JPH0653789B2 - Epoxy resin composition and semiconductor device - Google Patents

Description

TECHNICAL FIELD The present invention relates to an epoxy resin composition which is preferably used as a molding material, a powder coating material, a semiconductor encapsulating material, and the like, particularly a semiconductor encapsulating material, and the composition. The present invention relates to a semiconductor device sealed with the cured product.

Conventional technology and problems to be solved by the invention Epoxy resin and an epoxy resin composition in which an inorganic filler and the like are mixed are generally more moldable, adhesive, electrical, and mechanical properties than other thermosetting resins. Since it is excellent in moisture resistance and the like, it is widely used as various molding materials, powder coating materials, electrical insulating materials, etc., and in recent years, it has attracted attention as a semiconductor sealing material.

In this case, since various free impurities are present in the epoxy resin, it is necessary to reduce these impurities. However, since there is a limit to the reduction of hydrolyzable chlorine existing as a free impurity, it is difficult to satisfactorily prevent aluminum wiring corrosion when the epoxy resin composition is used as a semiconductor encapsulant. .

This aluminum wiring corrosion can be improved to some extent by using an organic phosphorus compound as a curing accelerator, but the degree of improvement is not sufficient.

In addition, the following general formula A _x O _y (NO ₃ ) _z (OH) _w · h (H ₂ O) (wherein A represents one or two or more trivalent to pentavalent transition metals, x = 1 to 5, y = 1 to 7, z = 0.2 to 3,
w = 0.2-3 and n = 0-2. ), The average particle size is 5 microns or less and the maximum particle size is 30
An epoxy resin composition in which a hydrolyzable chlorine concentration is reduced by incorporating an inorganic ion exchanger having a particle size of not more than a micron has been proposed. However, when this epoxy resin composition is incorporated with an organic phosphorus compound as a curing accelerator, As the curability deteriorates, it becomes difficult to capture chlorine ions satisfactorily, and in this case also, the effect of preventing aluminum wiring corrosion is insufficient.

Therefore, in the epoxy resin composition, sufficient improvement of corrosion of the aluminum wiring of the cured product is desired.

The present invention has been made in view of the above circumstances, the concentration of free impurities such as hydrolyzable chlorine is low, and when used as a semiconductor encapsulant, a cured product with excellent curing and very little aluminum wiring corrosion is obtained. It is an object of the present invention to provide an epoxy resin composition to be given and a semiconductor device sealed with a cured product of the composition.

Means and Actions for Solving the Problem The present inventor has conducted extensive studies to achieve the above-mentioned object, and as a result, contains a curable epoxy resin, a curing agent, an inorganic filler, and an organic phosphorus compound as a curing accelerator. The epoxy resin composition has the following general formula (I) Sba _Bi b _O c (NO ₃ ) _d (OH) _e · f (H ₂ O) (I) (where a and b are 1 to 2, respectively, c is 4 to 10,
d is 0.02 or more and less than 0.1, e is 0.2 to 3, and f is 0.
~ Is a number of 2. When the inorganic ion exchanger represented by the formula (3) is blended in an amount of preferably 0.5% (% by weight, the same applies hereinafter) of the entire composition, the inorganic ion exchanger ensures that free impurities such as hydrolyzable chlorine and bromine are contained. An epoxy resin composition that can be captured and effectively suppresses aluminum wiring corrosion due to a cured product of the composition, has a good curability of the composition, and can be suitably used as a semiconductor encapsulant or the like can be obtained. Based on this finding, the present invention has been completed.

Therefore, the present invention provides an epoxy resin composition containing a curable epoxy resin, a curing agent, an inorganic filler, and an organic phosphorus compound as a curing accelerator, represented by the following general formula (I) Sb _a Bi _b O _c (NO ₃ ) _d (OH) _e · f (H ₂ O) (I) (where a and b are 1 to 2 respectively, c is 4 to 10,
d is 0.02 or more and less than 0.1, e is 0.2 to 3, and f is 0.
~ Is a number of 2. The present invention provides an epoxy resin composition comprising an inorganic ion exchanger represented by the formula (4) and a semiconductor device sealed with a cured product of the composition.

Hereinafter, the present invention will be described in more detail.

First, the curable epoxy resin constituting the composition of the present invention is an epoxy resin having two or more epoxy groups in one molecule, and this epoxy resin can be cured by various curing agents as described below. There are no particular restrictions on the molecular structure, molecular weight, etc., and various conventionally known compounds can be used. For example, an epoxy resin synthesized from epichlorohydrin and various novolac resins including bisphenol, an alicyclic epoxy resin,
An epoxy resin having a halogen atom such as chlorine or bromine atom introduced therein can be used.

