JP2001081157A - Epoxy resin composition for sealing semiconductor and semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition for sealing semiconductor, excellent in fluidity and mold filling property, and useful as a composition for electronic material by compounding an epoxy resin, a hardener of molecular weight control-type, an inorganic filler and optionally a hardening accelerator. SOLUTION: This resin composition comprises (A) an epoxy resin (e.g. a bisphenol), (B) a hardener of molecular weight control-type, for example, a phenolic multifunctional hardener of molecular weight control-type (e.g. a reaction product of a phenol with dicyclopentadiene, (C) an inorganic filler (e.g. clay, talc or alumina) and optionally (D) a hardening accelerator (e.g. triphenylphosphine or diazabicycloundecene). It is preferable that, in the above composition, the component B is contained in an amount of 0.3-1.5 equivalent to the epoxy group in the component A, the component C is 60-92 wt.% in the composition, and the component D is in an amount of 0.2-5.0 pts.wt. based on 100 pts.wt. of the component A.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxy resin composition having excellent fluidity and mold filling properties, which is used for a semiconductor sealing material.

[0002]

2. Description of the Related Art Epoxy resins are used for various electric and electronic parts because of their excellent heat resistance, electric properties, mechanical properties and the like. In particular, transistors, ICs, LSIs
As a sealing material for semiconductor elements such as the above, epoxy resin is mostly used. In recent years, with the trend of miniaturization of electronic and electric products, the miniaturization and thinning of semiconductor elements are progressing. However, when encapsulating small and thin semiconductor elements, the fluidity of the encapsulating resin composition is reduced. In addition, mold filling greatly affects the yield of semiconductor products. Under these circumstances, the fluidity of the resin composition for semiconductor encapsulation and mold filling properties are increasingly regarded as important, and the resin composition for semiconductor encapsulation having excellent fluidity and mold filling properties has been developed. Highly required.

[0003]

However, the combination of a novolak-type epoxy resin and a phenolic multifunctional curing agent, which are conventionally used for semiconductor encapsulation, has limitations in improving fluidity and mold filling. is there. Other properties (handling properties, reactivity, storage stability) for compositions with improved flowability and mold filling properties using other low-viscosity resins
There was a problem that was damaged.

[0004]

Means for Solving the Problems The present inventors have assiduously studied to achieve the above object, and have reached the present invention. That is, the present invention provides (1) an epoxy resin, b) a molecular weight-controllable curing agent, c) an inorganic filler, and d) a curing accelerator if necessary, comprising (2) b) The resin composition for semiconductor encapsulation according to the above (1), wherein the molecular weight controlling type curing agent is a molecular weight controlling type phenolic polyfunctional curing agent; The resin composition for semiconductor encapsulation according to the above (1) or (2), wherein the proportion of the total weight of the components having a binuclear body or less and the components having the nucleus or more is 55% by weight or less, (4) an inorganic filler The resin composition for semiconductor encapsulation according to any one of the above (1) to (3), wherein (1) to (5) are contained in an amount of 60 to 92% by weight in the composition. (4) A semiconductor device sealed with the resin composition for semiconductor sealing according to any one of (4).

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
In the following, w nucleus (w represents an integer) in the molecular weight control type curing agent of component b) refers to a phenolic polyfunctional curing agent containing w aromatic rings having hydroxyl groups bonded in one molecule. Represents the molecule that is being used. In the present invention, a preferred example of the aromatic ring is a benzene ring or a naphthalene ring.

The epoxy resin used in the present invention may be any one usually used for electric and electronic parts, and can be obtained by glycidylation of a compound having two or more phenolic hydroxyl groups. Specific examples of epoxy resins that can be used include bisphenols such as tetrabromobisphenol A, tetrabromobisphenol F, bisphenol A, tetramethylbisphenol F, bisphenol F, bisphenol S or bisphenol K, and biphenols such as biphenol or tetramethylbiphenol. Or hydroquinone, methylhydroquinone, dimethylhydroquinone,
Trimethylhydroquinone or di-ter. Hydroquinones such as butyl hydroquinone, or resorcinols such as resorcinol or methyl resorcinol, or catechols such as catechol or methyl catechol, or glycidylated compounds or phenols of dihydroxynaphthalenes such as dihydroxynaphthalene, dihydroxymethylnaphthalene or dihydroxydimethylnaphthalene or Condensates of naphthols with aldehydes, or condensates of phenols or naphthols with xylylene glycol, or condensates of phenols with isopropenylacetophenone, or reactants of phenols with dicyclopentadiene, or Glycidylated products of condensates of bismethoxymethylbiphenyl with naphthols or phenols are exemplified. These can be obtained commercially or by a known method.

