JPH0563323A - Board for circuit use - Google Patents

Abstract

PURPOSE:To provide a board for circuit use reinforced with glass films, which are easy in fiber formation, are high also in dielectric constant, have a good chemical durability and are constituted in a composition, and having superior dielectric characteristics. CONSTITUTION:A board for circuit use is formed by reinforcing a resin 2, in which inorganic dielectric particles 4 are dispersed, with high-dielectric constant glass fibers 1. The board is characterized by that the fibers 1 respectively contain 40 to 65mol% of SiO2, 20 to 45mol% of at least one of MgO, CaO, SrO and BaO, 5 to 25mol% of at least one of TiO2 and ZrO2 and 0.5 to 15mol% of NbO5/2, the total amount of these oxides is 85mol% or higher and the fibers consist of a glass composition having a fiber formation suitability of a specific inductive capacity (1 MHz, 25 deg.C) of 9 or more.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a circuit board used for a printed wiring board or the like.

[0002]

2. Description of the Related Art In the advanced information age, information transmission tends to be faster and higher in frequency. In mobile radio such as car phones and personal radios, satellite broadcasting, satellite communications, and new media such as CATV, downsizing of devices is being promoted, and accordingly, microwave circuit elements such as dielectric resonators are being used. However, miniaturization is strongly desired.

The size of the microwave circuit element is based on the wavelength of the electromagnetic wave used. The wavelength λ of the electromagnetic wave propagating through the dielectric having the relative permittivity ε _r is λ = λ ₀ / (ε _r ) ^0.5 when the propagation wavelength in vacuum is λ ₀ . Therefore, the device becomes smaller as the dielectric constant of the printed circuit board used increases. Further, when the dielectric constant of the substrate is large, electromagnetic energy is concentrated in the substrate, which is convenient because there is little leakage of electromagnetic waves.

As the above-mentioned circuit board, there is a board obtained by reinforcing a resin (such as PPO resin having excellent high frequency characteristics) with a glass fiber reinforcing material. This circuit board is attracting attention because it can take advantage of the resin, such as the large area compatibility and excellent post-processing (cutting, punching, bonding, etc.), as compared with a ceramic substrate such as alumina.

[0005]

However, the above-mentioned circuit board is not practical in terms of the essential dielectric constant. As the resin, there is a method of using a resin having a high dielectric constant such as polyvinylidene fluoride (ε _r = 13) or cyano resin (ε _r = 16 to 20), but in this case, the dielectric loss is large and the dielectric characteristics in the high frequency range are high. There is also a problem with stability and lack of suitability for high frequencies (especially 100 MHz or higher), so it cannot be said that it is a very appropriate measure.

Therefore, the inorganic dielectric particles (for example, Ti
O ₂ particles, BaTiO ₃ particles, etc.) are dispersed in the resin to increase the dielectric constant, but it is often the case that an appropriate amount of inorganic dielectric particles has a desired dielectric constant (ε _r of 10 or more). Can not. This is because the glass reinforcing material (for example, glass cloth) does not have a higher dielectric constant. Although increasing the amount of addition of the inorganic dielectric particles increases the dielectric constant, if the amount of addition is too large, disadvantages such as high cost and easy interface trouble occur, so increasing the addition amount of the inorganic dielectric particles is not recommended. Not a proper policy.

Further, when the dielectric constant of the glass reinforcing material is low, there is a problem of dielectric constant fluctuation due to the structure, and it is difficult to use. One is that a low dielectric constant glass reinforcing material region and a high dielectric constant resin region containing inorganic dielectric particles are intermingled with each other to cause microscopic dielectric constant variation. The other is that when a low dielectric constant glass reinforcing material region and a high dielectric constant resin region containing inorganic dielectric particles are mixed, there is a change in the dielectric constant due to a change in the amount of the high dielectric constant resin region.

A usual glass cloth for reinforcing material is composed of fibers of a SiO ₂ —Al ₂ O ₃ —CaO glass composition called E glass. The E glass, more _{specifically,} SiO 2: 50-60 wt%, Al ₂ O _3: 13~
16 wt%, B ₂ O _3: 5~9 wt%, MgO: 0~6
% By weight, CaO: 15 to 25% by weight, Na ₂ O + K
_It has a composition of ₂ O: 0 to 1% by weight and F: 0 to 1% by weight, has a relative dielectric constant of about 6 to 7, and is not so high.

A lead glass composition containing a large amount of PbO has a high relative dielectric constant. For example, PbO: 72 wt%, S
iO ₂ : 26% by weight, B ₂ O ₃ : 1.5% by weight, K
₂ O: 0.5% by weight of the lead-based glass composition is 1
It has a relative dielectric constant of 3.0. However, in the case of a lead-based glass composition, there is a problem that it is difficult to form fibers (7 to 9 μm in diameter). Evaporation of PbO is intense during glass melting, resulting in inhomogeneity and frequent yarn breakage in the spinning process. Also,
In the case of a lead-based glass composition, there is a problem that it is difficult to form an appropriate glass cloth. In the case of manufacturing glass cloth, there is a heat treatment step for removing the primary binder, but the lead-based glass composition has a low strain point and is easily deteriorated, so that it is difficult to perform sufficient treatment. The glass cloth, which is not sufficiently treated to remove the primary binder, causes deterioration in long-term reliability of the substrate. In addition, the lead-based glass composition has a problem that it is not easy to handle because lead is toxic.
There is also a problem that the dielectric loss (tan δ) in a high frequency region of 00 MHz or higher is large.

Further, the glass used as a reinforcing material for the printed circuit board is required to have chemical durability. This is because various chemical treatments are performed when forming a circuit on a printed circuit board, and it is necessary that the reinforcing material is not damaged by this treatment. On the other hand, in the case of a circuit board for high frequency, PPO resin is preferable in terms of dielectric properties, but physical properties such as heat resistance, thermal expansion (dimensional stability), and physical strength (rigidity) are not sufficient. .. If these physical properties are improved, the usefulness is further increased.

Further, the inorganic dielectric particles have a strong effect of improving the dielectric constant, and when the inorganic dielectric particles are dispersed in the resin varnish at the manufacturing stage, it is difficult for the particles to settle and separate. Increase. In view of the above circumstances, the present invention provides a circuit board having excellent dielectric properties, which is reinforced with glass fiber having a composition that is easily fiberized, has a high dielectric constant, and has good chemical durability. It is an issue.

In addition to the first problem, the second problem is to provide a circuit board having a high high frequency suitability in which a PPO-based resin having improved physical properties is used, and the circuit board is dispersed in the resin. A third object is to provide a circuit board which is a particle in which the inorganic dielectric particles are hard to settle and separate in the resin varnish and has a strong dielectric constant improving action.

