JP2003039587A - Laminated sheet and multilayer sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thin type laminated sheet which has both of excellent processability and a high relative dielectric constant and of which the insulating layer has electrical insulation properties ensured sufficiently. SOLUTION: The laminated sheet is formed by laminate molding of conductor layers on both sides of a dielectric layer constituted of a cured material of a resin composition comprising a thermosetting resin and an inorganic filler and of a base. The dielectric layer contains a barium titanate zirconate as the inorganic filler. The thickness of the whole dielectric layer is 10-60 μm and the volume resistivity of the layer on the occasion of impressing a voltage of 500 V thereon is 10<12> -10<16> Ω/cm when the thickness of the layer 40-60 μm, while it is 10<10> -10<16> Ω/cm when the thickness of the layer is 10-40 μm.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated board and a multilayer board used for a printed wiring board.

[0002]

2. Description of the Related Art In recent years, while the functions of electronic devices have increased and the functions thereof have rapidly become higher, the miniaturization of electronic parts incorporated in electronic devices and the densification of packaging have advanced, resulting in miniaturization of electronic devices. Lightening and thinning have progressed rapidly.

[0003] In the trend toward higher functionality, lighter, thinner, shorter, and smaller electronic devices, an insulating layer of a laminated board to be processed into a printed wiring board is used as a dielectric, and a bypass capacitor is formed there. Combined with patterns to form composite circuits. In order to form such a composite circuit, a thin insulating substrate having a high relative dielectric constant is required, and this is used as an insulating layer of a laminated board.

[0004]

Generally, an organic substrate made of an organic material such as epoxy resin or polyimide resin has a relative dielectric constant of about 5, whereas a ceramic made of an inorganic material such as alumina or aluminum nitride. Since the relative permittivity of the substrate is about 10, this ceramic substrate has been used as an insulating substrate having a high relative permittivity until now, but the workability of the ceramic substrate is worse than that of the organic substrate, and therefore the ceramic substrate is actually used. Was difficult.

Therefore, it has been attempted to provide a high relative permittivity and good workability by using an organic substrate containing barium titanate as an inorganic filler, but it is thin and has a high relative permittivity. When trying to get a plate,
The volume resistivity of the organic substrate was insufficient, and it was difficult to secure the insulating property of the insulating layer.

The present invention has been made in view of the above points, and is a thin laminated plate having both excellent workability and a high relative dielectric constant, and the electric insulation of the insulating layer is sufficiently ensured. It is intended to provide a multilayer board using the.

[0007]

A laminated board according to claim 1 of the present invention has a dielectric layer composed of a cured material of a resin composition containing a thermosetting resin and an inorganic filler, and a substrate. In the laminated plate in which the conductor layer is laminated and formed, the dielectric layer contains barium zirconate titanate as an inorganic filler, the total thickness of the dielectric layer is 10 to 60 μm, and a voltage of 500 V is applied. The volume resistivity is 40 and the thickness of the dielectric layer is 40.
Is 10 ¹² to 10 ¹⁶ Ω · cm in the case of ˜60 μm, and 10 ¹⁰ to 10 ^{16 in} the case of the thickness of the dielectric layer is ¹⁰ to 40 μm.
It is characterized in that it is Ω · cm.

The invention of claim 2 is characterized in that, in claim 1, the relative dielectric constant of the entire dielectric layer is 10 to 100 and the electric capacity is 0.15 to 3.1 nF / cm ^2. Is.

A third aspect of the present invention is the method according to the first or second aspect, wherein the composition ratio Ti: Zr of titanium atoms and zirconium atoms in barium zirconate titanate in the dielectric layer.
In the range of 95: 5 to 60:40.

The invention of claim 4 is characterized in that in any one of claims 1 to 3, the dielectric layer contains barium zirconate titanate synthesized by a hydrothermal synthesis method. To do.

According to the invention of claim 5, in any one of claims 1 to 4, the barium zirconate titanate in the dielectric layer has an average particle size of 0.01 to 5 μm and has a particle size distribution. Particles with a diameter of 50 μm or more are 5 of all particles
% Or less.

The invention of claim 6 is characterized in that, in any one of claims 1 to 5, the volume fraction of the inorganic filler in the dielectric layer is 25 to 50% by volume.

The invention of claim 7 is characterized in that, in any one of claims 1 to 6, the relative dielectric constant of the inorganic filler in the dielectric layer is 50 to 10,000.

The invention of claim 8 is characterized in that, in any one of claims 1 to 7, the thermosetting resin in the resin composition is an epoxy resin.

