JPS6337118A - Epoxy resin composition for semiconductor encapsulation - Google Patents

Abstract

PURPOSE:To obtain the titled composition for sealing, coating and insulation of electronic parts, consisting of an epoxy resin, novolak phenol resin, specific terminal amine type imide compound and a specific amount of an inorganic filler and having excellent heat resistance. CONSTITUTION:The aimed composition containing 25-90wt% of (A) an epoxy resin (preferably o-cresol novolak type epoxy resin), (B) a novolak type phenolic resin, (C) a terminal amine type imide compound expressed by the formula (Ar1 and Ar2 are aromatic residue; R1 is H or 1-10C alkyl; R2 is H, 1-20C alkyl, alkoxy or OH; n is 0-80) and (D) an inorganic filler (preferably silica powder or alumina). The molar ratio [alpha/(beta+gamma)] of epoxy group (alpha) of component (A) to OH groups (beta) of component (B) and active hydrogen atoms (gamma) of component (C) is preferably 0.6-1.5.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention is an epoxy for semiconductor sealing with excellent heat resistance! ! :J
Concerning fatty acid products.

<Prior art and its problems> Conventionally, electronic components such as diodes, transistors, and integrated circuits have been encapsulated using thermosetting resin. This resin sealing pressure is widely used because it is more economical than hermetic sealing.

Among thermosetting resins, epoxy resins are most commonly used in terms of bone attachment, cost, and reliability. It's a great hardening agent! Novolac type phenolic resins are widely used because of their p-type properties, moisture resistance, reliability, etc.

However, compositions using novolac type phenolic resin as a curing agent have a drawback of being inferior in heat resistance due to the increased density of electronic components.

In order to improve the heat resistance of the cured product, it is conceivable to use an aromatic imide compound as a curing agent.

Aromatic imide compounds are generally produced using aromatic tetracarboxylic anhydride and aromatic diamine as raw materials,
Pyromellitic acid hydrothermal hydrate or benzophenone tetracarboxylic acid anhydride are well known as typical aromatic tetracarboxylic acids. However, the aromatic imide compounds obtained using these acid anhydrides have poor W solubility with epoxy resins, making it difficult to use them as curing agents for epoxy resins and improve their performance. .

Means for Solving the Problems> In view of the above, the present inventors conducted extensive studies on imide compounds with excellent solubility and compatibility, and found that they contain formula (II) in the molecule. where R1 is a hydrogen atom or has 1 to 1 carbon atoms
The alkyl group of θ, R2 is a hydrogen atom or has 1 to 2 carbon atoms
0 alkyl group, alkoxy group, or hydroxyl group. ] It has been found that an imide compound having a structural unit represented by the above is extremely easily soluble in an epoxy resin, and furthermore, the above-mentioned problem of low heat resistance can be solved by using the imide compound in combination with an epoxy resin; -Heading, leading to the present invention.

That is, the present invention provides (A) an epoxy resin, (B) a novolac type phenolic resin, and (C) a terminal amine type ionic compound represented by the general formula (in formula (I),
Ar1 and Ar2 are each independently an aromatic residue, R1
is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, B2
represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, or a hydroxyl group, and n represents an integer of θ to 30. ] CD) An epoxy resin composition for semiconductor encapsulation, which contains an inorganic filler as an essential component and contains 25 to 90 Ii weight percent of the inorganic filler based on the resin composition.

The (mu)epoxy resin used in the present invention is a compound having two or more epoxy groups in the molecule, and is not particularly limited, and can include a wide range of commonly used resins. For example, bisphenol A1, bisphenol F, hydroquinone, resorcinol, phloroglycin, tris-(
Derived from dihydric or tri(IIIi or higher) phenols such as 4-hydrodiphenyl)methane, 1,1.2.2-tetrakis(4-hydroxyphenyl)ethane, or halogenated bisphenols such as tetrabromobisphenol A. Glycidyl ether compounds, phenol, 0-cresol, etc. (7) Novolac-based epoxy tree IIL derived from novolak resin, which is a reaction product of phenols and formaldehyde 4, 4'-sia-mainly nodiphenylmethane, 4.4' - Amine-based epoxy resin derived from diamide, nodiphenyl ether, etc.
Examples include alicyclic epoxy resins such as vinyl cyclohexene oxide, 8゜4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and these epoxy resins can be used in combination of two or more. Particularly preferred is an 0-cresol novolac type epoxy resin.

(B) Novolac type phenol tMi used in the present invention
Examples of ll include novolac-type funol resins obtained by reacting phenols such as phenol and alkylphenols with formaldehyde or paraformaldehyde.

The (C) terminal amine type imide compound (formula (I)) used in the present invention will be explained.

