JP2001040186A - Epoxy resin composition for sealing semiconductor and semiconductor apparatus using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition excellent in adhesion, low hygroscopicity and stiffness against the surface of a semiconductor element by compounding a modified phenolic resin, a silane coupling agent having a glycidoxy group, an accelerator and an inorganic filler to an epoxy resin. SOLUTION: A modified phenolic resin used is obtained by melt-reacting a mixture of a phenolic resin composed of an epoxy resin represented by Formula I and a phenolic resin represented by Formulas II and III with a silane coping agent having a mercapto group. In Formula I, R is a 1-6C alkyl or a halogen; each (m) and (n) is 0-4; R' is H or a 1-4C alkyl, in Formula II, R is H, a 1-4C alkyl or a halogen; each (p) and (q) is a positive integer, and in Formula III, (r) is a positive number. A mixing ratio of the phenolic resin of the Formulas II and III is 8/2-2/8 (based on weight), and the silane coupling agent having the mercapto group is preferably 0.1-10 pts.wt. to 100 pts.wt. of the phenolic resin mixture.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is intended to significantly improve the adhesiveness to the surface of a semiconductor element, particularly to the element surface using a polyimide-based coating agent on the element surface. The present invention relates to an epoxy resin composition for semiconductor encapsulation having excellent toughness, and a semiconductor device using the same, particularly having high soldering resistance even in an ultra-thin package.

[0002]

2. Description of the Related Art Conventionally, transistors, ICs, and LSIs have been used.
Semiconductor elements such as are sealed with a plastic package or the like to form a semiconductor device from the viewpoint of protection from the external environment and easy handling of the semiconductor elements.
And, as a sealing material used for the plastic package, an epoxy resin composition is generally used,
In recent years, a sealing material using a biphenyl-based epoxy resin as an epoxy resin has been used to obtain excellent low moisture absorption.

[0003]

However, in a semiconductor device using a conventional epoxy resin composition, the adhesiveness between the cured body as a sealing resin and the surface of the semiconductor element is poor, and the semiconductor element is not sealed during solder mounting. There was a disadvantage that peeling occurred at the interface with the resin. Particularly in recent years, semiconductor devices are also becoming thinner. For example, in ultra-thin packages such as TSOP (Thin Small Outline Package) and TQFP (Think Quad Flat Package), an epoxy resin composition serving as a sealing material is used. The demand for soldering resistance is high, and there is a demand for a sealing material with lower moisture absorption and high adhesion. It is difficult for conventional sealing materials using a biphenyl-based epoxy resin to sufficiently meet the above requirements. Met.

The present invention has been made in view of such circumstances, and an epoxy resin composition for semiconductor encapsulation having excellent adhesiveness to a semiconductor element surface, low hygroscopicity and toughness, and an epoxy resin composition using the same are obtained. It is an object of the present invention to provide a semiconductor device having excellent solder resistance reliability.

[0005]

In order to achieve the above object, the present invention provides, as a first gist, an epoxy resin composition for semiconductor encapsulation containing the following components (A) to (E).

(A) An epoxy resin represented by the following general formula (1).

[0007]

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(B) a phenolic resin mixture comprising a phenolic resin represented by the following general formula (2) and a phenolic resin represented by the following general formula (3), and a silane coupling agent having a mercapto group: Is a modified phenolic resin curing agent obtained by a melt reaction of

[0009]

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[0010]

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(C) A silane coupling agent having a glycidoxy group. (D) a curing accelerator. (E) an inorganic filler.

A second aspect of the present invention is a semiconductor device in which a semiconductor element is resin-sealed using the above-described epoxy resin composition for semiconductor encapsulation.