[0013]

SUMMARY OF THE INVENTION In order to solve the first problem, the inventors have made SiO ₂ --BaO--TiO ₂ --Z.
Attention was paid to the rO ₂ type glass composition. This is because this glass composition is lead-free, has good dielectric properties, and has excellent chemical durability (acid resistance, alkali resistance, water resistance).
However, there is a problem that the devitrification temperature is high and it is difficult to form fibers. When obtaining glass fibers, the melt is drawn out from the small holes of a platinum pot called a bushing having 200 to 800 small holes at the bottom to obtain the fibers.
If the devitrification temperature is high, crystals due to devitrification occur at the bottom of the bushing, which prevents the melt from flowing out and causes yarn breakage. Normally, glass fibers are obtained while suppressing devitrification by controlling the temperature of the bottom of the bushing and the winding speed of the fiber, but when the devitrification temperature exceeds the temperature at which the melt viscosity becomes 10 ^2.5 poise (316 poise). You cannot control it. That is, conventional high relative permittivity (ε _r is 9 or more) SiO ₂ —BaO—Ti
The devitrification temperature of the O ₂ -ZrO ₂ glass composition exceeded the temperature at which the melt viscosity was 10 ^2.5 poise (316 poise), and it was lacking in fiberization suitability.

Therefore, the present inventors have continued to make intensive studies in search of a method for imparting the fiberization suitability while ensuring the required dielectric properties and chemical durability, and the addition of an appropriate amount of NbO _5/2 solves the problem. We were able to obtain the first finding that it was effective. Not only that, but the simultaneous addition of an appropriate amount of NbO _5/2 and an appropriate amount of AlO _3/2 will also increase the devitrification temperature and 10 ^2.
It was also possible to obtain the second finding that it is very effective in solving problems because a remarkable difference is likely to occur between the ⁵ Poise temperatures.

[0015] SiO ₂ -BaO-TiO ₂ -ZrO ₂ based glass composition of cristobalite crystals and BaO-TiO ₂ -ZrO ₂ system SiO ₂ system by devitrification in the composition range that can ensure the necessary dielectric properties crystals Is mainly deposited. The addition of an appropriate amount of NbO _5/2 is equivalent to the latter BaO-T
The devitrification temperature lowers in order to suppress the precipitation of the iO ₂ -ZrO ₂ -based crystal, but the former precipitation of the SiO ₂ -based cristobalite crystal cannot be suppressed and there is a limit to the degree of the devitrification temperature decrease. There was. That is a proper amount of Al
The addition of O _3/2 also sufficiently suppresses the precipitation of SiO ₂ -based cristobalite crystals, so that the devitrification temperature can be further lowered, and the melt viscosity increases, so that the devitrification temperature and 10 ^2.5 They found that the difference from the Poise temperature became larger.

Therefore, the circuit board according to the invention (first invention) according to claim 1 which solves the first problem completed based on the first knowledge has inorganic dielectric particles dispersed in a resin. 40 to 65 mol% of SiO ₂ , ₂₀ to 45 mol% of at least one of MgO, CaO, SrO, and BaO, 5 to 25 mol% of at least one of TiO ₂ and ZrO ₂ , and 0 of NbO _5/2 . ．
5 to 15 mol% each, the total amount of these oxides is 85 mol% or more, and the relative dielectric constant (1 MHz, 25 ° C.)
A high dielectric constant glass fiber made of a glass composition having a fiber-forming aptitude of 9 or more is used to strengthen the structure.
In the case of the first invention, the glass composition is
In addition, the content of SiO ₂ is 46 to 60 mol%, Mg
The content of at least one of O, CaO, SrO and BaO is 25 to 40 mol%, the content of at least one of TiO ₂ and ZrO ₂ is 7 to 24 mol%, NbO
The content of _5/2 is preferably 1 to 10 mol%.

Further, the first completed based on the second knowledge
The invention (second invention) according to claim 3 for solving the above problem
Such circuit boards have inorganic dielectric particles dispersed in resin.
Along with SiO₂40-65 mol%, Ca
20 to 4 of at least one of O, SrO and BaO
5 mol%, TiO₂And ZrO₂At least one of
5 to 25 mol%, NbO_5/20.5 to 15 mol%,
AlO_3/20.5 to 15 mol% respectively,
The total amount of oxides of 85 mol% or more, the relative dielectric constant
(1 MHz, 25 ° C) Glass with fiber suitability of 9 or higher
A structure reinforced with a high dielectric constant glass fiber composed of a composition
In the case of the second invention, the glass composition is
As in claim 4, in addition, SiO₂Content of 46-
60 mol%, at least CaO, SrO and BaO
One content is 25-40 mol%, TiO₂And Z
rO₂The content of at least one of 7 to 24 mol%,
NbO _5/2Content of 1 to 10 mol%, AlO_3/2Including
The content is preferably 1 to 10 mol%.

In the present invention, since the glass for reinforcing high-dielectric-constant glass fiber has the above-mentioned compositional constitution, the relative dielectric constant of 9 or more (1 MHz, 25 ° C.) and good fiberization suitability are as follows. As a result, excellent characteristics can be secured.
It has a high dielectric constant of 9 or more in the relative dielectric constant (1 MHz, 25 ° C.). Dielectric loss (1 MHz, 25 ° C.) or tan δ0.
Low loss of 6% or less.

Even in a high frequency range of 100 MHz or higher, the changes in the relative permittivity and the dielectric loss are small and the high frequency dielectric characteristics are excellent. Has excellent chemical durability (acid resistance, alkali resistance, water resistance). The devitrification temperature is 10 and the melt viscosity is 10.
It is below the temperature of ^2.5 poise. Devitrification temperature and 10 ^2.5
The larger the difference in Poise temperature, the better the fibering suitability. N
In the case of the second invention in which bO _5/2 and AlO _3/2 are used together, it is easy to make the difference between the devitrification temperature and the 10 ^2.5 Poise temperature reach about 90 ° C.

The strain point is as high as about 600 ° C. The reason for limiting the composition range of the glass composition of the present invention as described above is as follows. SiO ₂ : 40 to 65 mol% (more preferably 46 to 6)
SiO ₂ is a component that forms the skeleton of glass, and
If it is less than mol%, the devitrification temperature will rise and the melt viscosity will decrease, making it difficult to secure the required fiberization aptitude, and the chemical durability will also become insufficient. If it exceeds 65 mol%, it is difficult to secure a relative permittivity of 9 or more, and the glass viscosity is high, and it is difficult to melt it, and it becomes difficult to form fibers.

At least one of MgO, CaO, SrO and BaO: 20 to 45 mol% (more preferably 2
5 to 40 mol%) ... In the case of the first invention MgO, CaO, SrO and BaO act as modifying ions of the glass structure, and facilitate melt-making. Also,
When used in combination, the devitrification temperature is lowered. CaO, SrO
And BaO serve to increase the relative dielectric constant. 20
If it is less than mol%, it is difficult to obtain a melt, the suitability for fiber formation is deteriorated, and it is difficult to secure a relative dielectric constant of 9 or more. 45 mol%
If it exceeds, the devitrification temperature will rise and the viscosity of the melt will decrease, making it difficult to secure the required fiberization suitability.