The invention of claim 9 is the resin composition according to any one of claims 1 to 8, wherein the resin composition contains a coupling agent, and the coupling agent is at least one of epoxysilane, aminosilane, and mercaptosilane. It is characterized by being.

Further, the invention of claim 10 is based on claims 1 to 9.
In any one of the above, the base material forming the dielectric layer is a sheet having a thickness of 5 to 40 μm.

The invention of claim 11 relates to claims 1 to 1.
0, the relative dielectric constant of the base material forming the dielectric layer is 5 to 30.

The twelfth aspect of the present invention provides the first aspect.
In any one of 1 above, the conductor layer is formed of a metal foil, and the surface roughness of the surface of the metal foil that contacts the dielectric layer is 1 to 7
It is characterized by being formed as μm.

Further, the invention of claim 13 is based on claims 1 to 1.
In any one of 2 above, after stirring the mixture containing the respective components constituting the resin composition with a stirrer, the inorganic filler is dispersed with a disperser, and the mixture is further passed through a filter having an opening of 30 μm or less. It is characterized by using the obtained resin composition.

A multilayer board according to claim 14 of the present invention is
A resin composition having a circuit formed on the conductor layer of the laminated plate according to any one of claims 1 to 13 and having a lower relative dielectric constant than the dielectric layer of the laminated plate outside the conductor layer on which the circuit is formed. It is characterized in that a low relative dielectric constant layer made of is formed.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below.

The laminated plate of the present invention is formed by laminating and molding conductor layers on both sides of a dielectric layer composed of a base material and a cured product of a resin composition containing a thermosetting resin and an inorganic filler. .

The substrate is not particularly limited as long as it is a sheet-shaped substrate used for preparing prepregs. For example, glass substrates such as glass cloth, glass mat and glass paper, and linter paper. A paper base material such as kraft paper can be used. This base material has a thickness of 5
It is preferable to use one having a thickness of -40 μm,
Since the thickness is 5 μm or more, the handleability is good, and the thickness is 40 μm or less, the dielectric layer can be thinned and the electric capacity of the laminated plate can be sufficiently increased. is there.

Further, it is preferable that the relative permittivity of the base material is 5 to 30, and in this case, the base material contributes to the improvement of the relative permittivity of the dielectric layer and the thermosetting of the dielectric layer. It is possible to prevent an excessive amount of the inorganic filler added to the thermosetting resin, and to manufacture a laminated board without impairing the original properties of the thermosetting resin. Here, the use of a base material having a higher relative dielectric constant can contribute to the improvement of the relative dielectric constant of the dielectric layer, but when the relative dielectric constant of the base material exceeds 30, the base material has a higher dielectric constant. It is necessary to mix or adhere an inorganic filler having a relative dielectric constant, which makes the base material very brittle and difficult to handle. On the contrary, when the relative dielectric constant of the base material is less than 5, it is laminated. This leads to a decrease in the electric capacity of the plate, and it becomes necessary to increase the amount of the inorganic filler added to the thermosetting resin, which may impair the original properties of the thermosetting resin.

The thermosetting resin is not particularly limited, and examples thereof include epoxy resin, polyimide resin, polyphenylene oxide resin (PPO resin), polyphenylene ether resin, bismaleimide triazine resin (BT resin), polybutadiene. A resin or the like can be used, and one of these can be used alone, or two or more can be mixed and used.

Further, as a particularly preferable thermosetting resin,
An epoxy resin such as a brominated bisphenol A type epoxy resin or a cresol novolac type epoxy resin. Such an epoxy resin has excellent properties such as adhesiveness, processability, and insulation properties, and is an insulating layer (dielectric layer) of a laminated plate. It is suitable for the formation of the above, and a high relative dielectric constant can be achieved by adding an inorganic filler to further increase the electric capacity.

The inorganic filler contains barium zirconate titanate, which improves the relative dielectric constant of the dielectric layer and the volume resistivity.

Barium titanate zirconate is used as Ba (T
i _x Zr _(1-x) ) O ₃ (0 <x <1), the composition ratio of titanium atoms and zirconium atoms is Ti:
Zr = 95: 5 to 60:40, that is, x in the formula is 0.
When it is in the range of 60 to 0.95, the relative permittivity and resistivity of the barium zirconate titanate are particularly high, and the relative permittivity and volume resistivity of the dielectric layer can be further improved.

As the barium zirconate titanate, it is preferable to use one synthesized by a hydrothermal synthesis method. In this hydrothermal synthesis method, for example, barium hydroxide and zirconium hydroxide are added to a hydrous titanium oxide slurry at a predetermined Ti / Ba ratio.
After mixing at a ratio of / Zr, the mixture can be placed in a reaction kettle and heated to allow the hydrothermal reaction to proceed.

