KR20020067627A - Thermosetting epoxy resin composition, its formed article and multilayer printed circuit board - Google Patents

Abstract

PURPOSE: To provide a thermosetting epoxy resin composition satisfying heat resistance, electrical insulating characteristic, and at the same time adhesion strength of a conductive layer on a built-up multilayer printed wiring board, and also excellent in storage stability, its molding, and a build-up multilayer printed wiring board made therefrom and capable of complying to high density. CONSTITUTION: This thermosetting epoxy resin composition contains (A) an epoxy resin having at least two epoxy groups in a molecule, (B) a curing agent having a phenolic hydroxyl group, and (C) an imidazole compound having a hydroxyl group as a curing accelerator.

Description

Thermosetting epoxy resin composition, its molded product and multilayer printed wiring board {THERMOSETTING EPOXY RESIN COMPOSITION, ITS FORMED ARTICLE AND MULTILAYER PRINTED CIRCUIT BOARD}

The present invention relates to a thermosetting epoxy resin composition useful as an interlayer resin insulating material or a solder resist material in the manufacture of a multilayer printed wiring board, a molded article formed on the support, and a multilayer printed wiring board produced using the same.

In particular, in a build-up multilayer printed wiring board, a thermosetting epoxy resin composition capable of satisfying heat resistance, electrical insulation properties, and adhesive strength of a conductor layer at the same time, a build-up multilayer capable of coping with high density of a conductor circuit manufactured using the same, and a molded article thereof. It relates to a printed wiring board.

Conventionally, as a multilayer printed wiring board for electronic devices, a predetermined number of prepregs formed by impregnating an epoxy resin and dicyandiamide on a substrate such as glass and drying the inner layer circuit board formed with a circuit are stacked on a predetermined number of sheets, and further, a metal foil such as copper foil is applied as necessary. The copper plating laminated sheet produced by laminating | stacking on one or both sides and vacuum-pressing for several hours at high temperature (180 degreeC back and front) is used.

Certainly, the laminated board of copper coating using the prepreg formed by impregnating the thermosetting composition which consists of such epoxy and dicyandiamide has the required characteristic for printed wiring boards, such as heat resistance, moisture resistance, crack resistance, and workability.

However, in recent multi-layer printed wiring boards, high-density installation and high integration of components, high density of conductor circuits, light and short reduction, and the like are required, and it is difficult to meet these demands with copper-clad laminates.

On the other hand, recently, the build-up multilayer printed wiring board which piles up a conductor circuit layer and an interlayer insulation layer attracts attention.

This build-up multi-layer printed wiring board uses a resin composition obtained by mixing a curing agent, a filler, or the like with an epoxy resin in place of the prepreg as an interlayer insulating layer, and a screen printing method, a roll coating method, a resin as a method of forming the interlayer insulating layer. Lamination method by a film, etc. are mentioned.

Furthermore, in recent years, the manufacturing method of the multilayer printed wiring board which apply | coats a resin composition on copper foil previously, and builds up using copper foil with resin made into the semi-hardened state (B-stage) is also employ | adopted.

However, such a buildup multilayer printed wiring board cannot be used as a thermosetting composition composed of epoxy resin and dicyandiamide because the vacuum press at a high temperature (around 180 ° C) is impossible in the manufacturing process.

On the other hand, the composition which uses the low temperature hardening | curing hardener system which consists of a dicyandiamide and an imidazole compound as an epoxy resin is proposed.

However, in such a curing agent system, the imidazole compound and the dicyandiamide are decomposed and react with the epoxy rapidly. Therefore, the surface roughness of the interlayer insulating resin formed by the roughening treatment of the surface of the resin insulating layer is not stable, the peel strength with the conductor layer is unstable and difficult to ensure. There was a problem that this occurred. Moreover, the composition of the hardening | curing agent type | system | group which has a fast hardening rate at such low temperature is bad in storage stability. Therefore, in the resin composition used by the use form, such as a film and copper foil with resin, even one storage stability is required and it becomes a problem in that point.

SUMMARY OF THE INVENTION The present invention has been made to solve the problems of the prior art as described above, and its main object is to provide heat resistance, electrical insulation properties, and adhesion to a conductor layer in a multilayer printed wiring board, particularly a buildup multilayer printed wiring board. The present invention provides a thermosetting epoxy resin composition that satisfies strength at the same time and has excellent storage stability, a molded article thereof, and a multilayer printed wiring board capable of coping with high density of conductor circuits produced using the same.

In order to achieve the above object, according to the present invention, (A) an epoxy having two or more epoxy groups in one molecule, (B) a curing agent having two or more phenolic hydroxyl groups in one molecule, and (C) a hydroxyl group as a curing accelerator There is provided a thermosetting epoxy resin composition comprising an imidazole compound having an aromatic ring. Preferably, as said hardening accelerator (C), the imidazole compound represented by following General formula (1) is used.

Wherein R ₁ represents CH ₃ or CH ₂ OH.

Moreover, according to a preferable aspect, the resin composition of this invention is 10- (2,5-dihydroxyphenyl) -10H- in the epoxy resin which the said epoxy resin (A) has one or more epoxy groups in 1 molecule previously. It is preferable to contain the phosphorus containing epoxy resin which reacts with oxaphosphene styrene = l0-oxide, and it is more preferable that the phosphorus content is 1-5 mass%.

