JP2002241590A - Flame-retardant epoxy resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame-retardant epoxy resin composition which exhibits excellent flame retardancy after its cure without containing a halogen-based compound and a phosphorous-based compound, and has a rough surface property required for forming a plated conductive layer after its cure on the production of multi-layered printed circuit boards and the like. SOLUTION: This epoxy resin composition is characterized by containing the following components (A) to (D) as essential components, wherein at least either one of (A) the epoxy resin having two or more epoxy groups in the molecule and (B) the phenolic curing agent has a condensed polycyclic aromatic skeleton. (A) An epoxy resin having two or more epoxy groups in the molecule. (B) A phenolic curing agent. (D) A phenoxy resin having a weight-average mol.wt. of 5,000 to 100,000. (D) An inorganic filler.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxy resin composition exhibiting flame retardancy without containing a halogen compound or a phosphorus compound, and further relates to an adhesive film, a prepreg and a multilayer print using the composition. The present invention relates to a wiring board, a laminated board, and a manufacturing method thereof.

[0002]

2. Description of the Related Art In recent years, as a method of manufacturing a multilayer printed wiring board, a build-up type manufacturing technique of alternately stacking organic insulating layers on conductor layers of an inner circuit board on which a circuit is formed has attracted attention. JP-A-7-304931, 7-3
In 04933, an epoxy resin composition is applied to an inner circuit board on which a circuit is formed, and after heating and curing, a roughening surface is formed on the surface with a roughening agent, and a conductive layer is formed by plating. A manufacturing method is disclosed. Also,
JP-A-8-64960 discloses a multi-layer printed wiring board by applying an undercoat adhesive, temporarily drying, bonding a film-like additive adhesive, heating and curing, roughening with an alkaline oxidizing agent, and forming a conductive layer by plating. There are known ways to do this.

[0003] Resin compositions used in these applications usually require flame retardancy from the viewpoint of fire safety. And conventionally, it was common to make the resin composition flame-retardant using a halogen-containing compound such as a brominated epoxy resin. However, although such organic halogen compounds have high flame retardancy, the use of such compounds tends to be restricted from the viewpoint of environmental safety such as dioxin.

[0004] In recent years, attempts have been made to impart flame retardancy to resin compositions without containing halogens, and typical examples include phosphorus-based flame retardants such as red phosphorus and phosphate esters. A method of adding the compound has been studied (for example, JP-A-2000-216549). However, such a phosphorus-based flame retardant may impair the basic physical properties of the resin such as heat resistance and moisture resistance, and a resin composition having higher safety is required.

[0005]

SUMMARY OF THE INVENTION The present invention provides excellent flame retardancy after curing without containing a halogen-based compound and a phosphorus-based compound. An object of the present invention is to provide a flame-retardant epoxy resin composition having a roughening property required for forming a layer. It is still another object of the present invention to provide an adhesive film, a prepreg, a laminate, and a multilayer printed wiring board using the epoxy resin composition.

[0006]

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a specific epoxy resin composition containing neither a halogen compound nor a phosphorus compound has high flame retardancy. They have found that they exhibit roughening properties and have completed the present invention. That is, the present invention includes the following contents.

The following components (A) to (D) are essential components,
An epoxy resin composition characterized in that at least one of (A) an epoxy resin having two or more epoxy groups in one molecule and (B) a phenolic curing agent has a condensed polycyclic aromatic skeleton. (A) an epoxy resin having two or more epoxy groups in one molecule (B) a phenolic curing agent (C) a phenoxy resin having a weight average molecular weight of 5,000 to 100,000 (D) an inorganic filler

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION In the component (A) of the present invention, the epoxy resin having two or more epoxy groups in one molecule and the component (B) phenol-based curing agent include the components (A) and (B). It is necessary that at least one of them has a condensed polycyclic aromatic skeleton. Here, having a condensed polycyclic aromatic skeleton means that the molecule has one or more condensed polycyclic structures in a molecule in which a plurality of aromatic rings such as naphthalene, anthracene, and fluorene are condensed. I do.