The above phenols include phenol, cresol, xylenol, butylphenol, amylphenol, nonylphenol, catechol, resorcinol, methylresorcinol, hydroquinone,
Examples thereof include phenylphenol, bisphenol A, bisphenol F, bisphenol K, bisphenol S, biphenol, and tetramethylbiphenol.

Next, examples of naphthols include 1-naphthol, 2-naphthol, dihydroxynaphthalene, dihydroxymethylnaphthalene, dihydroxydimethylnaphthalene, trihydroxynaphthalene and the like.

Further, aldehydes include formaldehyde, acetaldehyde, propylaldehyde, butyraldehyde, valeraldehyde, caproaldehyde, benzaldehyde, chlorbenzaldehyde, bromobenzaldehyde, glyoxal, malonaldehyde, succinaldehyde, glutaraldehyde, adipine aldehyde, Merinaldehyde, sebacinaldehyde, acrolein, crotonaldehyde, salicylaldehyde, phthalaldehyde, hydroxybenzaldehyde, furfural, 3-furaldehyde, 3-methylfurfural, 5-methylfurfural, 5-ethylfurfural, 2-thiophene carboxyaldehyde, 3 -Thiophene carboxyaldehyde, 3-methyl-2-thiophene carboxyalde De, and the like. The epoxy resin used in the present invention is exemplified above, but is not limited thereto, and may be used alone or as a mixture of several kinds.

Further, since it is used for electricity and electronics,
Those having a low hydrolyzable chlorine concentration are preferred. That is, the epoxy resin is dissolved in dioxane, and the hydrolyzable chlorine is preferably 0.2% by weight or less, preferably 0.15% by weight, as defined by desorbed chlorine when treated with 1N KOH under reflux for 30 minutes. The following are more preferred.

The molecular weight-controlling curing agent of the present invention comprises a condensate of a phenol or naphthol with an aldehyde,
Or a condensate of phenols or naphthols with xylylene glycol or a condensate of phenols with isopropenyl acetophenone, or a reaction product of phenols with dicyclopentadiene, or bismethoxymethylbiphenyl with naphthols or phenols Can be obtained by column treatment or heat distillation under high vacuum.

When GPC (gel permeation chromatography, the same applies hereinafter) measurement is performed on the thus-obtained molecular weight-controlling curing agent, the total weight of the dinuclear component and the heptanuclear component is measured. The proportion is preferably 55% by weight or less, more preferably 50% by weight or less.

The phenols used as raw materials for the above curing agent include phenol, cresol, xylenol, butylphenol, amylphenol, nonylphenol, catechol, resorcinol, methylresorcinol, hydroquinone, phenylphenol, bisphenol A, bisphenol F and bisphenol K. , Bisphenol S, biphenol, tetramethylbiphenol and the like.

Next, examples of naphthols also used as a raw material of the curing agent include 1-naphthol, 2-naphthol, dihydroxynaphthalene, dihydroxymethylnaphthalene, dihydroxydimethylnaphthalene, trihydroxynaphthalene and the like.

The aldehydes also used as raw materials for the curing agent include formaldehyde, acetaldehyde, propylaldehyde, butyraldehyde, valeraldehyde, capraldehyde, benzaldehyde, chlorbenzaldehyde, bromobenzaldehyde, glyoxal, malonaldehyde, and succinaldehyde. , Glutaraldehyde, adipaldehyde, pimeraldehyde, sebacaldehyde, acrolein, crotonaldehyde, salicylaldehyde, phthalaldehyde, hydroxybenzaldehyde, furfural, 3-furaldehyde, 3-methylfurfural, 5
-Methylfurfural, 5-ethylfurfural, 2-
Examples thereof include thiophene carboxyaldehyde, 3-thiophene carboxyaldehyde, and 3-methyl-2-thiophene carboxyaldehyde.

[0016] The resin composition of the present invention may be used
The above-mentioned molecular weight control type curing agents can be used alone or as a mixture of several types. Further, it may be used in combination with another curing agent such as an amine type or an acid anhydride type. When used in combination, the proportion of the molecular weight-controlling curing agent is preferably at least 30% by weight, particularly preferably 4% by weight.
0% by weight or more is preferred.