At least one of CaO, SrO and BaO: 20 to 45 mol% (more preferably 25 to 40)
Mol%) ... In the case of the second invention CaO, SrO, and BaO act as modifying ions of the glass structure, and facilitate melt-making. Further, the combined use brings about a decrease in devitrification temperature. CaO, SrO and B
aO functions to increase the relative dielectric constant. If it is less than 20 mol%, it is difficult to obtain a melt, the suitability for fiber formation is reduced, and it is difficult to secure a relative dielectric constant of 9 or more. If it exceeds 45 mol%, the devitrification temperature will rise and the viscosity of the melt will decrease, making it difficult to secure the required fiber-forming aptitude.

At least one of TiO ₂ and ZrO ₂ : 5 to 25 mol% (more preferably 7 to 24 mol%) TiO ₂ and ZrO ₂ have a function of increasing the relative dielectric constant and a function of increasing chemical durability. .. The combined use of TiO ₂ and ZrO ₂ is desirable, and TiO ₂ is often made larger than ZrO ₂ . If it is less than 5 mol%, it is difficult to secure a relative dielectric constant of 9 or more and necessary chemical durability. When it exceeds 25 mol%, the devitrification temperature rises and the suitability for fiber formation is lost.

NbO _5/2 : 0.5 to 15 mol% (more preferably 1 to 10 mol%) NbO _5/2 has a function of significantly lowering the devitrification temperature without lowering the relative dielectric constant. If it is less than 0.5 mol%, the necessary addition effect does not appear, and if it exceeds 15 mol%, the devitrification temperature rises. AlO _3/2 : 0.5-15 mol% (more preferably 1-
10 mol%) AlO _3/2 is a component that forms the skeleton of glass, and causes a decrease in devitrification temperature and an increase in melt viscosity. If it is less than 0.5 mol%, the necessary addition effect is not exhibited, and if it exceeds 15 mol%, the relative dielectric constant is lowered and the glass viscosity is excessively increased, which makes it difficult to melt and become fibrous.

The content of at least one of MgO, CaO, SrO and BaO (or CaO, SrO and BaO) is 28 to 35 mol%, and the content of NbO _5/2 is 2.
When it is up to 9 mol%, the devitrification temperature and the melt viscosity are 1
It seems that the difference from the temperature of 0 ^2.5 poise tends to be remarkable. Further, if the total amount of the above oxides is less than 85 mol%, it is difficult to secure a relative permittivity of 9 or more, and it becomes difficult to secure the required fiberization suitability (fiber moldability).

The glass compositions of the first and second inventions contain Li ₂ O, N within the range of 15 mol% or less in addition to the essential components.
a ₂ O, K ₂ O, ZnO, MnO ₂ , TaO _5/2, BO
_It may contain at least one oxide such as _{3/2 ,} LaO _3/2 , and CeO ₂ . As a raw material for making the above glass composition, oxides (including complex oxides), carbonates,
Various compounds such as sulfates, chlorides and fluorides can be used, as long as the above composition is obtained.

The high-dielectric-constant glass fiber in the circuit board of the present invention improves the mechanical strength and dimensional stability of the board and is usually in the shape of a cloth, but in addition, it is in the shape of a mat or a simple filament. Also used in (fiber) form. In the case of cloth or mat, the fiber diameter is usually 0.5
The thickness is about 20 μm and the thickness is about 15 μm to 1.5 mm.

In the case of filaments, the fiber diameter is usually 2 to 5
Those having a length of 0 μm and a length of about 20 to 300 μm are used. The resin to be composited with the glass fiber is not particularly limited, but in the application in the high frequency range, there is little high frequency loss (low t.
an δ) resin is preferable, and examples thereof include PPO (polyphenylene oxide) resin, fluororesin (for example, Teflon: polyfluorinated ethylene-based resin such as the product name of DuPont), polycarbonate, polyethylene, polyethylene terephthalate, polypropylene, polystyrene and the like. Be done. Resins with higher relative permittivity (for example, epoxy resin, polyester resin, polyvinylidene fluoride,
In the case of a phenolic resin or the like), it is preferable in terms of relative permittivity, but it has a large dielectric loss and is not suitable for high frequencies.

As the resin, as in claim 5,
It would be very useful if a PPO-based composition containing PPO and a crosslinkable polymer and / or a crosslinkable monomer is used. PPO as a resin used in this invention is
For example, the following general formula (1)

[0030]

[Chemical 1]

[Wherein R represents hydrogen or a carbon number of 1 to 3]
Represents a hydrocarbon group, and each R may be the same or different. ], And one example thereof is poly (2,6-dimethyl-1,4-phenylene oxide). Such PPO can be synthesized, for example, by the method disclosed in USP 4059568. Although not particularly limited, for example, the weight average molecular weight (Mw) is 50,0.
00, a polymer having a molecular weight distribution Mw / Mn = 4.2 (Mn is a number average molecular weight) is preferably used.

The crosslinkable polymer is not particularly limited to these, but for example, 1,2-polybutadiene, 1,4-polybutadiene, styrene-butadiene copolymer, modified 1.2-polybutadiene (malein modified, acrylic modified , Epoxy modified), rubbers, etc.
Each is used alone or in combination of two or more. The polymer state may be elastomer or rubber.

Further, polystyrene may be added to the PPO resin composition within a range not hindering achievement of the object of the present invention. Examples of the crosslinkable monomers include ester acrylates, epoxy acrylates, urethane acrylates, ether acrylates, melamine acrylates, alkyd acrylates, silicon acrylates and other acrylic acids, triallyl cyanurate, triallyl isocyanurate, Examples include polyfunctional monomers such as ethylene glycol dimethacrylate, divinylbenzene and diallyl phthalate, monofunctional monomers such as vinyltoluene, ethylvinylbenzene, styrene and paramethylstyrene, and polyfunctional epoxies, either alone or in combination with two. The above is used together, but is not limited to these.

As the crosslinkable monomer, it is preferable to use triallyl cyanurate and / or triallyl isocyanurate because it has good compatibility with PPO and is preferable in terms of crosslinkability, heat resistance and dielectric properties. Besides this, PP
An initiator is usually added to the O-based resin composition. As the initiator, dicumyl peroxide, tert-butyl cumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexyne-3,2. 5-Dimethyl-2,5-
Di- (tert-butylperoxy) hexane, α ・ α'-
Peroxides such as bis (tert-butylperoxy-m-isopropyl) benzene [also referred to as 1.4 (or 1.3) -bis (tert-butylperoxyisopropyl) benzene], Biscumyl of NOF Corporation And the like, and each is used alone or in combination of two or more, but is not limited thereto.

The blending ratio of the above raw materials is not particularly limited, but PPO is 7% by weight or more with respect to the total amount of PPO, the crosslinkable polymer and / or the crosslinkable monomer, and the initiator added as necessary. , Less than 93% by weight of crosslinkable polymer and / or crosslinkable monomer, and 0.
1 to 5% by weight. More preferably, PPO is 7% by weight or more, the crosslinkable polymer is less than 93% by weight, the crosslinkable monomer is 70% by weight or less, and the initiator is 0.1% by weight with respect to the total amount.
1 to 5% by weight or less, and even more preferably PP
O is 10% by weight or more, the crosslinkable polymer is 20% by weight or less,
The crosslinkable monomer content is 60% by weight or less, and the initiator content is 0.5 to 3% by weight.

