JP2000017148A - Thermosetting resin composition and interlaminar adhesive film for printed wiring board using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare a thermosetting resin composition meeting densification, high thermostability, electric insulation and strength of adhesive bonding to the layer of conductive material at the same time by including an epoxy resin, a phenolic resin, an aromatic diamine compound having an imide group, rubber component and a hardening accelerator. SOLUTION: This thermosetting resin composition contains (A) an epoxy resin (e.g. phenol novolak-type epoxy resin, etc.), (B) a phenolic resin (e.g. phenol novolak resin, etc.), (C) an aromatic diamine having an imide group pref. a compound of the formula [Ar1 and Ar2 are each an aromatic residue; R1 is H or a 1-10C alkyl; R2 is H, a 1-20C alkyl, an alkoxy, a halogen; (n) is 0-30]}, (D) a rubber component (e.g. polybutadiene rubber, etc.), and (E) a hardening accelerator (e.g. imidazole compounds, phosphines, etc.).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a thermosetting resin composition and an interlayer adhesive film for a printed wiring board using the same.
The present invention relates to a prepreg for a laminate and a printed wiring board.

[0002]

2. Description of the Related Art In recent years, as electronic devices have become smaller and higher in performance, printed wiring boards have been increasing in density and multilayered. As a method of manufacturing such a high-density multilayer printed wiring board, an insulating resin layer is alternately laminated on a conductor layer without using a conventional copper foil, a prepreg and a laminating press method using an inner layer material, and the wiring is formed by a via hole. The development of build-up type multilayer printed wiring boards for connection is being actively conducted. Build-up type printed wiring boards are semiconductor packages,
It is expected to be used as a substrate for MCM and the like.

A method of forming a via hole in a printed wiring board of a build-up type includes a photo via method in which a photosensitive resin is used for an insulating resin layer and exposure and development, and a method in which a via hole is formed by laser processing using a thermosetting resin. Is being considered. As a method of using a photosensitive resin for the insulating resin layer, there is an advantage that via holes can be formed at once, but since a low molecular compound such as a polymerization initiator or a sensitizer remains in the insulating layer, it may be used during a post-process. To elute,
There was a problem with long-term insulation reliability. Further, the peel strength (adhesive strength) between the conductor layer, the insulating resin layer and the insulating layer is not sufficiently satisfied. In order to solve this problem, addition of fine resin powder soluble in an oxidizing agent has been performed. However, since chromic acid is used as the oxidizing agent, there have been problems in safety and workability. on the other hand,
Japanese Patent Application Laid-Open No. Hei 7-304931 discloses a method of using a thermosetting resin for the insulating resin layer. However, calcium carbonate or the like is used as a filler for securing the peel strength (adhesive strength) between the conductor layer and the insulating resin layer. At present, substrates that require high density and high reliability such as package substrates and MCM substrates are not sufficiently satisfied in terms of heat resistance and insulation reliability.

Further, in a copper-clad laminate using a conventional lamination press method, a through-hole plating step is included, so that the outer conductor is formed by adding a copper plating copper thickness to a copper foil, thereby increasing the copper thickness and forming a fine pattern. Is difficult. JP 05-29A
No. 5554 proposes a method in which a resin obtained by dispersing and hardening a plating catalyst is powdered, and this powder is mixed with a varnish to laminate and form a prepreg impregnated in a base material. Therefore, there is a problem of deteriorating characteristics such as electric insulation, and cannot be applied to a recent high-density printed wiring board. Also, after removing the copper foil of the copper-clad laminate by etching and then again performing copper plating to form a conductor layer, or after laminating the prepreg and the inner layer material,
A method in which the surface is treated by a mechanical (physical) method to form a circuit by copper plating (Japanese Patent Application Laid-Open No. 9-8458) has also been proposed, but in any case, the adhesive strength between the resin and the copper plating is not sufficient and the printed wiring board is not sufficient. There was a problem with its use.