According to another preferred aspect, in the resin composition of the present invention, the curing agent (B) preferably contains 10- (2,5-dihydroxyphenyl) -10H-oxaphosphenanthrene = 10-oxide. .

According to a further preferred aspect, the resin composition of the present invention preferably contains an inorganic filler and / or an organic filler having an average particle diameter of 5 μm or less, and more preferably 40 mass% or less with respect to the solid content of the composition. Do.

The thermosetting epoxy resin composition can be liquefied in one liquid, and the molded article of the present invention using the resin composition is obtained by coating and drying the above-mentioned thermosetting epoxy composition on a support film and film-forming, or the above-mentioned thermosetting epoxy resin composition. It applied and dried on the support copper foil, and it was set as the resin foil with resin.

Moreover, the multilayer printed wiring board of this invention is produced using the thermosetting epoxy composition or molded object which were mentioned above.

The thermosetting epoxy composition of the present invention is characterized by including an imidazole compound having a hydroxyl group and an aromatic ring as the curing accelerator (C), including a compound having two or more phenolic hydroxyl groups as the curing agent (B). Since the imidazole compound having a hydroxyl group and an aromatic ring has a benzene skeleton in its molecule, its melting point is high (190 DEG C or higher) and its basicity is low, so that the curing reaction of the thermosetting epoxy resin composition does not proceed rapidly, and the internal stress is not increased. Can be prevented, so that an interlayer insulating layer having good characteristics and stable can be formed. Furthermore, the surface of the interlayer insulating layer made of a cured product of a thermosetting resin composition containing a hydroxyl group and an imidazole compound having an aromatic ring as a curing accelerator has high hydrophilicity, enabling uniform roughness in a short time, and stable peel strength with the conductor layer. It can be ensured and does not cause peeling or the like even in the heat resistance test.

In the manufacture of wiring boards, annealing is usually performed to alleviate internal stress. In that case, in the low temperature fast-curable hardening | curing agent system which consists of a dicyandiamide and an imidazole compound, the adhesive strength falls by the excessive hardening by an anil. In this regard, according to the curing agent system of the present invention, there is no decrease in the adhesion strength due to annealing, and it is effective in improving the intimacy.

Furthermore, the thermosetting epoxy resin composition of the present invention does not undergo rapid curing reaction of epoxy, so that it is possible to liquefy one liquid, and excellent in storage stability, and even in the form of a film or a resin-clad copper foil, the reaction does not proceed during storage. It is possible to set the manufacturing conditions of the stable wiring board without.

Hereinafter, each component of the thermosetting epoxy resin composition of the present invention will be described in detail.

First, as an epoxy (A) having two or more epoxy groups in one molecule, bisphenol A type epoxy resins (e.g., Epicoat 828 manufactured by Japan Epoxy Resin Co., Ltd., Epiklon 1050 manufactured by Dainippon Ink Chemical Co., Ltd.) , Bisphenol A type novolac epoxy resin, bisphenol F type epoxy resin (e.g., Epiclon 830 manufactured by Dainippon Ink Chemical Co., Ltd., YDF-20, -0l manufactured by Doto Chemical Co., Ltd.), bisphenol S type epoxy resin ( For example, Epiclon EXA-1514 manufactured by Dainippon Ink and Chemicals Co., Ltd., a phenol novolak-type epoxy resin (e.g., Epicoat 152,154 manufactured by Japan Epoxy Resin Co., Ltd.), cresol novolac-type epoxy resin (e.g. For example, Dinipon Ink Chemical Co., Ltd. Epikron N-660, N-673, N-695), Biphenyl type epoxy (for example, Epi-epoxy resin Co., Ltd. Epicoat YX-4000) Naphthalene type Epoxy resin (for example, HP-4032 by Dainippon Ink and Chemicals Co., Ltd.), dicyclopentadiene type epoxy resin (for example, Dainippon Ink and Chemicals Co., Ltd. H P-7200), epoxy resins such as N-glycidyl epoxy resins and alicyclic epoxy resins, triglycidyl isocyanurate, urethane-modified epoxy resins, rubber-modified epoxy resins (e.g., Japanese procurement) (Current) BF-1000, Poly bd R-45EPI manufactured by Idemitsu Petrochemical Co., Ltd., YR-450 manufactured by Tohwa Chemical Co., Ltd., Eporit PB-36 00, manufactured by Daicel Chemical Industries, Ltd. PB-4700 and the like) and known epoxy resins such as those obtained by adding bromine or phosphorus compounds to the epoxy resins can be used, but are not limited to these, and there are no problems in using several kinds at the same time.

As a hardening | curing agent (B) which has two or more phenolic hydroxyl groups in 1 molecule, a phenol novolak resin (for example, Maywa Chemical Co., Ltd. H-1), a cresol novolak resin, an aralkyl phenol resin (for example, , Mitsui Chemical Co., Ltd. XL225), terpene phenol resin (e.g., Epua MP402 by Japan Epoxy Resin Co., Ltd.), naphthol-modified phenolic resin (e.g., Kayakua NHN manufactured by Nippon Kayaku Co., Ltd.) , Dicyclopentadiene-modified phenol resin (e.g., DDP-M manufactured by Nippon Seki Chemical Co., Ltd.), bisphenol A novolac phenol resin (e.g., Mewa Chemical Co., Ltd. BPA-D) Although well-known phenol resins, such as an amino triazine novolak resin (For example, ATN resin by Dainippon Ink and Chemicals, Inc.), copolymers of 4-hydroxy styrene etc. can be used, it is not limited to these. As the phenolic hydroxyl group-containing phosphorus compound, 10- (2,5-dihydroxyphenyl) -10H-oxa phosphenanthrene = 10-oxide (for example, HCA-HQ manufactured by Sanco Co., Ltd.) can be used. .