The curing agent is used in an amount of usually 0.3 to 1.5 equivalents, preferably 0.1 equivalent to the epoxy group in the epoxy resin.
5-1.3 equivalents. In the case of 0.3 equivalent or less, the amount of unreacted epoxy groups increases, and in the case of 1.5 equivalents or more, the amount of unreacted curing agent increases, and thermal and mechanical properties when a cured product is reduced are preferable. Absent.

Specific examples of the curing accelerator used if necessary include phosphines such as triphenylphosphine and bis (methoxyphenyl) phenylphosphine; imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole; and trisdimethylamino. Tertiary amines such as methylphenol and diazabicycloundecene are exemplified.

The amount of the curing accelerator used is 10
The amount is usually 0.2 to 5.0 parts by weight, preferably 0.2 to 4.0 parts by weight, per 0 parts by weight.

The inorganic filler used in the present invention comprises:
Electric and electronic components may be used as long as they are used in the epoxy resin composition, and specific examples of inorganic fillers that can be used include calcium carbonate, clay, talc, diatomaceous earth, silica, aluminum nitride, silicon nitride, Alumina, magnesia, carborundum, diamond and the like are exemplified. In order to uniformly disperse the hard inorganic filler in the composition, kneading and mixing are preferably performed with a roll, a kneader or the like. Further, the resin composition for semiconductor encapsulation of the present invention, if necessary,
Pigments, release agents, flame retardants, silane coupling agents and the like can be added.

The resin composition for encapsulating a semiconductor of the present invention (hereinafter referred to as “resin composition”)
In the resin composition of the present invention), the content of the inorganic filler is optional, but if it is less than 60% by weight, the solder crack resistance is significantly reduced, and if it is more than 92% by weight, the viscosity of the composition is too high. Sharply increases, so that the molding characteristics are significantly reduced. Therefore, the content of the inorganic filler in the resin composition is preferably from 60 to 92% by weight.

The resin composition of the present invention can be obtained by uniformly mixing the components at a predetermined ratio. The resin composition of the present invention can be easily made into a cured product by a method similar to a conventionally known method. For example, an epoxy resin and a curing agent are previously melted at 100 ° C. to 200 ° C. at least one of the epoxy resin and the curing agent, and the other is dissolved in the melt. Fillers, and if necessary pigments,
It can be obtained by adding and mixing a release agent, a flame retardant, a silane coupling agent and the like and a curing accelerator. Also, optionally without a melting step epoxy resin, curing agent, inorganic filler, and if necessary curing accelerator, pigment,
Extruder for release agent, flame retardant, silane coupling agent, etc.
You may mix with a roll, a kneader, etc. The obtained resin composition is usually molded and cured by using a transfer molding machine or the like, and the performance is further improved by performing post-curing at 80 to 200 ° C. for 2 to 10 hours. When a liquid epoxy resin is used as the liquid encapsulant, the resin composition of the present invention can be mixed and produced at room temperature, or can be prepared in a form dissolved in a solvent. The semiconductor device of the present invention has a cured product sealed and cured with the resin composition of the present invention.
Examples of the semiconductor device include a DIP (dual inline package), a QFP (quad flat package), a BGA (ball grid array), a CSP (chip size package), and the like.

[0023]

The present invention will be described in more detail with reference to Synthesis Examples and Examples. Note that the present invention is not limited to these examples. Further, in the examples, the ratio of the total weight of components having two or less nuclei and components having seven or more nuclei, ICI viscosity, and softening point in GPC were measured under the following conditions.
In the examples, unless otherwise specified, parts are parts by weight.

(1) Proportion of total weight of dinuclear or less nucleus component and heptanuclear or more nucleus component of the curing agent A sample was analyzed by a GPC analyzer and determined from the area percentage of peaks corresponding to each component.

GPC analysis conditions Column: Shodex KF-803 (2) + KF-
802.5 (two) Column temperature: 40 ° C. Solvent: tetrahydrofuran Detection: UV (254 nm) Flow rate: 1 ml / min.

(2) ICI viscosity Melt viscosity in cone plate method at 150 ° C. Measurement machine: cone plate (ICI) high temperature viscometer (RESE)
ARCH EQUIPMENT (LONDON) LTD. : 3 (measurement range: 0 to 20 poise) Sample amount: 0.15 ± 0.01 (g).

(3) Softening point Measured by a method according to JIS K-7234.