[0005]

In view of the above circumstances, a thermosetting resin composition which simultaneously satisfies high density, high heat resistance, electrical insulation properties and adhesive strength of a conductive layer, and a printed wiring board using the same. An object of the present invention is to provide an interlayer adhesive film, a prepreg for a laminate, and a laminate.

[0006]

Means for Solving the Problems In order to solve the above problems, the present inventors have conducted intensive studies and found that the following thermosetting resin compositions, interlayer adhesive films for printed wiring boards using the same, and laminates The present inventors have found that prepregs and laminates, printed wiring boards, and multilayer printed wiring boards for use have extremely excellent performance, and have completed the present invention. That is, the present invention relates to a thermosetting resin composition comprising (A) an epoxy resin, (B) a phenolic resin, (C) an aromatic diamine compound having an imide group, (D) a rubber component, and (E) a curing accelerator as essential components. They are interlayer adhesive films for printed wiring boards, prepregs for laminated boards, and laminated boards using the same.

Further, in the thermosetting resin composition,
(C) An aromatic diamine compound having an imide group is a thermosetting resin composition represented by the following general formula (1).

Embedded image (Wherein, Ar ₁ and Ar ₂ each independently represent an aromatic residue, R
₁ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms,
R ₂ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, or a halogen group, and n represents an integer of 0 to 30. )

(1) An interlayer adhesive film for a printed wiring board is laminated on at least one surface of an inner layer material formed with an inner layer circuit under pressure and heating conditions, and a support base film is peeled off and removed, if necessary. The interlayer adhesive film is cured by heat, (2) a roughened surface is formed on the cured surface by a roughening agent treatment, and (3) a conductor layer is formed on the roughened surface. It is a multilayer printed wiring board.

Further, (1) a prepreg for a laminate is laminated on the inner layer material on which a circuit is formed so that the surface thereof becomes a surface to obtain a multilayer laminate, and (2) the surface of the multilayer laminate is treated with a roughening agent. (3) A multilayer printed wiring board characterized by forming a roughened surface in an uneven shape and (3) forming a conductor layer on the roughened surface of the multilayer laminate.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The thermosetting resin composition used in the present invention comprises (A) an epoxy resin, (B) a phenolic resin, (C) an aromatic diamine compound having an imide group, (D) a rubber component, and (E) ) A curing accelerator is constituted as an essential component. Each component is described below. Specific examples of the epoxy resin (A) include a phenol novolak type epoxy resin (eg, Epicoat 152, 154 manufactured by Yuka Shell Epoxy Co., Ltd.) and a cresol novolak type epoxy resin (eg, manufactured by Dainippon Ink and Chemicals, Inc.) Epicron N-67
3, N-695), bisphenol A type epoxy resin,
Bisphenol F type epoxy resin, (eg, Yuka Shell Epoxy Co., Ltd. Epicoat 828EL, 807) Bisphenol S type epoxy resin (eg, Dainippon Ink & Chemicals, Inc. Epicron EXA-1514), biphenyl type epoxy resin (example) : Eicoat Shell Epoxy Co., Ltd. Epicoat YX-4000) naphthalene type epoxy resin (Example:
Epoxy resin such as HP-4032 manufactured by Dainippon Ink and Chemicals, dicyclopentadiene type epoxy resin (eg, HP-7200 manufactured by Dainippon Ink and Chemicals, Inc.) N-glycidyl type epoxy resin, alicyclic epoxy resin, etc. , Triglycidyl isocyanurate, and a phenoxy resin from the viewpoint of imparting flexibility (eg, YP-50S manufactured by Toto Kasei Co., Ltd.),
Urethane-modified epoxy resin, rubber-modified epoxy resin, brominated epoxy resin (Example: YDB-50 manufactured by Toto Kasei Co., Ltd.)
A known epoxy resin such as Nippon Kayaku Co., Ltd. BREN) can be used.