Among these, substituted and unsubstituted novolac type epoxy resins and bisphenol A type epoxy resins are preferably used. You may use the said epoxy resin individually by 1 type or in mixture of 2 or more types.

When using the epoxy resin, a monoepoxy compound may be appropriately used in combination. Examples of the monoepoxy compound include styrene oxide, cyclohexene oxide, propylene oxide, methyl glycidyl ether, ethyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, octylene oxide, dodecene oxide and the like.

As the curing agent, an amine type curing agent represented by diaminodiphenylmethane, diaminodiphenylsul, metaphenylenediamine, etc., an acid anhydride type curing agent such as phthalic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, or phenol. Examples include phenol novolac curing agents having two or more hydroxyl groups in one molecule such as novolac and cresol novolac.

Further, in the present invention, an organic phosphorus compound is blended as a curing accelerator used for the purpose of accelerating the reaction between the above curing agent and an epoxy resin. Examples of the organic phosphorus compound include triphenylphosphine and tris (p- Anisyl) phosphine, tris (p-tolyl) phosphine, tetraphenylphosphine tetraphenylborate and the like can be mentioned.

The amount of the curing agent used is the amount usually used,
The compounding amount of the curing accelerator can be set within the usual range.

The inorganic filler used in the present invention is not limited in its type, and is appropriately selected depending on the application of the epoxy resin composition, for example, crystalline silica, natural silica such as amorphous silica, synthetic high-purity silica. , Synthetic spherical silica, talc,
One or more selected from mica, silicon nitride, boron nitride, alumina and the like can be used.

Further, the blending amount of the inorganic filler is preferably 100 to 1000 parts by weight, and more preferably 250 to 750 parts by weight, based on 100 parts by weight of the total amount of the epoxy resin and the curing agent. If the compounding amount is less than 100 parts by weight, the resulting epoxy resin composition may not have satisfactory results in terms of physical properties such as crack resistance, while if it exceeds 1000 parts by weight, the fluidity becomes poor and the inorganic filler May be difficult to disperse.

The composition of the present invention contains the above-mentioned epoxy resin, curing agent, curing accelerator and inorganic filler together with the following formula (I) Sb _a Bi _b O _c (NO ₃ ) _d (OH) _e · f (H ₂ O ) (I) (where a and b are 1-2, c is 4-10,
d is 0.02 or more and less than 0.1, e is 0.2 to 3, and f is 0.
~ Is a number of 2. ) The inorganic ion exchanger represented by

In this case, the inorganic ion exchanger of the formula (I) has an effect of trapping free impurity ions in the epoxy resin composition, and the number d of NO ₃ groups in the formula (I) is 0.02 or more and 0.1 or more.
It is less than 0.05, preferably more than 0.05 and less than 0.1. d is 0.
When it is less than 02, the impurity ions cannot be sufficiently captured, and when d is 0.1 or more, the curability of the composition is deteriorated. In addition, it is preferable that c is 5 to 8, e is 0.5 to 1.5, and f is 0.2 to 1 with respect to 1 and 2 of a and b in the formula (I). Specific examples include Sb ₂ Bi _1-2 O _6.8 (NO ₃ ) _0.08 (OH) _0.8 · 0.4H ₂ O.

Further, it is preferable that the inorganic ion exchanger of the formula (I) has an average particle size of 5 μm or less, particularly 0.1 to 2 μm in order to enhance the effect of trapping impurity ions.

Furthermore, the compounding amount of the inorganic ion exchanger is 0.
It is preferably 5% or more, particularly preferably 1 to 5%. If the blending amount is less than 0.5%, trapping of impurity ions may be insufficient.

The composition of the present invention may further contain various additives depending on the purpose, use, etc., if necessary. For example, waxes, release agents such as fatty acids such as stearic acid and metal salts thereof, pigments such as carbon black, dyes, antioxidants, flame retardants, surface treatment agents (γ-glycidoxypropyltrimethoxysilane, etc.) ), Various low-stress agents, other additives and the like can be added in usual amounts.

The composition of the present invention is prepared by uniformly stirring and mixing predetermined amounts of the above-mentioned components, and kneading with a kneader, roll, extruder or the like preheated to 70 to 95 ° C, cooling, and pulverizing. Obtainable. There is no particular limitation on the order of mixing the components.

INDUSTRIAL APPLICABILITY The epoxy resin composition of the present invention can be suitably used as a molding material and a powder coating material, as well as for sealing semiconductor devices such as ICs, LSIs, transistors, thyristors and diodes, and for manufacturing printed circuit boards. Can also be used effectively.