The raw materials having the above composition are usually dissolved in a solvent (solvent) and mixed (solution mixture). At this time, a coupling agent may be used according to a usual method. This is to improve the adhesion between the inorganic dielectric particles and the other resin components (including monomers) and to improve the physical properties of the final product. When dissolving in a solvent, PP
The resin solid content of the O-based resin composition is 10 to the solvent.
It is preferably in the range of 30% by weight. After mixing, the solvent is removed to obtain a PPO resin composition.
Examples of the solvent include halogenated hydrocarbons such as trichloroethylene, trichloroethane, chloroform and methylene chloride, aromatic hydrocarbons such as chlorobenzene, benzene, toluene and xylene, acetone and carbon tetrachloride, and trichloroethylene is particularly preferable. Each may be used alone or in combination of two or more, but is not limited thereto. Note that the mixing may be performed by another method.

The inorganic dielectric particles used in the present invention are
Normally, the inorganic dielectric particles are dense and non-porous particles,
It should not be too small considering dispersion suitability, and should not be too large considering avoiding aggregation and sedimentation. From such a viewpoint, in the case of the non-porous inorganic dielectric particles, the average particle size is 0.3 to 5 μm and the average specific surface area is 0.2 to 7.0 m ² / g (preferably the average particle size 1 to 5
It is suitable to use those having an average specific surface area of 0.2 to 3.0 m ² / g). However,
As a result of the study by the inventors, as shown in FIG. 2, there are a large number of voids including holes and cracks that open toward the surface, and a porous material that allows a part of the resin to enter the voids. It has been found that fine particles are preferable for effectively increasing the relative dielectric constant of the circuit board. In the case of the porous inorganic dielectric particles, those having an average particle diameter of 5 to 100 μm and an average specific surface area of 0.3 to 7.0 m ² / g are preferable. These non-porous particles and porous particles may be used in combination.

When the particle size exceeds 100 μm, unevenness due to particles appears on the surface of the circuit board, resulting in poor smoothness, poor moisture resistance (water resistance), and poor dielectric loss characteristics. In addition, there is a tendency that the particles are easily broken during manufacturing and the dielectric properties vary. If the particle size is less than 5 μm, the effect of improving the dielectric constant tends to be insufficient.

If the specific surface area exceeds 7.0 m ² / g, the moisture resistance (water resistance) tends to be poor and the dielectric loss characteristics tend to deteriorate. When the specific surface area is less than 0.3 m ² / g, the effect of improving the dielectric constant tends to be insufficient. The porous inorganic dielectric particles may be secondary particles formed by assembling primary particles. The secondary particles are porous with voids between the primary particles. In this case, it is preferable that the primary particles constituting the porous particles are physically and chemically bonded to each other by sintering.

The porous inorganic dielectric particles are preferably composed of a compound having a high dielectric constant composition having a perovskite type crystal structure. Examples of the porous inorganic dielectric particles include BaTiO ₃ series, SrTiO ₃ series, PbTi _1/2 Z
r _1/2 O ₃ system, Pb (Mg _2/3 Nb _1/3 ) O ₃ system, Ba
(Sn _X Mg _Y Ta _Z ) O ₃ system, Ba (Zr _X Zn _Y T
Specific examples include those having a perovskite type crystal structure (or complex perovskite type crystal structure) such as a _z ) O ₃ system, and other inorganic compounds such as TiO ₂ , ZrO ₂ and SnO ₂ alone and their complex oxides. Can be mentioned. The porous inorganic dielectric particles may have a spherical or various block-like shape, and the shape thereof is not particularly limited.

The porous inorganic dielectric particles are, for example,
The inorganic dielectric block obtained by making the sintered density low and porous is crushed, or the inorganic particles are bound with a binder (for example, PVA = polyvinyl alcohol aqueous solution).
It can be obtained by dispersing it in a medium and spraying it in a dry atmosphere (for example, a temperature atmosphere of about 130 ° C.) to obtain a granular material, which is then fired at a temperature of about 1100 ° C. In the latter case, various types of inorganic particles can be selected, but in the case of firing, in the particles obtained by spraying, the particles in the individual particles are physically and chemically bonded by sintering. This occurs, especially when the starting material is fine particles, but grain growth occurs. The sintered particles have pores and cracks opened on the surface and voids inside,
It is porous.

In this sintering, a sintering aid may be used if necessary. As the sintering aid, any auxiliary may be used as long as it is usually used for sintering such particles, but if it is forcibly defined, it will not destroy the dielectric composition and It is preferable to provide a sufficient reinforcing effect without impairing the above. The amount of the sintering aid to be used may be appropriately selected depending on the purpose and the type of the sintering aid, but usually 0.1 to 5% by weight based on the inorganic dielectric particles. preferable. The particle size of the sintering aid can be any as long as it is in the range of 0.01 to 100 μm, but it is preferably about 0.1 to 50 μm for uniform dispersion. The sintering aid may be added at any time during the stage of preparing the inorganic dielectric compound and the stage of firing. For example, when the inorganic particles are dispersed in the binder, the sintering aid is dispersed at the same time.

When the sintering aid is used, not only the effect of facilitating the sintering but also the strength of the porous particles is improved as compared with the case where the sintering aid is not used. The additional effect of being able to prevent the collapse of the porous dielectric particles in the above, and because it becomes possible to sinter at a relatively low temperature, it is possible to form porous particles with a larger porosity and to improve the dielectric constant of the circuit board. In some cases, an additional effect such as improvement can be exhibited.

The following are specific examples of the sintering aid. _{That, BaO-SiO 2 -B 2 O} 3, CaO
_{-SiO 2 -B 2 O 3, Li} 2 O-SiO 2 -B
_{2 O 3, Li 2 O-} Al 2 O 3 -SiO 2, Na 2 O-
_{Al 2 O 3 -SiO 2, Li} 2 O-GeO 2, CdO-
_{PbO-SiO 2, Li 2 O} -SiO 2, B 2 O 3 -B
_{i 2 O 3, PbO-SiO} 2 -BaO, Na 2 O-Pb
Boric acid-based glass such as O—SiO ₂ , PbO—GeO ₂ ,
Lead glass, bismuth glass, cadmium glass,
CuO, Bi ₂ O ₃ , B ₂ O such as lithium-based glass
₃ , CdO, Li ₂ O, PbO, WO ₃ , Pb ₅ Ge ₃
O ₁₁ , oxides such as Li ₂ SiO ₃ and LiF,
It is a fluoride such as CuF ₂ , ZnF ₂ and CaF ₂ .

When sintering the inorganic dielectric compound particles,
Generally, it is performed to control the particle growth and the electrical characteristics of the sintered body by the action of the additive, but in the present invention, it is possible to use various conventionally known additives for the same purpose. it can. As the porous inorganic dielectric particles,
As described above, it is preferable that the average particle size is 5 to 100 μm and the average specific surface area is 0.3 to 7.0 m ² / g.
When the primary particles are aggregated to form secondary particles, the primary particles have a size of, for example, about 0.1 to 5 μm. When the particles are spheres, this is d (particle diameter of primary particles), ρ
This is because there is a relationship of d = 6 / (ρ × Sw) between (true specific gravity of primary particles) and Sw (specific surface area of secondary particles).
Therefore, for example, in the case of barium titanate, the particle size of primary particles is about 0.14 to 3.3 μm.

In the present invention, the compounding ratio of the matrix resin, the inorganic dielectric particles and the glass fiber as the reinforcing material is usually resin: 25 to 95 vol% (volume%), inorganic dielectric particles: 5 to 75 vol%. And the high dielectric constant glass fiber for reinforcement is in the range of 5 to 70 vol%. The circuit board of the present invention is manufactured, for example, as follows.

The PPO resin composition is obtained by dissolving and mixing the above raw materials in a solvent, and the inorganic dielectric particles are added and dispersed therein, and then impregnated into the glass cloth. After impregnation, the solvent is removed by air drying and / or drying with hot air to obtain a prepreg. A predetermined number of prepregs produced in this manner are combined so as to have a predetermined design thickness, if necessary, a metal foil is also combined and laminated on both sides or one side, and the resin is melted by heating and pressing, etc.,
The prepregs are adhered to each other or the prepreg and the metal foil are adhered to each other to obtain a laminate. By this fusion, strong adhesion can be obtained, but if the crosslinking reaction by the radical initiator is carried out by heating at this time, even stronger adhesion can be obtained. The cross-linking reaction may be performed by irradiation with ultraviolet rays.
When thermal crosslinking or photocrosslinking is not performed, radiation crosslinking may be performed. Further, the crosslinking by irradiation of radiation may be performed after the thermal crosslinking or the photocrosslinking. In the cured product of the PPO-based resin composition, the resin slightly flows before curing, and thus exhibits a good fusion property with respect to the metal. However, an adhesive may be used together.

As the metal foil, copper foil, aluminum foil or the like is used. Since the pressing is performed for joining the prepregs, for joining the metal foil and the prepreg, and for adjusting the thickness of the laminated plate, the pressing conditions are selected as necessary. At the same time, conditions are set so that the inorganic dielectric particles are not crushed. When the crosslinking is carried out by heating, the crosslinking reaction depends on the reaction temperature of the initiator used and the like, so the heating temperature may be selected according to the type of the initiator. The heating time may also be selected according to the type of initiator and the like. For example, a temperature of 150 to 300 ° C., a pressure of 20 to 40
kg / cm ² , time is about 10 to 60 minutes. It is also possible that a predetermined number of sheets and / or prepregs are heat-laminated in advance, metal foils are superposed on one or both sides of the sheets, and the sheets are heat-pressed again. In this way, as shown in FIG. 1, for example, a double-sided printed circuit board in which the inorganic dielectric particles 4 are dispersed in the resin 2, reinforced with the high dielectric constant glass fiber 1, and the metal foil 3 is adhered on both sides is obtained. You can get it. The thickness of the circuit board is usually
It is about 0.1 to 2 mm.

The scope of the present invention is not limited to the above-exemplified compounds, numerical ranges or processing methods.

[0050]

In the case of the first invention, the high-dielectric-constant glass fiber for reinforcement in the circuit board of the present invention contains SiO _{2 in an amount} of 40-6.
5 mol%, 20 to 45 mol% of at least one of MgO, CaO, SrO and BaO, TiO ₂ and Zr
5 to 25 mol% of at least one of O ₂ and NbO _5/2
A glass composition containing 0.5 to 15 mol% of each, and the total amount of these oxides being 85 mol% or more,
In the case of the second invention, SiO ₂ is 40 to 65 mol%, Ca
20 to 4 of at least one of O, SrO and BaO
5 mol%, at least one of TiO ₂ and ZrO ₂ is 5 to 25 mol%, NbO _5/2 is 0.5 to 15 mol%,
Since the glass composition contains AlO _{3/2 in an amount} of 0.5 to 15 mol% and the total amount of these oxides is 85 mol% or more, it has a high relative dielectric constant (1 MHz, 25 ° C.) of 9 or more. Permittivity, dielectric loss (1MHz, 25 ℃) or ta
n δ 0.6% or less low loss and 100M
Even in the high frequency range of Hz, the change in the relative permittivity and the dielectric loss is slight and the high frequency dielectric property is also excellent.

Therefore, the action of improving the dielectric constant by the inorganic dielectric particles is not hindered, and the microscopic variation of the internal dielectric constant and the variation of the dielectric constant due to the change of the amount of the resin / inorganic dielectric particles are also suppressed. Further, in the case of the above composition, the high dielectric constant glass fiber is rich in chemical durability (acid resistance, alkali resistance, water resistance) (E
Since it is far superior to glass), there is no problem of damage due to chemical treatment during processing, there is no problem of toxicity in the case of lead-based glass containing a large amount of PbO, and the devitrification temperature has a melt viscosity of 10
^{Since the} temperature is ^2.5 poises or less, it can be made into a high dielectric constant glass fiber for reinforcing material because it is suitable for fiberization. Moreover, the strain point is as high as about 600 ° C, and the primary binder is removed at the time of crossing. Since the treatment can be performed appropriately, a glass cloth suitable as a reinforcing material can be obtained.

When a polyphenylene oxide-based composition containing polyphenylene oxide and a crosslinkable polymer and / or a crosslinkable monomer is used as the resin,
Crosslinking can be easily generated in the obtained circuit board, and physical strength such as heat resistance, tensile strength, impact strength, and breaking strength and dimensional stability can be sufficiently ensured. When the inorganic dielectric particles are porous particles, the effect of improving the dielectric constant is strong. The effect of improving the dielectric constant is that when the porous particles of the same weight are compared with each other, the volume ratio of the porous particles and the non-porous particles is the same, but the former porous inorganic dielectric particles are It is presumed that this is because the apparent occupied volume is large due to the swelling due to the voids, and the wide region including the void portions of the porous inorganic dielectric particles functions as a high dielectric constant region. Besides, the porous particles are
Since it has voids inside compared to non-porous particles, it is difficult to settle and separate in the resin varnish, and the production is easy. In addition, even when processing (cutting, punching, etc.) circuit boards, it breaks more easily than non-porous inorganic dielectrics of the same particle size, so the processed surface is good and processing consumables are not deteriorated. There is also the advantage of being small.

[0053]

EXAMPLES Examples and comparative examples will be described below. Well
First, the glass compositions for Examples and Comparative Examples were prepared as follows.
I created it. The composition should be as shown in Tables 1-8.
The raw materials for the composition are mixed, put in a platinum crucible and heated (at 4:00
(1500 ° C.) and melted. As a raw material, S
iO₂Is SiO₂To MgO, CaO, SrO and
BaO is carbonate, TiO₂Anatase type TiO
₂To ZrO₂ZrO₂To NbO_5/2NbO
_5/2Each of the first grade reagents was used.

Next, the melt was cast onto a carbon plate, shaped into a plate, and annealed to obtain a plate glass. The following data were obtained for the glass plates for each example and comparative example. —Relative Dielectric Constant and Dielectric Loss— First, the obtained plate-shaped glass was partially cut and polished to prepare a sample for dielectric property evaluation. Then, gold electrodes were formed by vapor deposition on both surfaces of this sample, and the relative permittivity and the dielectric loss (dielectric loss tangent) were measured by an impedance analyzer. The measurement frequency is 1 MHz and 1 GHz, and the temperature is 25 ° C.

[0055] -10 ^2.5 poise temperature - were measured measured 10 ^2.5 poise temperature the viscosity of the melt is dissolved a portion of sheet glass by a platinum ball pulling method. -Devitrification temperature-Part of the plate-like glass was made into particles of 297 to 500 µm, put in a platinum boat and kept in an electric furnace having a temperature gradient for 16 hours, then allowed to cool in air and the devitrification appearance position was obtained under a microscope. It was measured by that.

-Agility for fiberizing-The rest of the plate glass is crushed and put into a platinum bushing, and the platinum bushing is directly energized to melt the glass, and the bushing temperature is set to 10 ^2.5 poise temperature. It was drawn out from the nozzle) and wound up to obtain glass fiber.

The above data are also shown in Tables 1-8. In addition,
In the above case, the glass fiber was obtained by making it into a plate glass and then remelting it, but the glass fiber may be obtained directly from the first melt. Glass fibers can likewise be obtained. For mass production, it is suitable to obtain the glass fibers directly from the initial melt.

[0058]

[Table 1]

[0059]

[Table 2]

[0060]

[Table 3]

[0061]

[Table 4]

[0062]

[Table 5]

[0063]

[Table 6]

[0064]

[Table 7]

[0065]

[Table 8]

Yes for the example glasses of compositions 1-32
Although the deviation could be made into fiber, in the case of the comparative glass of composition X,
TiO₂And ZrO₂Too much content and N
bO _5/2Nb in the case of the comparative glass having the composition Y
O_5/2Since it did not contain, it could not be formed into fibers. Also, the group
AlO is also used in the case of the comparative glass made of Z_3/2Including but NbO
_5/2The devitrification temperature is 10 because it does not contain^2.5Exceeds Poise temperature
It could not be made into fiber. AlO_3/2Must be alone
It is not possible to secure the required fiber suitability. 10 ^2.5Pore
The temperature and devitrification temperature data should be checked for fiber suitability.
I support it. In the case of the glass for the examples, the dielectric
The characteristics are very good, including high frequencies.

Example 1 BaTi _0.7 Zr _0.3 O ₃ particles 5 having an average particle size of 0.1 μm
00 g, 2.5 g of borosilicate glass (manufactured by Iwaki Glass) and 50 ml of a 5 wt% polyvinyl alcohol solution were well wet-mixed in 1 liter of ion-exchanged water, and then spray granulated. Next, this is heat-treated at 1050 ° C. for 2 hours to obtain an average particle size of 20 μm and an average specific surface area of 1
． Particles of 0 m ² / g were obtained as porous inorganic dielectric particles.

Next, this porous BaTi _0.7 Zr _0.3 O
180 parts by weight of ₃ particles (30 vol%), PPO resin 7
4 parts by weight (70 vol%) was weighed, 300 parts by weight of trichlene (Toagosei Kagaku Kogyo Co., Ltd. trichloroethylene) was added and stirred, and a 2 liter reactor equipped with a defoaming device was used. Then, the PPO resin was completely dissolved and defoamed to obtain a varnish.

On the other hand, a fiber made of glass having the above composition 3
Was used to obtain a glass cloth by a conventional method. This glass
Loss is plain weave glass cloth, thickness: 100μ
m, fiber diameter: 7 μm, weave density: per 25 mm, length 60
There are 58 horizontal books. Stir the varnish well and then flatten
Woven glass cloth was impregnated and dried at 50 ° C. Got
Resin and Ba in varnish impregnated glass cloth
Ti_0.7Zr _0.3O₃Of a mixture of particles and glass cloth
The ratio is a mixture of resin and particles: 62 wt% (about 70 vol.
%), Glass cloth: 38 wt% (about 30 vol%)
It was. 5 pieces of varnish-impregnated cloth obtained in this way
Overlap and place copper foil (thickness 17 μm) on the top and bottom,
50 ° C, pressure 33 kg / cm²Pressurize under molding condition for 10 minutes
Molded to obtain a double-sided copper foil-clad printed circuit board.

-Comparative Example 1-A double-sided copper foil-clad printed circuit board was obtained in the same manner as in Example 1 except that the glass cloth was made of lead-based glass having the following composition. "Lead glass" composition PbO: 41.2 mol%, Si
O _2: 55.3 mol%, B ₂ O _3: 2.8 mol%, K ₂
O: 0.7 mol% relative permittivity 1 MHz: 13.0, 1 GHz: 12.9 tan δ (%) 1 MHz: 0.09%, 1 GHz: 0.54% -Comparative example 2-Glass cloth of the following composition E A double-sided copper foil-clad printed circuit board was obtained in the same manner as in Example 1 except that it was prepared using glass.

[0071] "E glass" composition SiO _2: 57.9 mol%, Al ₂ O _3: 8.7 mol%, B ₂ O _3: 7.3 mol%, CaO: 24.2 mol%, MgO: 1 0.6 mol%, K ₂ O: 0.3 mol% Relative permittivity 1 MHz: 6.5, 1 GHz: 6.5 tan δ (%) 1 MHz: 0.15%, 1 GHz: 0.28% -Example 2 7-A circuit board was obtained in the same manner as in Example 1 except that the resin varnish made of the PPO resin composition shown in Table 9 was used, and the molding temperature was 200 ° C and the molding time was 30 minutes.

[0072]

[Table 9]

In Table 9, SBS is styrene butadiene copolymer, TAIC is triallyl isocyanurate, p-TAIC is TAIC polymer, and A is 2
Represents 5-dimethyl-2,5-di- (tert-butylperoxy) hexyne-3. As the 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexyne-3, Perhexin 25B manufactured by NOF CORPORATION was used.

Example 8 As non-porous inorganic dielectric particles, an average particle size of 20 μm,
Average specific surface area 0.2 m ²/ G BaTi_0.7Zr_0.3O
₃Both were carried out in the same manner as in Example 1 except that the particles were used as they were.
A copper foil-clad printed circuit board was obtained. -Example 9-The non-porous inorganic dielectric particles have an average particle size of 1.6 m.
, Average specific surface area of 1.5m²/ G BaTi_0.7Zr
_0.3O₃As in Example 1 except that the particles were used as they were.
Then, a double-sided copper foil-clad printed circuit board was obtained.