The epoxy resin having two or more epoxy groups in one molecule as the component (A) in the present invention includes, for example, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol Novolak type epoxy resin, alkylphenol novolak type epoxy resin, biphenol type epoxy resin, dicyclopentadiene type epoxy resin, epoxidized product of condensate of phenols and aromatic aldehyde having phenolic hydroxyl group, triglycidyl isocyanurate, alicyclic An epoxy resin such as an epoxy resin can be used. These epoxy resins may be used alone or in combination of two or more. Further, it may contain a monofunctional epoxy resin as a reactive diluent.

When the epoxy resin having two or more epoxy groups in one molecule as the component (A) has a condensed polycyclic aromatic skeleton, that is, one molecule in which the component (A) has a condensed polycyclic aromatic skeleton Examples of the epoxy resin having two or more epoxy groups therein include an epoxy resin of a modified phenol resin composed of a condensed polycyclic aromatic phenol / formaldehyde, and a specific example thereof is Epicoat YL6850. (Japan Epoxy Resin Co., Ltd.
Manufactured).

Examples of the phenolic curing agent which is the component (B) in the present invention include a phenol novolak resin, an alkylphenol novolak resin, a bisphenol A novolak resin, a dicyclopentadiene type phenol resin, a Xylok (Xylok) type phenol resin,
Examples include phenolic curing agents such as terpene-modified phenolic resins and polyvinylphenols. These phenolic curing agents may be used alone or in combination of two or more.

When the phenolic curing agent as the component (B) has a condensed polycyclic aromatic skeleton, that is, when the component (B) is a phenolic curing agent having a condensed polycyclic aromatic skeleton, A modified phenolic curing agent composed of condensed polycyclic aromatic phenol / formaldehyde is exemplified, and specific examples thereof include Epicron EXB9724 manufactured by Dainippon Ink and Chemicals, Inc.

If a phenolic curing agent containing a nitrogen atom is used as the component (B), the flame retardancy and adhesion of the flame retardant resin composition of the present invention are improved. Examples of the phenolic curing agent having a nitrogen atom include novolak resins containing a triazine structure (for example, phenolite 7050 series: manufactured by Dainippon Ink and Chemicals, Inc.) and melamine-modified phenol novolak resins (for example, Japan Epoxy Resin Co., Ltd.) YLH828).

Regarding the blending amount of the phenolic curing agent,
It is desirable to blend a phenolic curing agent equivalent to 0.5 to 1.3 phenolic hydroxyl group equivalents per epoxy equivalent of an epoxy resin having two or more epoxy groups in one molecule of the component (A). The epoxy resin composition obtained out of this range may not have sufficient performance in terms of heat resistance.

An example of a more preferable combination of the component (A) and the component (B) is an epoxy resin having two or more epoxy groups in one molecule having a condensed polycyclic aromatic skeleton as the component (A). And a case where a phenolic curing agent containing a nitrogen atom is used as the component (B).

Next, the phenoxy resin having a weight average molecular weight of 5,000 to 100,000, which is the component (C) in the present invention, will be described. Weight average molecular weight of 5000
Examples of the phenoxy resin having a molecular weight of 1 to 100,000 include phenothoto YP50 (manufactured by Toto Kasei Co., Ltd.)
256 (manufactured by Japan Epoxy Resin Co., Ltd.).

As the component (C), particularly, a bisphenol S skeleton having a weight average molecular weight of 5,000 to 1,000
Phenoxy resins that are 00 are preferred. Specific examples of such a phenoxy resin include YL6747H30 (manufactured by Japan Epoxy Resins Co., Ltd.) [bisphenol A type epoxy resin (Epicoat 828) and bisphenol S
Cyclohexanone varnish of a phenoxy resin consisting of: 30% by weight of non-volatile content, weight average molecular weight 47000].

Since the phenoxy resin has a sulfone group, the compatibility with the epoxy resin is deteriorated. Therefore, the phenoxy resin is compatible in a resin varnish obtained by dissolving the epoxy resin composition in a solvent. Phase separates to form a sea-island structure. Therefore, a good roughened surface can be easily obtained without adding a roughening component such as a rubber component. In addition, since the phenoxy resin itself has a high glass transition point and excellent flame retardancy, the heat resistance and flame retardancy performance of the flame retardant resin composition of the present invention can be further improved. There is also.

If the weight average molecular weight of the phenoxy resin is less than 5,000, the roughening performance of the flame retardant resin composition of the present invention is not sufficient, and if it exceeds 100,000, the solubility in an organic solvent is remarkably high. And practical use becomes difficult.

