JP2001261786A - Epoxy resin composition for electric laminate - Google Patents

Abstract

(57) [Summary] [PROBLEMS] To reduce the amount of a halogen-based flame retardant used in an electric laminate, or to combine excellent solder resistance and chemical resistance without using a halogen-based flame retardant. SOLUTION: A modified phenol resin (B) obtained by polycondensing an epoxy resin (A) with a petroleum heavy oil or pitches, phenols and aldehydes, and 9.1,
A phosphorus-based flame retardant (C) represented by 0-dihydro-9-oxa-phosphaphenanthrene.

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 useful as a flame-retardant resin. More specifically, the present invention relates to an epoxy resin composition having a halogen content useful as a material for an electric laminate (electric printed wiring board). An epoxy resin composition which does not use reduced or halogen.

[0002]

2. Description of the Related Art Epoxy resins are widely used mainly in electric and electronic material parts because of their excellent properties such as heat resistance, adhesion, and electrical properties (electrical insulation).

[0003] Among these electric and electronic material parts, high flame retardancy (V-0 in a UL-94 combustion test) is required for electric laminate applications such as glass epoxy laminates for electric printed wiring boards. Usually, a compound containing a halogen element such as a brominated epoxy resin is used. For example, an epoxy resin laminate for an electric printed circuit generally uses an epoxy resin containing a brominated epoxy resin as a main raw material and an epoxy resin curing agent such as dicyanodiamide or a phenol compound.

However, the use of such a halogen atom-containing compound is one of the causes of environmental problems typified by dioxin in recent years, and also has an adverse effect on long-term electrical reliability due to halogen dissociation in a high temperature environment. Due to adverse effects and the like, there is a strong demand for reducing the amount of halogenated compounds used and for developing flame retardants using other compounds that can be substituted for halogenated compounds or other flame retardant formulations.

[0005] As an alternative to the flame-retardant prescription using such a halogen-based compound, for example, various techniques for using or replacing a phosphate ester-based compound or the like as a flame retardant have been studied.

[0006]

However, in order to ensure high flame retardancy (for example, V-0 level in a UL-94 combustion test) by using a phosphoric ester compound as a flame retardant, it is necessary to use these flame retardants. It is necessary to add a considerable amount of a flame retardant, which has a serious drawback in that the heat resistance, water resistance, chemical resistance to acid or alkali, etc., which are important properties of the molded product, are reduced.

The problem to be solved by the present invention is to dramatically improve the heat resistance, water resistance and chemical resistance of molded products, and to reduce the use of halogen-based flame retardants especially in electric laminates. An object of the present invention is to provide an epoxy resin composition for an electric laminate that can exhibit excellent solder resistance and chemical resistance without using a halogen-based flame retardant.

[0008]

The inventors of the present invention have studied to solve the above problems, and as a result, have found that a phenol and a condensed polycyclic aromatic compound are used as epoxy resin curing agents, and an alkylidene group is used as a linking group. By using a modified phenolic resin, it has been found that flame resistance can be obtained without lowering laminate properties such as heat resistance, water resistance, and chemical resistance,
The present invention has been completed.

That is, the present invention relates to an epoxy resin composition comprising the epoxy resin (A) and the curing agent (B) as essential components, wherein the curing agent (B) includes a phenol (b1) and an aromatic condensed polycyclic ring. It has a structure in which the structural site (b2) is bonded via an alkylidene bond, and has an aromatic hydrocarbon fraction fa value of 0.40 to 0.95 and an aromatic ring hydrogen amount Ha of 20.
The present invention relates to an epoxy resin composition for a laminated board, characterized in that a modified phenolic resin of up to 80% by weight is used, and in addition to the components (A) and (B), a phosphorus-based flame retardant is further used in combination.

