JP2000103939A - Epoxy resin molding material for sealing and device for electronic part - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an epoxy resin molding material excellent in dehalogenation, deantimonation and high-temperature releasing characteristics and useful as an electronic device, or the like, by compounding an epoxy resin with a specific cyclic phosphazene as a flame retardant. SOLUTION: This epoxy resin molding material consists essentially of (A) an epoxy resin having two or more epoxy groups in one molecule, (B) a compound having two or more phenolic hydroxyl groups in one molecule, (C) a cyclic phosphazene compound containing formula I and/or formula II [(m) and (n) are each 1-10; R1 to R4 and R5 to R8 are each a (substituted) 1-12C alkyl, aryl or the like; A is a 1-4C alkylene or allylene] as a recurring unit in the main chain skeleton and (D) inorganic filler, and the content of the component D is >=70 wt.% based on total molding material. Furthermore, it is preferable that a molar ratio (m/n) of formula I and/or formula II is (1/0) to (1/4) and the content of the component C is 0.2-5.0% expressed in terms of phosphorus atom amount based on total amount of compounding component excluding the component D.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sealing epoxy resin molding material, particularly a halogen-free sealing epoxy resin molding material required from the viewpoint of environmental friendliness. The present invention relates to a molding material suitable for sealing a VLSI requiring strict reliability such as characteristics, and an electronic component device in which an element is sealed with the molding material.

[0002]

2. Description of the Related Art Conventionally, epoxy resin molding materials have been widely used in the field of sealing elements for electronic parts such as transistors and ICs. The reason for this is that the epoxy resin is balanced in various properties such as electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesiveness to insert products. Flame retardation of these epoxy resin molding materials is mainly carried out by combining a brominated resin such as diglycidyl ether of tetrabromobisphenol A with antimony oxide.

[0003]

In recent years, the problem of dioxin originated from the viewpoint of environmental protection, and there has been a movement to regulate halogenated resins such as decabrom. Similarly, antimony compounds are being regulated from the viewpoint of toxicity, and there is a demand for dehalogenation (debromination) and deantimony of epoxy resin molding materials for encapsulating electronic components. It is also known that bromide ions have an adverse effect on the high-temperature storage characteristics of plastic-sealed ICs. From this viewpoint, it is desired to reduce the amount of brominated resin. The present invention has been made in view of such circumstances, and has as its object to provide an epoxy resin material for encapsulation which is dehalogenated and deantimonized and has excellent high-temperature storage characteristics.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the inventors have found that the above object can be achieved by blending a specific cyclic phosphazene compound as a flame retardant. They have found and completed the present invention.

That is, the present invention relates to (1) (A) an epoxy resin having two or more epoxy groups in one molecule, (B) a compound having two or more phenolic hydroxyl groups in one molecule, (C) A) a cyclic phosphazene compound containing the following formula (I) and / or the following formula (II) as a repeating unit in the main chain skeleton and (D) an inorganic filler as essential components, and the content of the component (D) is a molding material. 7 for the whole
0% by weight or more of an epoxy resin molding material for sealing,

Embedded image (Here, m in the formula (I) is an integer of ¹ to 10, and R ¹ to
R ⁴ is selected from an alkyl group and an aryl group having 1 to 12 carbon atoms which may have a substituent, and all may be the same or different, but at least one is a group having a hydroxyl group;
A represents an alkylene group having 1 to 4 carbon atoms or an arylene group. N in the formula (II) is an integer of 1 to 10, and R ^{5 to} R ⁸ are selected from an alkyl group or an aryl group having 1 to 4 carbon atoms which may have a substituent. Well,
A represents an alkylene group having 1 to 4 carbon atoms or an arylene group. (2) (A) an epoxy resin having two or more epoxy groups in one molecule, (B) a compound having two or more phenolic hydroxyl groups in one molecule, and (C) a compound having the following formula in the main chain skeleton. (II
A cyclic phosphazene compound containing (I) and / or the following formula (IV) as a repeating unit and (D) an inorganic filler are essential components, and the content of the (D) component is 70% based on the whole molding material.
% By weight or more, an epoxy resin molding material for sealing,