The compounding amount of the phenoxy resin of the component (C) varies depending on the type of the phenoxy resin, but the total amount of the epoxy resin of the component (A) and the phenolic curing agent of the component (B) is different. It is preferably in the range of 5 to 50 parts by weight based on 100 parts by weight. If the content is less than 5% by weight, sufficient roughening properties may not be obtained. If the content is more than 50% by weight, problems such as phase separation of the resin varnish itself and inversion of the sea-island structure of the cured product may occur. There is.

Examples of the inorganic filler of the component (D) in the present invention include barium sulfate, barium titanate, silicon oxide powder, amorphous silica, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide and the like. be able to. These inorganic fillers may be used alone or in combination of two or more.

By adding an inorganic filler, the strength of the film or prepreg when a film or prepreg is produced using the epoxy resin composition can be reinforced, and when the epoxy resin composition is cured. Can also reinforce the strength of the cured product. In addition, inorganic fillers also play a role in assisting in flame retardancy and roughening performance.

The compounding amount of the inorganic filler is preferably in the range of 5 to 200 parts by weight based on 100 parts by weight of the total of the epoxy resin of the component (A) and the phenolic curing agent of the component (B). If the amount of the inorganic filler is too large, the mechanical strength after curing is reduced. If the amount is too small, the effect of the addition of the inorganic filler may be insufficient.

Further, in addition to the above-mentioned essential components, other thermosetting resins and additives may be used in the epoxy resin composition of the present invention, as long as the effects of the present invention are not impaired. Examples of the thermosetting resin include a blocked isocyanate resin, a xylene resin, a radical generator and a polymerizable resin. Examples of the additives include organic fillers such as silicon powder, nylon powder, and fluorine powder, thickeners such as asbestos, olben, and bentone, silicone-based, fluorine-based, polymer-based antifoaming agents or leveling agents, and imidazole-based additives. , Thiazole-based, triazole-based, silane coupling agents, etc., and coloring agents such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, titanium oxide, and carbon black.

Next, the adhesive film of the present invention will be described. After dissolving the epoxy resin composition of the present invention in an organic solvent to form a resin varnish, the resin varnish is applied on a base film (support base film) serving as a support, and the solvent is dried by hot-air blowing or the like to form an adhesive film. Can be manufactured. Preferably, the thickness of the epoxy resin composition layer is laminated on the supporting base film having a thickness of 10 to 200 μm, which is not less than the conductor thickness of the inner circuit board, and preferably 10 to 1 μm.
A layer is formed in a range of 50 μm. 1 to 40 on the surface of the epoxy resin composition layer on which the supporting base film is not adhered.
A protective film conforming to a μm-thick support film may be further laminated, wound up in a roll shape, and stored.

Examples of the supporting base film include polyolefins such as polyethylene and polyvinyl chloride, polyesters such as polyethylene terephthalate, polycarbonate, and the like.
Examples thereof include polyimide, release paper, metal foil such as copper foil and aluminum foil, and the like.

The support base film may have been subjected to a mold release treatment in addition to a mud treatment and a corona treatment.
Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone and cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, acetic acid esters such as propylene glycol monomethyl ether acetate and carbitol acetate, cellosolves such as cellosolve and butyl cellosolve, and carbitol. And carbitols such as butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide and the like. These organic solvents may be used alone or in combination of two or more.

Next, the prepreg of the present invention will be described. A prepreg can be produced by impregnating the sheet-like reinforcing substrate made of fiber with the epoxy resin composition of the present invention by a hot melt method or a solvent method and semi-curing by heating. In other words, a prepreg in which the epoxy resin composition is impregnated in a sheet-like reinforcing substrate made of fibers can be obtained.

As a sheet-like reinforcing substrate made of fibers,
For example, those commonly used as prepreg fibers, such as glass cloth and aramid fibers, can be used.

In the hot melt method, without dissolving the resin in an organic solvent, the resin is once coated on a coated paper having good releasability from the resin, and the resin is laminated on a sheet-like reinforcing substrate or directly by a die coater. This is a method of producing a prepreg by coating. The solvent method is
As in the case of the adhesive film, the sheet-shaped reinforcing substrate is immersed in a resin varnish in which a resin is dissolved in an organic solvent, the resin varnish is impregnated in the sheet-shaped reinforcing substrate, and then dried.