In formula (I), Arl, Ar2, R1, R2, n
are as described above, and to explain in more detail Ar1 and Ar2, Ar1 and Ar2 are each independently a mononuclear or polynuclear divalent aromatic residue, and the aromatic ring is a lower alkyl group, a halogen, It includes substituted and unsubstituted lower alkoxy groups. More specifically, both Arl and Ar2 are residues of aromatic cyanine, and examples of the aromatic diamines include 4.4'-diaminodiphenylmethane, 8.8'-
Diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 8,4-diaminodiphenyl ether'
4e 4'-diaminodiphenylpropane, 4.4
'-Sia [nodiphenylsulfone, 8°8'-diaminodiphenylsulfone, 2,4-toluenediamine,
2.6-) Luenediamine, m-phenylenediamine,
P-phenylenediamine, benzidine, 4,4'-diaminodiphenyl sulfide, 8,8'-dichloro-4
, 4'-diaminodiphenylsulfone, 8, 8'
-dichloro-4,4'-diaminodiphenylpropane,
8.8'-dimethyl-4,4'-diaminodiphenylmethane, 8.8'-dimethoxy-4,4'-diaminobiphenyl, 8.8'-dimethyl-4,4'-diaminobiphenyl, 1,8-bis (4-a[nophenoxy)benzene, 1,8-bis(8-aminophenoxy)benzene, 1,4-bis(4-7minophenoxy)benzene, 2
．． 2-bis(4-aminophenoxyphenyl)propane, 4,4'-bis(4-aminophenoxy)diphenylsulfone, 4,4'-bis(8-aminophenoxy)diphenylsulfone, 9,9'-bis(4 −
aminophenyl)anthracene, 9,9'-bis(4-
(aminophenyl)fluorene, 8,8'-dicarboxy-4,4'-diaminodiphenylmethane, 2,4-diaminoanisole, bis(8-aminophenyl)methylphosphine oxide, 8,8'-diaminobenzophenone, 0-toluidine Sulfone, 4,4'-methylene-bis-lowchloroaniline, tetrachlorodiaminodiphenylmethane, m-xylylenediamine, p-xylylenediamine, 4,4'-diaminostilbene, 5-
Amino-1-(4'-aminophenyl-1,8,3-trimethylindane, 6-amino-1-(4'-aminophenyl)-1,8,8-trimethylindane, 5-amino-6-methyl -1-(8'-amino-4'-methylphenyl)-1,8,a-trimethylindane, 7-amino-6-methyl-1-(8'-amino-4'-methylphenyl)-1, 8,8-Trimethylindane, 6-amino-6-methyl-1-(4'-amino-8'-methylphenyl)-i,a,a-trimethylindane, 6-amino-6-methyl-1-(4' -amino-di-methylphenyl)-1,8,8-trimethylindane, or the like.

R1 and R2 are as described above, but R1 is particularly preferably an alkyl group having 1 to 1 o carbon atoms.

To illustrate the manufacturability of the terminal amino type imide compound [formula (I)] of the present invention, when Ar1 and Ar2 are different aromatic residues, the aforementioned aromatic diamine corresponding to Ar2 and the formula (IiI) [formula ( In m), the compound represented by R1 and 2 are the same as above] was made deficient in aromatic diamine to form the following compound formula (I
V) is produced, [Formula (■)] [In formula (IV), 1L1 + R2 is the same as above, Ar2 is an aromatic residue, and n represents an integer from θ to 80.

] Further, it can be obtained by reacting an aromatic diamine corresponding to a different Arl with the compound. Also, the formula (I
) in which A r 1 and M r 2 are the same aromatic residues, it can be produced by carrying out a normal imidization reaction with a compound of formula (Iff) using an excess of aromatic diamine.

To illustrate the method for synthesizing the acid anhydride represented by the formula CTfl), a compound represented by the formula: [In the formula, R1 and R2 are the same as described above. ] It is obtained by reacting maleic anhydride at a molar ratio of V2 in the absence of a radical polymerization catalyst and in the presence or absence of a radical polymerization inhibitor. Examples of compounds represented by formula (to) include styrene, α-methylstyrene, α
, P-dimethylstyrene, α9m-dimethylstyrene,
1 such as isopropylstyrene, vinyltoluene, P-t-butylstyrene, p-isopropenylphenol, m-isopropenylphenol, l-methoxy-8-isopropenylbenzene, 1-methoxy-4-isopropenylbenzene, vinylxylene, etc. There are one species or two or more species.

The terminal amine type imide compound of the present invention thus obtained has excellent compatibility with epoxy resins. Use 1 of the terminal amine type imide compound is 0.51 equivalent or less, preferably 0.8 ti equivalent or less, based on the epoxy resin 1i equivalent,
It is 0.05P equivalent or more. , 0.055' equivalent, the effect of improving heat resistance is poor;
If used in excess of y-equivalent, moldability will be impaired.