The barium zirconate titanate obtained by such a hydrothermal reaction has a particle shape close to a sphere, is excellent in dispersibility in the composition, and has a uniform relative dielectric constant and resistivity throughout. A dielectric layer can be formed.

As the barium zirconate titanate, one having an average particle size of 0.01 to 5 μm and a content of particles having a particle size of 50 μm or more of 5% by mass or less is further used. It is possible to achieve a high dielectric constant of the dielectric layer and improve the electric capacity of the laminate. If the average particle size is less than 0.01 μm, the surface area of the inorganic filler in the composition becomes too large and the viscosity of the composition increases, making it difficult to impregnate the base material with the composition. ,
If the average particle size exceeds 5 μm, the large-diameter particles increase, and the large-diameter particles are likely to be exposed on the surface of the dielectric layer composed of the cured product of the composition. When the thickness of the conductor layer is small, the particles may penetrate the conductor layer. Even if the average particle size of the inorganic filler is within this range, the particle size is 50 μm.
When the content of the above particles exceeds 5% by mass, the large particles also increase, and the large particles are exposed on the surface of the dielectric layer composed of the cured product of the composition. There is a risk that the adhesion will be reduced, the adhesion between the dielectric layer and the conductor layer will be reduced, and if the conductor layer is thin, particles will penetrate the conductor layer. The smaller the content of the particles having a particle size of 50 μm or more, the better, and the content is particularly preferably 0% by mass.

The dielectric constant of the inorganic filler in the dielectric layer is preferably in the range of 50 to 10,000. If the relative dielectric constant is less than 50, a large amount of inorganic filler must be added in order for the laminate to have a sufficient electric capacity, and the handling property such as an increase in the viscosity of the resin composition will deteriorate. If the relative permittivity exceeds 10,000, the temperature change of the relative permittivity of the inorganic filler becomes large, and it becomes difficult to obtain a laminated plate having a stable electric capacity.

Here, as the inorganic filler, any one other than the above barium zirconate titanate may be used in combination as long as the relative dielectric constant is in the range of 50 to 10,000. For example, titanium dioxide ceramics or titanic acid. Barium ceramics, lead titanate ceramics, strontium titanate ceramics, calcium titanate ceramics,
A bismuth titanate-based ceramic, a magnesium titanate-based ceramic, a zirconate-based ceramic, or the like can be used. However, in order for the dielectric layer to have a sufficiently large volume resistivity, the content of barium zirconate titanate is preferably 50 to 100 mass% with respect to the total amount of the inorganic filler.

Such an inorganic filler is used in the dielectric layer composed of the resin composition and the base material so that the volume fraction of the dielectric layer is within the range of 25 to 50% by volume. It is preferable to adjust the content in the composition and the amount of the resin composition impregnated into the base material, which can further increase the dielectric constant of the dielectric layer and improve the electric capacity. If this volume fraction is less than 25% by volume, it will be difficult to impart sufficient electric capacity to the laminate, and if it exceeds 50% by volume, the viscosity of the resin composition will increase and the dielectric layer and the conductor layer There is a risk that the adhesiveness with

Further, it is preferable that one or more of epoxy silane, amino silane and mercapto silane be blended as a coupling agent in the resin composition. The adhesiveness (affinity) between the resin and the inorganic filler in (3) is improved, the dispersibility of the inorganic filler is improved, and the viscosity increase of the resin composition is suppressed to improve the handling property. The amount of the coupling agent blended is preferably in the range of 0.5 to 3.0% by mass, and if it is less than 0.5% by mass, the dispersibility of the inorganic filler may not be sufficiently improved. Yes, if the added amount exceeds 3.0% by mass,
There is a possibility that the electrical characteristics of the manufactured laminated board or the printed wiring board obtained by processing the laminated board may deteriorate.

In the resin composition, a curing agent such as dicyandiamide, a crosslinkable monomer such as triallyl isocyanurate, a curing accelerator such as 2-ethyl-4-methylimidazole, and the initiation of polymerization of dicumyl peroxide and the like. Various additives such as agents can also be blended.

When the substrate is impregnated with such a resin composition, a varnish can be prepared by dissolving the resin composition in a solvent and diluting it, and then impregnating the substrate with the varnish. Here, the solvent is not particularly limited, and for example, methyl ethyl ketone, methyl cellosolve, N, N-dimethylformamide, N-methylpyrrolidone, toluene and the like can be used, and one of them can be used alone. Alternatively, two or more kinds may be mixed and used.