As the phenol resin of the component (B), phenol novolak resin (for example, TD-2090 manufactured by Dainippon Ink and Chemicals, BRG- manufactured by Showa Polymer Co., Ltd.)
556) Cresol novolak resin, (Example: Resin X, Mitsubishi Yuka Co., Ltd.), polyvinylphenol resin (Example:
Maruza Linker manufactured by Maruzen Petrochemical Co., Ltd.), bisphenol A resin, bisphenol F resin, bisphenol S type resin, biphenol resin, resol type phenol resin,
Triazine skeleton-containing phenol novolak resin (eg, phenolite 7052 manufactured by Dainippon Ink and Chemicals, an addition compound of cyclopentadiene and phenol, an addition compound of liquid polybutadiene and phenol (Nippon Petrochemical Co., Ltd.)
Special phenolic resin PP-1000-180, DP
A known phenol resin such as PM, DPA-155) special novolak phenol resin (Xylok manufactured by Mitsui Petrochemical Co., Ltd.) can be used.

It is generally known that a thermosetting resin composition using an aromatic diamine compound as a curing agent for an epoxy resin is excellent in heat resistance and chemical resistance. For example, diaminodiphenylmethane (DDM), diaminodiphenylsulfone ( D
An aromatic diamine compound represented by DS) or the like has poor solubility in an epoxy resin or an organic solvent, and thus is difficult to handle due to a problem of crystallization during storage or a need for mixing by heating. The aromatic diamine compound having an imide group (C) of the present invention is a cyclized compound obtained by reacting a tetracarboxylic anhydride such as pyromellitic anhydride, 1 mole of bis (4-aminophenyl) ether and 2 moles. A condensed compound, an addition compound of bismaleimide and diaminodiphenylmethane (DDM) and the like can be used. From the viewpoint of heat resistance and solubility, an aromatic diamine compound having an imide group represented by the following general formula (Formula 1) (eg, Sumitomo) Chemical Vest Rex S
M-20) is preferably used.

The contents of the components (B) and (C) are as follows:
(A) Epoxy group in epoxy resin used for component 1.
It is desirable that the sum of the active hydrogen groups in the components (B) and (C) be in the range of 0.3 to 1.0 with respect to 0. If the amount is less than this, the heat resistance is hardly reduced.

Examples of the rubber component (D) include polybutadiene rubber (R-45HT manufactured by Idemitsu Petrochemical Co., Ltd., G-1000 manufactured by Nippon Soda Co., Ltd.), urethane modification, maleation, acrylation, methacrylation, Various polybutadiene derivatives such as epoxy modified (Idemitsu Petrochemical Co., Ltd. R-45E
PI, Nippon Soda Co., Ltd. BN-1015, GQ-100
0), core-shell rubber fine particles (Takeda Pharmaceutical Co., Ltd.)
Staphyloid, manufactured by Nippon Zeon Co., Ltd., etc.) or a fine particle rubber-dispersed epoxy resin in which fine particle rubber is previously dispersed in an epoxy resin (YR manufactured by Toto Kasei Co., Ltd.)
-570, YR-528) and the like.

The content of these rubber components is desirably 40 parts by weight or less based on 100 parts by weight of the epoxy resin. If the addition amount is more than this, heat resistance and the like are undesirably reduced.

Specific examples of the curing accelerator (E) include tertiary amines, quaternary ammonium salts, imidazole compounds or organic acid salts thereof, phosphine compounds, guanamine compounds, boron trifluoride compounds. , But preferably imidazole compounds and phosphine compounds.

The thermosetting resin composition can be applied to a substrate by a known method such as screen printing, curtain coating, roll coating, spray coating and the like. In each application method, filler,
Known and publicly used fillers and additives such as a solvent, an antifoaming agent, a thixotropic agent, a pigment and a dye can be used.