Example 10 As the non-porous inorganic dielectric particles, the average particle size is 3.4 μm.
Of TiO ₂ (rutile) with an average specific surface area of 1.7 m ² / g
A double-sided copper foil-clad printed circuit board was obtained in the same manner as in Example 1 except that 347 g of the particles were used as they were. —Example 11— Ba _0.7 Sr _0.3 TiO ₃ particles 5 having an average particle size of 0.1 μm
After thoroughly wet-mixing 00 g, 1.7 g of CuO, and 50 ml of a 5 wt% polyvinyl alcohol solution in 1 liter of ion-exchanged water, spray granulation was performed. Next, this is heat-treated at 1000 ° C. for 2 hours to obtain an average particle size of 2 including a plurality of primary particles.
1 μm, average specific surface area 1. Particles of 3 m ² / g were obtained as porous inorganic dielectric particles. Aside from this, a double-sided copper foil-clad printed circuit board was obtained in the same manner as in Example 1.

Example 12-BaTi _0.7 Zr _0.3 O ₃ particles 5 having an average particle size of 0.1 μm
After thoroughly wet-mixing 00 g and 50 ml of a 5 wt% polyvinyl alcohol solution in 1 liter of ion-exchanged water, spray granulation was performed. Next, this was heat-treated at 1100 ° C. for 2 hours to obtain particles composed of a plurality of primary particles having an average particle size of 80 μm and an average specific surface area of 5.6 m ² / g as porous inorganic dielectric particles. Aside from this, a double-sided copper foil-clad printed circuit board was obtained in the same manner as in Example 1.

Example 13 BaTi _0.7 Zr _0.3 O ₃ particles 1 having an average particle size of 0.1 μm
After thoroughly wet-mixing 00 g, 1.7 g of CuO, and 10 ml of a 5 wt% polyvinyl alcohol solution in 1 liter of ion-exchanged water, spray granulation was performed. Next, this is heat-treated at 1100 ° C. for 2 hours to obtain an average particle size of 6 including a plurality of primary particles.
Particles having a micrometer and an average specific surface area of 5.3 m ² / g were obtained as porous inorganic dielectric particles. Aside from this, a double-sided copper foil-clad printed circuit board was obtained in the same manner as in Example 1.

Example 14 A double-sided copper foil-clad printed circuit board was obtained in the same manner as in Example 1 except that the glass cloth was made of the glass composition of Composition 26. -Example 15-A double-sided copper foil-clad printed circuit board was obtained in the same manner as in Example 2 except that the glass cloth was made of the glass composition of Composition 26.

Example 16 A double-sided copper foil-clad printed circuit board was obtained in the same manner as in Example 3 except that the glass cloth was made of the glass composition of Composition 26. -Example 17-A double-sided copper foil-clad printed circuit board was obtained in the same manner as in Example 4 except that the glass cloth was made of the glass composition of Composition 26.

Example 18 A double-sided copper foil-clad printed circuit board was obtained in the same manner as in Example 5 except that the glass cloth was made of the glass composition of Composition 26. Example 19 A double-sided copper foil-clad printed circuit board was obtained in the same manner as in Example 6 except that the glass cloth was made of the glass composition of Composition 26.

Example 20 A double-sided copper foil-clad printed circuit board was obtained in the same manner as in Example 7 except that the glass cloth was made of the glass composition of Composition 26. -Example 21-A double-sided copper foil-clad printed circuit board was obtained in the same manner as in Example 8 except that the glass cloth was made of the glass composition of Composition 26.

Example 22 A double-sided copper foil-clad printed circuit board was obtained in the same manner as in Example 9 except that the glass cloth was made of the glass composition of Composition 26. -Example 23-A double-sided copper foil-clad printed circuit board was obtained in the same manner as in Example 10 except that the glass cloth was made of the glass composition of Composition 26.

Example 24 A double-sided copper foil-clad printed circuit board was obtained in the same manner as in Example 11 except that the glass cloth was made of the glass composition of Composition 26. -Example 25-A double-sided copper foil-clad printed circuit board was obtained in the same manner as in Example 12 except that the glass cloth was made of the glass composition of Composition 26.

Example 26 A double-sided copper foil-clad printed circuit board was obtained in the same manner as in Example 13 except that the glass cloth was made of the glass composition of Composition 26. In addition, Examples 2 to 26 and Comparative Examples 1 and 2
Then, the volume ratio of the inorganic dielectric particles and the PPO resin composition is 30:70, and the volume ratio of the mixture of the inorganic dielectric particles and the PPO resin composition fat and the glass cloth is 70: 3.
0, which was the same as in Example 1.

With respect to each of the obtained circuit boards, the relative permittivity (ε _r ), the dielectric loss tangent (tan δ), the peeling strength, and the solder heat resistance were examined. Tables 10 and 11 show measurement results of relative permittivity (ε _r ) and dielectric loss tangent (tan δ), and Tables 12 and 13 show measurement results of peeling strength and solder heat resistance.

[0086]

[Table 10]

[0087]

[Table 11]

[0088]

[Table 12]

[0089]

[Table 13]

As can be seen from the table, the printed circuit board of Example 1 is 1% less than that of Comparative Example 1 using lead glass.
Comparative Example 2 using E glass with low dielectric loss at GHz
It can be seen that it has a higher relative dielectric constant than the substrate No. 1 and is suitable as a substrate in the high frequency range. Comparing Examples 2 to 7 and Examples 15 to 20 with other examples, it is well understood that the use of the PPO resin composition which is easily crosslinked improves the heat resistance.

Examples 1-7, 11-13 and Examples 8-1
0, or comparing Examples 14 to 20 and 24 to 26 with Examples 21 to 23, it is clear that the porous inorganic dielectric particles have a strong effect of improving the dielectric constant. Porous inorganic dielectric particles used in Examples 1 to 7, 11, 13 to 20, 24 and 26 (with a sintering agent) and porous inorganic dielectric particles used in Examples 12 and 25 (without a sintering agent). ) To the PC
The particle strength was examined using a T (grain strength) tester (manufactured by Shimadzu Corporation). The former is in the range of 7.0 to 8.5 kg / mm ² , the latter is in the range of 3.5 to 3.8 kg / mm ² , and the use of a sintering agent indicates that the grain strength is increased. confirmed.

[0092]

As described above, the circuit board according to the first and second inventions is reinforced with glass fiber having a composition which is easy to be formed into a fiber, has a high dielectric constant, and has a good chemical durability. It is useful because it has excellent dielectric properties and is easy to manufacture. The circuit board according to any one of claims 5 to 8 additionally uses a crosslinkable PPO-based resin composition as a resin component, so that crosslink easily occurs, and heat resistance starts, tensile strength, and impact strength. It is a very useful substrate because the burst strength is greatly increased.