Embedded image (Where m in the formula (III) is an integer of ¹ to 10, and R ¹ to
R ⁴ is selected from an alkyl group and an aryl group having 1 to 12 carbon atoms which may have a substituent, and all may be the same or different, but at least one is a group having a hydroxyl group;
A represents an alkylene group having 1 to 4 carbon atoms or an arylene group. N in the formula (IV) is an integer of 1 to 10, and R ^{5 to} R ⁸ are selected from an alkyl group or an aryl group having 1 to 12 carbon atoms which may have a substituent. A represents an alkylene group having 1 to 4 carbon atoms or an arylene group. (3) The encapsulation according to the above (1), wherein the component (C) is a cyclic phosphazene compound containing the following formula (V) and / or the following formula (VI) as a repeating unit in the main chain skeleton. Epoxy resin molding material,

Embedded image (Here, m in the formula (V) in an integer from 1 to 10, R ⁹ ~
R ¹² is selected from hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group, an aryl group, a hydroxyl group, an amino group, and an epoxy group, all of which may be the same or different, but at least one of them represents a hydroxyl group. N in the formula (VI) is an integer of 1 to 10, and R ^{13 to} R ¹⁶ are selected from hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group, an aryl group, a hydroxyl group, an amino group, and an epoxy group. They may be the same or different. (4) The epoxy for sealing according to the above (2), wherein the component (C) is a cyclic phosphazene compound containing the following formula (VII) and / or (VIII) as a repeating unit in the main chain skeleton. Resin molding materials,

Embedded image (Here, m in the formula (VII) in an integer from 1 to 10, R ⁹ ~
R ¹² is selected from hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group, an aryl group, a hydroxyl group, an amino group, and an epoxy group, all of which may be the same or different, but at least one of them represents a hydroxyl group. N in the formula (VIII) is an integer of 1 to 10, R ^{13 to} R ¹⁶ are hydrogen, an alkyl group having 1 to 4 carbon atoms,
It is selected from an alkoxyl group, an aryl group, a hydroxyl group, an amino group, and an epoxy group, and all may be the same or different. (5) ^One of R ^{1 to} R ⁴ in formulas (I) to (IV) contained in the main chain skeleton of the component (C) is a hydroxyphenyl group, the other three are phenyl groups, ^The above (1) or (2), wherein all of ^{5 to} R ⁸ are phenyl groups and A is a phenylene group.
(6) The molar ratio (m / n) of the formulas (I) to (VIII) contained in the main chain skeleton of the component (C) is 1/0 to 1; The epoxy resin molding material for sealing according to any one of the above (1) to (5), wherein the content of the component (C) is not more than the inorganic filler (D). The epoxy resin molding material for sealing according to any one of the above (1) to (6), wherein the amount of the phosphorus atom is 0.2 to 5.0% by weight with respect to (8) (A) The epoxy resin molding material for sealing according to any one of the above (1) to (7), wherein the component contains an epoxy resin represented by the following formula (IX):

Embedded image (Here, n represents 0 to 3, and R ^{17 to} R ²⁰ are selected from hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkoxyl group, an aryl group and an aralkyl group, all of which may be the same or different.) (9) An electronic component device including an element sealed with the sealing epoxy resin molding material according to any one of (1) to (8).

[0006]

DETAILED DESCRIPTION OF THE INVENTION (A) used in the present invention
The epoxy resin having two or more epoxy groups in one molecule of the component is not particularly limited as long as the epoxy resin is generally used in an epoxy resin molding material for sealing. Resins, novolak resins of phenols and aldehydes such as ortho-cresol novolak epoxy resins, epoxidized bisphenol A, bisphenol F, bisphenol S, diglycidyl ethers such as alkyl-substituted or unsubstituted biphenols, diaminodiphenylmethane Glycidylamine type epoxy resin obtained by reaction of polyamine such as isocyanuric acid and epichlorohydrin, epoxidized product of cocondensation resin of dicyclopentadiene and phenol, trimethylolpropane type epoxy resin, ter Down-modified epoxy resins, linear aliphatic epoxy resins obtained by oxidizing with a peracid such as peracetic acid an olefinic bond, and an alicyclic epoxy resins.
They may be used alone or in combination of two or more. Among them, biphenyl diepoxy resins represented by the following general formula (IX) are preferable from the viewpoint of adhesiveness and hygroscopicity. Thereby, a molding material having excellent reflow crack resistance and moisture resistance can be obtained.