When the above-mentioned thermosetting resin composition is used as an interlayer adhesive film for a printed wiring board, a component for improving mechanical strength and flexibility and facilitating handling is a component having a weight average molecular weight of 5,000 to 100,000. A binder polymer in the range "is required. If the weight average molecular weight is less than 5,000, the effect of improving mechanical strength and flexibility is not exhibited, and if it exceeds 100,000, the solubility in organic solvents and the compatibility with the epoxy resin become poor, so that it cannot be used. The amount added is preferably in the range of 5 to 50% by weight. If the amount is less than 5% by weight, the effect of improving mechanical strength and flexibility is not exhibited, and if it exceeds 50% by weight, the heat fluidity deteriorates, which is not preferable. The binder polymer also has the effect of preventing cissing on the support film in the drying step during film production. Specifically, (bromination)
Phenoxy resin, polyacrylic resin, polyimide resin,
Examples thereof include a polyamide imide resin, a polycyanate resin, a polyester resin, and a thermosetting polyphenylene ether resin. These may be used in combination of two or more.

The interlayer adhesive film for a printed wiring board of the present invention is obtained by applying a resin varnish dissolved in a predetermined organic solvent using a base film as a support, and then drying the solvent by heating and / or blowing with hot air to obtain a resin composition which is solid at room temperature. It can be manufactured as a product. Examples of the supporting base film include polyolefins such as polyethylene and polyvinyl chloride, polyesters such as polyethylene terephthalate, polycarbonate, and release paper, metal foils such as copper foil and aluminum foil. The thickness of the supporting base film is generally from 10 to 150 μm. The support film may be subjected to a release treatment in addition to the mud treatment and the corona treatment. As the organic solvent, usually solvents, for example, ketones such as acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, acetic acid esters such as carbitol acetate,
Cellosolves such as cellosolve and butyl cellosolve, carbitols such as carbitol and butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like alone or in combination of two or more Can be used. The thus obtained interlayer adhesive film for a printed wiring board of the present invention is stored as it is or by further laminating a protective film such as a support film on the other surface of the resin composition, winding it up in a roll shape, and storing it.

Next, a multilayer printed wiring board using the interlayer adhesive film for a printed wiring board of the present invention will be described.
When bonding the interlayer adhesive film of the present invention to the patterned inner layer circuit board, after removing the protective film, if present, press the room temperature solid resin composition from the support base film side. Laminate while heating. As the inner circuit board, a glass epoxy, metal board, polyester board, polyimide board, thermosetting polyphenylene ether board, or the like can be used, and the circuit surface may be roughened in advance. The lamination may be a batch type or a continuous type with a roll under reduced pressure, and it is preferable to laminate both surfaces simultaneously. The above lamination conditions vary depending on the hot melt viscosity of the room-temperature solid resin composition of the present invention and the inner-layer circuit board used.
℃, pressure is 1-10kgf / cm2, 20mmH
Laminate under reduced pressure of not more than g. After lamination, the support base film is peeled off after cooling to around room temperature. Thereafter, heat curing is performed if necessary, and a predetermined through-hole and / or via-hole is opened by a laser and / or a drill, and the surface of the resin composition is treated with a roughening agent to form fine irregularities. Next, a conductor layer is formed by dry and / or wet plating to obtain a multilayer printed wiring board. The conditions of the heat curing are selected in the range of 120 to 250 ° C. for 10 to 90 minutes. Specific examples of the roughening agent that can be used as the roughening agent include oxidizing agents such as dichromate, permanganate, ozone, hydrogen peroxide / sulfuric acid, and nitric acid, and N-methyl-2-pyrrolidone. , N, N-dimethylformamide, methoxypropanol and the like; an alkaline aqueous solution such as caustic soda and caustic potassium; an acidic aqueous solution such as sulfuric acid and hydrochloric acid; or various plasma treatments. These processes may be used in combination. After forming an anchor having fine irregularities on the surface of the resin composition as necessary, a conductor layer is formed by dry plating such as vapor deposition, sputtering, or ion plating and / or wet plating such as electroless or electrolytic plating. At this time, a plating resist having a pattern opposite to that of the conductor layer may be formed, and the conductor layer may be formed only by electroless plating. After the conductor layer is thus formed, the thermosetting resin composition is annealed at a temperature higher than the glass transition temperature of the cured product for 10 to 60 minutes, whereby the curing of the thermosetting resin progresses, The peel strength of the layer can be further improved.