Next, a method for producing the multilayer printed wiring board of the present invention using the epoxy resin composition of the present invention will be described. The epoxy resin composition of the present invention is applied to a patterned inner layer circuit board, dried when containing an organic solvent, and then cured by heating. As the substrate used for the inner circuit board, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, or the like can be used.

In the present invention, the inner-layer circuit board means a board on which a patterned conductor layer (circuit) is formed on one or both sides of the board. Also, in the multilayer printed wiring board in which conductor layers and insulating layers are alternately formed, a multilayered printed wiring board in which one or both sides are patterned conductor layers (circuits) is also referred to as an inner layer according to the present invention. Included in circuit board. In other words, the multilayer printed wiring board of the present invention also includes an inner circuit board manufactured using the epoxy resin composition of the present invention.
The surface of the conductive circuit layer may be previously subjected to a roughening treatment such as a blackening treatment.

The above-mentioned drying conditions are 70 to 130 ° C. and 5 to
Preferably, it is 40 minutes. Heat curing conditions are 130 ~
It is preferably in the range of 15 to 90 minutes at 180 ° C.

In the case of using an inner layer circuit board having a through hole, a through hole can be formed again by heat-curing and then, if necessary, by drilling with a drill, laser, plasma or the like. Similarly, after heat curing, a via hole may be formed by drilling with a drill, laser, plasma, or the like, if necessary.

Next, permanganate, dichromate,
The surface of the epoxy resin composition layer (insulating layer) cured with an oxidizing agent such as ozone, hydrogen peroxide / sulfuric acid, nitric acid or the like is roughened,
Form an uneven anchor.

Further, a conductor layer can be formed by plating. For plating, a method combining electroless plating and electrolytic plating can usually be used. 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. Specific examples of the plating method include a subtractive method and a semi-additive method known to those skilled in the art.

After the conductor layer is formed, the temperature is set at 150 to 180 ° C.
By annealing for 20 to 60 minutes, the remaining unreacted epoxy resin is cured, and the peel strength of the conductor layer can be further improved.

Next, a method for producing the multilayer printed wiring board of the present invention using the adhesive film of the present invention will be described. The adhesive film of the present invention is laminated on a patterned inner layer circuit board. In the lamination, when the adhesive film has a protective film, after removing the protective film, the adhesive film is pressure-bonded to the inner circuit board while applying pressure and heat.

The conditions for lamination are as follows: the adhesive film and the inner layer circuit board are preheated as necessary, the pressing temperature is preferably 70 to 130 ° C., and the pressing pressure is preferably 1 to 11
kgf / cm ² and lamination under reduced pressure is preferred. Also,
The method of lamination may be a batch method or a continuous method using a roll. After lamination, the support base film is peeled off after cooling to around room temperature, and the epoxy resin composition of the present invention is cured by heating on the inner circuit board.

When a support film subjected to a release treatment is used, the support film may be peeled off after being cured by heating. After that, similarly to the method described above, the surface of the epoxy resin composition cured by the oxidizing agent is roughened, and then the conductor layer is formed by plating, whereby a multilayer printed wiring board can be manufactured.

Next, a method of manufacturing the multilayer printed wiring board of the present invention using the prepreg of the present invention will be described.
One or a plurality of prepregs of the present invention are stacked on the patterned inner layer circuit board, and a laminate press is performed under pressure and heating conditions with a metal plate interposed therebetween through a release film. The pressure is preferably 5 to 40 kgf / cm ² , and the temperature is preferably 120 to 180 ° C. for 20 to 100 minutes. It can also be manufactured by the above-described method using a laminate. Thereafter, in the same manner as described above, the surface of the prepreg cured by the oxidizing agent is roughened, and then the conductor layer is formed by plating, whereby a multilayer printed wiring board can be manufactured.

