JP2002226678A - Flame retardant epoxy resin composition and semiconductor-sealing material and semiconductor device each using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame retardant epoxy resin composition which has high flame retardancy without using halogen-based compounds or a phosphorus flame retardant and also improves fluidity and further prevents deterioration of product characteristics, and also to provide a semiconductor using the same. SOLUTION: The flame retardant epoxy resin is prepared by formulating as an essential component an epoxy resin having at least two epoxy groups in one molecule, a curing agent, and a compound with a thermal decomposition temperature of 330-650 deg.C wherein a metallic atom is bonded with an aromatic compound or a heterocyclic compound through ionic or coordinate bond. Preferably, the curing agent (B) comprises a compound or a resin each having at least two phenolic hydroxy groups in one molecule, or the compound (C) has 250-800 deg.C at weight loss of 10% in a thermogravimetric decrease method when temperature is increased at temperature rising rate of 10 deg.C/min in nitrogen atmosphere.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant epoxy resin composition exhibiting excellent flame retardancy without using a halogen-based compound or a phosphorus-based flame retardant, and a semiconductor sealing material using the same. And a semiconductor device.

[0002]

2. Description of the Related Art Epoxy resins have less adhesive shrinkage during curing than other thermosetting resins such as unsaturated polyester resins and phenolic resins, so they have good adhesion to metals and inorganic substances, and are encapsulated in semiconductors. Although used as a material, in recent years, in many cases, flame retardancy has been imparted in order to ensure safety against fire. Conventionally, halogen-based compounds such as brominated epoxy resins have been generally used to make these resins flame-retardant.

[0003] Although these halogen compounds have high flame retardancy, aromatic bromine compounds not only release corrosive bromine and hydrogen bromide by thermal decomposition but also decompose in the presence of oxygen. Is a highly toxic polybenzofuran,
May form polybromodibenzoxazine. Further, it is extremely difficult to treat aging waste materials and refuse containing bromine.

[0004] For these reasons, phosphorus-based flame retardants have been widely studied as flame retardants in place of halogenated compounds. However, when a phosphoric acid ester or the like is added to the epoxy resin-based composition, bleeding or hydrolyzability is a problem, resulting in a drawback that electrical characteristics and reliability are significantly deteriorated. Therefore, as a flame retardant instead of halogenated compounds,
JP-A-2000-204227 proposes a flame-retardant technique using a compound having a metal atom. However, even if the addition amount is increased, the flame retardancy does not improve so much, and the curability decreases with the increase in the addition amount. Therefore, further improvement in flame retardancy is desired.

Japanese Patent Application Laid-Open No. H11-269349 discloses an epoxy resin composition using cyclopentadiene iron (ferrocene) as a flame retardant. 10 ° C /
When the temperature is raised in min, the temperature at the time of 10% weight loss is 146
° C, and the solder resistance decreases.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a highly flame-retardant, improved fluidity and deteriorated product characteristic without adding a halogen compound or a phosphorus-based flame retardant. SUMMARY OF THE INVENTION It is an object of the present invention to provide a flame-retardant epoxy resin composition having no resin, a semiconductor encapsulating material using the same, and a semiconductor device encapsulated by a cured product thereof.

[0007]

DISCLOSURE OF THE INVENTION The present invention has been studied in view of the current situation of flame retardancy of epoxy resins, and as a result of further studies, as a compound to be added to the epoxy resin composition, a metal atom and an aromatic compound are added. By using a compound in which a compound or a heterocyclic compound is bonded by an ionic bond or a coordination bond, more preferably, by using a compound having a specific range of thermal decomposition temperature, curability can be maintained, and the compound is thermally heated to a temperature at which the resin decomposes. It has been found that the compound is stable, has no adverse effect on other physical properties, exhibits an effect as a flame retardant during combustion, can exhibit higher flame retardancy, and can further improve fluidity, and completes the present invention. It has been reached.

That is, the present invention relates to an epoxy resin (A) having at least two epoxy groups in one molecule, a curing agent (B), and a metal atom and an aromatic compound or a heterocyclic compound, each of which has an ionic bond or a bond. A flame-retardant epoxy resin composition containing a compound (C) bonded by a position bond as an essential component, and a semiconductor sealing material using the same.