The present inventors have conducted a series of studies to obtain an epoxy resin composition which is a sealing material having excellent adhesion to a semiconductor element and low moisture absorption and excellent toughness. As a result, when the epoxy resin represented by the general formula (1), which exhibits a lower hygroscopic property than the conventionally used biphenyl-based epoxy resin, is used, the sealing resin cured body and the semiconductor element and the lead frame can be separated. It was found that the adhesion was improved. As a result of further study, a mixture of the two specific phenolic resins and a silane coupling agent having a mercapto group are melt-mixed and reacted together with the epoxy resin represented by the above formula (1). When used in combination with a modified phenolic resin curing agent,
The inventors have found that the above-mentioned objects such as excellent toughness are achieved, and as a result, a semiconductor device having excellent soldering resistance can be obtained, and have reached the present invention. That is, of the modified phenol resin curing agent, the low hygroscopicity of the phenol resin represented by the above formula (2) and the toughness of the phenol resin represented by the above formula (3) are arbitrarily crosslinked. ,
The interaction between low hygroscopicity and toughness is obtained, and the effect of reinforcing the adhesiveness with a silane coupling agent having a mercapto group is obtained, and the above excellent toughness and adhesiveness, low hygroscopicity are obtained. It is thought that it will be able to be obtained.

[0014]

Next, embodiments of the present invention will be described in detail.

The epoxy resin composition for encapsulating a semiconductor according to the present invention is a modified phenol obtained by melting and reacting a specific epoxy resin (component A), a mixture of two specific phenolic resins and a specific silane coupling agent. Obtained using a resin curing agent (B component), a specific silane coupling agent (C component) different from the above silane coupling agent, a curing accelerator (D component), and an inorganic filler (E component). It is usually in the form of a powder or a tablet obtained by compressing the powder.

The specific epoxy resin (component A) is an epoxy resin represented by the following general formula (1).

[0017]

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In the general formula (1), n, m
Are each 0, it is an epoxy resin represented by the following general formula (1a).

[0019]

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Among the epoxy resins represented by the general formula (1), those in which R 'in the formula (1) is H are preferable, and from the viewpoint of low moisture absorption, the following formula (1) It is preferable to use an epoxy resin represented by the following formula (4) and a mixture of an epoxy resin represented by the following formula (4) and an epoxy resin represented by the following formula (5). Equation (4) above
In the mixture of the epoxy resin represented by the formula (5) and the epoxy resin represented by the formula (5), the mixing ratio is represented by a molar ratio [the epoxy resin represented by the formula (4)] / [the formula (5) Epoxy resin] = 7/3 to 5/5 is preferred.

[0021]

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[0022]

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The epoxy resin represented by the general formula (1) has an epoxy equivalent of 200 to 22.
It is preferably in the range of 0, and particularly preferably the epoxy equivalent is in the range of 205 to 215. The melting point is 1
The melting point is preferably in the range of 35 to 145 ° C, particularly preferably in the range of 130 to 140 ° C.

In the epoxy resin composition for semiconductor encapsulation of the present invention, the epoxy resin component may be composed of only the epoxy resin (component A) represented by the general formula (1), An epoxy resin component obtained by using a conventionally known epoxy resin together with the epoxy resin (component A) represented by 1) may be used. When the conventionally known epoxy resin is used in combination, the combination ratio is set so that the epoxy resin (A component) represented by the above general formula (1) accounts for at least 70% by weight of the entire epoxy resin component. preferable. Particularly preferred is at least 80% by weight of the entire epoxy resin component. Examples of the conventionally known epoxy resins include, for example, bisphenol A type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin and the like. Used together. Among them, it is preferable to use a biphenyl type epoxy resin and a triphenylmethane type epoxy resin, for example, a biphenyl type epoxy resin represented by the following general formula (6),
A triphenylmethane-based epoxy resin represented by the following general formula (7) is used.

[0025]

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[0026]

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Of the alkyl groups having 1 to 5 carbon atoms represented by R _{1 to} R ₄ in the general formula (6), the alkyl groups include a methyl group, an ethyl group, n
- propyl group, an isopropyl group, n- butyl group, isobutyl group, sec- butyl group, a linear or branched lower alkyl group such as a tert- butyl group are exemplified, particularly preferably a methyl group, the R ₁ ~ R ₄ may be the same or different. Among them, from the viewpoint of low hygroscopicity and reactivity, the R ₁ to R ₄ are all biphenyl type epoxy resin having a structure represented by the following formula is a methyl group (6a), the R ₁ to R ₄ are all A biphenyl type epoxy resin having a structure represented by the following formula (6a), which is a methyl group, and a biphenyl type epoxy resin having a structure in which all of R _{1 to} R ₄ are hydrogen are mixed at a mixing weight ratio of 1: 1. It is particularly preferred to use a mixture of the two.