Next, a method for producing the laminate of the present invention using the epoxy resin of the present invention will be described. A laminate can be obtained by applying the epoxy resin composition of the present invention to a surface of a double-sided copper-clad laminate from which a copper foil has been etched out or at least one surface of an unclad plate, and curing by heating. The above-mentioned unclad plate is obtained by using a release film or the like instead of copper foil at the time of manufacturing a double-sided copper-clad laminate. The laminate thus obtained is composed of permanganate, dichromate, ozone, hydrogen peroxide / sulfuric acid,
By performing the roughening treatment with an oxidizing agent such as nitric acid, an uneven anchor is formed on the surface of the laminate, and the conductor layer can be directly formed on the surface of the laminate by plating in the same manner as described above.

The laminated film can also be obtained by laminating the adhesive film of the present invention on the surface of the double-sided copper-clad laminate on which the copper foil has been etched out or on at least one surface of the unclad plate, and curing by heating. Lamination can be performed according to the method described above. In the laminate thus obtained, a conductor layer can be directly formed on the surface of the laminate by plating after the roughening treatment in the same manner as described above.

Further, the prepreg of the present invention is applied to the copper foil of the double-sided copper-clad laminate on at least one side of the etched-out copper foil or at least one side of the unclad board. A laminate can also be obtained by performing a laminate press under heating conditions. In the laminate thus obtained, a conductor layer can be directly formed on the surface of the laminate by plating after the roughening treatment in the same manner as described above.

Further, a plurality of (two or more) prepregs of the present invention are stacked as required, a metal plate is sandwiched via a release film, and a laminate is obtained by performing a laminate press under pressure and heating conditions. Can also. The laminate thus obtained can similarly form a conductor layer directly on the surface of the laminate by plating after roughening treatment.

[0046]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Example 1 20 parts by weight of bisphenol A type epoxy resin (epoxy equivalent: 185, Epicoat 828 manufactured by Japan Epoxy Resin Co., Ltd.), component (A)
As a condensed polycyclic aromatic epoxy resin (epoxy equivalent 2
30, Epikote YL manufactured by Japan Epoxy Resin Co., Ltd.
6850) 45 parts by weight of methyl ethyl ketone (hereinafter referred to as M
Recorded as EK. ) Is heated and dissolved with stirring, and cooled to room temperature. Then, as a component (B), MEK varnish of phenol novolak resin (Phenolite TD-2090-60M manufactured by Dainippon Ink and Chemicals, Ltd. Hydroxyl equivalent 105) 45 parts by weight, component (C)
Phenoxy resin varnish (YP manufactured by Toto Kasei Co., Ltd.)
50-EK35) and 30 parts by weight of aluminum hydroxide as the component (D) were added to prepare an epoxy resin composition. Apply the varnish-like epoxy resin composition to a thickness of 3
On a 8 μm PET film, the thickness after drying is 60 μm
Apply with a die coater so that
For 10 minutes to obtain an adhesive film.

Example 2 20 parts by weight of a bisphenol A type epoxy resin (epoxy equivalent 185, Epicoat 828 manufactured by Japan Epoxy Resin Co., Ltd.), component (A)
45 parts by weight of a MEK varnish of a cresol novolac type epoxy resin (epoxy equivalent: 219; Epicron N-690-75M manufactured by Dainippon Ink and Chemicals, Inc.); a MEK varnish of a condensed polycyclic aromatic phenol resin as a component (B) (Ex made by Dainippon Ink and Chemicals, Inc.
B9724, nonvolatile content 70%, nonvolatile phenolic hydroxyl equivalent 129) 45 parts by weight, phenoxy resin varnish (YP50-EK3 manufactured by Toto Kasei KK) as the component (C)
5) 40 parts by weight and 15 parts by weight of finely divided silica as the component (D) were added to prepare an epoxy resin composition. The varnish-like epoxy resin composition is applied on a 38 μm-thick PET film by a die coater so that the thickness after drying becomes 60 μm, and dried at 80 to 120 ° C. for 10 minutes.
An adhesive film was obtained.