The epoxy resin (A) used in the present invention is not particularly limited. Examples thereof include bisphenol A epoxy resin, bisphenol F epoxy resin,
2,2 ', 6,6'-tetrabromobisphenol A type epoxy resin, 2,2', 6,6'-tetramethyl bisphenol A type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, tetramethyl Bisphenol A type epoxy resin, bisphenol type epoxy resin such as bis-β-trifluoromethyldiglycidyl bisphenol A,

1,6-diglycidyloxynaphthalene type epoxy resin, 1- (2,7-diglycidyloxynaphthyl) -1- (2-glycidyloxynaphthyl) methane, 1,1-bis (2,7-di Naphthalene epoxy resins such as glycidyloxynaphthyl) methane and 1,1-bis (2,7-diglycidyloxynaphthyl) -1-phenyl-methane;

Other bifunctional epoxy resins such as biphenol type epoxy resin, bisphenol hexafluoroacetone diglycidyl ether and resorcinodiglycidyl ether;

Phenol novolak type epoxy resin, orthocresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol AD
Novolak epoxy resins such as novolak epoxy resins, brominated phenol novolak epoxy resins, and brominated bisphenol A epoxy resins;

An epoxy resin obtained by copolymerizing the bisphenol type epoxy resin and the novolak type epoxy resin via bisphenol and / or halogenated bisphenol;

A cycloaliphatic epoxy resin typified by an epoxidized polyadduct of dicyclopentadiene and phenol;

Glycidyl ester type epoxy resins such as diglycidyl phthalate, diglycidyl tetrahydrophthalate, diglycidyl hexahexaphthalate, diglycidyl p-oxybenzoic acid, glycidyl dimer and triglycidyl ester;

Glycidylamine type epoxy resins such as tetraglycidylaminodiphenylmethane, triglycidyl p-aminophenol, and tetraglycidyl m-xylylenediamine;

A heterocyclic epoxy resin such as a hydantoin type epoxy resin and triglycidyl isocyanurate;

In addition, phlorogrisinol triglycidyl ether, trihydroxybiphenyl triglycidyl ether, trihydroxyphenylmethane triglycidyl ether, glycerin triglycidyl ether,
[4- (2,3-epoxypropoxy) phenyl] -2
-[4- [1,1-bis [4- (2,3-epoxypropoxy) phenyl] ethyl] phenyl] propane, 1,
3-bis [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1- [4- [1- [4- (2,3-
Epoxypropoxy) phenyl] -1-methylethyl]
Phenyl] ethyl] phenoxy] -2-propanol,
Epoxy resins such as tetrahydroxyphenylethane tetraglycidyl ether, tetraglycidyl benzophenone, bisresorcinol tetraglycidyl ether, and tetraglycidoxybiphenyl are exemplified. Each of the above epoxy resins may be used alone, or a mixture of two or more thereof, or a modified epoxy resin may be used in combination.

Among these epoxy resins, those having an epoxy equivalent of 150 g / eq to 1000 g / eq are preferable. That is, in the region where the epoxy equivalent is 1000 g / eq or less, the crosslinked density of the cured product is increased, Tg (glass transition point), heat resistance, solder heat resistance, etc. are improved, and the performance as a laminate is improved.

Among them, it is preferable to use a novolak type epoxy resin from the viewpoint of high Tg, high water resistance and excellent soldering resistance, and the content of the novolak type epoxy resin is particularly preferably 20% or more. If the novolak type epoxy resin content is less than that, no effect is exhibited. It is more preferable to use a non-halogenated epoxy resin among the epoxy resins (A) because the amount of dioxins generated during combustion can be reduced or eliminated.

In the present invention, an epoxy-based reactive diluent such as cyclohexene oxide, tricyclodecene oxide, or cyclopentene oxide may be used in combination with the epoxy resin (A).

Next, the curing agent (B) has a structure in which a phenol (b1) and an aromatic condensed polycyclic structure site (b2) are bonded through an alkylidene bond, and is an aromatic hydrocarbon. A modified phenol type resin having a fraction fa value of 0.40 to 0.95 and an aromatic ring hydrogen content Ha of 20 to 80% by weight is used.

The aromatic hydrocarbon fraction fa value and the aromatic ring hydrogen content Ha are represented by the following equations. Fa value = Number of aromatic carbons / Total carbon number Ha value = Number of aromatic hydrogens / Total hydrogen number × 100 This fa value can be determined by ¹³ C-NMR. The Ha value can be determined by ¹ H-NMR.