Here, when the resin composition or varnish as described above is prepared, a mixture of the components is first stirred by a stirrer to predisperse the inorganic filler, and then the disperser is used. Disperse using, further open 30μm
It is preferable to pass the following filter. In this case, the particles of the inorganic filler are not aggregated in the resin composition or the varnish, and the primary particles of the inorganic filler are highly dispersed (primary dispersion), and the dielectric layer is entirely distributed. By having a uniform relative permittivity and volume resistivity, the laminated plate has a stable electric capacity and improved insulation reliability, and particles with a large diameter exceeding the opening of the filter are As a result, the inorganic filler particles can be prevented from penetrating the conductor layer and causing insulation failure.

As the above-mentioned stirrer, it is possible to use a stirrer that has a blade-shaped rotor at the tip of the shaft and gives shear stress by rotating this in a resin composition or varnish to stir the inorganic filler. . In addition, as a disperser, spherical beads are filled in a dispersion tank, and a resin composition or varnish is passed through a rotating dispersion tank to give strong shear stress from the beads to disperse the inorganic filler. Can be used.

The lower limit of the aperture of the filter is not particularly limited, but in order to minimize the filter passage time of the resin composition or varnish, the aperture of the filter is 50 to 30% of the thickness of the dielectric layer. It is preferably in the range of.

Then, this varnish is impregnated into the above-mentioned base material and dried in a dryer at a temperature of about 120 to 160 ° C. for 2 to 10
By drying for about a minute, a prepreg in which the thermosetting resin is in a semi-cured state (B-stage) can be produced.

Next, one prepreg prepared as described above or a stack of a required number of prepregs,
Overlap the metal foil on one side or both sides, for example 1
A laminated board for processing into a printed wiring board can be manufactured by heating and pressurizing under conditions of 70 to 220 ° C., 2 to 5 MPa, and 50 to 90 minutes for laminate molding.

As a result, a dielectric layer is formed of a cured product of one or more prepregs, and a conductor layer is formed of a metal foil on the outside of the dielectric layer.

Alternatively, one or a plurality of prepregs may be cured and formed without laminating metal foils to form a dielectric layer, and a conductor layer may be formed outside the dielectric layer by a plating method or the like. When the conductor layer is formed using a metal foil, the type is not particularly limited, and for example, copper foil, silver foil, aluminum foil, stainless steel foil, etc. can be used, but copper foil is used. Is preferred.

Further, it is preferable that the surface of the metal foil to be superposed on the prepreg, that is, the surface of the laminated plate which comes into contact with the dielectric layer has a surface roughness in the range of 1 to 7 μm. By setting the surface roughness to 1 μm or more, the adhesion between the conductor layer and the dielectric layer is further improved, and by setting the surface roughness to 7 μm or less, the dielectric layer is interposed. Prevents the distance between conductor layers from becoming short locally,
Particularly in a thin laminated plate, the insulation between the conductor layers can be surely ensured.

The total thickness of the dielectric layers of the laminate thus manufactured is 10 to 60 μm, and
The volume resistivity of the dielectric layer when a voltage of 500 V is applied between both surfaces of the dielectric layer is such that the thickness of the dielectric layer is 40 to 60 μm.
In the case of, the composition of the resin composition and the base material are selected so as to be 10 ¹² to 10 ¹⁶ Ω · cm, and when the thickness of the dielectric layer is ¹⁰ to 40 μm, 10 ¹⁰ to 10 ¹⁶ Ω · cm. It is a thing. When the thickness of the dielectric is less than 10 μm, it becomes difficult to handle the laminated plate, and conversely the thickness is 60 μm.
If it exceeds, the electric capacity of the laminated plate will decrease.
Further, since the volume resistivity of the dielectric layer is within the above range, the dielectric layer has a sufficient resistance value even if it is thinned,
The electrical insulation can be ensured.

The relative dielectric constant of the dielectric layer of the laminated plate is 10 to
100, it is preferable to select the composition of the resin composition and the base material so that the electric capacity is 0.15 to 3.1 nF / cm ^2, and thus the dielectric constant and the electric capacity are high, and the handling property is high. A high laminate is obtained. If the relative dielectric constant of the laminate is less than 10, it may not be possible to obtain a laminate having a high relative permittivity and high electric capacity. It is necessary to increase the amount of the inorganic filler added to the curable resin, which may impair the inherent properties of the thermosetting resin such as embrittlement of the dielectric layer. The electric capacity of the laminated plate is 0.15
When it is less than nF / cm ² , the electric capacity is small, and there is a possibility that the electric capacity is not so different from that of the conventional material. On the contrary, when it exceeds 3.1 nF / cm ² , the amount of the inorganic filler in the resin is increased. The need to reduce the thickness of the dielectric,
It may become brittle and inferior in handleability.