Example 3 Condensed polycyclic aromatic epoxy resin (epoxy equivalent 230, Epicoat YL6850 manufactured by Japan Epoxy Resin Co., Ltd.) 70 as component (A)
A part by weight is heated and dissolved in MEK while stirring and cooled to room temperature. Then, as a component (B), MEK varnish of a phenol novolak resin containing a triazine structure (Phenolite LA-7052, manufactured by Dainippon Ink and Chemicals, nonvolatile) 60%, phenolic hydroxyl equivalent of non-volatile content 12
0) Cyclohexanone varnish of 50 parts by weight, a phenoxy resin comprising Epicoat 828 and bisphenol S as component (C) (YL manufactured by Japan Epoxy Resin Co., Ltd.)
6747H30, 30% by weight of non-volatile content, 50 parts by weight of weight average molecular weight 47000) and 20 parts by weight of aluminum hydroxide as component (D) were added to prepare an epoxy resin composition. The varnish-like epoxy resin composition is impregnated into a glass cloth, dried at 150 ° C., and has a resin content of 45% by weight.
A prepreg having a thickness of about 0.1 mm was obtained.

Comparative Example 1 20 parts by weight of bisphenol A type epoxy resin (epoxy equivalent: 185, Epicoat 828 manufactured by Japan Epoxy Resin Co., Ltd.), MEK varnish of cresol novolak type epoxy resin (epoxy equivalent: 219, Dainippon Ink & Chemicals, Inc.) Epicron N manufactured by
-690-75M) 45 parts by weight, 45 parts by weight of MEK varnish of phenol novolak resin (Phenolite TD-2090-60M manufactured by Dainippon Ink and Chemicals, Inc., phenolic hydroxyl equivalent 105), and 15 parts by weight of aluminum hydroxide The mixture was added to prepare an epoxy resin composition. The varnish-like epoxy resin composition is coated with a 38 μm thick PE
The film was applied on a T film using a die coater so that the thickness after drying was 60 μm, and dried at 80 to 120 ° C. for 10 minutes to obtain an adhesive film.

Comparative Example 2 20 parts by weight of bisphenol A type epoxy resin (epoxy equivalent: 185, Epicoat 828 manufactured by Japan Epoxy Resin Co., Ltd.), MEK varnish of cresol novolac type epoxy resin (epoxy equivalent: 219, Dainippon Ink & Chemicals, Inc.) Epicron N
-690-75M) 45 parts by weight, MEK varnish of phenol novolak resin (manufactured by Dainippon Ink and Chemicals, Inc.)
45 parts by weight of phenolite TD-2090-60M, phenolic hydroxyl group equivalent 105), 30 parts by weight of a phenoxy resin varnish (YP50-EK35 manufactured by Toto Kasei KK), and 9,10-dihydro-9-oxa-10 15 parts by weight of phosphaphenanthrene-10 oxide (a phosphorous flame retardant HCA manufactured by Sanko Chemical Co., Ltd.) was added to prepare an epoxy resin composition. The varnish-like epoxy resin composition is applied on a 38 μm-thick PET film by a die coater so that the thickness after drying becomes 60 μm.
After drying at 120 ° C. for 10 minutes, an adhesive film was obtained.

Example 4 Copper foil 35 μm, plate thickness 0.2 m
m of the double-sided copper-clad double-sided copper-clad laminate, and the adhesive film obtained in Example 1 was subjected to a vacuum laminator at a temperature of 110 ° C., a pressure of 1 kgf / cm ² , and a pressure of 5 mmH.
After laminating on both sides under the condition of g or less, the PET film was peeled off and cured by heating at 170 ° C. for 30 minutes. Thereafter, a hole is formed by a laser to form a through hole and a via hole, and then the surface of the epoxy resin composition cured with an alkaline oxidizing agent of permanganate is roughened, electrolessly and electrolytically plated, and subjected to a subtractive method. A layer printed wiring board was obtained. After that, 150 ° C
For 30 minutes.

Example 5 A four-layer printed wiring board was obtained in the same manner as in Example 4 using the adhesive film obtained in Example 2.

Example 6 Two prepregs obtained in Example 3 were stacked, sandwiched between metal plates via a release film, and laminated and pressed at 120 ° C. and 10 kgf / cm ² for 15 minutes. The laminate was pressed at 60 ° C. and 40 kgf / cm ² for 60 minutes to obtain a laminate having a thickness of 0.2 mm. Then, the surface was roughened with an alkaline oxidizing agent of permanganate, and a conductor layer was formed on the entire surface by electroless plating and electrolytic plating.

<Comparative Example 3> Using the adhesive film obtained in Comparative Example 1, a four-layer printed wiring board was obtained in the same manner as in Example 4.

