JPH0977846A - Epoxy resin composition for semiconductor-sealing material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition giving cured products excellent in heat resistance and toughness and useful as a semiconductor-sealing material by compounding an epoxy resin having a specific structure, a curing agent and, if necessary, a curing accelerator. SOLUTION: This composition comprises (A) an epoxy resin produced by the reaction of 4,4'-dihydroxybenzophenone with an epichlorohydrin, preferably an epoxy resin of the formula (n is 0-10), (B) a curing agent (e.g. an aliphatic amine, aromatic amine or acid anhydride curing agent) as essential components and, if necessary, (C) a curing accelerator, and (D) a filler. The epoxy equivalent of the component A is preferably 163-350, especially preferably 163-300. The reaction for obtaining the component A is preferably performed e.g. by epoxidizing 1mol of 4,4'-dihydroxybenzophenone with 1.4-20mol of epichlorohydrin in the presence of a base at 20-120 deg.C for 2-7hr.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel and useful epoxy resin composition for semiconductor encapsulant, and more specifically, to an epoxy resin obtained by reacting 4,4′-dihydroxybenzophenone with epichlorohydrin. The present invention relates to a composition for providing a semiconductor encapsulating material having excellent heat resistance and toughness.

[0002]

BACKGROUND OF THE INVENTION Epoxy resins, when cured with various curing agents, generally become cured products having excellent mechanical properties, water resistance, chemical resistance, heat resistance, electrical properties, etc. It is used in a wide range of fields such as paints, laminates, molding materials, casting materials and semiconductor encapsulation materials.

The most general-purpose epoxy resins are liquid and solid bisphenol A type epoxy resins obtained by reacting bisphenol A with epichlorohydrin.
These give a cured product having excellent toughness, but since the number of glycidyl groups per molecule is not more than 2, the crosslink density is low and the cured product tends to be inferior in heat resistance.

In order to improve such defects, so-called polyfunctional epoxy resins such as novolac type epoxy resins are used. In these cases, although the heat resistance is certainly improved, the toughness is low. Have

[0005]

Therefore, it has been desired to develop an epoxy resin having both the toughness of the bisphenol A type epoxy resin and the heat resistance of the novolac type epoxy resin.

[0006]

In view of these circumstances, the inventors of the present invention have conducted diligent research for a tough epoxy resin composition such as a novolac type epoxy resin, and as a result, 4,4 '
-A composition prepared by reacting dihydroxybenzophenone with an epoxy resin obtained by reacting epichlorohydrin as an essential component, and mixing the epoxy resin component with a curing agent and, if necessary, a curing accelerator, as described above. We found that it has characteristics,
The present invention has been completed.

That is, the present invention contains an epoxy resin obtained by reacting 4,4'-dihydroxybenzophenone and epichlorohydrin, and a curing agent as essential components, which is an epoxy resin composition for semiconductor encapsulating materials. And an epoxy resin represented by the following general formula [II], and a curing agent as essential components.

[0008]

Embedded image

[N represents 0 to 10] ]

The epoxy resin used in the present invention is 4,4 '.
-Dihydroxybenzophenone, ie structural formula (I)

[0011]

Embedded image

It can be easily obtained by reacting the compound of formula (1) with epichlorohydrin in the presence of a base.

The reaction conditions in this case are the same as the conventional epoxy resin production conditions and are not particularly limited. For example, 1.4 to 20 mol of epichlorohydrin is added to 1 mol of 4,4′-dihydroxybenzophenone, and 20 to 120 mol of epichlorohydrin is added in the presence of a base.
The epoxidation can be carried out at a temperature of 2 to 7 hours.

The base used for the epoxidation is not particularly limited, but examples thereof include potassium hydroxide, sodium hydroxide, potassium carbonate and sodium carbonate. The structure of the epoxy resin obtained as described above is not particularly specified, but from the viewpoint of heat resistance, the epoxy equivalent is preferably 163 to 350, and particularly the epoxy equivalent is 163 to 300. The effect of improving heat resistance becomes remarkable. The specific structure of the obtained epoxy resin is represented by the following general formula [II],

[0015]

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[N represents 0 to 10] ] The epoxy resin shown by these is mentioned. Also in this case, n is 0 to 1.
In the case of 3, the heat resistance is good, and particularly n is 0 to 0.
In the case of 9, the effect is remarkable.

The molecular weight, epoxy equivalent, and softening point of such an epoxy resin can be adjusted by adjusting the excess ratio of the number of moles of epichlorohydrin to the number of moles of 4,4'-dihydroxybenzophenone.
That is, when the excess ratio of epichlorohydrin is decreased, the molecular weight of the epoxy resin is increased, and a cured product having high toughness is provided. is there. However, in general, if the excess ratio exceeds 8 times, it becomes difficult to obtain an epoxy resin that gives a cured product having more excellent heat resistance.
The excess rate is preferably 10 times or less.

The epoxy resin composition for semiconductor encapsulation material of the present invention contains an epoxy resin obtained by reacting 4,4'-side hydroxybenzophenone and shrimp chlorohydrin, a curing agent and essential components. Usually, the desired semiconductor encapsulating material can be easily obtained by mixing these components, the filler, and, if necessary, the curing accelerator by a known and commonly used method.