[0007]

Embedded image (Here, n represents 0 to 3, and R ^{17 to} R ²⁰ are selected from hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkoxyl group, an aryl group and an aralkyl group, all of which may be the same or different.) For example, 4,4'-bis (2,3-epoxypropoxy) biphenyl and 4,4'-bis (2,3-epoxypropoxy) -3,3 ', 5,5'-tetramethylbiphenyl An epoxy resin containing a main component is exemplified, and among them, an epoxy resin containing 4,4′-bis (2,3-epoxypropoxy) -3,3 ′, 5,5′-tetramethylbiphenyl as a main component is preferable. When this biphenyl type diepoxy resin is used, its blending amount is preferably at least 60% by weight based on the total amount of the epoxy resin. If it is less than 60% by weight, the epoxy resin has low moisture absorption,
This is because the feature of high adhesiveness is not exhibited, and the effect on solder resistance is small.

[0008] One of the components (B) used in the present invention
Compounds having two or more phenolic hydroxyl groups in the molecule include phenols such as phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F and naphthols such as α-naphthol, β-naphthol and dihydroxynaphthalene. And a resin obtained by condensing or co-condensing aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and salicylaldehyde under an acidic catalyst, a polyparavinylphenol resin, a xylylene group synthesized from phenols and dimethoxyparaxylene And a phenol aralkyl resin having the formula (1), which may be used alone or in combination of two or more.

The equivalent ratio of the epoxy resin of the component (A) to the phenol compound of the component (B) and the cyclic phosphazene compound of the component (C) (the sum of the number of hydroxyl groups in the component (B) and the number of hydroxyl groups in the component (C) / The number of epoxy groups (A) is not particularly limited, but is preferably set in the range of 0.7 to 1.3 in order to reduce the amount of unreacted components.

[0010] A curing accelerator for accelerating the curing reaction between the epoxy resin and the phenol resin can be used as required. As this curing accelerator, for example, 1,8
-Diazabicycloalkenes and derivatives thereof such as diazabicyclo (5,4,0) undecene-7 and tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol and tris (dimethylaminomethyl) phenol Imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole and 2-heptadecylimidazole; organic phosphines such as tributylphosphine, methyldiphenylphosphine and triphenylphosphine; and tetraphenylphosphonium. Tetra-substituted phosphonium / tetra-substituted borate such as tetraphenyl borate, 2-ethyl-4-methylimidazole / tetraphenyl borate, N-methylmorpholine / tetraphenyl borate And the like tetraphenyl boron salts bets like.

The cyclic phosphazene compound of the component (C) used as a flame retardant in the present invention has the following formula (I) and / or the following formula (II) in the main chain skeleton or the substitution position with respect to the phosphorus atom in the fazene ring. Is a compound containing different formulas (III) and / or (IV) as repeating units.

Embedded image

Embedded image Here, m in the formulas (I) and (III) is an integer of 1 to 10, and R ^{1 to} R ⁴ have 1 to 12 carbon atoms which may have a substituent.
And all may be the same or different, but at least one is a group having a hydroxyl group, and A represents an alkylene group having 1 to 4 carbon atoms or an arylene group. In the formulas (II) and (IV), n is an integer of 1 to 10, and R ^{5 to} R ⁸ have 1 to 1 carbon atoms which may have a substituent.
2 alkyl groups or aryl groups, all of which may be the same or different, and A represents an alkylene group having 1 to 4 carbon atoms or an arylene group. In the formula, m R ¹ , R ² ,
R ³ and R ⁴ may all be the same or different, and n
R ⁵ , R ⁶ , R ⁷ , and R ⁸ may all be the same or different.

In the above formulas (I) to (IV), R ¹ to
The alkyl or aryl group having 1 to 12 carbon atoms which may have a substituent represented by R ⁸ is not particularly limited,
For example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, te
alkyl group such as rt-butyl group, phenyl group, 1-naphthyl group, aryl group such as 2-naphthyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,3-xylyl group, 2, 4-xylyl group, o-cumenyl group, m-cumenyl group, p-cumenyl group, alkyl-substituted aryl groups such as mesityl group, benzyl group, aryl-substituted alkyl groups such as phenethyl group, and the like. Examples of the substituent to be substituted include an alkyl group, an alkoxyl group, an aryl group, a hydroxyl group, an amino group, an epoxy group, a vinyl group, a hydroxyalkyl group, and an alkylamino group. Among them, an aryl group is preferable from the viewpoint of heat resistance and moisture resistance of the epoxy resin molding material, and a phenyl group or a hydroxyphenyl group is more preferable. Among them, at least one of R ^{1 to} R ⁴ is preferably a hydroxyphenyl group, and all of R ^{1 to} R ⁸ may be a hydroxyphenyl group, but one of R ^{1 to} R ⁴ may be a hydroxyphenyl group. More preferred. When all of R ^{1 to} R ⁸ are hydroxyphenyl groups, the cured epoxy resin tends to be brittle, and when all of R ^{1 to} R ⁸ are phenyl groups, they are not incorporated into the crosslinked structure of the epoxy resin. Is likely to have reduced heat resistance. Further, the above formulas (I) to
The alkylene group having 1 to 4 carbon atoms or the arylene group represented by A in the formula (IV) is not particularly limited. Examples thereof include a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, an isobutylene group, and a phenylene group. Groups, a tolylene group, a xylylene group, a naphthylene group and the like. From the viewpoint of heat resistance and moisture resistance of the epoxy resin molding material, an allylene group is preferable, and a phenylene group is more preferable.

The cyclic phosphazene compound of the component (C) is
A polymer of any of the above formulas (I) to (IV), a copolymer of the above formula (I) and the above formula (II), or a polymer of the above formula (II)
It is a copolymer of I) and the above formula (IV). In the case of a copolymer, even a random copolymer or a block copolymer,
Any of alternating copolymers may be used. Its copolymer molar ratio m /
n is not particularly limited, but is preferably 1/0 to 1/4, more preferably 1/0 to 1 / 1.5 from the viewpoint of improving the heat resistance and strength of the cured epoxy resin. Further, the degree of polymerization m + n is 1 to 20, preferably 2 to 8, and more preferably 3 to 6.

Preferred examples of the cyclic phosphazene compound as the component (C) of the present invention include a polymer represented by the following formula (X) and a copolymer represented by the following formula (XI).

Embedded image (Here, m in the formula (X) is an integer of 0 to 9, and R ¹ to
R ⁴ each independently represents hydrogen or a hydroxyl group. )

Embedded image Here, m and n in the above formula (XI) are integers of 0 to 9,
R ^{1 to} R ⁴ are each independently selected from hydrogen or a hydroxyl group and at least one is a hydroxyl group, and R ^{5 to} R ⁸ are each independently selected from hydrogen or a hydroxyl group. In addition, the above formula (X
The cyclic phosphazene compound represented by I) has the following m repeating units (a) and n repeating units (b)
May be included alternately, in a block, or randomly, but is preferably included at random.

Embedded image Among them, one having one of R ^{1 to} R ^{4 in} the above formula (X) and a polymer having m of 3 to 6 as a main component or ^one of R ^{1 to} R ^{4 in} the above formula (XI). One is a hydroxyl group, R ^{5 to} R ⁸ are all hydrogen or one is a hydroxyl group, and m / n is 1/2 to 1/1 /
3, those having a copolymer in which m + n is 3 to 6 as a main component are preferable.

The amount of the cyclic phosphazene compound of the component (C) is 0.2 to 5.0% by weight based on all the other components except the inorganic filler of the component (D). It is preferably within the range, more preferably 1.0 to 3.0.
% By weight. When the amount is less than 0.2% by weight, the flame retardant effect is not exhibited, and when the amount is more than 5.0% by weight, the moisture resistance tends to be lowered.

In the present invention, the use of the cyclic phosphazene compound of the component (C) containing a specific repeating unit in the main chain skeleton enables excellent reliability and moldability to be achieved,
An object of the present invention is to provide a non-antimony and flame-retardant epoxy resin molding material for sealing. It is generally known that the combined use of a phosphorus compound and a nitrogen compound is good for flame retardancy.However, the present invention relates to the use of a phosphorus atom as a flame retardant component of a sealing epoxy resin molding material capable of exhibiting excellent reliability. It is intended to provide a compound containing both nitrogen atoms in the structure.