Synthesis Example 1 A phenol novolak resin (PN-A) was obtained by subjecting phenol novolak to a column treatment. The softening point of the obtained phenol novolak is 81 ° C,
The ICI viscosity at 150 ° C. was 1.3 poise, and the ratio of the total weight of the components having two or less nuclei and the components having seven or more nuclei of the curing agent was 37% by weight.

Examples 1 and 2 and Comparative Examples 1 and 2 The compositions shown in the column of composition of the compositions in Table 1 were uniformly mixed with a mixing roll (90 ° C. before / 100 ° C. after) to obtain the resin of the present invention. A composition was obtained. This composition was crushed and tablets were obtained on a tablet machine. The fluidity (spiral flow value) and mold filling property of the obtained tablet were measured under the following conditions. Table 1 shows the results. In addition, the numerical value in the column of the composition of the composition in Table 1 represents part.

Flow conditions: Mold: conforming to EMMI-1-66 Mold temperature: 175 ° C. Transfer pressure: 70 kg / cm ² .

Evaluation condition of mold filling property Using the tablet, a lead frame (96 PinQ)
FP (Package size: 14 x 14 x 1.35 m thickness)
m, chip size: 7 × 7 × 0.4 mm thick) using a transfer molding machine (175 ° C. × 60 seconds).
Forty packages were prepared for one composition, and the external appearance of the package was visually observed. The external appearance favorable ratio (the ratio of the number of packages having no external appearance defects to the total number of packages) was 80.
% Or more, ○: good appearance ratio is 50% or more and less than 80% Δ,
An appearance good rate of 50% or less was evaluated as x. Table 1 shows the results.

Table 1 Example 1 Example 2 Comparative Example 1 Comparative Example 2 Composition of Formulation EOCN-1020-55 10.0-9.9-EOCN-1020-62-10.1-10.0 PN-A 5.2 5.2--PN--5.3 5.3 TPP 0.2 0.1 0.2 0.1 FB-74 58.8 58.8 58.8 58.8 ZA-30 25. 2 25.2 25.2 25.2 Release agent 0.3 0.3 0.3 0.3 KBM-303 0.3 0.3 0.3 0.3 Spiral flow value (cm) 114 102 88 80 Mold filling ○ ○ × ×

In Table 1, abbreviations indicate the following. EOCN-1020-55: o-cresol type epoxy resin (Nippon Kayaku Co., Ltd., epoxy equivalent: 194 g / e)
q. EOCN-1020-62: o-cresol type epoxy resin (Nippon Kayaku Co., Ltd., epoxy equivalent: 197 g / e)
q. PN-A: phenol novolak of controlled molecular weight obtained in Synthesis Example 1 PN: phenol novolak (hydroxyl equivalent: 103 g / e)
q, Nippon Kayaku Co., Ltd. 59% by weight of total weight of dinuclear or lower nucleus component and heptanuclear or higher component 59% TPP: Triphenylphosphine (Junsei Chemical Co., Ltd.) FB-74: Spherical silica (Asahi Denka Co., Ltd.) ZA-30: crushed silica (Tatsumori Co., Ltd.) Release agent: fine powder carnauba (Toa Kasei Co., Ltd.) KBM-303: silane coupling agent (Shin-Etsu Chemical Co., Ltd.)

[0034]

The resin composition containing the molecular weight-controlling curing agent of the present invention has excellent fluidity and mold filling properties, and is useful for electronic material compositions, particularly for semiconductor encapsulation.

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Claims (5)

[Claims] 1. A resin composition for semiconductor encapsulation comprising: a) an epoxy resin; b) a molecular weight-controlling curing agent; c) an inorganic filler; and, if necessary, d) a curing accelerator. 2. The resin composition for semiconductor encapsulation according to claim 1, wherein the molecular weight controlling type curing agent of b) is a molecular weight controlling type phenolic polyfunctional curing agent. 3. The proportion of the total weight of the dinuclear or lower nucleus component and the heptanuclear or higher nucleus component of the molecular weight control type curing agent of b) is 55% by weight.
The resin composition for semiconductor encapsulation according to claim 1 or 2, which is: 4. An inorganic filler comprising from 60 to 92% by weight of the composition.
The resin composition for semiconductor encapsulation according to any one of claims 1 to 3, wherein the resin composition is contained at a ratio of: 5. A semiconductor device encapsulated with the resin composition for semiconductor encapsulation according to claim 1.