The laminated plate obtained as described above has a workability superior to that of the ceramic substrate because the dielectric layer, which is the insulating layer, is composed of the cured product of the resin composition and the base material. In addition, since the dielectric is formed using a predetermined material as the base material and the inorganic filler, the dielectric layer has a high relative dielectric constant and a large electric capacity.
Further, the volume resistivity of the dielectric layer is high, and a thin laminated plate having a high electric capacity can be obtained.

A printed wiring board is obtained by forming a circuit on the conductor layer of such a laminated board. In this case, the wiring pattern can be formed on the outer conductor layer of the laminate by applying a circuit forming method such as a subtractive method.

A multilayer printed wiring board can be obtained by forming a multilayer board using this laminated board as an inner layer base material. In this case, the relative dielectric constant is lower than that of the dielectric layer by, for example, applying and drying a thermosetting resin composition having a lower dielectric constant than that of the dielectric layer on the surface of the laminated plate on which the wiring pattern is formed. A low relative dielectric constant layer is formed. Further, a conductor layer is provided on the surface of the low relative dielectric constant layer by plating or other means to obtain a multilayer board.

Then, by forming a wiring pattern on the conductor layer outside the low relative dielectric constant layer in this multilayer board and forming a via hole or the like to establish conduction between the conductor layers, a multilayer printed wiring board is obtained. An electronic component such as a semiconductor chip such as an IC chip is mounted on the surface of the conductor layer outside the low relative dielectric constant layer in this multilayer printed wiring board.

Here, as the resin composition for forming the low relative dielectric constant layer, an epoxy resin, a polyphenylene oxide resin (PPO resin) or a resin containing at least polyphenylene oxide (PPO resin), a polyimide resin, Prepared by using a resin component selected from polyphenylene ether resin, bismaleimide / triazine resin (BT resin), polybutadiene resin, fluororesin, etc., and adding a curing agent such as dicyandiamide and a crosslinkable monomer such as triallyl isocyanurate. What has been done can be used. Both the dielectric layer and the low relative dielectric constant layer can be formed by using an epoxy resin. In this case, by adjusting the presence or absence of addition of an inorganic filler and the compounding amount thereof, the dielectric layer The difference in relative dielectric constant between the layer and the low relative dielectric constant layer can be adjusted.

In the laminated board, the multilayer board, or the printed wiring board obtained as described above, a capacitor (particularly a bypass capacitor) is formed by forming conductor layers on both surfaces of a dielectric layer, and high speed signal transmission is achieved. It is possible to remove the noise that accompanies the noise, and supply a stable power supply voltage. In particular, a multilayer board having a structure in which a dielectric layer and a low relative dielectric constant layer are multi-layered and a printed wiring board formed from this multilayer board can support high-speed signal transmission due to the low relative dielectric constant layer. At the same time, the bypass capacitor formed of the high relative dielectric constant layer can remove noise accompanying high-speed signal transmission.

[0054]

EXAMPLES The present invention will be described in detail below with reference to examples.

Example 1 Each component of the thermosetting resin composition and its blending amount are as shown below. Brominated bisphenol A type epoxy resin: 88 parts by mass (epoxy equivalent 500, manufactured by Tohto Kasei Co., Ltd. "Y
DB-500 ")-Cresol novolac type epoxy resin: 9.7 parts by mass (epoxy equivalent 220, manufactured by Toto Kasei Co., Ltd." YD "
CN-701 ")-Dicyandiamide: 2.3 parts by mass 2-Ethyl-4-methylimidazole: 0.097 parts by mass-Epoxysilane: 3 parts by mass (" A-187 "manufactured by Nippon Unicar Co., Ltd.)-Titanic acid Barium zirconate (Ba (Ti _0.8 Z
r _0.2 ) O ₃ ): 300 parts by mass (commercially available product synthesized by hydrothermal synthesis method, “BTZ-05-8020” manufactured by Sakai Chemical Co., Ltd .;
Average particle size 0.5 μm; relative dielectric constant: 260) A solvent containing 50% by mass of methyl cellosolve and 50% by mass of N, N-dimethylformamide is added to the epoxy resin composition obtained by mixing the above components. In addition, a varnish having a resin concentration of 80% by mass was prepared.

This varnish was stirred using a stirrer ("MH-50" manufactured by Asada Iron Works Co., Ltd.) under the conditions of 1200 rpm / 90 minutes, and then a disperser ("GM-50 manufactured by Asada Iron Works Co., Ltd."
H-G20M ”) was used to disperse the inorganic filler under the conditions of 1200 rpm / 90 minutes, and the mixture was further passed through a filter having an opening of 25 μm.