The method for producing this modified phenol type resin is as follows:
Although not particularly limited, it can be produced by polycondensing heavy petroleum oils or pitches, phenols, and aldehydes under certain conditions in the presence of an acid catalyst. Among them, the petroleum heavy oils or pitches preferably have an aromatic hydrocarbon fraction fa value of 0.40 to 0.95 and an aromatic ring hydrogen content Ha of 20 to 80% by weight. When the fa value is less than 0.40, the amount of aromatic components in the cured product is reduced, and various properties such as heat resistance, water resistance and chemical resistance as well as flame retardancy are not exhibited. On the other hand, when the fa value is 0.
When it is larger than 95, the reactivity between the aromatic ring hydrogen and the aldehyde becomes low, and the effect of the present invention is not exhibited.

When the Ha value is less than 20% by weight,
Insufficient crosslinking of the aromatic ring component by aldehydes,
Flame retardancy, heat resistance, water resistance and chemical resistance are not exhibited. On the other hand, if it is more than 80% by weight, the strength of the modified phenol type resin is lowered, and the strength of the laminate using the modified phenol type resin is undesirably reduced.

In producing the modified phenol type resin, phenols to be used are not particularly limited, but phenol, brominated phenol, chlorinated phenol, o-cresol, m-cresol, p-cresol, 2,4-xylenol, 2,6-xylenol, resorcinol, catechol, hydroquinone, α
-Naphthol, β-naphthol and the like. These may be used alone or in combination.

As the petroleum heavy oils or pitches, those containing an aromatic condensed polycyclic compound as a main component are preferable, and specific examples thereof include naphthalene, anthracene, benzopyrene, phenanthrene, and coronene. Or their substituents such as an alkyl group and an alkenyl group.

The aldehyde to be reacted with the above-mentioned phenols and petroleum heavy oils or pitches is not particularly limited, but includes formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and the like. These may be used alone or in combination. When formaldehyde is used, an aqueous solution thereof or a polymer such as paraformaldehyde or polyoxymethylene may be used.

The modified phenol type resin used as the curing agent (B) preferably has a solid softening point of 60 ° C. or higher. If a modified phenol resin having a lower softening point is used, tackiness may remain in the B-staged state, which may impair workability such as handling of the prepreg.

It is more preferable to use a modified phenol type resin which is not halogenated among the curing agents (B) since the amount of dioxin generated during combustion can be reduced or eliminated.

Here, Japanese Patent Application Laid-Open No. Hei 5-16276 discloses a technique using a compound having the same structure as the curing agent (B) as an epoxy resin curing agent. The disclosed invention does not provide sufficient flame retardancy as an electric laminate. On the other hand, the present invention further comprises using a phosphorus-based flame retardant (C) in combination.
It exhibits a superior flame retardant effect due to a synergistic effect with the curing agent (B).

Next, the phosphorus-based flame retardant (C) is, for example, UL
It is added to obtain higher flame retardancy such as V-0 level in a -94 combustion test.

The phosphorus-based flame retardant (C) is not particularly restricted but includes, for example, red phosphorus, trimethyl phosphate, triethyl phosphate, triallyl phosphate, tributyl phosphate, trioctyl phosphate, 2-ethylhexyl diphenyl phosphate. , Trisbutoxyethylphosphate, triphenylphosphate, trigresylphosphate, trixylenylphosphate, xylendiphenylphosphate, cresylbis (di2,6-xylenyl) phosphate, cresyldiphenylphosphate, octyldiphenylphosphate, resorcinolbis (diphenyl )
Phosphate, bisphenol A bis (diphenyl) phosphate, bisphenol A bis (dicresyl) phosphate, resorcinyl diphenyl phosphate, resorcinol bis (2,6-xylenyl) phosphate,
Triphenylphosphine, triphenylphosphinoxide, tetrakis (hydroxymethyl) sulfate,
Triphenylphosphoramide, diethyl-N, N-bis (2-hydroxyethyl) aminomethylphosphate, ammonium polyphosphate, ammonium phosphate, ammonium hydrogenphosphate, melamine phosphate, melamine pyrophosphate, phenoxyphosphazene, dipropoxyphosphazene Aminophosphazene, polyphosphazene, tris (3-glycidyloxyphenyl) phosphinoxide, diphenylphosphinylhydroquinone diglycidyl ether, diphenylphosphinylnaphthoquinone diglycidyl ether, bis (3-glycidyloxy) phenylphosphine oxide, 10- (2 ', 5'-bis (glycidyloxy) phenyl) -9,10-dihydro-9-oxa-10-phosphaphenanthalene-10-
Oxide, and the like.