The hardening | curing agent (B) which has these phenolic hydroxyl groups does not interfere even if it uses several types simultaneously.

As for the usage-amount of this hardening | curing agent (B), it is preferable that the hydroxyl group containing a phenolic hydroxyl group is 0.2-1.3 equivalent range with respect to the epoxy group 1.0 equivalent in epoxy resin (A). The reason for this is that the addition amount of the curing agent is less than 0.2 equivalent, because the unreacted epoxy group has a large number of unreacted epoxy groups and the heat resistance is lowered. Can not do it.

As a specific example of the imidazole compound (C) which has a hydroxyl group and an aromatic ring as a hardening accelerator, 2-phenyl-4, 5- dihydroxy methylimidazole represented by the said General formula (1) (for example, Shikoku Kogyo Co., Ltd. ( Note 2) PHZ), 2-phenyl-4-methyl5-hydroxymethylimidazole: (e.g., 2P4 MHZ manufactured by Shikoku Kagaku Kogyo Co., Ltd.) and the like.

These hardening accelerators can be used individually or in combination of 2 or more types.

It is preferable to make the addition amount of this hardening accelerator (C) into 0.5-10 mass% with respect to an epoxy resin (A). This reason is not preferable because less than 0.5% by mass leads to insufficient curing of the epoxy resin, while when it exceeds 10% by mass, it is too hard to be easily vulnerable.

The thermosetting epoxy composition of this invention can mix | blend an inorganic filler and / or an organic filler with an average particle diameter of 5 micrometers or less as needed. Its content is 40 mass% or less, More preferably, it is desirable to set it as 30 mass% or less. By adding this filler, the thermosetting epoxy resin composition excellent in the laser hole perforation performance, and its molded object can be obtained.

The inorganic filler and / or the organic filler is not stabilized when the average particle diameter exceeds 5 μm, and the surface roughness of the resin insulating layer is not stabilized. On the other hand, when the content exceeds 40 mass% in the resin composition, the carbon dioxide (CO ₂ ) laser is used. The shape of the small-diameter vias to be formed is deteriorated, so that the plating adhesion is poor, problems in connection reliability are caused, and the productivity of the laser beam is lowered.

Examples of the inorganic fillers include barium sulfate, calcium carbonate, magnesium carbonate, magnesium oxide, aluminum hydroxide, magnesium hydroxide, barium titanate, silicon oxide powder, spherical silica, amorphous silica, tark, clay, and mica powder. Etc. can be used. As organic fillers, for example, silicone powder, nylon powder, fluorine powder, urethane powder, powder of precured epoxy resin, crosslinked acrylic polymer fine particles, melamine resin, guanamine resin, urea resin, and these amino resins And finely ground after thermal curing.

In addition, an inorganic filler and / or an organic filler is not limited to these, Moreover, even if several kinds are used simultaneously, it does not interfere.

Furthermore, in the resin composition of the present invention, if necessary, flame retardants such as red phosphorus, antimony trioxide, antimony pentoxide, thickeners such as orphen or benton, antifoaming agents of silicon, fluorine, polymer and / or leveling agent, Additives, such as adhesive imparting agents, such as an imidazole series, a thiazole series, a triazole series, and a silane coupling agent, can be used.

Furthermore, if necessary, known common colorants such as phthalocyanine blue, phthalocyanine green, iodine green, Japan disazo yellow, titanium oxide, carbon black, and dyes can be used.

Moreover, also in such an additive, it is preferable to make an average particle mass 5 micrometers or less about the solid form thing for the reason mentioned above.

Further, the resin composition of the present invention can be diluted using an organic solvent for liquefaction or viscosity adjustment in accordance with various coating processes.

Examples of the organic solvent include solvents known in the art, such as acetone, methyl ethyl ketone, ketones such as cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate In addition to aromatic hydrocarbons, such as cellosolves such as cellosolves, butyl cellosolves, carbitols such as carbitol and butyl carbitol, toluene and xylene, dimethyl formamide, dimethylacetoamide, and N-methylpyrrolidone Polar solvents can be used individually or in combination of 2 or more types.

Next, the multilayer printed wiring board using the thermosetting epoxy resin composition of this invention or its molded object is demonstrated.

(1) formation of interlayer dielectric layers with thermosetting epoxy compositions

First, the thermosetting epoxy resin composition of the present invention is applied and dried on an insulating substrate on which an inner conductor circuit is formed, using known methods such as screen printing, curtain coating, roll coating, and spray coating. Drying conditions at this time vary depending on the solvent used, but are generally selected in the range of 5 to 60 minutes at about 60 to 150 ° C.

Subsequently, after drying, thermosetting is performed as necessary to form an interlayer insulating layer. The thermosetting conditions at this time are selected in about 15 to 90 minutes at about 130 to 200 ℃.