The semiconductor device can be sealed by a conventionally used molding method such as transfer molding, injection molding, or casting method. In this case, the molding temperature of the epoxy resin composition is 150
~ 180 ℃, post cure at 150 ~ 180 ℃ 2 ~
It is preferably carried out for 16 hours.

As described above, the epoxy resin composition of the present invention,
It rapidly cures to give a cured product with very little aluminum wiring corrosion, and can be suitably used as a sealing material for semiconductors, etc., and the semiconductor device sealed with the composition of the present invention is of high quality. .

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

In the following examples, all parts are parts by weight.

[Examples 1 and 2, Comparative Examples 1 to 3] Epoxidized cresol novolac resin (curable epoxy resin) having an epoxy equivalent of 200, phenol novolac resin having a phenol equivalent of 110, triphenylphosphine, 2-phenylimidazole, and the following formulas. The polysiloxane represented by the formula (1) and the inorganic ion exchanger shown below were used in the respective amounts shown in Table 1, and 10 parts of the brominated epoxy novolac resin and 1 part of antimony trioxide were used.
0 parts, 3-glycidoxypropyltrimethoxysilane 1.5 parts, wax E 1.5 parts, carbon black 1.
Epoxy resin compositions (Examples 1 and 2 and Comparative Examples 1 to 3) were produced by uniformly mixing and mixing the compound obtained by adding 0 parts and 300 parts of fused silica with a hot two-roll mill.

Inorganic ion exchanger A: Sb ₂ Bi _1.2 O _6.8 (NO ₃ ) _0.08 (OH) _0.8・ 0.4H ₂ O Inorganic ion exchanger B: Sb ₂ Bi _1.2 O _6.4 (NO ₃ ) _0.5 (OH) _0.9・ 0 .5H ₂ O inorganic ion exchanger C: Sb ₂ Bi _1.2 O _6.8 (OH) _0.8 · 0.5H _{2 For} these epoxy resin compositions, the following (a) to
Various tests of (e) were conducted.

The results are also shown in Table 1.

(A) Spiral flow value Using a mold conforming to the EMNI standard, 175 ° C, 70
It was measured under the condition of kg / cm ² .

(B) Hardness at heat 175 ° C, 70 kg / cm ² , according to JIS K6911,
A 10 × 4 × 100 mm bending bar was molded under the condition of a molding time of 2 minutes, and the hardness at the time of heating was measured by a Barcol hardness meter GY2J-935.
(Manufactured by Barber Coleman).

(C) After molding at a glass transition temperature of 175 ° C., 70 kg / cm ² and a molding time of 2 minutes,
Cured at 180 ° C for 4 hours, 4 mmφ x 1 of this cured product
5 minutes per minute with a dilatometer using a 5 mm test piece
The value when the temperature was raised at a rate of ° C was measured.

(D) Purity of extracted water 25 pieces of 50 mmφ × 3 mm test piece of cured product similar to (c)
The following tests were carried out for those that were deteriorated under conditions of 0 ° C. for 20 hours and those that were not deteriorated.

5g of powder crushed sample and passed through 70 mesh sieve
And 50 ml of pure water was put into a pressure vessel, and after 20 hours at 160 ° C., the extracted water was analyzed.

(E) 50% corrosion occurrence time 14pin DIP TE under the same molding and curing conditions as (c)
G element (aluminum wiring width: 5 macron) is sealed, 140
A pressure cooker test was carried out under the conditions of 85 ° C. and 85% RH, and the time at which the corrosion occurrence rate of aluminum wiring reached 50% was examined.

From the results shown in Table 1, it was confirmed that the composition of the present invention had good curability, had a low free impurity concentration and high purity, and the cured product had very little aluminum wiring corrosion.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number in the agency FI Technical indication location H01L 23/31 (72) Inventor Kazutoshi Tomiyoshi 2-13-1 Isobe, Annaka-shi, Gunma Shin-Etsu Gakukogyo Co., Ltd. Silicone Electronic Materials Research Laboratory (56) References JP-A-61-285242 (JP, A) JP-A-63-146917 (JP, A)

Claims (2)

[Claims] 1. An epoxy resin composition containing a curable epoxy resin, a curing agent, an inorganic filler, and an organic phosphorus compound as a curing accelerator is added to the following general formula (I) Sb _a Bi _b O _c (NO ₃ ) _d (OH) _e · f (H ₂ O) (I) (where a and b are 1 to 2 respectively, c is 4 to 10 and d is
Is 0.02 or more and less than 0.1, e is 0.2 to 3, and f is 0.
It is a number of two. ) An epoxy resin composition comprising an inorganic ion exchanger represented by: 2. A semiconductor device encapsulated with the cured product of the epoxy resin composition according to claim 1.