Preferably, the curing agent (B) comprises a compound or resin having at least two phenolic hydroxyl groups in one molecule, or the compound (C) comprises
In the thermogravimetric reduction measurement, the heating rate was 10
The temperature at a 10% weight loss when the temperature is raised at a rate of ° C./min is 250 to 800 ° C. Furthermore, the present invention is a semiconductor device sealed with a cured product of the semiconductor sealing material.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The flame-retardant epoxy resin composition of the present invention and a semiconductor encapsulating material using the same do not use a halogenated compound such as a halogenated epoxy resin or a phosphorus-based flame retardant. The addition of the compound (C) in which a metal atom and an aromatic compound or a heterocyclic compound are bonded by an ionic bond or a coordination bond does not significantly reduce fluidity, curability, moisture resistance reliability, and solder resistance. The main point is to provide excellent flame retardancy.

The epoxy resin (A) used in the present invention
May be one having at least two epoxy groups in one molecule, and specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolak type epoxy resin, cresol Novolak type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, N-glycidyl compound derived from aromatic amine and heterocyclic nitrogen base, for example, N, N-diglycidylaniline, triglycidyl isocyanurate, N, N , N ', N'-
Examples include tetraglycidyl-bis (para-aminophenyl) -methane, but are not particularly limited thereto. These can be used alone or in combination of several kinds.

However, halogenated epoxy resins such as a brominated bisphenol A type epoxy resin and a brominated novolak type epoxy resin are excluded in principle because the present invention aims at a resin composition containing no halogen compound. Even if a halogenated epoxy resin is contained in a small amount or partially, it is of course included in the technical scope of the present invention. In addition, chlorine contained in a normal epoxy resin originating from epichlorohydrin inevitably remains in the production process of the epoxy resin, and is unavoidable in the present invention, and is not excluded. The amounts are at levels known to those skilled in the art, on the order of hundreds of ppm of hydrolyzable chlorine.

As the curing agent (B) used in the present invention, all those known to those skilled in the art can be used. Specifically, C such as ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, etc.
Linear aliphatic diamine of ₂ -C _20, meta-phenylenediamine, para-phenylenediamine, para-xylene diamine,
4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylether, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodicyclohexane, bis (4-aminophenyl) Phenylmethane, 1,5-diaminonaphthalene, metaxylenediamine, paraxylenediamine, 1,1-bis (4-
Amines such as aminophenyl) cyclohexane and dicyanodiamide; resole-type phenol resins such as aniline-modified resole resins and dimethyl ether resole resins;
Phenol novolak resin, cresol novolak resin, tertiary-butylphenol novolak resin,
Examples include novolak phenol resins such as nonylphenol novolak resins, polyoxystyrenes such as polyparaoxystyrene, phenol resins such as phenol aralkyl resins, and acid anhydrides, but are not particularly limited thereto.

As a curing agent for a semiconductor encapsulating material, a compound or resin having at least two phenolic hydroxyl groups in one molecule is preferable from the viewpoint of moisture resistance reliability and the like, and a phenol novolak resin and a cresol novolak resin are preferable. And tertiary-butylphenol novolak resins, nonylphenol novolak resins, and other novolak phenol resins, resole phenol resins, polyoxystyrenes such as polyparaoxystyrene, and phenol aralkyl resins.

In the present invention, at least 2
When the curing agent (B) is a phenolic compound, the mixing ratio of the curing agent (B) to the epoxy equivalent of the epoxy resin (A) is as follows. The ratio of the hydroxyl equivalent is 0.5 to 2.0.
It is preferable to mix in the range of. When the curing agent (B) is an acid anhydride, it is preferable to mix the acid anhydride equivalent to the epoxy equivalent in the range of 0.8 to 1.4.
When the curing agent (B) is an amine compound, the ratio of the amine compound active hydrogen equivalent to the epoxy equivalent is 0.5.
It is preferred to mix in the range of -2.0.