In the circuit board of claim 9, the non-porous inorganic dielectric particles have an average particle size of 0.3 to 5 μm and an average specific surface area of 0.2 to 7.0 m ² / gr. Agglomeration / sedimentation can be avoided and the dispersibility can be improved, the circuit board can be easily manufactured, and the non-uniformity of the dielectric constant can be suppressed. In addition to the circuit board according to any one of claims 10 to 14, the inorganic dielectric particles dispersed in the resin are particles that are difficult to settle and separate and have a high effect of improving the dielectric constant. Since it is excellent, it is a very useful substrate. In the circuit board according to claim 10, in addition, the average particle diameter of the porous inorganic dielectric particles is 5 to 100 µm, and the average specific surface area is 0.3 to.
Since it is 7.0 m ² / gr, the effect of improving the dielectric constant is more remarkably exhibited.

In the circuit board according to the twelfth aspect, in addition, the porous inorganic dielectric particles are secondary particles formed by aggregating the primary particles, and as a result, the porous particles are easy to produce. Circuit boards are easy to manufacture. In the circuit board according to the thirteenth aspect, in addition, since the primary particles in the porous inorganic dielectric particles are bonded to each other by sintering, the effect of improving the dielectric constant is more remarkably exhibited.

In the circuit board of claim 14, since the strength of the porous inorganic dielectric particles is improved, particle destruction does not occur in the compounding step, stable performance can be expected, and particle production is easy. Becomes

In the circuit board according to the fifteenth aspect, since the porous inorganic dielectric particles are composed of the compound having the perovskite type crystal structure, the effect of improving the dielectric constant is more remarkable.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view showing a configuration example of a circuit board according to the present invention.

FIG. 2 is a cross-sectional view showing an example of porous inorganic dielectric particles used in the circuit board of the present invention.

[Explanation of symbols]

 1 glass cloth (high dielectric constant glass fiber) 2 resin 3 metal foil 4 porous inorganic dielectric particles

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] April 4, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0037

[Correction method] Change

[Correction content]

The inorganic dielectric particles used in the present invention are
Usually a dense, non-porous particle, but does not agglomerate
So as not too small too much taking into account that this is some of the dispersion suitability, also, to avoid too large too much in consideration of the fact that avoid sedimentation. From such a viewpoint, in the case of the non-porous inorganic dielectric particles, the average particle size is 0.3 to 5 μm and the average specific surface area is 0.2 to 7.0 m ² / g (preferably the average particle size is 1 to 5 μm). And the average specific surface area is 0.2 to 3.
It is suitable to use one having a range of 0 m ² / g).
However, as a result of the study by the inventors, as shown in FIG. 2, there are a large number of voids such as holes and cracks that open toward the surface, and some of the resin can enter into these voids. It has been found that such porous particles are preferable for effectively increasing the relative dielectric constant of the circuit board. In the case of these porous inorganic dielectric particles, the average particle size is 5 to 100 μm.
m, and an average specific surface area of 0.3 to 7.0 m ² / g are preferable. These non-porous particles and porous particles may be used in combination.

Claims (15)

[Claims] 1. A circuit board comprising inorganic dielectric particles dispersed in a resin and reinforced with a high dielectric constant glass fiber, comprising:
The high dielectric constant glass fiber contains 40 to 65 mol% of SiO ₂ , ₂₀ to 45 mol% of at least one of MgO, CaO, SrO and BaO, 5 to 25 mol% of at least one of TiO ₂ and ZrO ₂ , and NbO. _5/2 to 0.
5 to 15 mol% each, the total amount of these oxides is 85 mol% or more, and the relative dielectric constant (1 MHz, 25 ° C.)
A circuit board comprising a glass composition having a fiberizing aptitude of 9 or more. _2. The content of SiO ₂ is 46 to 60 mol%,
The content of at least one of MgO, CaO, SrO and BaO is 25 to 40 mol%, TiO ₂ and ZrO.
The content of at least one of ₂ is 7 to 24 mol%, Nb
The circuit board according to claim 1, wherein the content of O _5/2 is 1 to 10 mol%. 3. A circuit board comprising inorganic dielectric particles dispersed in a resin and reinforced with a high dielectric constant glass fiber,
The high dielectric constant glass fiber contains 40 to 65 mol% of SiO ₂ , ₂₀ to 45 mol% of at least one of CaO, SrO and BaO, 5 to 25 mol% of at least one of TiO ₂ and ZrO ₂ , and NbO _{5 / 2} to 0.5 to 15
Mol%, AlO _3/2 0.5 to 15 mol% respectively, the total amount of these oxides is 85 mol% or more,
A circuit board comprising a glass composition having a fiber formability of 9 or more in a relative dielectric constant (1 MHz, 25 ° C.). 4. The content of SiO ₂ is 46 to 60 mol%,
The content of at least one of CaO, SrO and BaO is 25 to 40 mol%, the content of at least one of TiO ₂ and ZrO ₂ is 7 to 24 mol%, and the content of NbO _5/2 is 1 to 10 mol%, The content of AlO _3/2 is 1 to 1
The circuit board according to claim 3, wherein the content is 0 mol%. 5. The circuit board according to claim 1, wherein a polyphenylene oxide-based composition containing polyphenylene oxide and a crosslinkable polymer and / or a crosslinkable monomer is used as the resin. 6. The amount of polyphenylene oxide is 7% by weight or more and less than 93% by weight of the crosslinkable polymer and / or the crosslinkable monomer based on the total amount of the polyphenylene oxide and the crosslinkable polymer and / or the crosslinkable monomer.
The described circuit board. 7. The crosslinkable polymer is at least one selected from the group consisting of 1,2 polybutadiene, 1,4 polybutadiene, styrene butadiene copolymer, modified 1,2 polybutadiene, and rubbers. 6. The circuit board according to item 6. 8. The crosslinkable monomer includes ester acrylates, epoxy acrylates, urethane acrylates, ether acrylates, melamine acrylates, alkyd acrylates, silicon acrylates, triallyl cyanurate, triallyl isocyanurate, ethylene glycol. 8. At least one selected from the group consisting of dimethacrylate, divinylbenzene, diallylphthalate, vinyltoluene, ethylvinylbenzene, styrene, paramethylstyrene and polyfunctional epoxies. The described circuit board. 9. The inorganic dielectric particles are non-porous particles, having an average particle diameter of 0.3 to 5 μm and an average specific surface area of 0.2 to
The circuit board according to any one of claims 1 to 8, which is of 7.0 m ² / g. 10. The circuit board according to claim 1, wherein the inorganic dielectric particles are porous particles. 11. The porous inorganic dielectric particles have an average particle size of 5 to 5.
The circuit board according to claim 10, which has a mean surface area of 100 μm and an average specific surface area of 0.3 to 7.0 m ² / g. 12. The circuit board according to claim 10 or 11, wherein the porous inorganic dielectric particles are secondary particles formed by assembling primary particles. 13. The circuit board according to claim 12, wherein the secondary particles are primary particles bonded to each other by sintering. 14. The circuit board according to claim 13, wherein the sintering is performed by adding a sintering aid. 15. The circuit board according to claim 1, wherein the inorganic dielectric particles are made of a compound having a perovskite type crystal structure.