Of these, tris (3-glycidyloxyphenyl) phosphinoxide, diphenylphosphinylhydroquinone diglycidyl ether, diphenylphosphinylnaphthoquinone diglycidyl ether, bis (3
-Glycidyloxy) phenylphosphine oxide,
A phosphorus compound containing an aromatic group such as 10- (2 ′, 5′-bis (glycidyloxy) phenyl) -9,10-dihydro-9-ox-10-10-phosphaphenanthalene-10-oxide is used. Is preferred from the viewpoint of flame retardancy and heat resistance.

Of course, these phosphorus-based flame retardants (C) may be used alone or in combination of two or more.

When the phosphorus-based flame retardant (C) has a reactive functional group with an epoxy group in its structure, the epoxy-modified flame-retardant (C) is preliminarily reacted with a part of the epoxy resin (A). A phosphorus compound may be used as the phosphorus flame retardant (C), or the epoxy resin (A) and the phosphorus flame retardant (C)
May be reacted in advance to obtain a varnish for a laminate.
Alternatively, the epoxy resin (A) and the phosphorus-based flame retardant (C) may react during the production of the prepreg or the production of the laminate.

It is more preferable to use a non-halogenated phosphorus compound among the phosphorus-based flame retardants (C), since the amount of dioxin generated during combustion can be reduced or eliminated.

The proportion of the phosphorus-based flame retardant (C) is such that the amount of phosphorus atoms contained in the epoxy resin composition is 0.5% of the total.
Preferably, it is up to 3% by weight. The effect on the flame retardancy is the same even if more than this is used, and conversely, other laminated board characteristics such as Tg deteriorate. If the amount is less than this, no effect is exhibited.

In the composition of the present invention, various organic solvents, curing accelerators, additives and the like can be appropriately added as necessary. Specifically, an inorganic filler can be added. It is desirable because higher flame retardancy can be obtained.

The inorganic filler is not particularly restricted but includes, for example, silica, talc, calcium carbonate, magnesium carbonate, aluminum hydroxide, magnesium hydroxide, aluminum oxide, magnesium oxide, aluminum silicate and lithium silicate. Aluminum, barium titanate, barium sulfate, silicon nitride, boron nitride, and the like.

The inorganic filler is a total of 1% of the epoxy resin (A), the curing agent (B) and the phosphorus-based flame retardant (C).
It is preferable to mix 25 to 150 parts by weight with respect to 00 parts by weight. The effect on the flame retardancy is the same even if more than this is used, and conversely, other laminated plate characteristics such as drilling workability deteriorate.

As a method for producing a laminate from the composition of the present invention, it can be produced by a known and commonly used method.

For example, a base material such as paper, glass cloth, glass non-woven fabric, carbon fiber cloth or carbon fiber non-woven fabric is impregnated with the composition at a ratio of 30 to 70% by weight of resin, and 100 to 200% by weight.
Dried in a dryer at a temperature of 0.5 to 30 minutes to produce a semi-cured epoxy resin prepreg, and using one or more of the produced prepregs, at a pressure of 5 to 100 k.
g / cm ² , temperature 120-220 ° C., time 20-240
Then, a laminated plate is manufactured by heating and pressing for a minute, and then a metal foil or a metal substrate is heated and pressed on the obtained resin laminated plate, or metal plating is performed.

When a metal foil is used, the prepreg, which has been semi-cured, may be heated and pressed together with the metal foil to form a laminate. Among these, the method of impregnating and drying the base material with the epoxy resin composition to obtain a prepreg and heating and press-molding the prepreg and the metal foil is preferable because it can be easily manufactured.