(2) Formation of interlayer insulating layer by molded body of thermosetting epoxy resin composition

① Preparation of moldings

The resin composition constituting the molded body includes a phenoxy resin, a polyacrylic resin, a polyimide resin, a polyamideimide resin, and a polycyanate, in addition to the component (A) constituting the resin composition of the present invention as a component that improves mechanical strength and plasticity. Resin, polyester resin, polyphenyl ether resin and the like can be blended.

These resin can also be used in combination of 2 or more type.

The thermosetting epoxy composition of the present invention is diluted with a predetermined organic solvent, coated on a support metal foil such as a support film or copper foil with a film coater, dried, and a film-shaped molded article or resin-clad copper foil is produced.

Here, as a support film, polyester, such as polyethylene, a polypropylene, polyethylene terephthalate, polycarbonate, etc. are mentioned. Copper foil etc. are mentioned as support metal foil.

In addition, such a support may be subjected to various pretreatments (made, corona treatment), and the thickness of the support is generally 5 to 100 m.

Moreover, it is preferable that this molded object is tack-protected by a protective film etc. and stored in a sheet form or a roll form.

② Formation of Interlayer Insulation Layer by Film Shaped Molded Body

First, the film-form molded product prepared in the same manner as described above is laminated on the insulating substrate on which the inner layer conductor circuit is formed and laminated under heating and reduced pressure. Further, the pressurization increases the smoothness of the substrate. As the lamination conditions, the compression pressure of about 0.1 to 20 MPa is common at a temperature of 70 to 150 ° C.

Subsequently, after lamination, thermosetting is performed as necessary to form an interlayer insulating layer.

The thermosetting conditions at this time are about 130 to 200 degreeC, and are selected in the range of about 15 to 90 minutes.

In addition, the method of the wiring board using the copper foil with resin is mentioned later.

(3) Manufacture of build-up wiring board

First, through-holes and via-holes are drilled or laser-punched at predetermined positions of the interlayer insulating layer formed in the same manner as described above, and then the surface of the insulating layer is treated with a roughening agent to remove minute irregularities. Form. At this time, if necessary, physical polishing with puff may be performed to stabilize the adhesiveness before the roughening agent treatment.

Here, as a method of roughening the surface of the insulating layer, the substrate on which the insulating layer is formed can be immersed in a solution such as an oxidant, or sprayed by a solution such as an oxidant.

It may also be carried out by various plasma treatments. In addition, these treatments may be used in combination. Moreover, as a specific example of a roughening agent, organic materials, such as dichromate, permanganate, ozone, oxidizing agents, such as hydrogen peroxide / sulfuric acid, acetic acid, N-methyl- 2-pyrrolidone, N, N- dimethylformamide, methoxypropanol, Solvents, and alkaline aqueous solutions, such as caustic soda and caustic acid, and acidic aqueous solutions, such as a sulfuric acid and hydrochloric acid, can be used.

Subsequently, the conductor layer is formed by dry plating such as vapor deposition, sputtering, ion plating, or wet plating such as electroless plating or electroless plating, and a conductor circuit is formed by pattern etching. Alternatively, 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.

In this way, the substrate on which the conductor circuit is formed is subjected to annealing, if necessary, so that curing of the thermosetting resin proceeds and the peeling strength of the conductor layer can be further improved.

Furthermore, by repeating these processes several times as necessary, a desired multilayer printed wiring board is obtained.

(3 ') Production of build-up wiring boards with resin-clad copper foil

First, the resin-clad copper foil prepared in the above (2) is laminated on the substrate on which the inner layer circuit is formed by a vacuum press, and drills or drills a predetermined through hole and a via hole with a drill or a laser, and the inside of the through hole and the via hole is desmia. Treatment to form fine unevenness. The formation method of this unevenness is the same as that of the roughening method of the interlayer insulation layer mentioned above.

Subsequently, the conductor layer is formed by dry plating such as vapor deposition, sputtering, ion plating, or wet plating such as electroless plating or electroless plating to form a conductor circuit by pattern etching.

In this way, the substrate on which the conductor circuit is formed is subjected to annealing, if necessary, so that curing of the thermosetting resin proceeds and the peeling strength of the conductive layer can be further improved.

Furthermore, if necessary, these processes are repeated several times, and after completion of the outermost layer circuit formation, the solder resist made of the thermosetting epoxy composition is subjected to pattern printing and thermosetting by screen printing, or to curtain coating, After the whole surface printing and thermosetting by the roll coat method, the spray coat method, etc., a pattern is formed by a laser and a desired multilayer printed wiring board is obtained.

EXAMPLE

Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not limited to the following Example.

Synthesis Example 1

324 g of 10- (2,5-dihydroxy phenyl) -10H-oxaphosphenanthrene = oxide-10 (made by Sanko Co., Ltd., HCA-HQ), 200 g of calbitol acetate, DEN431 (Dow) in 1 L of flask 525 g of Chemical Japan Co., Ltd., 380 g of Epicoat 828 (manufactured by Japan Epoxy Resin Co., Ltd.), and 1 g of triphenylphosphine were added and allowed to react at 150 ° C for 100 minutes. The epoxy equivalent of the produced phosphorus containing epoxy resin was 415g / eq, and phosphorus content was 2.5 mass%.

Hereinafter, this resin is called phosphorus containing epoxy A.