Next, a glass cloth (thickness 30
μm; relative dielectric constant 5.8), and impregnated with the above varnish, and then dried by heating at a heating temperature of 160 ° C. for 4 minutes to obtain a prepreg having a resin adhesion amount of 84 mass%.

Next, a double-sided roughened copper foil having a thickness of 35 μm and a surface roughness of 3 μm was used as the copper foil, and the copper foil was laminated on both sides of one prepreg obtained as described above so as to face each other.
A laminated plate was obtained by heat-pressing this for 120 minutes under conditions of 170 ° C. and 3 MPa.

Example 2 A laminated plate was obtained in the same manner as in Example 1 except that the coupling agent was not used.

(Example 3) Ba (Ti _0.9 Z) obtained by hydrothermal synthesis method as barium zirconate titanate
r _0.1 ) O ₃ (average particle size 0.5 μm; relative dielectric constant: 230)
A laminated board was obtained in the same manner as in Example 1 except that was used.

Example 4 180 barium zirconate was added.
1.8 parts by weight of epoxysilane as a coupling agent
A laminated board was obtained in the same manner as in Example 1 except that the parts by mass were used.

(Example 5) A laminated board was obtained in the same manner as in Example 1 except that 3 parts by mass of aminosilane ("A-1100" manufactured by Nippon Unicar Co., Ltd.) was used as a coupling agent.

Example 6 Ba (Ti _0.7 Z) obtained by hydrothermal synthesis method as barium zirconate titanate
A laminated plate was obtained in the same manner as in Example 1 except that r _0.3 ) O ₃ (average particle size 0.5 μm; relative dielectric constant 210) was used.

Comparative Example 1 A laminated plate was obtained in the same manner as in Example 1 except that 300 parts by mass of barium titanate (BaTiO ₃ ; average particle size 1.0 μm; relative dielectric constant 200) was used as an inorganic filler. It was

Comparative Example 2 A laminated plate was obtained in the same manner as in Example 1 except that 300 parts by mass of calcium titanate (CaTiO ₃ ; average particle size 1.0 μm; relative dielectric constant 180) was used as the inorganic filler. It was

(Evaluation) With respect to each of the above Examples and Comparative Examples, the relative permittivity, electric capacity, peel strength and volume resistivity (500 V) of the laminated plate were measured based on IPC-TM-650. The results are shown in Tables 1 and 2.

[0067]

[Table 1]

[Table 2]

As shown in Tables 1 and 2, each of the examples has a high relative permittivity and a high electric capacity, and further, the volume resistivity of the dielectric layer is high.

Further, comparing Example 1 and Example 2, it can be confirmed that the peel strength is improved by adding the coupling agent to the thermosetting resin.

Further, comparing Example 1 and Example 4,
It can be confirmed that although the peel strength is improved by reducing the content of the inorganic filler, the relative dielectric constant and the electric capacity are reduced.

On the other hand, in Comparative Examples 1 and 2, it is confirmed that the volume resistivity is smaller than that of each Example, although the relative dielectric constant and the electric capacity are high.

[0072]

As described above, the laminated plate according to the first aspect of the present invention has both surfaces of a dielectric layer composed of a base material and a cured product of a resin composition containing a thermosetting resin and an inorganic filler. In the laminated plate in which the conductor layer is laminated and formed, the dielectric layer contains barium zirconate titanate as an inorganic filler, the total thickness of the dielectric layer is 10 to 60 μm, and a voltage of 500 V is applied. Volume resistivity, dielectric layer thickness is 40 ~
It is 10 ¹² to 10 ¹⁶ Ω · cm when the thickness is 60 μm, and 10 ¹⁰ to 10 ¹⁶ Ω when the thickness of the dielectric layer is ¹⁰ to 40 μm.
・ Since it is cm, it has excellent workability due to the dielectric layer composed of the cured product of the resin composition and the base material, and the dielectric layer has a high relative dielectric constant and volume resistivity, and is thin and has high electrical conductivity. It is possible to obtain a laminated board having a capacity, and it is particularly suitable for manufacturing a printed wiring board having a built-in bypass capacitor.

According to a second aspect of the present invention, in the first aspect, the relative dielectric constant of the entire dielectric layer is 10 to 100 and the electric capacity is 0.15 to 3.1 nF / cm ² . While maintaining the high adhesion between the dielectric layer and the conductor layer without impairing the original characteristics of the thermosetting resin such as the embrittlement of the dielectric layer due to the increase of the compounding amount, the high dielectric constant and A high electric capacity can be achieved.