Further, the base material such as glass cloth, glass non-woven fabric, carbon fiber cloth or carbon fiber non-woven fabric is not used, and the composition is coated on a metal foil to form a semi-cured metal foil with an epoxy resin. The composition may be similarly produced using an epoxy resin adhesive film in a film-like semi-cured state.

The metal laminated on the resin substrate is not particularly limited, and includes, for example, copper, gold, silver, aluminum and the like. Usually, copper is used as copper foil, gold and silver are used for plating, and , Aluminum is used as a substrate. The laminate obtained in this manner may be further superposed plurally and used as a multilayer laminate.

[0048]

The present invention will be described below in more detail with reference to examples and comparative examples. However, these do not limit the present invention. In the examples, “example” and “%” are based on weight unless otherwise specified.

Example 1 100 parts by weight of a phenol novolak type epoxy resin "EPICLONN-770" (manufactured by Dainippon Ink and Chemicals, Inc., epoxy equivalent: 189 g / eq), and a modified phenolic resin "FPI-4038" (Kashima) Petroleum Co., Ltd., phenolic hydroxyl equivalent 128 g / eq,
68 parts by weight, fa value 0.69, Ha value 29%, softening point 76 ° C.)
-200 "(manufactured by Daihachi Chemical Industry Co., Ltd., phosphorus content 9.0)
%) 45 parts by weight is dissolved in a mixed solvent of 83 parts by weight of methyl cellosolve and 83 parts by weight of methyl ethyl ketone, and 0.3 parts by weight of "2-ethyl-4-methylimidazole" (manufactured by Shikoku Chemicals Co., Ltd.) as a curing accelerator Add about 55 solids
% And an epoxy resin varnish having a phosphorus content of 1.9% (in terms of solid content).

The resin varnish was coated with a glass cloth “WE-18K-104BZ2” (manufactured by Nitto Boseki Co., Ltd.)
(Thickness: 180 μ), and dried and B-staged in a 170 ° C. drier so that the gel time of the prepreg measured at 170 ° C. was about 120 seconds, to prepare an epoxy resin prepreg.

Eight prepregs were obtained, and 3
Laminate 5μ copper foil, pressure 30kg / cm ² , temperature 170
The mixture was cured at a temperature of 60 ° C. for a heating time of 60 minutes to produce a laminate having a thickness of 1.6 mm.

The copper foil of the obtained laminate was removed by etching, and the heat resistance (glass transition point Tg), flame retardancy, and moisture and heat resistance (solder resistance) were measured. Table 1 shows the results.
In addition, each test method followed the following method. Tg: Measured by the TMA method (heating rate 3 ° C./min). Flame retardancy: Measured according to the UL94 flame retardancy test. Moisture and heat resistance: A test piece treated in hot pressurized water at 121 ° C. for 4 hours was floated on a 260 ° C. molten solder for 30 seconds, and the appearance of the test piece, particularly the presence or absence of “bulging”, was evaluated by visual judgment. (Judgment criteria: ：: no change in appearance, ×: occurrence of blistering) Alkali resistance: Change in weight was measured according to JIS K-7114. The test conditions were immersion in a 10% aqueous sodium hydroxide solution at room temperature for one week.

Example 2 Using 100 parts by weight of an epoxy resin "EPICLON N-770", 68 parts by weight of a modified phenol resin "FPI-4038" and 10 parts by weight of a phosphorus-based flame retardant "PX-200", Similarly, an epoxy resin varnish having a solid content of about 55% and a phosphorus content of 0.5% (in terms of solid content) was prepared using a mixed solvent of methyl cellosolve and methyl ethyl ketone. Using this resin varnish, a laminate was prepared and evaluated in the same manner as in Example 1. Table 1 shows the results.

Example 3 75 parts by weight of a bisphenol A type epoxy resin "EPICLON 1051" (epoxy equivalent: 470 g / eq, manufactured by Dainippon Ink and Chemicals, Inc.) as an epoxy resin and an o-cresol novolak type epoxy resin "EPI"
CLON N-690 ”Dainippon Ink and Chemicals, Inc.
25 parts by weight of epoxy equivalent, 215 g / eq), 35 parts by weight of modified phenolic resin "FPI-4038", 60 parts by weight of phosphorus-based flame retardant "PX-200", curing accelerator "2-
Ethyl-4-methylimidazole ”(Shikoku Chemicals Co., Ltd.)
Epoxy resin varnish having a solid content of about 55% and a phosphorus content of 2.8% (in terms of solid content) using 0.4 parts by weight of a mixed solvent of methyl cellosolve and methyl ethyl ketone in the same manner as in Example 1. Was adjusted. Using this resin varnish,
A laminate was prepared and evaluated in the same manner as in Example 1. Table 1 shows the results.

Example 4 100 parts by weight of an epoxy resin "EPICLON N-770" and "FPI-5127" as a modified phenol resin
(Kashima Oil Co., Ltd., phenolic hydroxyl equivalent 147 g /
eq, fa value 0.56, Ha value 24%, softening point 81 ° C)
Using 78 parts by weight and 40 parts by weight of a phosphorus-based flame retardant "PX-200", using a mixed solvent of methyl cellosolve and methyl ethyl ketone in the same manner as in Example 1, a solid content of about 55% and a phosphorus content of 1.7% An epoxy resin varnish (in terms of solid content) was prepared. Using this resin varnish, a laminate was prepared and evaluated in the same manner as in Example 1. Table 1 shows the results.

Example 5 100 parts by weight of an epoxy resin "EPICLON N-770", 56 parts by weight of a modified phenol resin "FPI-4038", and a reactive phosphorus compound "HCA" as a phosphorus-based flame retardant
(Official compound name 9,10-dihydro-9 manufactured by Sanko Co., Ltd.
-Oxa-phosphaphenanthrene, phosphorus content 1
Using 20 parts by weight of 4.4%, active hydrogen equivalent 216 g / eq) and using a mixed solvent of methyl cellosolve and methyl ethyl ketone as in Example 1, a solid content of about 55% and a phosphorus content of 1.6% ( An epoxy resin varnish (solid basis) was prepared. Using this resin varnish, a laminate was prepared and evaluated in the same manner as in Example 1. Table 1 shows the results.

Example 6 75 parts by weight of epoxy resin "EPICLON 1051", 25 parts by weight of "EPICLON N-690", 35 parts by weight of modified phenol resin "FPI-4038", 10 parts by weight of phosphorus-based flame retardant "PX-200" , Curing accelerator "2-
Ethyl-4-methylimidazole ”(Shikoku Chemicals Co., Ltd.)
Epoxy resin varnish prepared using 0.4 parts by weight of a mixed solvent of methyl cellosolve and methyl ethyl ketone in the same manner as in Example 1, and aluminum hydroxide powder (Sumitomo Chemical Industries, Ltd.) as an inorganic filler. 35)
A part by weight was added and dispersed, and an epoxy resin varnish having a solid content of about 40% and a phosphorus content of 0.6% (in terms of solid content excluding the inorganic filler) was readjusted. Using this resin varnish, a laminate was prepared and evaluated in the same manner as in Example 1. Table 1 shows the results.

Comparative Example 1 100 parts by weight of epoxy resin "EPICLON N-770" and unmodified phenolic resin "Phenolite TD-2090" (Dainippon Ink & Chemicals, Inc.)
Using phenolic hydroxyl group equivalent of 105 g / eq), 56 parts by weight of phosphorus-based flame retardant "PX-200" and 42 parts by weight of the solid content using a mixed solvent of methyl cellosolve and methyl ethyl ketone in the same manner as in Example 1. An epoxy resin varnish having 55% and a phosphorus content of 1.9% (solid content) was prepared. Using this resin varnish, a laminate was prepared and evaluated in the same manner as in Example 1. Table 1 shows the results.