It is necessary to use an inorganic filler as the filler from the viewpoint of reducing the hygroscopicity and improving the strength.
The inorganic filler as the component (D) in the present invention is not particularly limited, and examples thereof include powders of fused silica, crystalline silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, boron nitride, beryllia, zirconia, and the like. ,
Alternatively, one or more kinds of spherical beads, potassium titanate, silicon carbide, silicon nitride, single crystal fiber such as alumina, glass fiber, and the like may be used. Further, examples of the inorganic filler having a flame-retardant effect include aluminum hydroxide, magnesium hydroxide, and zinc borate. These may be used alone or in combination. Among the above inorganic fillers, from the viewpoint of reducing the linear expansion coefficient, fused silica,
Alumina is preferred from the viewpoint of high thermal conductivity, and the shape of the filler is preferably spherical from the viewpoint of fluidity during molding and mold abrasion. The compounding amount of the inorganic filler is required to be 70% by weight or more, and preferably 80 to 95% by weight, from the viewpoints of hygroscopicity, reduction of linear expansion coefficient and improvement of strength.

Other additives include release agents such as higher fatty acids, higher fatty acid metal salts, ester waxes and polyolefin waxes, coloring agents such as carbon black, epoxy silane, amino silane, ureido silane, vinyl silane, alkyl silane and mercapto. Coupling agents such as silane, organic titanate, and aluminum alcoholate can be used.

The molding material in the present invention can be prepared by any method as long as various raw materials can be uniformly dispersed and mixed. As a general method, a predetermined amount of raw materials are sufficiently mixed by a mixer or the like. After mixing, melt-kneading with a mixing roll, extruder, etc., cooling,
A pulverizing method can be used.

For supporting members such as lead frames, wired tape carriers, wiring boards, glass and silicon wafers,
Electronic components mounted with active elements such as semiconductor chips, transistors, diodes, thyristors, etc., and passive elements such as capacitors, resistors, coils, etc., and sealing necessary parts with the molding material for sealing of the present invention. The device can be manufactured. An example of such an electronic component device is a TCP in which a semiconductor chip connected to a tape carrier by a bump is sealed with the molding material of the present invention. Also, active elements such as semiconductor chips, transistors, diodes, thyristors, and / or passive elements such as capacitors, resistors, and coils are connected to wiring formed on a wiring board or glass by wire bonding, flip chip bonding, soldering, or the like. Is sealed with the molding material of the present invention.
A B module, a hybrid IC, a multi-chip module, and the like can be given. As a method for sealing the electronic component device, a low-pressure transfer molding method is most common, but an injection molding method, a compression molding method, or the like may be used.

[0021]

Next, the present invention will be described with reference to examples, but the scope of the present invention is not limited to these examples.

Synthesis Example 1 (Synthesis of cyclic phosphazene compound 1) 15.0 g (0.043 mol) of hexachlorocyclotriphosphazene and 12.1 g of phenol were placed in a 1-liter four-necked flask equipped with a stirrer, a condenser and a thermometer.
(0.13 mol), 89.0 g of potassium carbonate (0.64
Mol) and 800 ml of acetone, and refluxed for 48 hours on an oil bath at 60 to 70 ° C. Thereafter, 72.0 g (0.65 mol) of hydroquinone and 10.0 g (0.031 mol) of tetrabutylammonium bromide were added, and the mixture was refluxed for 55 hours. After the reaction, potassium carbonate was filtered, and then acetone as a solvent was distilled off under reduced pressure. The obtained product is neutralized with dilute hydrochloric acid, washed with water, and dried at room temperature under reduced pressure. The following formula (XII) and the following formula (X
A cyclic phosphazene compound 1 containing III) as a repeating unit was obtained. The yield of compound 1 was 88%, and the hydroxyl equivalent measured by the acetic anhydride-pyridine method was 676.

Embedded image (Here, one of R ^{1 to} R ⁴ is a hydroxyl group and the remaining three are hydrogen, and m and n are each an integer of 1 to 10.) Synthesis Example 2 (Synthesis of cyclic phosphazene compound 2) In a 1 liter four-necked flask equipped with a condenser and a thermometer, 15.0 g (0.043 mol) of hexachlorocyclotriphosphazene and 14.2 g of phenol were added.
(0.15 mol), 89.0 g of potassium carbonate (0.64
Mol) and 800 ml of acetone, and refluxed for 22 hours on an oil bath at 60 to 70 ° C. Thereafter, 59.4 g (0.54 mol) of hydroquinone and 10.0 g (0.031 mol) of tetrabutylammonium bromide were added, and a reflux reaction was further performed for 90 hours. After the reaction, potassium carbonate was filtered, and then acetone as a solvent was distilled off under reduced pressure. The obtained product is neutralized with dilute hydrochloric acid, washed with water, and dried under reduced pressure at room temperature to obtain a cyclic phosphazene compound 2 in the form of a powder containing the above formula (XII) and the above formula (XIII) as a repeating unit in a skeleton. Was. The yield of compound 2 was 85% and acetic anhydride-
The hydroxyl equivalent measured by the pyridine method was 1,300. Synthesis Example 3 (Synthesis of cyclic phosphazene compound 3) 15.0 g (0.043 mol) of hexachlorocyclotriphosphazene and 20.4 g of phenol were placed in a 1-liter four-necked flask equipped with a stirrer, a condenser, and a thermometer.
(0.22 mol), 89.0 g of potassium carbonate (0.64 mol)
Mol) and 800 ml of acetone, and refluxed for 31 hours on an oil bath at 60 to 70 ° C. Thereafter, 23.9 g (0.22 mol) of hydroquinone and 10.0 g (0.031 mol) of tetrabutylammonium bromide were added, and the mixture was refluxed for 55 hours. After the reaction, potassium carbonate was filtered, and then acetone as a solvent was distilled off under reduced pressure.
The obtained product was neutralized with dilute hydrochloric acid. Further, the product is dissolved in acetone and then reprecipitated with water. The obtained product is washed with methanol, dried at room temperature under reduced pressure, and contains the above formula (XIII) as a repeating unit in a skeleton in a powder form. The cyclic phosphazene compound 3 was obtained. The yield of compound 3 is 2
At 0%, the melting point was 111 ° C.

Examples 1 to 6 Cresol novolak type epoxy resin having an epoxy equivalent of 200 and a softening point of 67 ° C., an epoxy equivalent of 188 and a melting point of 106
Biphenyl skeleton type epoxy resin (manufactured by Yuka Shell Epoxy; Epicoat YX-4000H), hydroxyl equivalent 10
6. Phenol novolak resin having a softening point of 83 ° C., hydroxyl equivalent 167, phenol aralkyl resin having a softening point of 70 ° C. (manufactured by Mitsui Toatsu; MILEX XL-225), triphenylphosphine, carnauba wax, carbon black, as a coupling agent As the γ-glycidoxypropyltrimethoxysilane, the fused silica, and the flame retardant, the compound (C) of the present invention and the compounds 1 to 3 obtained in the above Synthesis Examples 1 to 3 were added in the weight ratio shown in Table 1. Roll kneading was performed under the conditions of a kneading temperature of 80 to 90 ° C. and a kneading time of 10 minutes to produce molding materials of Examples 1 to 6.

Comparative Examples 1 and 2 In the same manner as in Example 1 except that a brominated bisphenol A type epoxy resin having an epoxy equivalent of 375, a softening point of 80 ° C., and a bromine content of 48% by weight and an antimony trioxide were used as flame retardants. The molding materials of Comparative Examples 1 and 2 were produced with the composition shown in Table 1.

[0025]

[Table 1]

The properties of the molding materials obtained in Examples and Comparative Examples were evaluated by the following methods. (1) Hot hardness Using a mold for forming a disk having a diameter of 100 mm and a thickness of 3 mm, using a transfer press at 180 ± 3 ° C and 6.9 ±.
A molding material is molded under the conditions of 0.17 MPa and 90 seconds, and the hardness of the molded product immediately after molding is measured by a Shore hardness tester (D type).
Determined by In addition, it is evaluated that the higher the value of the hardness at the time of heating, the better. (2) Water absorption 50 mm in diameter and 3 in thickness according to JIS-K-6911
mm disc, and prepared at 85 ° C. and 85% RH for 72 hours.
Humidification was performed for a period of time, and the weight was determined before and after humidification. (3) Adhesiveness A molding material was molded on a 30 μm aluminum foil by a transfer press under the conditions of 180 ± 3 ° C., 6.9 ± 0.17 MPa, 90 seconds, and then the aluminum foil was peeled in a 90 ° direction. The strength was measured. (4) Flame retardancy Using a mold for molding a test piece 1/16 inch thick,
180 ± 3 ° C, 6.9 ± 0.1 with transfer press
The molding material is molded under the conditions of 7 MPa and 90 seconds.
Post-curing was performed at 80 ± 5 ° C. for 5 hours. The evaluation followed the UL94 test method. (5) High temperature storage characteristics Line / space is 10 μm on a silicon substrate having an outer size of 5 × 9 (mm) and an oxide film of 5 μm.
Using a test element having an aluminum wiring formed thereon, it was connected to a 42-alloy lead frame partially plated with silver with a silver paste, and a thermosonic wire bonder was used to connect the alloy.
At 0 ° C, the bonding pads and inner leads of the device are Au
Connected by wire. After that, transfer molding
A pin-type DIP (Dual Inline Package) was prepared, and the obtained test IC was stored in a high-temperature bath at 200 ° C., taken out every predetermined time, and subjected to a continuity test to determine the number of defects. The IC package for evaluation was molded by a transfer press under the conditions of 180 ± 3 ° C., 6.9 ± 0.17 MPa, 90 seconds, and then cured at 180 ± 5 ° C. for 5 hours. . Table 2 shows the obtained evaluation results.

[0027]

[Table 2]

In Examples 1 to 6 of the present invention, high-temperature storage characteristics are remarkably improved as compared with Comparative Examples 1 and 2 containing a brominated resin and an antimony compound. In particular, in Examples 4 to 6, the adhesiveness is good because the biphenyl skeleton type epoxy resin is used. All of the examples using the flame retardant of the present invention have good high-temperature storage characteristics and excellent flame retardancy, but compound 3 has no functional group capable of reacting with an epoxy group. In the case where it is used, as shown in Examples 3 and 6, the adhesiveness is improved, but the hardness when heated is slightly lowered. In addition, since Compound 1 and Compound 2 have a hydroxyphenyl group capable of reacting with an epoxy group, Examples 1, 2, 4, and 5 using the compound are particularly excellent in the balance between hardness when heated and adhesiveness.

[0029]

The epoxy resin molding material for encapsulating electronic parts obtained by the present invention can achieve flame retardancy with non-halogen and non-antimony as shown in the examples, and is used for electronic parts such as ICs and LSIs. Is sealed, the product is excellent in moldability, and a product having excellent reliability such as moisture resistance and high-temperature storage characteristics can be obtained, and its industrial value is great.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01L 23/29 H01L 23/30 R 23/31 (72) Inventor Shinsuke Hagiwara 48 Wadai, Tsukuba, Ibaraki, Hitachi F term in Tsukuba Development Laboratory, Kasei Kogyo Co., Ltd. (Reference) AB07 AD03 AD04 AD07 AD08 AD21 AF06 AF08 AH07 AH19 AJ07 AJ08 AK06 DA01 DA04 DC43 FA01 FA02 FA05 FA06 FB08 JA07 4M109 AA01 BA01 BA03 CA21 EA03 EB03 EB04 EB06 EB07 EB08 EB09 EB12 EC01 EC03 EC05

Claims (9)

[Claims] 1. An epoxy resin having two or more epoxy groups in one molecule, (B) a compound having two or more phenolic hydroxyl groups in one molecule, and (C) a compound having two or more phenolic hydroxyl groups in one molecule. A cyclic phosphazene compound containing the formula (I) and / or the following formula (II) as a repeating unit: (Here, m in the formula (I) is an integer of ¹ to 10, and R ¹ to
R ⁴ is selected from an alkyl group and an aryl group having 1 to 12 carbon atoms which may have a substituent, and all may be the same or different, but at least one is a group having a hydroxyl group;
A represents an alkylene group having 1 to 4 carbon atoms or an arylene group. N in the formula (II) is an integer of 1 to 10, and R ^{5 to} R ⁸ are selected from an alkyl group or an aryl group having 1 to 12 carbon atoms which may have a substituent. A represents an alkylene group having 1 to 4 carbon atoms or an arylene group. (D) an inorganic filler, which is an essential component, wherein the content of the component (D) is 70% by weight or more based on the whole molding material; (A) an epoxy resin having two or more epoxy groups in one molecule; (B) a compound having two or more phenolic hydroxyl groups in one molecule; and (C) a compound having two or more phenolic hydroxyl groups in one molecule. A cyclic phosphazene compound containing the formula (III) and / or the following formula (IV) as a repeating unit: (Where m in the formula (III) is an integer of ¹ to 10, and R ¹ to
R ⁴ is selected from an alkyl group and an aryl group having 1 to 12 carbon atoms which may have a substituent, and all may be the same or different, but at least one is a group having a hydroxyl group;
A represents an alkylene group having 1 to 4 carbon atoms or an arylene group. N in the formula (IV) is an integer of 1 to 10, and R ^{5 to} R ⁸ are selected from an alkyl group or an aryl group having 1 to 12 carbon atoms which may have a substituent. A represents an alkylene group having 1 to 4 carbon atoms or an arylene group. (D) an inorganic filler, which is an essential component, wherein the content of the component (D) is 70% by weight or more based on the whole molding material; 3. The encapsulation according to claim 1, wherein the component (C) is a cyclic phosphazene compound containing the following formula (V) and / or (VI) as a repeating unit in the main chain skeleton. Epoxy resin molding material. Embedded image (Here, m in the formula (V) in an integer from 1 to 10, R ⁹ ~
R ¹² is selected from hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group, an aryl group, a hydroxyl group, an amino group, and an epoxy group, all of which may be the same or different, but at least one of them represents a hydroxyl group. N in the formula (VI) is an integer of 1 to 10, and R ^{13 to} R ¹⁶ are selected from hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group, an aryl group, a hydroxyl group, an amino group, and an epoxy group. They may be the same or different. ) 4. The encapsulation according to claim 2, wherein the component (C) is a cyclic phosphazene compound containing the following formula (VII) and / or (VIII) as a repeating unit in the main chain skeleton. Epoxy resin molding material. Embedded image (Here, m in the formula (VII) in an integer from 1 to 10, R ⁹ ~
R ¹² is selected from hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group, an aryl group, a hydroxyl group, an amino group, and an epoxy group, all of which may be the same or different, but at least one of them represents a hydroxyl group. N in the formula (VIII) is an integer of 1 to 10, R ^{13 to} R ¹⁶ are hydrogen, an alkyl group having 1 to 4 carbon atoms,
It is selected from an alkoxyl group, an aryl group, a hydroxyl group, an amino group, and an epoxy group, and all may be the same or different. ) 5. ^One of R ^{1 to} R ⁴ in formulas (I) to (IV) contained in the main chain skeleton of the component (C), one is a hydroxyphenyl group, the other three are phenyl groups, R ⁵ all to R ⁸ is a phenyl group, a is an epoxy resin molding material for sealing according to claim 1 or claim 2, wherein a phenylene group. 6. The molar ratio (m / n) of the formulas (I) to (VIII) contained in the main chain skeleton of the component (C) is 1/0 to 1/1.
The epoxy resin molding material for sealing according to any one of claims 1 to 5, which is 4. 7. The content of the component (C) is from 0.2 to 0.2% of the total amount of the components except the inorganic filler (D).
The epoxy resin molding material for sealing according to any one of claims 1 to 6, wherein the amount is 5.0% by weight. 8. An epoxy resin molding material for sealing according to claim 1, wherein the component (A) contains an epoxy resin represented by the following formula (IX). Embedded image (Here, n represents 0 to 3, and R ^{17 to} R ²⁰ are selected from hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkoxyl group, an aryl group and an aralkyl group, all of which may be the same or different.) 9. An electronic component device comprising an element sealed with the sealing epoxy resin molding material according to any one of claims 1 to 8.