(Examples 1 to 8 and Comparative Examples 1 to 3)

First, the components of the thermosetting epoxy compositions of Examples 1 to 8 and Comparative Examples 1 to 3 are mixed in a component (mass part) shown in Table 1 with a dissolving agent, and uniformly dispersed in three roll mills. It was produced by adjusting the viscosity with a diluent solvent.

Subsequently, the thermosetting epoxy resin composition thus prepared was applied onto the FR-4 inner layer (core thickness 0.5 mm, copper foil thickness 18 μm) substrate on which the inner layer circuit was formed by screen printing, and dried at l10 ° C. for 20 minutes, and then 150 ° C. It hardened | cured for 30 minutes, and the interlayer insulation layer was formed.

Then, a hole was drilled at a predetermined position of the interlayer insulating layer with a drill or a laser to swell with a mixture of an alkaline aqueous solution and a solvent, and then treated with an alkaline permanganate aqueous solution, followed by a reducing agent, and subjected to a roughening treatment.

Then, the conductor layer of 35 micrometers in thickness of copper was formed by electroless copper plating and electrolytic copper plating, and further annealing was performed at 150 degreeC for 60 minutes, and the multilayer printed wiring board was produced.

(Examples 9 and 10)

First, the thermosetting epoxy resin compositions of Examples 9 and 10 were mixed with a dissolving agent in a component composition (mass part) shown in Table 1 by dissolving with three roll mills, and then the viscosity was adjusted with a diluting solvent. Made.

Subsequently, the thermosetting epoxy resin composition thus produced was applied and dried on a supporting film, and the molded product formed on the substrate was formed on both sides of a FR-4 inner layer (core thickness 0.5 mm, copper foil thickness 18 μm) by a vacuum laminator on a substrate having an inner layer circuit. It laminated and hardened at 150 degreeC for 30 minutes, and formed the interlayer insulation layer. The lamination conditions at this time were made into the press of temperature 80 degreeC, pressure 1 MPa, and 25 second.

Then, a hole was drilled at a predetermined position of the interlayer insulating layer by a drill or a laser and swollen with a mixture of an alkaline aqueous solution and a solvent, and then treated with an alkaline permanganate aqueous solution and a reducing agent, followed by a roughening agent treatment.

Thereafter, a conductor layer having a copper thickness of 35 µm was formed by electroless copper plating and electrolytic copper plating, and annealing was further performed at 150 ° C. for 60 minutes to produce a multilayer printed wiring board.

(Examples 11 and 12)

First, in the thermosetting epoxy compositions of Examples l1 and l2, the components (mass parts) shown in Table 1 are mixed with dissolving components, solvents and the like by dissolving them, and then uniformly dispersed in three roll mills. Made by.

Subsequently, the molded product obtained by applying and drying the thermosetting epoxy resin composition thus prepared on a supporting copper foil was formed on both sides of the FR-4 inner layer (core thickness 0.5 mm, copper foil thickness 18 μm) substrate having an inner layer circuit. The resin layer was laminated so as to form a resin foil layer with a heat press for 1 hour at a pressure of 2.5 MPa and a temperature of 170 ° C.

Then, a hole was drilled at a predetermined position of the resin-clad copper foil layer by a drill or a laser and subjected to desmia treatment, followed by copper plating to form a conductive layer having a copper thickness of 35 μm, thereby producing a multilayer printed wiring board.

The below-mentioned content was evaluated about the thermosetting epoxy resin composition and multilayer printed wiring board of each Example and each comparative example produced in the same manner to the above.

The results are shown in Table 2.

In addition, the detail of each compound of Table 1 is as follows.

Epicoat 828, Epicoat 1010: Bisphenol A epoxy resin, Japan epoxy resin Co., Ltd.

Epicoat 5051: brominated bisphenol A epoxy resin, Japan epoxy resin Co., Ltd.

Epicoat YX-4000H: Biphenyl type epoxy resin, Japan epoxy resin

Epicoat 157S70: bisphenol A novolac epoxy resin, Japan epoxy resin

Epicron l53: brominated bisphenol A epoxy resin, manufactured by Dainippon Ink and Chemicals Co., Ltd.

Epiclone N-690: Cresol novolac epoxy resin, made by Dainippon Ink & Chemicals Co., Ltd.

Poly bd R-45 EPI: Epoxide in end hydroxyl group-containing molecule, manufactured by Idemitsu Petrochemical Co., Ltd.

Resin-containing resin A: Prepared in Synthesis Example 1.

Shonol BRG-556: Phenolic novolac resin, Showa Polymer Co., Ltd. product

BPA-D: bisphenol A novolac resin, manufactured by Meiwa Kasei Co., Ltd.

HCA-HQ: 10- (2,5-dihydroxyphenyl) -10H-oxaphosphenanthrene = 10-oxide, manufactured by Sanko Co., Ltd.

2PHZ: 2-phenyl-4,5-dihydroxymethylimidazole, the Shikoku Chemical Co., Ltd. make

2P4MZ: 2-phenyl-4-methyl-5-hydroxymethylimidazole, the Shikoku Chemical Co., Ltd. make

2E4MZ: 2-ethyl-4-methylimidazole, manufactured by Shikoku Chemical Industry Co., Ltd.

2MZ-A: 2,4-diamino-6- (2'-methylimidazole (1 '))-ethyl-s-triadine, manufactured by Shikoku Kagaku Kogyo Co., Ltd.

Heidilite H-42M: Aluminium hydroxide, made by Showa Electric Co., Ltd.