Comparative Example 4 A four-layer printed wiring board was obtained in the same manner as in Example 4 using the adhesive film obtained in Comparative Example 2.

<Evaluation of Flame Retardancy and Roughness> The flame retardancy was evaluated by the following flammability test. [Combustibility test based on UL94 standard] An adhesive film obtained using the epoxy resin composition described in Examples 1 and 2 and Comparative Examples 1 and 2 was subjected to a non-halogen core substrate (Matsushita Electric Works, Ltd.) using a vacuum laminator. R-1566 (plate thickness: 0.2 mm), and then laminated on both sides, and then heated and cured at 170 ° C. for 90 minutes to obtain a cured plate. From these cured products and the laminate obtained in Example 6, a length of 125 m
m and 12.5 mm wide test pieces were cut out and used by Underwriters Lab.
oratories Inc.) Test for Fragility of Plastic Materials-UL 94 (Te
A test of the combustion behavior of each test piece was performed in accordance with st for Flammability of Plastic Materials-UL 94).

The roughening property was evaluated based on the peel strength of the plated conductor layer and the heat resistance in a solder bath after moisture absorption. [Peel strength measurement] Japanese Industrial Standard (JIS) C6481
It evaluated according to. The conductor plating thickness was about 30 μm. [Heat-absorbing solder heat resistance] After being treated at 120 ° C and 100% humidity for 1 hour, it was immersed in a 260 ° C solder bath for 60 seconds for evaluation. The evaluation was performed by visual judgment of the appearance of the test substrate based on the following criteria. 〇: No abnormality, X: Swelling, peeling or measling occurred.

The results of the above evaluations are shown in Table 1 below. Table 1

Table 1 shows that the multilayer printed wiring boards (Examples 4 to 6) produced using the epoxy resin composition of the present invention have excellent flame retardancy. Further, as a result of the formation of copper plating having excellent adhesion due to the roughening, it can be seen that a multilayer printed wiring board having excellent heat resistance and peel strength has been obtained. On the other hand, in the multilayer printed wiring board (Comparative Example 3) manufactured using the resin composition of Comparative Example 1, flame retardancy was not obtained, and the peel strength of copper plating was low, and sufficient roughening was achieved. I understand that there is no. In addition, although the flame retardancy was obtained in the multilayer printed wiring board (Comparative Example 4) manufactured by the resin composition to which the phosphorus-based flame retardant was added as in Comparative Example 2, the conductor was peeled off due to the moisture absorption solder heat resistance. And it can be seen that sufficient roughening has not been achieved.

[0061]

The epoxy resin composition of the present invention has excellent flame retardancy after curing without containing halogen compounds and phosphorus compounds such as conventionally used halogen flame retardants and phosphorus flame retardants. Demonstrates, and also has a roughening property by an oxidizing agent after curing, and has excellent peel strength and heat resistance of the conductor layer formed by plating, and is a halogen-free laminate that does not contain halogen, especially laminated boards and multilayer printed wiring boards. An epoxy resin composition excellent for use in the production of boards and multilayer printed wiring boards. The epoxy resin composition of the present invention can be used as an adhesive film or prepreg, and these adhesive films and prepregs are also similarly used for laminated boards and multilayer printed wiring boards, especially halogen-free laminated boards and multilayer printed wiring boards containing no halogen. The resulting epoxy resin composition is excellent for use in manufacturing boards.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09J 7/00 C09J 7/00 5E346 163/00 ZAB 163/00 ZAB 171/10 171/10 H05K 3/46 H05K 3/46 EGTF term (reference) 4F072 AA02 AA07 AB06 AB09 AB28 AD13 AD23 AD28 AD42 AE00 AF03 AF04 AF06 AG03 AH02 AH04 AH31 AJ04 AL13 4J002 BC12X CC03X CD00W CD02W CD05W CD06W CD14W CE00DJ DJ086 DJ14 FD016 GF00 GJ01 GQ01 4J004 AA13 AB05 CA06 CB01 CB03 CC02 FA05 4J036 AA01 AD07 AD08 AD21 AE07 AF06 AF08 AF36 AJ08 AJ18 FA03 FA04 FA05 FA11 FB08 FB12 JA06 JA08 JA11 4J040 EB062 EB0812 EB08 EC12 EB102 EB102 EB102 EC06 HA356 JA01 JB02 KA16 KA36 KA42 LA01 LA08 MB03 NA12 NA20 PA30 5E346 AA12 AA43 CC04 CC05 CC09 CC3 2 DD02 DD03 DD23 DD25 EE02 EE09 EE33 FF13 GG17 GG22 GG27 GG28 HH18 HH40

Claims (18)

[Claims] 1. The following components (A) to (D) are essential components, and at least one of (A) an epoxy resin having two or more epoxy groups in one molecule and (B) a phenolic curing agent is used. An epoxy resin composition having a condensed polycyclic aromatic skeleton. (A) an epoxy resin having two or more epoxy groups in one molecule (B) a phenolic curing agent (C) a phenoxy resin having a weight average molecular weight of 5,000 to 100,000 (D) an inorganic filler 2. An epoxy resin having two or more epoxy groups per molecule (A) having a condensed polycyclic aromatic skeleton, and (B) a phenolic curing agent being a triazine-modified phenolic curing agent. The epoxy resin composition according to claim 1. (C) a weight average molecular weight of 5000 to 1
2. The epoxy resin composition according to claim 1, wherein the phenoxy resin of 00000 has a bisphenol S skeleton. 4. The inorganic filler (D) is at least one selected from the group consisting of barium sulfate, barium titanate, silicon oxide powder, amorphous silica, talc, clay, mica powder, aluminum hydroxide and magnesium hydroxide. The epoxy resin composition according to claim 1, which is at least one kind. 5. The weight average molecular weight of (C) is 50 relative to 100 parts by weight of the total amount of (A) an epoxy resin having two or more epoxy groups in one molecule and (B) a phenolic curing agent.
A phenoxy resin of from 00 to 100000
2. The epoxy resin composition according to claim 1, wherein 0 parts by weight and (D) 5 to 200 parts by weight of an inorganic filler are blended. 6. An adhesive film, wherein the epoxy resin composition according to claim 1 is formed as a layer on a supporting base film. 7. A prepreg, wherein the epoxy resin composition according to claim 1 is impregnated in a sheet-like reinforcing substrate made of fiber. 8. A multilayer printed wiring board comprising an insulating layer obtained by curing the epoxy resin composition according to claim 1. 9. A multilayer printed wiring board, wherein the epoxy resin composition according to claim 1 is cured on an inner circuit board, and a conductor layer is formed on the cured resin composition layer. 10. An epoxy resin composition according to claim 1, which is heated and cured on an inner circuit board, the surface of the epoxy resin composition layer cured by an oxidizing agent is roughened, and a conductor layer is formed by plating. A method for manufacturing a multilayer printed wiring board. 11. An epoxy resin composition formed on a supporting base film by laminating the adhesive film according to claim 6 on an inner layer circuit board under pressure and heating conditions, peeling off a supporting base film if necessary. After heat-curing, the support base film, if present, is peeled off, the surface of the epoxy resin composition layer cured by the oxidizing agent is roughened, and the conductive layer is formed by plating. Manufacturing method of wiring board. 12. A multilayer printed wiring board obtained according to the method of claim 11. 13. After laminating the prepreg according to claim 7 on an inner layer circuit board by curing under pressure and heating conditions, the surface of the prepreg layer cured by an oxidizing agent is roughened, and the conductor layer is plated by plating. Forming a multilayer printed wiring board. 14. A multilayer printed wiring board obtained according to the method of claim 13. 15. An epoxy resin composition according to claim 1, which is applied to at least one surface of an uncladded plate or a surface of a double-sided copper-clad laminate on which a copper foil is etched out, and cured by heating. Laminated board. 16. The adhesive film according to claim 6, which is laminated on a surface of the double-sided copper-clad laminate on which a copper foil is etched out or on at least one surface of an unclad plate under pressure and heating conditions, if necessary. Peel off the support base film,
A laminate obtained by removing the supporting base film, if present, after heat curing. 17. A prepreg according to claim 7, which is obtained by laminating the copper foil of a double-sided copper-clad laminate on a surface where copper foil is etched out or on at least one surface of an unclad plate under pressure and heating conditions. Laminated board. 18. A laminate obtained by laminating a plurality of prepregs according to claim 7 and laminating them under pressure and heating conditions.