According to a third aspect of the present invention, in the first or second aspect, the composition ratio Ti: Zr of titanium atoms and zirconium atoms in barium zirconate titanate in the dielectric layer.
In the range of 95: 5 to 60:40, the relative permittivity and resistivity of barium zirconate titanate are particularly high, and the relative permittivity and volume resistivity of the dielectric layer are further improved. Is something that can be done.

The invention according to claim 4 is characterized in that, in any one of claims 1 to 3, the dielectric layer contains barium zirconate titanate synthesized by a hydrothermal synthesis method.
This barium zirconate titanate has a particle shape close to a sphere, is excellent in dispersibility in the composition, and is capable of forming a dielectric layer having a uniform relative permittivity and resistivity throughout. is there.

According to a fifth aspect of the present invention, in any one of the first to fourth aspects, the average particle size of barium zirconate titanate in the dielectric layer is 0.01 to 5 μm, and the particles in the particle size distribution are Particles with a diameter of 50 μm or more are 5 of all particles
% Or less, the resin composition is impregnated into the base material and the adhesion between the dielectric layer and the conductor layer is maintained, and particles of the inorganic filler are prevented from penetrating the conductor layer. It is possible to achieve a high dielectric constant of the dielectric layer and improve the electric capacity.

Further, in the invention of claim 6 according to any one of claims 1 to 5, since the volume fraction of the inorganic filler in the dielectric layer is 25 to 50% by volume, the resin composition is used as a base material. While maintaining the impregnating property of and the adhesion between the dielectric layer and the conductor layer,
It is possible to further increase the dielectric constant of the dielectric layer and improve the electric capacity.

The invention according to claim 7 is the method according to any one of claims 1 to 6, wherein the relative dielectric constant of the inorganic filler in the dielectric layer is 50 to 10000, so that an increase in the viscosity of the resin composition is suppressed. At the same time, the electric capacity can be improved, and the laminated plate having a stable electric capacity can be obtained by suppressing the change of the electric capacity due to the temperature change.

Further, in the invention of claim 8 according to any one of claims 1 to 7, since the thermosetting resin in the resin composition is an epoxy resin, the dielectric layer has excellent adhesiveness, processability and insulation. It is particularly excellent, and the relative dielectric constant of the dielectric layer can be further improved to further increase the electric capacity.

The invention according to claim 9 is the resin composition according to any one of claims 1 to 8, wherein the resin composition contains a coupling agent, and the coupling agent is at least one of epoxysilane, aminosilane, and mercaptosilane. Therefore, the adhesiveness (affinity) between the resin and the inorganic filler in the resin composition is improved, the dispersibility of the inorganic filler is improved, and the viscosity increase of the resin composition can be suppressed. It is a thing.

Further, the invention of claim 10 is based on claims 1 to 9.
In any one of the above, since the base material forming the dielectric layer is a sheet having a thickness of 5 to 40 μm, the base material has good handleability, and the dielectric layer is thinned,
The electric capacity can be further improved.

Further, the invention of claim 11 relates to claims 1 to 1.
In any of 0, since the relative dielectric constant of the base material forming the dielectric layer is 5 to 30, the base material contributes to the improvement of the relative dielectric constant of the dielectric layer, and the thermosetting resin of the dielectric layer. It is possible to prevent the amount of the inorganic filler to be added to an excessive amount, and to manufacture a laminated board without impairing the original characteristics of the thermosetting resin.

Further, the invention of claim 12 relates to claims 1 to 1.
In any one of 1 above, the conductor layer is formed of a metal foil, and the surface roughness of the surface of the metal foil that contacts the dielectric layer is 1 to 7
Since the thickness is set to μm, the adhesion between the conductor layer and the dielectric layer is further improved, and the distance between the conductor layers via the dielectric layer is prevented from being locally shortened, and the insulation property between the conductor layers is improved. Is ensured.

Further, the invention of claim 13 is based on claims 1 to 1.
In any one of 2 above, after stirring the mixture containing the respective components constituting the resin composition with a stirrer, the inorganic filler is dispersed with a disperser, and the mixture is further passed through a filter having an opening of 30 μm or less. Since the obtained resin composition is used, the particles of the inorganic filler are not aggregated in the resin composition, and the primary particles of the inorganic filler are highly dispersed (primary dispersion). Has a uniform relative permittivity and volume resistivity over the whole, and the laminated plate has a stable electric capacity and improved insulation reliability, and has a large diameter exceeding the aperture of the filter. Since the particles have been removed by the filter, it is possible to prevent the particles of the inorganic filler from penetrating the conductor layer and from causing insulation failure.