After laminating the interlayer adhesive film for printed wiring boards on the inner circuit board, if necessary, heat-curing a resin composition and further laminating a copper foil with an adhesive or a copper foil thereon to form an integrated layer. And a multilayer printed wiring board can be obtained. The conditions for the heat curing depend on the type of the material of the inner layer circuit board and, when a copper foil with an adhesive is used, the curing temperature, but are selected in the range of 120 to 250 ° C. for 20 to 90 minutes.

The prepreg for a laminate according to the present invention and a method for manufacturing a printed wiring board using the laminate will be described below.

A prepreg for a laminate using the thermosetting resin composition of the present invention is obtained by impregnating a paper-like or cloth-like base material with a resin varnish dissolved in an organic solvent and then heating and / or blowing with hot air. It can be made by drying.
Examples of the organic solvent include usually solvents such as ketones such as acetone, methyl ethyl ketone and cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate; cellosolves such as cellosolve and butyl cellosolve. Carbitol, butyl carbitol and the like, carbitols such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like can be used alone or in combination of two or more. For the paper-like or cloth-like substrate used, woven or non-woven fabrics made of inorganic fibers such as paper or glass fibers and carbon fibers, or polyester fibers, aramid fibers (eg, Technora manufactured by Teijin Ltd.) A woven or nonwoven fabric made of an organic fiber such as an aromatic polyester fiber (eg, Vectran manufactured by Kuraray Co., Ltd.) can be used. The surface of these fibers may be subjected to a surface treatment such as a coupling agent or the like before use. It is particularly preferable to use organic fibers from the viewpoint of reducing the weight of the printed wiring board and the processability of via hole processing by laser irradiation, and it is preferable to use a nonwoven fabric from the viewpoint of improving surface smoothness.

The laminate of the present invention can be produced as long as the prepreg for the laminate is disposed on at least one surface. In addition, the present invention also includes one obtained by curing only one prepreg for a laminate according to the present invention. In addition, a known method can be used as a curing method, but a lamination press is preferable from the viewpoint of the thickness accuracy of the laminated plate. At this time, the conditions of the laminating press are determined in order to control the layer configuration of the prepreg to be used and the cured state, but it is preferable that the conditions are 120 to 250 ° C., 20 to 120 minutes, and 20 to 60 kgf / m 2. . If the temperature is lower than this for a short time, the curing becomes insufficient, and problems such as drill workability of through holes and surface flaws occur. Conversely, when the temperature is high and the time is long, it is difficult to form a roughened surface. Subsequently, a predetermined through-hole and / or via-hole is perforated by a laser and / or a drill, and if necessary, the surface of the laminate is subjected to a roughening treatment to form fine irregularities. Next, the conductor layer is formed by dry and / or wet plating to produce a multilayer printed wiring board. Specific examples of the roughening agent that can be used as the roughening agent treatment include bichromate,
Oxidizing agents such as permanganate, ozone, hydrogen peroxide / sulfuric acid, and nitric acid; organic solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, methoxypropanol;
Further, an alkaline aqueous solution such as caustic soda or potassium hydroxide, an acidic aqueous solution such as sulfuric acid or hydrochloric acid, or various plasma treatments can be used. These processes may be used in combination. After forming an anchor with fine irregularities on the surface of the resin composition as necessary, evaporation, sputtering,
The conductor layer is formed by dry plating such as ion plating and / or wet plating such as electroless plating and electrolytic plating. At this time, a plating resist having a pattern opposite to that of the conductor layer may be formed, and the conductor layer may be formed only by electroless plating. After the conductor layer is formed in this manner, by annealing for 10 to 90 minutes at a temperature higher than the glass transition temperature of the cured product of the epoxy resin composition, the curing of the thermosetting resin progresses and the peel of the conductor layer is peeled off. The strength can be further improved.

The present invention relates to a method for producing a multilayer printed wiring board by a lamination press using a circuit-formed inner layer material and a laminate prepreg. Make a multilayer laminate. At this time, the conditions of the laminating press are determined by the inner layer material used, the prepreg, and the intended layer configuration of the multilayer printed wiring board.
To 120 minutes. The pressure is determined in consideration of the embedding property of the inner layer material between the patterns. If the temperature is lower than this for a short time, the curing of the resin becomes insufficient, and there are problems such as drillability of through holes and surface flaws. Conversely, when the temperature is high and the time is long, it is difficult to form a roughened surface. Subsequently, predetermined through-holes and / or via-holes are drilled with a laser and / or a drill, and if necessary, the surface of the multilayer laminate is subjected to a roughening treatment to form fine irregularities. Next, the conductor layer is formed by dry and / or wet plating to produce a multilayer printed wiring board. Specific examples of the roughening agent that can be used as the roughening agent include oxidizing agents such as dichromate, permanganate, ozone, hydrogen peroxide / sulfuric acid, and nitric acid, and N-methyl-2-pyrrolidone. , N, N-dimethylformamide, methoxypropanol and the like; an alkaline aqueous solution such as caustic soda and caustic potassium; an acidic aqueous solution such as sulfuric acid and hydrochloric acid; or various plasma treatments. These processes may be used in combination. After forming an anchor having fine irregularities on the surface of the resin composition as necessary, a conductor layer is formed by dry plating such as vapor deposition, sputtering, or ion plating and / or wet plating such as electroless or electrolytic plating. At this time, a plating resist having a pattern opposite to that of the conductor layer may be formed, and the conductor layer may be formed only by electroless plating. After the conductor layer is formed in this manner, by annealing for 10 to 90 minutes at a temperature higher than the glass transition temperature of the cured product of the epoxy resin composition, the curing of the thermosetting resin progresses and the peel of the conductor layer is peeled off. The strength can be further improved.

Hereinafter, the present invention will be described in detail with reference to examples.

[0027]

Examples 1 to 5 Thermosetting resin compositions were prepared with the compositions shown in the examples of Table 1 (the numerical values are parts by weight). Regarding the preparation of the thermosetting resin composition of each example, each resin and a curing accelerator were uniformly mixed in a methyl ethyl ketone solvent to prepare a resin varnish. A resin varnish is applied to a circuit-formed substrate by a bar coater so that the thickness after drying becomes 50 μm, dried at 80 ° C. for 20 minutes, and cured at 170 ° C. for 80 minutes. To perform a roughening agent treatment. Here, after swelling with a mixture of an alkaline aqueous solution and a solvent, a treatment with an alkaline permanganate aqueous solution, and subsequently with a reducing agent, electroless copper plating, electrolytic copper plating, and copper plating with a copper thickness of 35 microns. A laminate was prepared. 250 ° C, 60
A minute annealing treatment was performed, and a copper-clad laminate wiring board was prepared and evaluated.

[0028]

Example 6 Compositions shown in Examples of Table 1 (numerical parts are parts by weight)
To prepare a thermosetting resin composition. For the preparation of the thermosetting resin composition, each resin and a curing accelerator were uniformly mixed in a methyl ethyl ketone solvent to prepare a resin varnish.
The varnish was applied on a 30 μm-thick polyethylene terephthalate (hereinafter referred to as PET) film using a roller coater so that the thickness after drying was 50 μm.
It dried at 0-100 degreeC for 10 minutes, and obtained the interlayer adhesive film for printed wiring boards. This film was bent at 180 degrees for evaluation of flexibility, but there was no abnormality such as crack in the resin portion. An interlayer adhesive film for a printed wiring board was simultaneously laminated on both sides of the circuit-formed inner layer circuit board by a vacuum laminator. 60 at 170 ° C
And cured to obtain a laminated substrate. Thereafter, predetermined through holes, via holes, and the like were drilled with a drill and a laser. Thereafter, a roughening agent treatment was performed using a roughening agent. Here, after swelling with a mixture of an alkaline aqueous solution and a solvent, a treatment with an alkaline permanganate aqueous solution, and subsequently with a reducing agent, electroless copper plating, electrolytic copper plating, and a 35 micron thick copper multilayer. A laminate was prepared.
Annealing treatment was performed at 200 ° C. for 60 minutes, and a four-layer printed wiring board on which a circuit was formed by a subtractive method was prepared and evaluated. The obtained printed wiring board is heated at 260 ° C. for 60 hours.
It was immersed in a solder bath for 2 seconds, and the solder heat resistance was observed. No abnormality was found. In addition, a thermal shock test (−65 ° C. to 15
(0 ° C., 500 cycles), no abnormality was found in the connection of the through holes and via holes.

[0029]

Example 7 A thermosetting resin composition having the composition shown in Example 2 in Table 1 (numerical parts by weight) was prepared, and a resin varnish was impregnated into a wholly aromatic polyester (Kuraray, Vectran fiber nonwoven fabric). And dried at 150 ° C. for 5 minutes, 0.1 mm
A thick prepreg for a laminate was produced. Six prepregs for a laminated board are laminated, and 170 ° C., 80 minutes, 40 kgf / m 2
A laminate was produced under the following pressing conditions. Thereafter, through-holes were formed with a drill, and a roughened surface was formed on the surface of the laminate using a roughening agent to obtain a surface-roughened laminate. Here, after swelling with a mixture of an alkaline aqueous solution and a solvent, a treatment with an alkaline permanganate aqueous solution, and subsequently with a reducing agent, electroless copper plating, electrolytic copper plating, and copper plating with a copper thickness of 35 microns. A laminate was prepared. 200 ° C, 6
A double-sided printed wiring board on which an annealing treatment was performed for 0 minutes and a circuit was formed by a normal subtractive method was manufactured and evaluated. The obtained printed wiring board was immersed in a solder bath at 260 ° C. for 60 seconds, and the solder heat resistance was observed. No abnormality was found. In addition, a thermal shock test (−65 ° C. to 150
(500 ° C., 500 cycles), no abnormality was found in the connection of the through holes and via holes.

[0030]

Example 8 A thermosetting resin composition was prepared with the composition shown in Example 3 in Table 1 (the numerical values are parts by weight), and a prepreg for a laminate having a thickness of 0.1 mm was prepared in the same manner as in Example 7. . A prepreg for a laminate was placed on a circuit-formed inner layer circuit board in a vacuum press at 170 ° C. for 80 minutes under a press condition of 40 kgf / m 2. Thereafter, predetermined through holes, via holes, and the like were drilled with a drill and a laser. Thereafter, a roughening agent treatment was performed using a roughening agent. Here, after swelling with a mixture of an alkaline aqueous solution and a solvent, a treatment with an alkaline permanganate aqueous solution, and subsequently with a reducing agent, electroless copper plating, electrolytic copper plating, and a 35 micron thick copper multilayer. A laminate was prepared. Annealing treatment was performed at 200 ° C. for 60 minutes, and a four-layer printed wiring board on which a circuit was formed by a subtractive method was prepared and evaluated. 260 ° C.
Immersion treatment in a solder bath for 60 seconds, and the solder heat resistance was observed, but no abnormality was found. The thermal shock test (-65 ° C
(Up to 150 ° C., 500 cycles), no abnormality was found in the connection of the through holes and via holes.

[0031]

Comparative Examples 1 to 3 Thermosetting resin compositions having the compositions shown in Comparative Examples in Table 1 were prepared. Regarding the preparation of the thermosetting resin composition of each example, each resin and a curing accelerator were uniformly mixed in a methyl ethyl ketone solvent to prepare a resin varnish. Preparation and evaluation samples of the thermosetting resin composition of each comparative example were based on Examples 1 to 5.

[0032]

[Table 1]

Table 2 shows the results. As is clear from Examples 1 to 5, when the thermosetting resin composition of the present invention was used, there was no problem in heat resistance and insulation properties, and good peel strength without swelling after annealing was obtained. There was no problem such as blistering in the soldering heat test. On the other hand, Comparative Example 1
In the cases of Nos. 1 to 3, swelling after annealing and swelling in a soldering heat test occurred, and the peel strength was insufficient. Comparative Example 3
However, although peel strength can be ensured, there is a problem in insulation properties.