The curing agent used in the present invention is not particularly limited, and any compound commonly used as a curing agent for epoxy resins can be used. Aliphatic amines such as diethylenetriamine and trietherenetetramine can be used. , Aromatic amines such as metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, polyamide resins and modified products thereof, maleic anhydride, phthalic anhydride, hexahydrophthalic anhydride,
Acid anhydride curing agents such as pyromellitic dianhydride, polyhydric phenols, compounds having phenolic hydroxyl groups such as novolac resins, dicyandiamide, imidazole, BF
Examples include latent curing agents such as 3-amine complexes and guanidine derivatives.

The amount of the curing agent used is not particularly limited, but the number of epoxy groups contained in one molecule of the epoxy resin and the activity of amino groups or imino groups, phenolic hydroxyl groups, etc. in the curing agent. The amount is generally such that the number of hydrogen groups or the number of acid anhydride groups is around the equivalent.

When each of the above-listed compounds is used as a curing agent, it is often necessary to additionally use a curing accelerator. In such a case, a tertiary amine such as dimethylbenzylamine is used. , Imidazoles,
It is needless to say that all known and commonly used curing accelerators including various metal compounds can be used. The composition of the present invention may further contain, if necessary, various additives such as known and commonly used epoxy resins and fillers, colorants, release agents, silane coupling agents, and tar. , Pitch, amino resin, alkyd resin, phenol resin and the like can be used together.

Since the epoxy resin composition for semiconductor encapsulating material of the present invention is excellent in both heat resistance and toughness, characteristics such as solder crack resistance when resin-encapsulated electrical and electronic parts are manufactured are remarkable. Get better

[0023]

EXAMPLES The present invention will now be specifically described with reference to production examples, examples and comparative examples. In the following, all parts are parts by weight unless otherwise specified.

Production Example 1 214 g (1 mol) of 4,4′-dihydroxybenzophenone was dissolved in 740 g (8 mol) of epichlorohydrin, and then 440 g of 20% NaOH aqueous solution at 80 ° C. with stirring.
(2.2 mol) was added dropwise over 5 hours, and 490 g of toluene was added to the product obtained by distilling and collecting the excess epichlorohydrin to uniformly dissolve the product, and 160 g of water was added to wash the product, followed by oil-water separation. After removing water from the oil layer by azeotropic distillation, the mixture was filtered and toluene was further distilled off to obtain 310 g of an epoxy resin (a) having an epoxy equivalent of 180.

Preparation Example 2 324 g (3.5 mol) of epichlorohydrin was used.
305 g of epoxy resin (b) having an epoxy equivalent of 197 was obtained in the same manner as in Production Example 1 except that the above was changed to.

Production Example 3 214 g (1 mol) of 4,4'-dihydroxybenzophenone was dissolved in a mixture of 231 g (2.5 mol) of epichlorohydrin and 54 g of toluene, and then stirred under stirring 80
5% 440 g (2.2 mol) of 20% NaOH aqueous solution at
After dripping over a period of time, reacting for an additional 1 hour, discarding the aqueous layer, and distilling and collecting the excess epichlorohydrin, 490 g of toluene was then added and uniformly dissolved in the product obtained, and 160 g of water was added to wash with water. After that, oil-water separation was performed, water was removed from the oil layer by azeotropic distillation, filtration was performed, and toluene was further distilled off to obtain 300 g of an epoxy resin (c) having an epoxy equivalent of 208.

Examples 1 to 3 and Comparative Examples 1 to 2 Epoxy resins (a) to (c) obtained in Production Examples 1 to 3 as epoxy resin, phenol novolac type epoxy resin EPICLON N-738 (Dainippon Ink and Chemicals) Industrial Co., Ltd., epoxy equivalent 180) or bisphenol A
Type epoxy resin EPICLON 840 (manufactured by the same company, epoxy equivalent 185), EPICLONB-5 as a curing agent
70 (manufactured by the same company, methyltetrahydrophthalic anhydride),
2-Ethyl-4-methylimidazole was used as a curing accelerator, and the composition shown in Table 1 was added so that one acid anhydride of the curing agent was present for each epoxy group of the epoxy resin. An epoxy resin composition for comparison and control was obtained. These epoxy resin compositions were cured at 100 ° C. for 2 hours, then at 160 ° C. for 2 hours, and further at 180 ° C. for 2 hours to give test pieces, and JIS K-6911 was used.
The heat distortion temperature, flexural strength, flexural modulus, tensile strength, tensile strength, tensile elongation law and boiling absorption rate were measured in accordance with. The results are shown in Table 1.

[0028]

[Table 1]

[0029]

According to the present invention, a cured product having both the toughness of a conventional cured product of a bisphenol A type epoxy resin and the heat resistance of a cured product of a novolak type epoxy resin can be provided. Since it is superior to the epoxy resin, it is possible to provide a semiconductor-encapsulated cured product having both toughness and heat resistance.

Claims (5)

[Claims] 1. An epoxy resin composition for a semiconductor encapsulating material, which comprises, as essential components, an epoxy resin obtained by reacting 4,4′-dihydroxybenzophenone and epichlorohydrin, and a curing agent. 2. An epoxy resin composition for semiconductor encapsulation, which contains an epoxy resin represented by the following general formula [II] and a curing agent as essential components. Embedded image [N represents 0 to 10] ] 3. The epoxy equivalent of the epoxy resin is 163.
The composition of claim 1 or 2 which is 350. 4. The composition according to claim 1, 2 or 3, wherein the epoxy equivalent of all epoxy resin components of the composition is 163-350. 5. The composition according to claim 1, which further comprises a filler.