) lanthanum titanate, b) at least one selected from the group consisting of calcium titanate, strontium titanate, barium titanate, titania and magnesium titanate, and c)
The glass ceramic sintered body according to claim 5, comprising at least one selected from zirconium-containing oxides. 7. The content of a) in the filler is x,
7. The glass-ceramic sinter according to claim 6, wherein x is in the range of 0.2 ≦ x ≦ 0.8 when the content of b) is expressed as (1-x) and the weight ratio of both components is expressed. Union. 8. When the content of c) is represented by y and the total amount of a) and b) is represented by (1-y) and the weight ratio of both components is expressed, y is 0.05 ≦ y ≦ 0. 8. The glass ceramic sintered body according to claim 6, wherein the glass ceramic sintered body is in a range of 0.3 to 3. 9. The thermal expansion coefficient at 40 to 400 ° C. is 8 ×
The glass-ceramic sintered body according to any one of claims 6 to 8, wherein the glass-ceramic sintered body has a dielectric constant of 10 ^-6 / ° C or higher and a dielectric constant at 1 MHz of 14 or higher. 10. A wiring board in which a metallized wiring layer is provided on a surface and / or inside of an insulating substrate made of at least one ceramic insulating layer, wherein the ceramic insulating layer is made of any one of claims 1 to 9. A wiring board, comprising: an insulating layer made of the glass ceramic sintered body according to any one of the above. 11. The wiring board according to claim 10, wherein a plurality of the insulating layers are stacked, and a dielectric constant of one of the insulating layers is different from a dielectric constant of another insulating layer.