Comparative Example 2 Using 100 parts by weight of an epoxy resin "EPICLON N-770", 68 parts by weight of a modified phenol resin "FPI-4038" and 5 parts by weight of a phosphorus-based flame retardant "PX-200", Similarly, an epoxy resin varnish having a solid content of about 55% and a phosphorus content of 0.3% (in terms of solid content) was prepared using a mixed solvent of methyl cellosolve and methyl ethyl ketone. Using this resin varnish, a laminate was prepared and evaluated in the same manner as in Example 1. Table 1 shows the results.

Comparative Example 3 Using 100 parts by weight of the epoxy resin “EPICLON N-770”, 68 parts by weight of the modified phenol resin “FPI-4038”, and 140 parts by weight of the phosphorus-based flame retardant “PX-200”, Similarly, an epoxy resin varnish having a solid content of about 55% and a phosphorus content of 4.1% (in terms of solid content) was prepared using a mixed solvent of methyl cellosolve and methyl ethyl ketone. Using this resin varnish, a laminate was prepared and evaluated in the same manner as in Example 1. Table 1 shows the results.

Comparative Example 4 100 parts by weight of an epoxy resin "EPICLON N-770", 68 parts by weight of a modified phenolic resin "FPI-4038", and without adding a phosphorus-based flame retardant, the same procedure as in Example 1 was carried out for methyl cellosolve and methyl ethyl ketone. An epoxy resin varnish having a solid content of about 55% was prepared using the mixed solvent. Using this resin varnish, a laminate was prepared and evaluated in the same manner as in Example 1. Table 1 shows the results.

[0062]

[Table 1]

[0063]

According to the present invention, the heat resistance, water resistance and chemical resistance of a molded product are remarkably improved, and the use amount of a halogen-based flame retardant is reduced particularly in an electric laminate.
Alternatively, it is possible to provide an epoxy resin composition for an electric laminate that can exhibit excellent solder resistance and chemical resistance without using a halogen-based flame retardant.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H05K 1/03 610 H05K 1/03 610L 610R F term (Reference) 4J002 CC272 CD021 CD041 CD051 CD061 CD131 CD141 DA056 DH056 EU186 EW046 FD136 FD142 GF00 GQ01 4J033 FA01 FA08 HB03 4J036 AA01 FA04 FA12 FB08 JA08

Claims (10)

[Claims] 1. An epoxy resin composition comprising an epoxy resin (A) and a curing agent (B) as essential components, wherein a phenol (b1) and an aromatic condensed polycyclic site (b2) are used as the curing agent (B). ) Has a structure bonded via an alkylidene bond, and has an aromatic hydrocarbon fraction fa value of 0.40 to 0.95 and an aromatic ring hydrogen content Ha of 20 to 80.
An epoxy resin composition for an electric laminate, comprising a modified phenol type resin in an amount of 1% by weight, and further using a phosphorus-based flame retardant (C) in addition to the above components (A) and (B). 2. The composition according to claim 1, wherein the curing agent (B) has a solid content softening point of 60 ° C. or higher. 3. The curing agent (B) is a phenol (b1)
And the aromatic hydrocarbon fraction fa value is 0.40 to 0.95,
3. The composition according to claim 1, which is obtained by reacting an aromatic condensed polycyclic compound (b2 ') having an aromatic ring hydrogen content Ha of 20 to 80% by weight with an aldehyde. 4. The composition according to claim 1, wherein the curing agent (B) is a modified phenolic resin containing no halogen atom. 5. The epoxy equivalent of the epoxy resin (A)
The composition according to any one of claims 1 to 4, wherein the composition is 150 to 1000 g / eq. 6. The composition according to claim 1, wherein the epoxy resin (A) is a novolak type epoxy resin. 7. The composition according to claim 1, wherein the epoxy resin (A) does not contain a halogen atom. 8. The composition according to claim 1, wherein the phosphorus-based flame retardant (C) is contained in a proportion such that the phosphorus atom content in the composition is 0.5 to 3% by weight. object. 9. The composition according to claim 8, wherein the phosphorus-based flame retardant (C) is an aromatic group-containing phosphorus compound. 10. The composition according to claim 1, wherein the phosphorus-based flame retardant (C) does not contain a halogen atom.