Next, the compound (C) in which a metal atom and an aromatic compound or a heterocyclic compound are bonded by an ionic bond or a coordinate bond is TG-DTA (manufactured by Seiko Instruments Inc.). In the measurement, when the temperature was raised at a rate of 10 ° C./min under a nitrogen atmosphere, 250 to 800
It preferably has a 10% weight loss temperature of 10 ° C., more preferably 330 to 650 ° C., even more preferably 350 to 600 ° C., and decomposes at a temperature higher than around the decomposition temperature of the epoxy resin. Is big. When the compound (C) having a temperature at the time of 10% weight loss of 330 ° C. or more is added, the fluidity is further improved.

The metal atom constituting the compound (C) is preferably selected from transition metals 2A and 3A to 2B of the periodic table, and among them, copper, cobalt and iron are more preferable. As the compound (C), a compound having at least one of these metal atoms is preferable. The periodic table is a physics dictionary (first edition, 1984
(September 30, p. 2315).

The compound (C) in which a metal atom and an aromatic compound or a heterocyclic compound are bonded by an ionic bond or a coordinate bond is preferably a phthalocyanine complex (formula 1) or a naphthalocyanine complex (formula 2) , Hydroxyquinoline (oxine) (formula 3), nitronaphthol complex (formula 4), phenanthroline complex (formula 5), bipyridine complex (formula 6), and benzoylmethanato complex (formula 7)
At least one complex compound selected from the group consisting of:

[0019]

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[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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In the formula, R _{1 to} R ₂₂ each represent a monovalent group selected from hydrogen, methyl group, ethyl group, tertiary butyl group, hydroxyl group, amino group and carboxyl group. A plurality of hydrogens on the same benzene ring may be substituted, and may be the same or different. M represents a metal atom selected from transition metals 2A and 3A to 2B in the periodic table. Also, (Equation 3)
In the formula (7), n is an integer of 1 or more.

The compound (C) in the present invention is preferably a phthalocyanine compound among the above complex compounds, and particularly preferably at least one complex selected from copper phthalocyanine (formula 9) and iron phthalocyanine (formula 10). Compound.

[0028]

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[0029]

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Further, as the compound (C) in the present invention,
Another preferred complex compound is a Schiff base iron complex having a structure of -CH = N-. The Schiff base-type iron complex is synthesized, for example, from a compound having at least one hydroxyl group and an aldehyde group in one molecule, a compound having two or more amino groups in one molecule, and an iron salt.

Specific examples of the Schiff base-type iron complex preferably include iron complex compounds represented by formulas (10) to (13), and at least one complex compound selected from these can be used. . Equations (10) and (1)
The iron complex compound represented by the formula (2) can be synthesized, for example, from a salicylaldehyde (hydroxybenzaldehyde) derivative, ethylenediamine, and an iron salt.
The iron complex compound represented by 3) is obtained by synthesizing a salicylalaldehyde derivative, a phenylenediamine derivative, and an iron salt.

[0032]

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[0033]

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[0034]

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[0035]

Embedded image In the formula, R _{23 to} R ₃₇ each represent a monovalent group selected from hydrogen, a methyl group, an ethyl group, a tertiary butyl group, a hydroxyl group, an amino group, and a carboxyl group. A plurality of hydrogens on the ring may be substituted, and may be the same or different.

More preferably, it is represented by the following formula (10).
The compound is a compound represented by the formula (10)_{twenty three}And R _{twenty four}Is hydrogen as
Salicylaldehyde-ethylenediamine iron complex (Fe-sal
en), R in equation (10)_{twenty three}And R_{twenty four}Is a hydroxyl group
Lithyl aldehyde-ethylenediamine iron complex (Fe-salen
OH), the compound represented by the formula (11)
R_{twenty five}, R₂₆, And R₂₇Salicylaldehyde as hydrogen
Do-phenylenediamine iron complex (Fe-saloph), formula (1)
1) R in_{twenty five}And R₂₆As a hydroxyl group, R₂₇As hydrogen
Salicylaldehyde-phenylenediamine iron complex (Fe
-salophOH), the compound represented by the formula (12) is represented by the formula (1)
2) R inside₂₈~ R₃₁Bis (salicylal)
Dehyde-ethylenediimine iron) ([Fesalen]_TwoO), R₂₈~
R₃₁Bis (salicylaldehyde-ethyl)
Range imine iron) ([Fe-salenOH]_TwoO), represented by equation (13)
Is a compound of the formula (13)₃₂~ R₃₇As hydrogen
Bis (salicylaldehyde-phenylenedimine iron)
([Fesaloph]_TwoO), R in the formula (13)₃₂, R₃₄, R₃₅,
And R₃₇As a hydroxyl group, R₃₃And R₃₆Is hydrogen as
(Salicylaldehyde-phenylenediimine iron) ([Fe
-salophOH]_TwoO).

The compounding amount of the compound (C) in the present invention is a total of 10% of the epoxy resin (A) and the curing agent (B).
The amount is preferably 0.01 to 15 parts by weight, more preferably 0.1 to 10 parts by weight, based on 0 parts by weight. If the amount is less than 0.01 part by weight, the effect of flame retardancy may be reduced. On the other hand, if it exceeds 15 parts by weight, the curability may be reduced. Compound (C) may be used alone or in combination of two or more. In the production of the resin composition, the compound (C) may be previously melted and mixed with the epoxy resin (A) or the curing agent (B) in order to improve dispersibility.

The semiconductor encapsulating material of the present invention is basically composed of the flame-retardant resin composition and a filler (D). Specific examples of the filler (D) include silica powder such as fused silica, alumina, talc, calcium carbonate, clay, and mica. The compounding amount of the filler (D) in the present invention is preferably from 60 to 95% by weight, but is practically preferably from 65 to 90% by weight.

In addition to the above components, the flame-retardant epoxy resin composition and the semiconductor encapsulating material of the present invention may further comprise, if necessary, natural waxes, synthetic waxes, metal oxides of linear aliphatic acids, Additives known to those skilled in the art such as release agents such as acid amides, esters and paraffins, coloring agents such as carbon black and red iron, various curing accelerators and coupling agents can be blended.

The flame-retardant epoxy resin composition of the present invention comprises an epoxy resin (A), a curing agent (B), and a compound (C).
In addition, the semiconductor encapsulating material is prepared by selecting the flame-retardant epoxy resin composition and the filler (D), and if necessary, other components to a predetermined composition ratio, and sufficiently using a mixer or the like. After mixing to be uniform, kneading with a hot roll, or kneading with a kneader, etc., cooling,
Each can be obtained by solidifying and pulverizing to an appropriate size. The obtained semiconductor encapsulating material is suitably used as a semiconductor device by being molded by a method such as transfer molding or injection molding. The semiconductor device of the present invention is obtained by encapsulating and curing an electronic component such as a semiconductor element by a molding method such as transfer molding or injection molding using the semiconductor encapsulating material obtained above.

Further, the flame-retardant epoxy resin composition of the present invention does not contain a halogen-based compound or a phosphorus-based flame retardant, exhibits excellent flame-retardant properties, and greatly reduces curability, fluidity, and moisture-resistance reliability. Since it is not used, it can be used not only as a sealing material for semiconductor elements, but also for electronic components and electrical components, and can also be suitably used for applications such as coating materials, insulating materials, laminates, and metal-clad laminates. .

[0042]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited thereto.

[Synthesis Example of Schiff Base Iron Complex] The synthesis of the Schiff base complex of Compound C was performed according to the fourth edition of Experimental Chemistry Course 17 (author: The Chemical Society of Japan, published on March 5, 1991). Synthetic examples are shown below, but are not necessarily limited to literature methods, reaction temperatures, and reaction times.

(Synthesis Example 1) 24 g of salicylaldehyde (manufactured by Kanto Chemical), 6 g of ethylenediamine (manufactured by Kanto Chemical),
Dissolve 28 g of iron sulfate (manufactured by Kanto Kagaku) in 500 ml of ethanol, put it in a 1 liter four-necked flask equipped with a thermometer and a stirrer, leave it at 110 ° C. (under reflux) for 3 hours, cool and filter. Thus, 30 g of a salicylaldehyde-ethylenediamine iron complex (Fe-salen) was obtained.

(Synthesis Example 2) 28 g of dihydroxybenzaldehyde (manufactured by Kanto Chemical), 6 g of ethylenediamine (manufactured by Kanto Chemical), and 28 g of iron sulfate (manufactured by Kanto Chemical) were added to ethanol 5
The mixture was dissolved in 00 ml, placed in a 1-liter four-necked flask equipped with a thermometer and a stirrer, left at 110 ° C. (under reflux) for 3 hours, cooled, and filtered to obtain 30 g of (Fe-salenOH). .

(Synthesis Example 3) Salicylaldehyde (manufactured by Kanto Chemical) 24 g, phenylenediamine (manufactured by Kanto Chemical) 11
g, 28 g of iron sulfate (manufactured by Kanto Chemical) in 500 m of ethanol
1 liter of 4 liters with thermometer and stirrer.
The mixture was placed in a one-necked flask, left at 110 ° C. (under reflux) for 3 hours, cooled and filtered to obtain 30 g of Fe-saloph.

(Synthesis Example 4) 28 g of dihydroxybenzaldehyde (manufactured by Kanto Kagaku), 11 g of phenylenediamine (manufactured by Kanto Kagaku) and 28 g of iron sulfate (manufactured by Kanto Kagaku) are dissolved in 500 ml of ethanol, and 1 liter equipped with a thermometer and a stirrer And then left at 110 ° C. (under reflux) for 3 hours, cooled and filtered (Fe-salophO).
35 g of H) were obtained.

(Synthesis Example 5) 24 g of salicylaldehyde (manufactured by Kanto Chemical), 6 g of ethylenediamine (manufactured by Kanto Chemical),
28 g of iron sulfate (manufactured by Kanto Kagaku) is dissolved in 500 ml of pure water, placed in a 1-liter four-necked flask equipped with a thermometer and a stirrer, and left at 110 ° C. (under reflux) for 3 hours.
The mixture was cooled and filtered to obtain 30 g of (Fe-salen) ₂ O ([Fe-salen] ₂ O) bound with oxygen.

(Synthesis Examples 6 to 8) The same procedures were performed as in Synthesis Examples 2 to 4 except that ethanol was replaced with water.
-salenOH] ₂ O), ([Fe-saloph] ₂ O) and ([Fe-salophOH] ₂ O) were obtained.

Next, a semiconductor encapsulating material was prepared with a predetermined formulation, and in order to evaluate its characteristics, spiral flow, Barcol hardness and flame retardancy were measured, and tests for moisture resistance reliability and solder resistance were performed. . The measuring method and conditions of each characteristic were as follows.

(1) Fluidity Evaluated by spiral flow, using a mold conforming to EMMI-1-66, using a transfer molding machine, mold temperature 175 ° C., injection pressure 6.86 MPa (70 kgf / cm ^2). ),
The curing time was measured under the condition of 120 seconds. The obtained measured values indicate that the larger the value, the better the fluidity.

(2) Curability A transfer molding machine is used to mold the mold at 175 ° C.
Molding was performed for 0 second, and the Barcol hardness (# 935) of the molded product 10 seconds after opening the mold was evaluated.

(3) Flame retardancy Test pieces (127 mm × 12.7 mm × 1.0 mm thick ,
(1.6 mm, 3.2 mm) using a transfer molding machine, a mold temperature of 175 ° C., and an injection pressure of 6.86 MPa (70 k).
gf / cm ² ), molded with a curing time of 120 seconds, 175 ° C, 8
After curing for a time, the flame retardancy was determined by measuring according to the UL-94 vertical method.

(4) Humidity Reliability Using the prepared semiconductor encapsulating material, a mold temperature of 175 ° C.
Injection pressure 6.86 MPa (70 kgf / cm ² ), curing time 1
Monitor I equipped with an aluminum simulation device under the condition of 20 seconds
A semiconductor device formed by molding C (16 pDIP) and post-curing at 175 ° C. for 8 hours was used. This was left for 200 hours while applying a 5.5 V voltage under a greenhouse condition of 125 ° C., 100% relative humidity, and 2.3 atm. Then, a conduction test was performed. . When the number of defective packages was a, the number was set to a / 20.

(5) Solder Resistance Using a transfer molding machine, a mold temperature of 175 ° C., an injection pressure of 7.35 MPa (75 kgf / cm ² ), a curing time of 2 minutes, and 80 pQFP (2 mm thick, chip size 9.0 mm ×
9.0 mm), and post-cured at 175 ° C. for 8 hours.
85 packages at 85 ° C and 85% relative humidity
For 168 hours, and then immersed in a 240 ° C. solder bath for 10 seconds. External cracks generated in the package were observed with a microscope. Also, internal peeling and internal cracks were observed using an ultrasonic flaw detector. An IC package having a crack or internal peeling even at one location was determined to be defective. When the number of defective packages was b, it was indicated as b / 20.

[Preparation of Semiconductor Encapsulating Material] (Example 1) Spherical fused silica (average particle size: 20 μm, maximum particle size: 100 μm) 85 parts by weight, biphenyl type epoxy resin (YX-4000HK, manufactured by Yuka Shell Epoxy Co., Ltd.), epoxy 7.6 g parts by weight, phenol aralkyl resin (XL-225 manufactured by Mitsui Chemicals, hydroxyl equivalent 175 g / e)
q) 6.8 parts by weight of copper phthalocyanine (Kanto Chemical)
67 parts by weight (5 parts by weight based on the total of 100 parts by weight of epoxy resin (A) and curing agent (B)), 0.3 parts by weight of triphenylphosphine, release agent (natural carnauba wax)
0.3 parts by weight, 0.2 parts by weight of a coloring agent (carbon black), and 0.3 parts by weight of an epoxysilane coupling agent (A-186 manufactured by Nippon Unicar) are compounded, and kneaded using a hot roll. A molding material for semiconductor encapsulation was obtained. The evaluation results of the characteristics are as shown in Table 1.

(Examples 2 to 10) Instead of copper phthalocyanine in Example 1, iron phthalocyanine and Synthesis Example 1 were used.
Schiff base iron complexes Fe-salen, Fe-salenO synthesized in
H, Fe-saloph, Fe-salophOH, [Fe-salen] ₂ O, [Fe-sal
enOH] ₂ O, [Fe-saloph] ₂ O, [Fe-salophOH] ₂ O,
Except having been blended according to Table 1, in the same manner as in Example 1,
A semiconductor encapsulating material was prepared. The evaluation results of the characteristics are summarized in Table 1.

(Comparative Examples 1 to 5) In Example 1, instead of copper phthalocyanine, resorcinol diphenyl phosphate (CDP manufactured by Daihachi Chemical), triphenylphosphine oxide (TPP manufactured by Daihachi Chemical), and cobalt naphthenate (Kanto Chemical) ) And cyclopentadienyl iron (ferrocene) (manufactured by Kanto Chemical Co., Ltd.), and a molding material was prepared in the same manner as in Example 1 except that the components were blended according to Table 1. The flame retardancy, reliability and solder resistance were evaluated. In addition, Comparative Example 1 shows a formulation example containing no flame retardant, Comparative Examples 2 and 3 show formulation examples containing a phosphorus-based flame retardant, and Comparative Examples 4 and 5 show formulation examples containing an organometallic flame retardant.

[0059]

[Table 1]

As can be seen from the results shown in Table 1, Comparative Example 1 was a result obtained when no flame retardant was added. And does not correspond to UL94.
Comparative Example 2 is an example in which resorcin diphenyl phosphate was used as a flame retardant, and although there was no problem in flow, curability, and flame retardancy, moisture resistance reliability and solder resistance were extremely low. In Comparative Example 3 using triphenylphosphine oxide, the fluidity was good, but the results were inferior in curability, flame retardancy, moisture resistance reliability, and solder resistance. In Comparative Example 4 using cobalt naphthenate, the flame retardancy did not reach V-0 of UL94 (V-1) in a test piece having a thickness of 1.0 mm and a thickness of 3.2 mm. In Comparative Example 5 using cyclopentadienyl iron (ferrocene), V-0 was achieved in the UL94 test for all test piece thicknesses, but the result was that the solder resistance was significantly reduced.

On the other hand, in Examples 1 to 1 in which the compound (C) in which the metal atom of the present invention and an aromatic compound or a heterocyclic compound are bonded by an ionic bond or a coordinate bond is used as a flame retardant.
At 0, the flame retardancy is UL94V-0, which is a very good result showing not only the flame retardancy but also good fluidity, curability, moisture resistance reliability and solder resistance compared to the conventional one. Met.

[0062]

According to the present invention, it has a high level of flame retardancy without adding a halogen compound or a phosphorus flame retardant, and does not deteriorate the characteristics of the product. Flame-retardant epoxy resin composition having excellent moisture resistance reliability, particularly good fluidity, and not using halogen and phosphorus required in the future, as compared with the case where a phosphorus-based flame retardant is blended. It can realize a semiconductor encapsulation material using, and is extremely useful as a semiconductor encapsulation material.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J002 CC052 CC062 CD051 CD061 CD141 CE002 EE047 EL136 EN036 EN076 EU007 EU067 EU207 FD152 FD156 FD207 GQ05 4J036 AA01 AD01 AD08 AD21 AF06 DC01 DC04 DC06 DC09 DC10 DC31 FA08 FA10 FA12 JA07 EA03 EB02 EB03 EB07 EC20

Claims (10)

[Claims] 1. An epoxy resin (A) having at least two epoxy groups in one molecule, a curing agent (B), and
A flame-retardant epoxy resin composition comprising, as an essential component, a compound (C) in which a metal atom and an aromatic compound or a heterocyclic compound are bonded by an ionic bond or a coordinate bond. 2. The flame-retardant epoxy resin composition according to claim 1, wherein the curing agent (B) comprises a compound or resin having at least two phenolic hydroxyl groups in one molecule. 3. The compound (C) has a 10% weight loss temperature of 250 to 800 ° C. when heated in a nitrogen atmosphere at a rate of 10 ° C./min in a thermogravimetric measurement. The flame-retardant epoxy resin composition according to claim 1. 4. The compound according to claim 1, wherein the compound (C) is a compound having at least one metal atom selected from transition metals 2A and 3A to 2B in the periodic table. Flame-retardant epoxy resin composition. 5. The compound (C) is a phthalocyanine complex (formula 1), a naphthalocyanine complex (formula 2), a hydroxyquinoline (oxine) (formula 3), a nitronaphthol complex (formula 4), or a phenanthroline complex (formula 5). , Bipyridine complex (formula 6) and benzoylmethanato complex (formula 7)
The flame-retardant epoxy resin composition according to any one of claims 1 to 4, which is at least one complex compound selected from the group consisting of: Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image In the formula, R _{1 to} R ₂₂ each represent a monovalent group selected from hydrogen, a methyl group, an ethyl group, a tertiary butyl group, a hydroxyl group, an amino group, and a carboxyl group. A plurality of hydrogens on the ring may be substituted, and may be the same or different. M represents a metal atom selected from transition metals 2A and 3A to 2B in the periodic table, and n is an integer of 1 or more. 6. The phthalocyanine complex is selected from copper phthalocyanine (formula 8) and iron phthalocyanine (formula 9).
The flame-retardant epoxy resin composition according to claim 5, which is at least one complex compound. Embedded image Embedded image 7. The flame-retardant epoxy resin composition according to claim 1, wherein the compound (C) is a Schiff base iron complex. 8. The flame-retardant epoxy resin composition according to claim 7, wherein the Schiff base-type iron complex is at least one complex compound selected from iron complex compounds represented by formulas (10) to (13). . Embedded image Embedded image Embedded image Embedded image In the formula, R _{23 to} R ₃₇ each represent a monovalent group selected from hydrogen, a methyl group, an ethyl group, a tertiary butyl group, a hydroxyl group, an amino group, and a carboxyl group. A plurality of hydrogens on the ring may be substituted, and may be the same or different. 9. A semiconductor encapsulant, which is basically composed of the flame-retardant epoxy resin composition according to claim 1 and a filler. 10. A semiconductor device sealed with a cured product of the semiconductor sealing material according to claim 9.