A multilayer board according to claim 14 of the present invention is
A resin composition having a circuit formed on the conductor layer of the laminated plate according to any one of claims 1 to 13 and having a lower relative dielectric constant than the dielectric layer of the laminated plate outside the conductor layer on which the circuit is formed. Since a low relative dielectric constant layer consisting of is formed, it is possible to cope with high-speed signal transmission by the low-dielectric constant layer, and by the bypass capacitor composed of the dielectric layer and the conductor layers on both sides, noise accompanying high-speed signal transmission. Can be eliminated, and a stable power supply voltage can be supplied without being affected by this noise.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 63/00 H05K 1/03 610R H05K 1/03 610 3/46 Q 3/46 T C08K 5/54 ( 72) Inventor Takayoshi Ozeki 1048 Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Works Co., Ltd. (72) Inventor Seiko Higashi 1048, Kadoma, Kadoma City, Osaka Matsushita Electric Works Co., Ltd. F-term (reference) 4F100 AA00A AA02A AB01B AB01C AB17 AB33B AB33C AG00 AH06A AK01A AK53A AR00B AR00C AS00A AT00A BA03 BA06 BA10B BA10C BA13 CA23A DD07B DD07C DE01A DG01 DH01 EJ08A EJ17 EJ42 EJ82 GB43 JA20A JB13A JG01B JG01C JG04 JG04A JG05A JL01 YY00A YY00B YY00C 4J002 BL011 CD051 CH071 CM041 DE186 EX067 EX077 EX087 GF00 5E346 AA06 AA12 AA13 AA15 AA32 AA33 AA51 CC02 CC08 CC16 CC21 CC31 CC32 DD02 DD12 DD22 DD32 DD33 EE06 EE07 EE09 EE13 EE31 EE35 HH01 HH06 HH11

Claims (14)

[Claims] 1. A laminated board in which a conductor layer is laminated and formed on both surfaces of a dielectric layer composed of a cured product of a resin composition containing a thermosetting resin and an inorganic filler, and a substrate. Contains barium zirconate titanate as an inorganic filler,
The total thickness of the dielectric layer is 10 to 60 μm and is 500 V
The volume resistivity when a voltage of 10 is applied is 10 ¹² to 10 ¹⁶ Ω · cm when the thickness of the dielectric layer is 40 to 60 μm, and 10 ¹⁰ to 10 ¹⁰ when the thickness of the dielectric layer is ¹⁰ to 40 μm.
A laminated board characterized by having a resistance of 10 ¹⁶ Ω · cm. 2. The relative dielectric constant of the entire dielectric layer is 10 to 10
0, the electric capacity is 0.15 to 3.1 nF / cm ² and the laminated plate according to claim 1. 3. The composition ratio Ti of titanium atoms and zirconium atoms in barium zirconate titanate in the dielectric layer:
Zr is set as 95: 5-60: 40 in the range, The laminated board of Claim 1 or 2 characterized by the above-mentioned. 4. The laminate according to claim 1, wherein the dielectric layer contains barium zirconate titanate synthesized by a hydrothermal synthesis method. 5. The barium titanate zirconate in the dielectric layer has an average particle size of 0.01 to 5 μm, and particles having a particle size distribution of 50 μm or more account for 5% or less of all particles in the particle size distribution. The laminated plate according to any one of claims 1 to 4, which is characterized in that. 6. The volume fraction of the inorganic filler in the dielectric layer is 2
The amount is 5 to 50% by volume.
The laminated plate according to any one of 1. 7. The dielectric constant of the inorganic filler in the dielectric layer is from 50 to 10,000.
7. The laminated plate according to any one of 1 to 6. 8. The laminate according to claim 1, wherein the thermosetting resin in the resin composition is an epoxy resin. 9. The resin composition contains a coupling agent, and the coupling agent is at least one of epoxysilane, aminosilane, and mercaptosilane. The laminated plate according to. 10. The base material forming the dielectric layer has a thickness of 5 to 5.
The laminated plate according to any one of claims 1 to 9, which is in the form of a sheet of 40 µm. 11. The laminate according to claim 1, wherein the base material forming the dielectric layer has a relative dielectric constant of 5 to 30. 12. The conductor layer is made of a metal foil, and the surface roughness of the surface of the metal foil which is in contact with the dielectric layer is 1 to 7 μm. The laminated plate according to. 13. A mixture obtained by mixing each component constituting a resin composition with a stirrer, then dispersing the inorganic filler with a disperser, and further passing through a filter having an opening of 30 μm or less. The laminated board according to any one of claims 1 to 12, wherein the laminated board is made of a resin composition. 14. A circuit board is formed on the conductor layer of the laminated plate according to claim 1, and a relative dielectric constant lower than that of the dielectric layer of the laminated plate is provided outside the circuit-formed conductor layer. A multilayer board comprising a low relative dielectric constant layer formed of a resin composition having: