JP2003119379A - Resin composition and utilization thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide both a resin composition capable of affording a cured product having all good characteristics such as a high permittivity, a low dielectric dissipation factor, mechanical strength, shock and thermal shock resistances and a material for electronic parts utilizing the composition. SOLUTION: This resin composition comprises a siloxane-containing polyamideimide resin represented by formula (I) [wherein, R1 is one kind selected from formulae (II); R2 is one kind selected from formula (III); R3 is represented by formula (IV); R4 and R5 are each a bivalent organic group; R6 to R9 are each independently one kind selected from an alkyl group, phenyl group or a substituted phenyl group; n is an integer of 0-90; m is an integer of 5-350;, p is an integer of 1-50; and the ratio of n to m is (7:3) to (0:10)], a high-permittivity filler and an epoxy resin. The cured product thereof has >=15 specific permittivity at 25 deg.C and 1 MHz. A wiring board material and a wiring board comprise an insulating layer composed of the resin composition.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition suitable for use in electronic components such as wiring boards, and a resin film, wiring board material, wiring board, and electronic components using the same.

[0002]

2. Description of the Related Art Due to the demand for high-density mounting of various parts on a wiring board, the wiring board has become multi-layered, and circuit layers (coil: L, capacitor: C, resistance: R) are formed in the inner layer. The use of boards is increasing. In the resin board,
A capacitor is formed by forming electrodes such that the resin layer serves as a dielectric and the wiring conductors above and below the dielectric layer face each other. Since the capacitance of a capacitor is proportional to the relative permittivity of the resin layer, increasing the permittivity of the resin layer has been studied in order to obtain a capacitor having a large capacitance.

A resin layer having a high dielectric constant is used as an insulating layer between the power supply and the ground in order to reduce the impedance between the power supply and the ground for suppressing high frequency noise. Since the impedance between the power supply and ground is inversely proportional to the square root of the relative dielectric constant of the insulating layer, the impedance is lowered by using a resin layer with a high dielectric constant, and high frequency noise is well bypassed to the ground to suppress high frequency noise. can do. Further, in order to shorten the wiring length, a resin layer having a high dielectric constant is used as an insulating layer in contact with the wiring conductor. Since the signal propagation wavelength is inversely proportional to the square root of the relative permittivity of the insulating layer in contact with the wiring conductor, using a resin layer with a high dielectric constant shortens the propagation wavelength, shortens the wiring length, and reduces the size of electronic components. Is possible.

In order to obtain such a high dielectric constant resin layer,
Conventionally, a resin is blended with an inorganic filler having a high dielectric constant such as barium titanate. For example, in JP-A-55-148308, a resin composition having a high dielectric constant is obtained by filling a thermosetting resin with ceramic dielectric powder (barium titanate). Also, US Pat.
In No. 977, a glass cloth is impregnated with an epoxy resin filled with lead zirconate titanate to obtain a high dielectric constant resin layer. Many combinations other than these are available, for example, in Journal of Materials in
This is summarized in the review by Bhattacharya et al., Published in Electronics, Vol. 11, pp. 253-268.

[0005]

However, when a large amount of a high-dielectric-constant filler is added in order to increase the dielectric constant of the resin composition, the cured product becomes hard and brittle, and the mechanical strength, impact resistance, and
There is a problem that the thermal shock resistance and the like are reduced. On the other hand, in order to prevent deterioration of mechanical strength, impact resistance, thermal shock resistance, etc., it is effective to use a resin having a low elastic modulus such as acrylic rubber, but the dielectric loss tangent of the cured product becomes high, There is a problem that it is not possible to obtain a device with a small electrical loss. In view of the above, the present invention is a resin composition capable of obtaining a cured product having good characteristics such as high dielectric constant and low dielectric loss tangent, mechanical strength, impact resistance, and thermal shock resistance, and the use thereof The purpose of the present invention is to provide a material for electronic parts.

[0006]

A resin composition according to the present invention contains a siloxane-containing polyamideimide resin represented by the following general formula (I), a high dielectric constant filler and an epoxy resin, and is at 25 ° C. and 1 MHz. The relative permittivity of the cured product is 15
That is all.

[Chemical 5] (In the formula, R ₁ is

[Chemical 6] R ₂ is one kind selected from

[Chemical 7] R ₃ is one selected from

[Chemical 8] And R ₄ and R ₅ are divalent organic groups, and R _{6 to} R ₉
Are each independently one selected from an alkyl group, a phenyl group or a substituted phenyl group. Also, n is 0 to 90, m
Is 5 to 350, p is an integer of 1 to 50, and n
The ratio of m to m is 7: 3 to 0:10. )

Since the siloxane-containing polyamideimide resin of the formula (I) contains the above-mentioned siloxane segment, it has a low elastic modulus derived from this. In order to obtain a resin composition having a high dielectric constant, a high dielectric constant filler is blended with this resin. However, in the present invention, even when a large amount of the high dielectric constant filler is blended, the low elastic modulus is still maintained. It is possible to obtain a high dielectric constant resin composition that gives a cured product having excellent mechanical strength, impact resistance, thermal shock resistance and the like. In addition, the siloxane-containing polyamideimide resin of the formula (I) has a low dielectric loss tangent due to the above siloxane segment.

When the resin composition according to the present invention is solid, it is possible to improve the coatability by adding a solvent to form a varnish, and to provide a resin film or a wiring board material having high thickness accuracy. . Further, it can be directly applied as a paste to a necessary portion.

The resin film according to the present invention comprises the resin composition according to the present invention. Here, “consisting of a resin composition” means “consisting of a cured product of the resin composition”.
It is a concept including things (the same applies to the present invention described below). By forming a film, the handling property and the alignment accuracy are improved, and the film can be suitably used as an insulating film, an adhesive film, etc. for various electronic parts.

The wiring board material according to the present invention comprises a resin layer made of the resin composition according to the present invention and a metal layer (metal layer not formed with a circuit). This resin layer is
Those obtained by using the resin film according to the present invention are also included. Further, for this metal layer, a metal used in a usual wiring board material, for example, a metal foil such as copper can be preferably used.

The wiring board according to the present invention includes an insulating layer and a wiring conductor (wired conductor, that is, a metal layer on which a circuit is formed), and at least one of the insulating layers is a resin composition according to the present invention. It consists of things. This insulating layer includes one obtained by using the resin film according to the present invention and one obtained by using the wiring board material according to the present invention.

By adjusting the blending amount of the high dielectric constant filler, an insulating layer having a relative dielectric constant suitable for each application can be easily obtained. Further, even when a large amount of the high dielectric constant filler is mixed, the mechanical strength and impact resistance of the insulating layer can be maintained, and the reliability of electronic parts using the same can be improved. By using this insulating layer for the layer corresponding to the capacitor, it is possible to provide a multilayer wiring board, etc. that has a built-in capacitor with a capacitance according to the application, and it is not necessary to mount a large number of separate capacitors. It is possible to reduce the number of elements and reduce the size of electronic components. Further, by using this insulating layer between the power supply and the ground, the impedance between the power supply and the ground is lowered and the high frequency noise can be satisfactorily bypassed, so that the high frequency noise can be suppressed and a stable power supply voltage can be supplied. . Furthermore, since the wiring length can be shortened by using this insulating layer for a resonance circuit such as an antenna and a stub, it is possible to miniaturize electronic parts using these. The wiring board according to the present invention can be preferably used as a substrate for mounting a semiconductor element in a semiconductor package. The structure of the wiring board may be a single layer (that is, the insulating layer is only one layer made of the resin composition according to the present invention) or a multilayer (that is, the insulating layer may be an insulating layer made of the resin composition according to the present invention). Including 2
Or more layers) and can be arbitrarily selected according to the application.

An electronic component according to the present invention comprises the resin composition according to the present invention, and uses one or more of the resin film, the wiring board material and the wiring board according to the present invention. It can be preferably obtained.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The resin composition according to the present invention contains a siloxane-containing polyamideimide resin of the above formula (I), an epoxy resin and a high dielectric constant filler, and the cured product thereof has a relative dielectric constant of 25. It is 15 or more at 1 ° C and 1 ° C. Here, the relative permittivity is L according to JIS standard C6481.
It is a value obtained from the capacitance measured using a CR meter HP4275A (trade name, manufactured by Agilent Technology Co., Ltd.). Capacitance required in high frequency circuit 0.5
In order to incorporate a capacitor of 10 pF into an insulating layer having a thickness of 10 to 300 μm and an electrode area of 1 mm ² , the insulating layer must have a relative permittivity of 15 or more.

Regarding the elastic modulus of the cured product of the resin composition,
From the viewpoints of handleability, workability, and reliability of electronic parts using the same, the storage elastic modulus at 40 ° C. measured by a wide-range viscoelasticity measuring device DVE-V4 (trade name of Rheology Co., Ltd.) is 5 GPa or less. It is preferable. If the modulus of elasticity is higher than this, the cured product becomes hard and brittle, and the mechanical strength, impact resistance, and thermal shock resistance tend to decrease.

A siloxane-containing polyamideimide resin of the formula (I) (hereinafter referred to as "SiPAI resin"):

[Chemical 9] (In the formula, R ₁ is

[Chemical 10] R ₂ is one kind selected from

[Chemical 11] R ₃ is one selected from

[Chemical 12] And R_Four, R₅Is a divalent organic group, R₆~ R₉
Are each independently an alkyl group, a phenyl group or a substituted phenyl group.
It is one kind selected from ru radical. Also, n is 0 to 90, m
Is 5 to 350, p is an integer of 1 to 50, and n
The ratio of m to m is 7: 3 to 0:10. ) Siloxane
Regarding the ratio of segments, the solvent when varnished
Drying property and work efficiency, and dielectric loss tangent and electricity of cured products
The ratio of n to m is from 7: 3 to 0:10 from the viewpoint of effective loss.
Is preferably selected, and more preferably 5: 5 to 0:10.
And are more preferable. Also, the weight average of this SiPAI resin
The average molecular weight is preferably 10,000 or more from the viewpoint of film formability.
It is preferably 200,000 or less from the viewpoint of synthesis cost.
It is preferably 20,000 to 100,000, and further preferably.
R is a divalent organic group _Four, R₅As a particular limitation
But C3 is a propylene group, isopropylene
Group, phenylene group, alkyl group such as methyl group and ethyl group
An alkyl-substituted phenylene group substituted by
For example, the following formula:

[Chemical 13] And a methyl group is substituted at the meta position with respect to Si). Examples of R _{6 to} R ₉ include an alkyl-substituted phenyl group such as a methyl group, an ethyl group, a phenyl group, and a toluyl group.

The high dielectric constant filler preferably has a relative permittivity of 50 or more at 25 ° C. and 1 MHz.
It is more preferably 0 or more, still more preferably 500 or more. When the relative dielectric constant of the filler is less than 50,
A large amount of filler is required to make the relative dielectric constant of the resin composition 15 or more, and molding may not be possible in some cases.

The high dielectric constant filler is specifically selected from barium titanate, strontium titanate, calcium titanate, magnesium titanate, lead titanate, titanium dioxide, barium zirconate, calcium zirconate and lead zirconate. It is preferably one or more selected from the group consisting of As these high dielectric constant fillers, those which have been surface-treated with a coupling agent in advance may be used, or the coupling agent may be added at the time of compounding to perform the surface treatment by an integral method. As such a coupling agent, a titanate coupling agent is preferable. As the shape of the high dielectric constant filler, any shape such as a granular shape, an amorphous shape, and a flake shape can be used in an arbitrary ratio. Further, the average particle diameter thereof is preferably 0.1 μm or more from the viewpoint of bulk density and filling property into the resin, and is preferably 20 μm or less from the viewpoint of the thickness accuracy of the resin layer, and 0.
It is more preferably 5 to 10 μm.

The compounding ratio of the SiPAI resin and the high dielectric constant filler is such that the compounding amount of the high dielectric constant filler with respect to 100 parts by weight of the SiPAI resin is 250 parts by weight or more from the viewpoint of ensuring the relative dielectric constant of the resin composition. From the viewpoint of moldability, it is preferably 3,000 parts by weight or less, and 4
More preferably, it is from 00 to 2000 parts by weight.

The epoxy resin may be any epoxy resin as long as it has two or more epoxy groups in one molecule, and examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin and fat. Cyclic epoxy resin, aliphatic chain epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, diglycidyl ether of biphenol, diglycidyl ether of naphthalene diol, diphenol of phenols There are glycidyl ether compounds, diglycidyl ether compounds of alcohols, and alkyl-substituted compounds and halides thereof, which may be used alone or in combination. The epoxy group in these epoxy resins reacts with NH of the amide group in the SiPAI resin to form a three-dimensional crosslinked structure, and imparts thermosetting property to the resin composition.

The blending ratio of the SiPAI resin and the epoxy resin is preferably such that the blending amount of the epoxy resin with respect to 100 parts by weight of the SiPAI resin is 5 parts by weight or more from the viewpoint of imparting thermosetting property, and the compatibility with the SiPAI resin. And from the viewpoint of appropriately maintaining the elastic modulus of the cured product, it is preferably 250 parts by weight or less.

The resin composition of the present invention may contain a curing agent for epoxy resin. For example, there are polyfunctional phenols, amines, imidazole compounds, acid anhydrides, organic phosphorus compounds and their halides, but it is preferable to use a curing agent that does not increase the dielectric loss tangent of the cured product. Moreover, you may mix | blend a hardening accelerator with the resin composition of this invention as needed. Typical curing accelerators include, but are not limited to, tertiary amines, imidazoles, and quaternary ammonium salts. Further, if necessary, a filler used in a general resin material for wiring boards, such as silica, alumina, clay, talc, etc., a colorant, a flame retardant, an adhesiveness-imparting agent, etc., is added to this resin composition. You may mix | blend an agent suitably.

When the resin composition is solid, the viscosity at the time of coating can be adjusted by adding a solvent to form a varnish, thereby improving workability and thickness accuracy. The solvent to be added is preferably one that dissolves the SiPAI resin and the epoxy resin. Specifically, N-methyl-2-pyrrolidone, N, N-dimethylacetamide,
N, N-dimethylformamide, ethylene glycol monomethyl ether, tetrahydrofuran or the like can be used. The amount of the solvent used for forming the varnish is the resin composition 10
From 0 part by weight, it is preferably 5 parts by weight or more from the viewpoint of viscosity, workability and coatability of the varnish, and preferably 900 parts by weight or less from the viewpoint of drying time and work efficiency, and 10 to 50 parts by weight.
It is more preferably 0 part by weight.

As a method for adjusting the varnish of the resin composition, known methods such as a mixer, a bead mill, a pearl mill, a kneader and a triple roll can be used. All of the various blending components may be added at the same time, the order of addition may be appropriately set, or if necessary, some of the blending components may be pre-kneaded in advance and then added.

The resin film of the present invention is obtained from the resin composition of the present invention, and the thickness thereof is 10 μm or more from the viewpoint of ensuring the thickness accuracy. The thickness is preferably 300 μm or less from the viewpoint of securing the electrostatic capacity in case of contact.

This resin film is produced by a known method using a varnished resin composition, for example, a blade coater,
A shear force can be applied in the plane direction parallel to the substrate, such as a rod coater, knife coater, squeeze coater, reverse roll coater, transfer coat coater, or
It is applied to one side of a carrier film such as polyester or polyimide by using a coating method capable of applying a compressive force in a direction perpendicular to the surface of the base material, and is, for example, 2-1 at 120 to 170 ° C.
It is obtained by heating and drying for 0 minutes to remove the solvent. It is preferably a semi-cured film without stickiness.

Next, a wiring board material and a wiring board using the resin composition and / or the resin film of the present invention will be described with reference to the drawings. FIG. 1 is a sectional view schematically showing an embodiment of a wiring board material according to the present invention. The wiring board material (1) includes a metal foil (12) as a metal layer and a resin layer (11) made of the resin composition according to the present invention.

The wiring board material is formed by applying the varnished resin composition of the present invention to a metal foil usually used as a wiring conductor, for example, a foil of gold, silver, copper, aluminum, nickel, chromium or the like. It may be dried afterwards, or the metal foil and the resin film of the present invention may be laminated and pressed. Moreover, you may form a metal foil on the resin film of this invention using methods, such as plating, vapor deposition, sputtering, and ion plating.

FIG. 2 is a sectional view schematically showing an embodiment of a wiring board according to the present invention. The wiring board (2) is the first
It is composed of an insulating layer (22), a first wiring conductor (23) and a second wiring conductor (21), and the first insulating layer (22) is composed of the resin composition of the present invention. The wiring board (2) may be a single-sided board without the second wiring conductor (21).

FIG. 3 is a sectional view schematically showing another embodiment of the wiring board according to the present invention. The wiring board (3) includes a first insulating layer (36), a first wiring conductor (37), a second insulating layer (34), a second wiring conductor (35), and a third insulating layer (3).
2), a third wiring conductor (33), and a fourth wiring conductor (31), which is a multilayer wiring board, and includes a first insulating layer (36) and a second wiring layer (36).
At least one layer of the insulating layer (34) and the third insulating layer (32) is composed of the resin composition of the present invention. Although not shown in the figure, the fourth, fifth, sixth ...
Insulating layers such as the above and wiring conductors may be alternately laminated.

In the case of a multilayer wiring board, it is sufficient that at least one of the insulating layers is composed of the resin composition of the present invention, and a plurality of layers having the same and / or different relative dielectric constants are used. The resin composition of the invention can also be used. Other insulating layers (resin layers) not using the resin composition of the present invention include epoxy resins, phenol resins, BT resins and the like which are usually used for wiring boards, and low dielectric constant resins such as polyphenylene oxide resins and cyanate esters. Resin, fluororesin, etc. can be used. First, second,
The third wiring conductors, etc. may be the same or different from each other.

Next, an example of a method for producing a multilayer wiring board using the resin composition of the present invention will be described. First, a wiring board material with a metal layer (metal foil) using the resin composition of the present invention is laminated on an inner layer circuit board using a press machine or the like under pressure and heating conditions and heat-cured. As the inner layer circuit board, a glass epoxy board, a polyester board, a polyimide board, a BT resin board, a thermosetting PPE board, a metal board, or the like can be used. The circuit surface may be roughened in advance. The conditions for heat curing are usually 120 ° C. or higher, preferably 150 to 200 ° C., and usually 20 to 180 minutes, preferably 60 to 120 minutes. After laminating the resin composition of the present invention on the inner layer circuit board and curing it as described above, perforation is performed using a drill or a laser to form a through hole or a via hole. As the laser drilling machine, a carbon dioxide gas laser, a YAG laser, an excimer laser, or the like can be used. Then, a chemical treatment using an oxidizing agent such as permanganate or dichromate is performed to remove the resin residue generated during laser drilling. Furthermore, after obtaining electrical conduction between the inner layer and the outer layer using a technique such as electroless copper plating or filling with a conductive paste,
Arbitrary circuit processing is performed on the laminated metal layer on the surface of the resin composition of the present invention by using a circuit-shaped method for a normal wiring board.

As another method for laminating the resin composition of the present invention on the inner layer circuit board, the resin composition of the present invention which has been varnished may be applied to the inner layer circuit board, dried and then heat-cured. Alternatively, the resin film of the present invention may be laminated on the inner layer circuit board using a press machine or the like under pressure and heating conditions, and then the carrier film may be peeled off and then heat cured. Alternatively, the resin film of the present invention from which the carrier film has been peeled off and the metal foil may be laminated simultaneously on the inner layer circuit board and heat-cured. Further, the inner layer circuit board and another inner layer circuit board may be bonded with the resin film of the present invention and heat-cured, or the varnished resin composition of the present invention may be applied onto the inner layer circuit board, and another The inner layer circuit boards may be laminated and cured by heating.

In addition to the wiring board described above, the resin composition of the present invention can also be used as a single electronic component such as a film capacitor, an LCR filter and an oscillator.

[0035]

EXAMPLES Next, the present invention will be specifically described by way of examples, but the present invention is not limited to these. In the following examples, "part" means "part by weight". [Examples 1 to 4, Comparative Examples 1 to 3] SiPAI shown in Table 1
Resins 1 to 4 were each synthesized with the formulation shown in Table 2 as follows. 25m with a cock connected to a reflux condenser
In a 1-liter separable flask equipped with a 1-liter water quantitative receiver, a thermometer, and a stirrer, a predetermined amount of reactive silicone oil "KF-8010" or "X-22-161A".
(Both products are manufactured by Shin-Etsu Chemical Co., Ltd.), BAPP
(2,2-bis [4- (4-aminophenoxy) phenyl] propane), trimellitic anhydride, N-methyl-2
-Pyrrolidone was charged and stirred at 80 ° C for 30 minutes. Then, add 100 ml of toluene, raise the temperature,
Refluxed at about 160 ° C. for 2 hours. While confirming that approximately 2.5 ml or more of water has accumulated in the moisture constant volume receiver and no outflow of water is observed, remove the effluent accumulated in the moisture constant volume receiver to obtain approximately 190 The temperature was raised to ° C and the toluene was removed. After that, the temperature of the solution is returned to room temperature, the moisture quantitative receiver is removed, and a predetermined amount of MDI is removed.
(4,4-Diphenylmethane diisocyanate) and triethylamine were added, and the mixture was reacted at 110 ° C. for 2 hours.
After completion of the reaction, N-methyl-2 of the obtained SiPAI resin
The concentration of the pyrrolidone solution was adjusted to 25% by weight each.

[0036]

[Table 1]

[0037]

[Table 2]

25 of the above-obtained SiPAI resins 1 to 4
Weight% N-methyl-2-pyrrolidone solution, barium titanate "BT-100PR" as a high-dielectric-constant filler (trade name, manufactured by Fuji Titanium Industry Co., Ltd., dielectric constant 1600 at 25 ° C, 1 MHz, average particle size 1 .5 μm) and titanium dioxide “TM-1” (trade name, manufactured by Fuji Titanium Industry Co., Ltd.,
Dielectric constant 96 at 25 ° C, 1MHz, average particle size 0.6μ
m), bisphenol A type epoxy resin "YD-8125" (trade name of Tohto Kasei Co., Ltd.) as an epoxy resin, and imidazole derivative "2PZ-" as a curing accelerator.
CN "(trade name of Shikoku Kasei Co., Ltd.), a titanate-based coupling agent" KR-38S "as a coupling agent.
(Ajinomoto Co., Inc. product name) was used and blended as shown in Table 3, and the mixture was stirred and defoamed for 10 minutes with a small-sized stirring and defoaming device MX-201 (Sinky Co., Ltd. product name). After filtering these with a 200-mesh nylon cloth, the mixture was again stirred and defoamed for 2 minutes using a small stirring and defoaming apparatus.
4 and varnishes of the resin compositions of Comparative Examples 1 to 3 were prepared.

[0039]

[Table 3]

[Comparative Example 4] 66 parts of YD-8125, o
-Cresol novolac type epoxy resin "YDCN-7"
03 "(trade name of Tohto Kasei Co., Ltd.), 34 copies, BT-1
00PR for 722 parts, TM-1 for 221 parts, bisphenol A-type phenoxy resin "YP-50" (trade name of Tohto Kasei Co., Ltd.) for 24 parts, bisphenol A novolac-type phenol resin "LF-2882" (Dainippon Ink Industry Co., Ltd. product name) 63 parts, 2PZ-CN 0.6
Parts, 1.1 parts of KR-38S, dispersant "Disperb
7 parts of "yk-110" (trade name of Big Chemie Japan Co., Ltd.) and 200 parts of methyl ethyl ketone as a solvent.
Each part was mixed and stirred at 1000 rpm for 1 hour using a bead mill (200 ml of sample in 500 ml of container, 150 ml of alumina beads) to prepare a varnish of the resin composition.

[Comparative Example 5] BT-100PR was 626.
Copy, TM-1 for 192 copies, YD-8125 for 26 copies, Y
26 parts of DCN-703, 14 parts of YP-50, LF-
2482 parts of 2882, 1 part of KR-38S, cyclohexanone as a solvent, and a beads mill (container 500 ml
The sample (200 ml, alumina beads 150 ml) was stirred at 1000 rpm for 1 hour. Epoxy group-containing acrylic rubber "HTR-860-P3" (trade name of Teikoku Chemical Industry Co., Ltd., weight average molecular weight 850,000)
Was mixed with 100 parts of 2PN-CN and stirred for 1 hour using a screw stirrer to prepare a varnish of the resin composition.

The resulting varnishes of Examples and Comparative Examples were dried at a drying chamber temperature of 140 to 160 ° C. using a multi coater (trade name of Hirano Techseed Co., Ltd., drying oven length 1 m).
Roll electrolytic copper foil "GT with feed rate 0.2-0.4m / min"
S-12 "(trade name of Furukawa Circuit Foil Co., Ltd.) and dried to prepare a wiring board material having a resin thickness of 50 μm.

Two of these wiring board materials were put together so that the resin surface was on the inside, and a high-temperature vacuum press (manufactured by Meiki Seisakusho Co., Ltd., 105 tons) was used to obtain a vacuum degree of 5.3 kPa.
Molding pressure was 2.45 MPa and molding temperature was 180 ° C. for 90 minutes under pressure and heating to produce wiring boards. In Comparative Example 2, the value of m in the formula (I) was less than 5, and SiPAI
Due to the low molecular weight of the resin, cracking occurred after drying, and a wiring board material could not be produced.

Using the wiring boards of Examples 1 to 4 and Comparative Examples 1, 3, 4, and 5, cured products of the resin composition were evaluated. JIS
LCR meter HP4275 according to standard C6481
25 ° C, 1M of the cured product obtained from the capacitance measured using A (trade name of Agilent Technology Co., Ltd.)
40 ° C. measured by relative permittivity and dielectric loss tangent at Hz, wide-range viscoelasticity measuring device DVE-V4 (trade name, manufactured by Rheology Co., Ltd.)
Table 4 collectively shows the storage elastic modulus in Table 1 and the handleability of the cured product having a thickness of 100 μm.

[0045]

[Table 4]

As is clear from Table 4, in each of Examples 1 to 4 according to the present invention, a cured product having a high dielectric constant, a low dielectric loss tangent and a low elastic modulus was obtained. In Comparative Example 1, the ratio of the siloxane segment of the SiPAI resin is low, so that the dielectric loss tangent is high. In Comparative Example 3, the dielectric constant is low because the filling amount of the high dielectric constant filler is small, and in Comparative Example 4,
Since the phenoxy resin was used instead of the SiPAI resin, the cured product had a high elastic modulus and was brittle.
Since the epoxy group-containing acrylic rubber was used instead of the iPAI resin, the elastic modulus was low, but the dielectric loss tangent was high.
The result was obtained.

[Embodiment 5] The wiring board material of Embodiment 2 is laminated on an inner layer circuit board made of a glass epoxy resin substrate on which a lower electrode is formed in advance, and then an upper electrode is formed by etching and laser drilling. A via hole was formed by using the above to electrically connect the lower electrode to the outer layer, and a capacitor built in a substrate having an electrode area of 1 mm ² and an insulating layer thickness of 50 μm was manufactured. As a result of measuring the capacitance of this capacitor using an LCR meter HP4275A, 25 ° C,
It was 4.8 pF at 1 MHz.

Comparative Example 6 Using the wiring board material of Comparative Example 3, a capacitor incorporated in a substrate having an electrode area of 1 mm ² and an insulating layer thickness of 100 μm was produced in the same manner as in Example 5. As a result of measuring the capacitance of the obtained capacitor, 2
It was 0.7 pF at 5 ° C. and 1 MHz.

[0049]

As described above, in the resin composition of the present invention, a cured product having a high dielectric constant can be obtained by filling the SiPAI resin and the epoxy resin with the high dielectric constant filler. By using the SiPAI resin, a cured product having a low elastic modulus can be obtained even when a large amount of a high dielectric constant filler is mixed, and a resin film or a wiring board material having a high dielectric constant and excellent mechanical strength, impact resistance, etc. And a highly reliable wiring board and an electronic component using the same can be provided. further,
Since the dielectric loss tangent is reduced by using the SiPAI resin, it is possible to provide a wiring board having a small electrical loss and an electronic component using the wiring board.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing an embodiment of a wiring board material of the present invention.

FIG. 2 is a sectional view showing an embodiment of a wiring board of the present invention.

FIG. 3 is a sectional view showing another embodiment of the wiring board of the present invention.

[Explanation of symbols]

1 Materials for wiring boards 11 Resin layer 12 metal foil 2 wiring board 21 Second wiring conductor 22 First insulating layer 23 First wiring conductor 3 wiring board 31 4th wiring conductor 32 Third insulating layer 33 Third wiring conductor 34 Second insulating layer 35 Second wiring conductor 36 First Insulating Layer 37 First wiring conductor

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 63/00 C08L 63/00 A C H05K 1/03 610 H05K 1/03 610L 610N 610R // H05K 3 / 46 3/46 T (72) Inventor Masanori Yamaguchi 1500 Ogawa, Shimodate, Ibaraki Prefectural Chemical Research Laboratory, Hitachi Chemical Co., Ltd. (72) Yasushi Shimada 1500 Ogawa, Shimodate, Ibaraki Hitachi Chemical Co., Ltd. (72) Inventor Kazuhisa Otsuka 1500 Ogawa, Shimodate-shi, Ibaraki Hitachi Chemical Co., Ltd., Research Institute (72) Inventor Kazunori Yamamoto 1500 Ogawa, Shimodate-shi, Ibaraki Hitachi Chemical Co., Ltd. Reference) 4F071 AA42 AA60 AB20 AE22 AF40Y AH13 BC01 4F100 AA33A AA34A AB17 AB33 AK50A AK53A AL05A BA0 1 BA02 CA23A GB43 JA07A JG05A JK07A 4J002 CD00X CD04X CD05X CD06X CD11X CM04W DE186 FD016 GQ01 5E346 AA01 AA12 AA15 BB01 BB20 CC09 CC10 CC31 DD02 DD32 EE02 EE06 EE07 FF01 GG28 HH01 HH11

Claims (13)

[Claims] 1. A resin containing a siloxane-containing polyamideimide resin represented by the following general formula (I), a high dielectric constant filler and an epoxy resin, and having a relative dielectric constant of 15 or more at 25 ° C. and 1 MHz. Composition. [Chemical 1] (In the formula, R ₁ is R ₂ is a compound selected from R ₃ is one selected from And R ₄ and R ₅ are divalent organic groups, and R _{6 to} R ₉
Are each independently one selected from an alkyl group, a phenyl group or a substituted phenyl group. Also, n is 0 to 90, m
Is 5 to 350, p is an integer of 1 to 50, and n
The ratio of m to m is 7: 3 to 0:10. ) 2. The resin composition according to claim 1, wherein the cured product has a storage elastic modulus at 40 ° C. of 5 GPa or less. 3. The resin composition according to claim 1, wherein the siloxane-containing polyamideimide resin has a weight average molecular weight of 10,000 to 200,000. 4. The high dielectric constant filler at 25 ° C., 1 MHz
The resin composition according to any one of claims 1 to 3, having a relative dielectric constant of 50 or more. 5. The group in which the high dielectric constant filler comprises barium titanate, strontium titanate, calcium titanate, magnesium titanate, lead titanate, titanium dioxide, barium zirconate, calcium zirconate, and lead zirconate. The resin composition according to any one of claims 1 to 4, containing at least one selected from the group consisting of: 6. The resin composition according to claim 1, wherein the compounding amount of the high dielectric constant filler is 250 to 3000 parts by weight with respect to 100 parts by weight of the siloxane-containing polyamideimide resin. 7. The compounding amount of the epoxy resin with respect to 100 parts by weight of the siloxane-containing polyamideimide resin is 5.
To 250 parts by weight, The resin composition according to any one of claims 1 to 6. 8. A resin film comprising the resin composition according to claim 1. 9. A thickness of 10 to 300 μm.
The resin film described. 10. A wiring board material comprising a resin layer made of the resin composition according to claim 1 and a metal layer. 11. An insulating layer and a wiring conductor are included, and at least one layer of said insulating layers is any one of Claims 1-7.
A wiring board comprising the resin composition according to the item. 12. The wiring board according to claim 11, wherein electrodes are formed on a part of wiring conductors above and below the insulating layer so as to face each other. 13. An electronic component using the resin composition according to claim 1.