Composition (mass part) Example Comparative example One 2 3 4 5 6 7 8 9 10 11 12 One 2 3 (A) ingredient Epicoat828 70 70 70 20 20 70 70 70 Epicron153 30 30 30 30 30 20 20 30 30 30 Epicoat5051 30 30 30 30 Epicoat 1010 15 15 15 15 Epicoat YX-4000H 30 30 Epicro N-690 35 35 35 35 Epicoat157S70 70 70 70 Phosphorus Resin A 100 70 Poly bd R-45EPI 20 20 20 20 20 20 20 20 (B) ingredient Shonol BRG-556 50 50 50 60 40 25 26 38 30 27 20 BPA-D 60 HCA-HQ 10 10 10 (C) component 2PHZ One One One One One One One One One One One 2P4MZ One Other Ingredients Dicyandiamide 5 5 5 2E4MZ 5 2MZ-A 5 Barium sulfate 20 20 20 20 Heidi Light H-42M 30 30 30

Test Items Example Comparative example One 2 3 4 5 6 7 8 9 10 11 12 One 2 3 shape Liquid Liquid Liquid Liquid Liquid Liquid Liquid Liquid Dry film Dry film Resin Copper Foil Resin Copper Foil Liquid Liquid Liquid Preservation stability of 1 liquid composition ○ ○ ○ ○ ○ ○ ○ ○ - - - - ○ × × Storage stability of the molded body - - - - - - - - ○ ○ ○ ○ - - - Reaction speed ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ × × × Curable ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ × ○ ○ Roughness ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ - - - × × Peeling off radish radish radish radish radish radish radish radish radish radish - - - U U Peel Strength (N / om) 12 13 12 12 12 12 12 11 11 11 15 15 - 3 5 Solder Heat Resistance ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ - × × Electrical Insulation Characteristics ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ - ○ ○

The measuring method of each evaluation item of the said Table 2 is as follows.

(1) Storage stability of the one-component composition:

The viscosity of the one-liquid composition stored at 20 ° C. was measured with a cone plate viscometer (25 ° C., 5 rpm), and a case where the viscosity change after 2 months was less than 20% and more than 20% was ×.

(2) Preservation stability of moldings:

The gel time (according to JIS C2105) of resin on 150 degreeC hotbed of the molded object stored below 10 degreeC is measured, and the case where the gel time change after 2 months is less than 20% and more than 20% is x. .

(3) Reaction rate:

The gel time (based on JIS C6521) of resin in the hotbed at l50 degreeC at the time of liquid resin composition was measured. Judgment criteria are as follows.

O: 3 to 20 minutes

x: less than 3 minutes or more than 20 minutes

(4) Curability:

It evaluated by sclerosis | hardenability when heating at 150 degreeC for 30 minutes.

Judgment criteria are as follows.

○: no stickiness of the surface

X: There is stickiness of the surface

(5) roughness:

The surface appearance after the roughening treatment was evaluated by observing with a microscope.

(Circle): The roughening shape (anchor) was formed.

X: The roughening shape was not formed.

(6) Peeling after annealing:

After annealing at 150 ° C. for 60 minutes, evaluation was made based on the presence or absence of peeling between the resin layer and the conductor layer.

(7) peeling strength:

For measuring the beta peel strength of the multilayer printed wiring board obtained in each example and each comparative example

The pattern was peeled off at 1 cm width, and peel strength (N / Cm) was measured according to JIS C6481L.

(8) Solder Heat Resistance:

After the rosin-type flux was apply | coated to the multilayer printed wiring board obtained by each Example and each comparative example, it immersed in the solder bath at 260 degreeC for 60 second, and the coating film state after the peeling test with a cellophane adhesion tape was evaluated.

0: No change in coating after peeling

x: Peeling after peeling.

(9) Electrical insulation

The applied voltage DC12V was applied to the comb-shaped electrode of IPC B-25B coupon, and it put in the constant temperature and humidity chamber of 85 degreeC and 85% RH for l000 hours, and measured the insulation resistance after applying the applied voltage DC500V for 1 minute.

O: Insulation resistance l.0 × 10 ⁸ Ω or more

x: Insulation resistance is less than 1.0 × 10 ⁸ Ω

(Example 13)

80.0 parts by mass of bisphenol A type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd .; epicoat 828), 20.0 parts by mass of biphenol type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd .; YX-4000), phenol novolac resin (Show 60.0 parts by mass of wa polymer (BG-556), 20.0 parts by mass of epoxide in terminal hydroxyl group molecule (manufactured by Idemitsu Petrochemical Co., Ltd .; Poly bd R-45 EPI), imidazole compound (Shikoku Chemical Co., Ltd.) The thermosetting epoxy resin composition which melt | dissolved 1.0 mass part of curazole 2PHZ) and 10.0 mass parts of hard calcium carbonates in 40 mass parts of carbitol acetate was produced.

The thermosetting epoxy composition was applied onto the FR-4 inner layer (air thickness: 0.5 mm, copper foil thickness: 18 μm) substrate on which the inner layer circuit was formed by screen printing, and then dried at 10 ° C. × 20 minutes, and cured at l50 ° C. × 30 minutes. The board | substrate which formed the insulation resin layer of 60 micrometers in thickness was produced. In addition, this substrate is immersed in an 80 ° C swelling solution for 5 minutes and washed with water, then immersed in an 80 ° C roughening solution for 10 minutes and washed with water, and further immersed in a reducing solution at 50 ° C for 5 minutes, and washed with water. The surface of the insulating resin layer was roughened. After that, a conductor layer having a copper thickness of 35 µm was formed by electroless copper plating and electrolytic copper plating, and further subjected to annealing at 150 ° C. for 60 minutes to produce a multilayer printed wiring board. In addition, the comb-tooth shaped electrode pattern and the solder heat resistance measuring pattern used for an evaluation board | substrate were formed using the etching resist.

Example 14

A multilayer printed wiring board was produced in the same manner as in Example 13 except that the hard calcium carbonate was removed from the thermosetting epoxy resin composition of Example 13.

Example 15

80.0 parts by mass of bisphenol A type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd .; Epicoat 828), 20.0 parts by mass of nonphenol type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd .; YX-4000), phenol novolac resin (Show 60.0 parts by mass of Wako Molecular Co., Ltd .; BRG-556), 20.0 parts by mass of phenolic terminal hydroxyl group intramolecular epoxide (manufactured by Mitsui Petrochemical Co., Ltd .; Poly bd R-45 EPI), imidazole compound (Shikoku Chemical Industry Co., Ltd. product; Curazole 2P4MZ) A thermosetting epoxy resin composition obtained by dissolving 1.0 part by mass and 10.0 parts by mass of hard calcium carbonate in 40 parts by mass of carbitol acetate was prepared.

Example 16

Bisphenol-A epoxy resin (made by Japan Epoxy Resin Co., Ltd .; Epicoat 828) 80.0 mass parts, Biphenol-type epoxy resin (Japan Epoxy Resin) Co., Ltd. make; YX-4000) 20.0 parts by mass, 40.0 parts by mass of phenol novolak resin (manufactured by Showa Polymer Co., Ltd .; BRG-556), 20.0 parts by mass of a phenolic hydroxyl group-containing phosphorus compound (Sanko Co., Ltd .; HCA-HQ) 20.0 parts by mass of epoxide in hydroxyl group molecule (manufactured by Idemitsu Petrochemical Co., Ltd .; Poly bd R-45 EPI), imidazole compound (manufactured by Shikoku Kagyo Kogyo Co., Ltd .; curazole 2PHZ) 1.0 parts by mass, hard calcium carbonate 10.0 The mass part was mix | blended, the thermosetting epoxy resin composition melt | dissolved in 40 mass parts of calbitol acetate was produced, and the multilayer printed wiring board like Example 13 was produced.

(Example 17)

Phosphorus-containing epoxy resin A80.0 parts by mass produced in Synthesis Example 1, non-phenol type epoxy resin (Japan Epoxy Resin Co., Ltd.); YX-4000) 20.0 parts by mass, phenol novolac resin (Showa Polymer Co., Ltd.) BRG-556) 30.0 parts by mass, epoxide in terminal hydroxyl group molecule (manufactured by Idemitsu Petrochemical Co., Ltd .; Poly bd R-45 EPI) 20.0 parts by mass, imidazole compound (Shikoku Chemical Co., Ltd.) A thermosetting epoxy resin composition in which 1.0 part by mass of azole 2P4MZ) and 10.0 parts by mass of hard calcium carbonate were dissolved in 40 parts by mass of carbitol acetate were prepared, and a multilayer printed wiring board was prepared in the same manner as in Example 13.

(Example 18)

Bisphenol A-type phenoxy resin (made by Doto Chemical Co., Ltd .; YP-50) 30.0 mass parts, Phenol novolak-type epoxy resin (Japan epoxy resin) Co., Ltd. agent; Epicoat 152) 30.0 parts by mass, nonphenol-type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd .; YX-4000), 30.0 parts by mass, phenol novolac resin (Showa Polymer Co., Ltd .; BRG-556) 35.0 parts by mass A thermosetting epoxy resin composition was prepared by dissolving 10.0 parts by mass of an imidazole compound (manufactured by Shikoku Chemical Co., Ltd .; Cuazole 2PHZ) and 10.0 parts by mass of hard calcium carbonate in propylene glycol monomethyl ether acetate.

This thermosetting epoxy composition was applied onto a polyethylene terephthalate film having a thickness of 38 µm so as to have a thickness of 60 µm after drying, thereby obtaining an adhesive film having a residual amount of 2 mass% or less at 110 ° C to 150 ° C. The obtained adhesive film was laminated at 70 ° C. with a vacuum laminator on a FR-4 inner layer (core thickness 0.5 mm, copper foil thickness 8 μm) substrate on which an inner layer circuit was formed, and thermally cured and roughened under the same conditions as in Example 13. Thereafter, a conductor layer having a copper thickness of 35 µm was formed by electroless copper plating and electrolytic copper plating, and further subjected to annealing at 150 ° C. for 60 minutes to prepare a multilayer printed wiring board.

In addition, the comb-tooth shaped electrode pattern and the solder heat resistance measurement pattern used for an evaluation board | substrate were formed using the etching resist.

Example 19

The thermosetting epoxy resin composition of Example 18 was applied to a copper foil roughened surface having a thickness of 18 μm so as to have a thickness of 80 μm, and dried at 130 ° C. to 150 ° C. to prepare a copper foil with a resin.