In addition, examples of inorganic fillers (CD) used in the present invention include silica powder, alumina, talc, calcium carbonate, titanium white, clay, mica, glass fiber, etc.
Particularly preferred are silica powder and alumina. Use side of inorganic filler (in case, 25 to 90% by weight of resin composition, 11%
It is.

If it is less than 25% by weight, moisture resistance, heat resistance, and moldability will decrease,
If it exceeds 90% by weight, moldability deteriorates and there is a practical problem.

The epoxy resin composition for semiconductor encapsulation of the present invention has the above-described (A) epoxy resin, (B) novolac type phenol resin, (C) terminal amine type imide compound, and CD) inorganic filler as essential components, and Natural waxes, synthetic waxes, stearic acid and its salts, release agents such as acid amides, flame retardants such as hexabromobenzene and antimony trioxide, colorants such as carbon black, coupling agents, tertiary amines, Curing accelerators such as imidazole compounds and triphenylphosphine can be added and blended as appropriate.

As a method for preparing the composition according to the present invention into a sealing material, heating bath Wi mixing is performed using a hot roll, a kneader, etc.
Next, it can be adjusted by cooling and solidifying it and then pulverizing it.

(Example) Hereinafter, the present invention will be explained in more detail with reference to Examples.The middle part of the example indicates part 11.

Reference example-1 A flask equipped with a stirrer, a thermometer, and a cooling aliquot device contains 4
．． 4'-diaminodiphenylmethane 29.7P(C,1
5 mol) and 1u-cresol 242? After dissolving diaminodiphenylmethane, 48.5P of xylene was added and the temperature was raised to 120°C. At this temperature, 1-methyl-
3,4-dicarboxy-1,2,8,4-tetrahydro-1-naphthaleneconollic acid anhydride 81.1'(C,1
mol) was added, the temperature was raised to 176°C, and the dehydration reaction was continued for 5 hours. After the reaction, the mixture was precipitated in a hexane/isopropanol mixture, washed twice in the same layer, and dried under reduced pressure to obtain an imide compound. The melting point of this product is 241°C, and the amine equivalent is 648 re (l).

Reference example-2 4,4'-diaminodiphenylmethane 29 of reference example-1
．． 71 (C, 15 mol) to 2.4-)luenediamine 2
A similar reaction was performed using 4.4F (C, 15 mol) to obtain an imide compound.

The melting point of this product is approximately 270°C, and the amine equivalent is 512 V.
6(l).

Examples-1 to 8 XI! Bo4shi E8CN-1'95xI, (o-cresol novolac type epoxy resin, epoxy equivalent weight 197P1
0 (1, Sumitomo Chemical Co., Ltd. product), a fu-nor novolac resin as a curing agent and the terminal amine type imide compound obtained in Reference Example 1 or 2, and 1,8-diazabicycloundecene (DBU) as a curing accelerator. ), carnauba wax as a mold release agent, and a silane coupling agent (Toshi Silicone 8H-6040) as a coupling agent.
), using fused silica as the filler and using the proportions shown in the table.
℃, mixed with two rolls for 5 minutes, cooled, and crushed to produce a sealing material. The sealing material was heated to 170°C, 70 K11512.
Transfer molding was carried out for 5 minutes, followed by post-curing in a 180° C. oven for 6 hours.

The physical properties of the cured product are shown in the table.

Comparative Example 1 A sealing material was produced, molded, and cured in the same manner as in Examples 1 to 8, except that the terminal amine type compound obtained in Reference Example 1 or 2 was not used. The physical properties of the cured product are shown in the table.

<Effects of the Invention> When the composition according to the present invention is applied to sealing, coating, insulating, etc. of electronic components, excellent heat resistance can be obtained.

The above examples also show that the cured product obtained using the epoxy resin composition according to the present invention has excellent heat resistance.

Claims (1)

[Claims] 1. (A) Epoxy resin (B) Novolak phenolic resin (C) General formula ▲ Numerical formula, chemical formula, table, etc. are available ▼ Terminal amine type imide compound represented by [Formula (I)] In formula (I), Ar_1 and Ar_2 are each independently an aromatic residue, and R_1 is a hydrogen atom or a carbon number of 1 to 10.
The alkyl group R_2 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, or a hydroxyl group, and n represents an integer of 0 to 80. (D) An epoxy resin composition for semiconductor encapsulation, which contains an inorganic filler as an essential component and contains 25 to 90% by weight of the inorganic filler based on the resin composition. 2. The epoxy group (a) of the epoxy resin, the phenolic hydroxyl group (b) of the novolak type phenolic resin, and the formula (
molar ratio of active hydrogen (c) in compound I) [a/(b+
c)] is within the range of 0.6 to 1.5, the epoxy resin composition for semiconductor encapsulation according to claim 1.