[0034]

[Table 2]

[0035]

As described above, the thermosetting resin composition of the present invention, that is, (A) an epoxy resin, (B) a phenolic resin, (C) an aromatic diamine compound having an imide group, (D) a rubber component, and (E) curing. By using a thermosetting resin composition containing a promoter as an essential component, an interlayer insulating layer having high heat resistance and excellent electrical insulation can be formed. Further, an interlayer adhesive film for a printed wiring board, a prepreg for a laminate, and a laminate can be obtained by using the thermosetting resin composition of the present invention. Further, by using these, it is possible to obtain a highly reliable multilayer printed wiring board which can cope with an increase in wiring density and has high heat resistance and excellent electrical insulation.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) H05K 3/38 H05K 3/38 E 3/46 3/46 TF term (Reference) 4F100 AB17 AK33B AK47B AK49B AK53B AL05B AN00B AR00C AS00C AT00A BA01 BA02 BA03 BA04 DD07 DG10D DG15D DH01 EJ082 EJ172 EJ303 EJ422 EJ642 EJ82D GB43 HB00C JB13B JG04 JJ03 4J002 AC034 BL014 CC042 CC052 CD06 CD04 CD04 CD04 CD04 CD04 CD04 CD04 CD04 CD04 CD04 CD04 CD04 CD04 CD04 CD04 CD04 CD041 AD07 AD08 AD21 AF06 AF07 AJ02 AJ08 AJ14 AJ18 AK02 CD04 CD09 DC05 DC19 DC26 DC41 DC42 DD07 FB05 FB07 FB08 FB14 GA02 GA06 JA08 5E343 AA07 AA13 AA15 AA16 AA17 AA18 BB24 BB67 CC02 CC03 CC04 CC43 CC45 CC47 CC04 CC43 CC45 CC04 CC43 CC45 CC47 CC08 CC09 CC10 CC32 DD12 DD22 EE04 EE06 EE08 EE09 EE12 EE19 HH08 HH18

Claims (8)

[Claims] 1. An epoxy resin (A), a phenolic resin (B) and an aromatic diamine compound having an imide group (D).
Thermosetting resin composition comprising rubber component and (E) curing accelerator as essential components 2. The thermosetting resin composition according to claim 1, wherein the (C) aromatic diamine compound having an imide group is represented by the following general formula (1). (Wherein, Ar ₁ and Ar ₂ each independently represent an aromatic residue, R
₁ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms,
R ₂ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, or a halogen group, and n represents an integer of 0 to 30. ) 3. The method according to claim 1, wherein the support base film is formed on a base film.
Interlayer adhesive film for printed wiring boards formed by forming a film of the thermosetting resin composition according to claim (1) The interlayer adhesive film for a printed wiring board according to claim 3 is laminated on at least one surface of the inner layer material on which the inner layer circuit is formed under pressure and heating conditions, and then the support base film is peeled off. Thereafter, if necessary, the interlayer adhesive film is heat-cured, (2) a roughened surface is formed on the hardened surface by a roughening agent treatment, and (3) a conductor layer is formed on the roughened surface. Multilayer printed wiring board characterized by the following: 5. A prepreg for a laminate, wherein the thermosetting resin according to claim 1 or 2 is impregnated in a paper-like or cloth-like base material. 6. A laminate obtained by laminating and pressing the prepreg according to claim 5 on at least one surface. (1) A roughened surface is formed on the surface of the laminate according to claim 6 by a roughening agent treatment, and (2) a conductor layer is formed on the roughened surface of the laminate. Printed wiring board characterized by being obtained 8. A multilayer laminate is obtained by laminating the prepreg for laminate according to claim 5 on the surface of the inner layer material on which the circuit is formed, and (2) roughening the surface of the multilayer laminate. And (3) forming a conductor layer on the roughened surface of the multilayer laminate, wherein the conductive layer is formed on the roughened surface of the multilayer laminate.