The resin-clad copper foil was heat-pressed at 170 ° C. for 1 hour by vacuum press on a FR-4 inner layer (core thickness 0.5 mm, copper foil thickness 18 μm) on which an inner layer circuit was formed, thereby forming a resin-clad copper foil layer. Furthermore, electroplating was carried out, the conductor layer of 35 micrometers in copper thickness was formed, and the multilayer printed wiring board was produced.

Moreover, the comb-tooth shaped electrode pattern and the solder heat resistance measuring pattern used for an evaluation board | substrate were formed using the etching resist.

(Comparative Example 4)

In the thermosetting epoxy composition of Example 13, a substrate was produced in the same manner as in Example 13, except that the imidazole compound was changed to Qazole 2E4MZ (manufactured by Shikoku Chemical Industry Co., Ltd.).

(Comparative Example 5)

In the thermosetting epoxy resin composition of Example 13, a substrate was produced in the same manner as in Example 13, except that the imidazole compound was changed to Qazole C ₁₁ Z (manufactured by Shikoku Chemical Industry Co., Ltd.).

(Comparative Example 6)

In the thermosetting epoxy resin composition of Example 13, a substrate was produced in the same manner as in Example l3, except that the imidazole compound was changed to Cazole 2MHZ (manufactured by Shikoku Chemical Industry Co., Ltd.).

(Comparative Example 7)

In the thermosetting epoxy composition of Example 17, a substrate was prepared in the same manner as in Example 16, except that the imidazole compound was changed to Curezol 2E4MZ (manufactured by Shikoku Chemical Industry Co., Ltd.).

The thermosetting epoxy resin composition and the molded product prepared in Examples 13 to 19 and Comparative Examples 4 to 7 were measured for storage stability, reaction rate and roughness shape.

In addition, the peeling strength, the solder heat resistance, and the electrical insulation characteristics were measured in the same manner as above using an evaluation substrate having the copper plating layer formed using the substrates prepared in Examples 13 to 9 and Comparative Examples 4 to 7. . The obtained results are shown in Table 3.

Test Items Example Comparative Example 13 14 15 16 17 18 19 4 5 6 7 shape Liquid Liquid Liquid Liquid Liquid Dry film Resin Copper Foil Liquid Liquid Liquid Dry film Storage stability of 1 liquid composition ○ ○ ○ ○ ○ - - × × × - Preservation safety of the molded body - - - - - ○ ○ - - - × Reaction speed ○ ○ ○ ○ ○ ○ ○ × × × × Roughness geometry ○ ○ ○ ○ ○ ○ ○ × × × × Peel Strength (N / cm) 13 12 10 12 11 12 14 3 4 9 3 Solder heat resistance ○ ○ ○ ○ ○ ○ ○ × × × × Electrical Insulation Characteristics ○ ○ ○ ○ ○ ○ ○ × × × ×

As described above, according to the present invention, a thermosetting epoxy resin composition, molded article thereof, and the like, which satisfy both heat resistance, electrical insulation properties, and adhesive strength of a conductor layer, in a multilayer printed wiring board, in particular, a build-up multilayer printed wiring board. It is possible to provide a buildup multi-layer printed wiring board which can cope with the increase in the density of the conductor circuit produced using these.

Claims (13)

(A) an epoxy resin having two or more epoxy groups in one molecule, (B) a curing agent having two or more phenolic hydroxyl groups in one molecule, and (C) a curing accelerator comprising an imidazole compound having a hydroxyl group and an aromatic ring Thermosetting epoxy resin composition characterized in. The method of claim 1, The said curing accelerator (C) is an imidazole compound represented by the following general formula (1), The thermosetting epoxy resin composition characterized by the above-mentioned. Wherein R ₁ represents CH ₃ or CH ₂ OH. The method of claim 1, The curing accelerator (C) is a thermosetting epoxy resin composition, characterized in that the imidazole compound having a melting point of 190 ℃ or more. The method of claim 1, The epoxy resin (A) is obtained by reacting 10- (2,5-dihydroxyphenyl) -10H-oxaphosphenanthrene = 10-oxide with an epoxy resin having one or more epoxy groups in one molecule in advance. A thermosetting epoxy resin composition comprising an oil epoxy resin. The method of claim 4, wherein The phosphorus-containing epoxy resin is phosphorus content of 1 to 5% by mass, the thermosetting epoxy resin composition. The method of claim 1, The said hardening | curing agent (B) is a thermosetting epoxy resin composition characterized by including 10- (2,5-dihydroxyphenyl) -10H-oxaphosphenanthrene = 10-oxide. The method of claim 1, Furthermore, (D) a thermosetting epoxy resin composition comprising an inorganic filler and / or an organic filler having an average particle diameter of 5 μm or less. The method of claim 7, wherein The thermosetting epoxy resin composition, wherein the content of the inorganic filler and / or the organic filler is 40% by mass or less based on the solid content of the composition. The method of claim 1, A thermosetting epoxy resin composition, characterized in that the thermosetting epoxy resin composition is liquefied. The molded object formed by apply | coating drying the thermosetting epoxy composition of any one of Claims 1-9 on a support film, and forming into a film. The molded object which consists of a resin foil copper foil which apply | coats and drys the thermosetting epoxy composition of any one of Claims 1-9 on a support copper foil. The multilayer printed wiring board produced using the thermosetting epoxy composition of any one of Claims 1-9. The multilayer printed wiring board produced using the molded object of Claim 10 or 1.