[0028]

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In the triphenylmethane epoxy resin represented by the above formula (7), R is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and particularly preferably, R is a hydrogen atom. The number of repetitions n is an integer of 0 to 5,
Particularly preferably, it is an integer of 0 to 3. The triphenylmethane epoxy resin represented by the above formula (7) preferably has an epoxy equivalent in the range of 160 to 180, and particularly preferably has an epoxy equivalent in the range of 162 to 175. Further, the softening point is preferably in the range of 50 to 80C, and particularly preferably the softening point is 55 to 65C.

The component B used together with the specific epoxy resin (component A) is a modified phenol resin curing agent obtained by melting and reacting a mixture of two specific phenol resins with a specific silane coupling agent.

The above two specific phenolic resin mixtures are phenolic resin mixtures comprising a phenolic resin represented by the following general formula (2) and a phenolic resin represented by the following general formula (3).

[0032]

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[0033]

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In the above formula (2), the number of repetitions p is preferably in the range of 1 to 10, and particularly preferably in the range of 1 to 4. The number of repetitions q is preferably in the range of 1 to 10, and particularly preferably in the range of 1 to 4. Further, R in the formula (2) is preferably H. The repeating units p and q may be any of random polymerization, alternating polymerization, and block polymerization.
Preferably, it is an alternate polymerization.

The phenolic resin represented by the general formula (2) preferably has a hydroxyl equivalent in the range of 150 to 170, and particularly preferably has a hydroxyl equivalent of 1 to 1.
The range is 50 to 165. The softening point is 60 to 90
It is preferable that the softening point is in the range of 70 to 80 ° C.

In the above formula (3), the number of repetitions r is preferably in the range of 1 to 10, particularly preferably in the range of 1 to 4.

The phenolic resin represented by the general formula (3) includes a hydroxyl equivalent of 160 to 190 and a softening point of 60 to 190.
It is preferable to use one having a temperature of 90 ° C, and particularly preferably one having a hydroxyl equivalent of 160 to 180 and a softening point of 70 to 85 ° C.

The specific silane coupling agent to be melt-reacted with a phenol resin mixture comprising the phenol resin represented by the general formula (2) and the phenol resin represented by the general formula (3) is a silane having a mercapto group. Specific examples of the coupling agent include γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltriethoxysilane, and the like. These may be used alone or in combination of two or more. Among them, it is particularly preferable to use γ-mercaptopropyltrimethoxysilane from the viewpoint that higher adhesiveness can be obtained.

The modified phenolic resin curing agent obtained by a melting reaction of the phenolic resin mixture with a silane coupling agent having a mercapto group is prepared, for example, as follows. That is, the phenol resin represented by the general formula (2), the phenol resin represented by the general formula (3), and the silane coupling agent having a mercapto group are charged into a melting pot, melt-mixed, and cooled. After solidification, it is produced by crushing as necessary. At this time, a curing accelerator (D
Ingredient) and melt-mixing are preferred from the viewpoint of increasing the crosslinking property of the curing agent.

The melt mixing conditions include, for example, 17
Stir-mixing at a temperature of 5 ° C. for 1 to 2 hours can be mentioned.

The mixing ratio of the phenolic resin represented by the general formula (2) and the phenolic resin represented by the general formula (3) is expressed by weight based on [phenol resin of the formula (2)] / [formula (3) ))] = 8/2 to 2/8, particularly preferably 6/4 to 4/6
It is. That is, when the mixing ratio of the two is out of the above range, the balance between low moisture absorption and toughness tends to be deteriorated.

The amount of the silane coupling agent having a mercapto group is determined by the amount of the phenolic resin mixture in the modified phenolic resin curing agent (component B) [the total amount of the phenolic resins represented by the formulas (2) and (3)]. Amount] 100
It is preferable that the amount be set in the range of 0.1 to 10 parts by weight (hereinafter abbreviated as "part"). Particularly preferably 0.5
~ 5 parts. That is, when the amount is less than the above range, the effect of improving the adhesive strength is small, and when the amount is too large, an abnormal reaction of the curing agent proceeds, and a tendency to be in a gel state is observed.

The mixing ratio of the epoxy resin component as the component A and the modified phenolic resin curing agent as the component B is usually one of the epoxy groups in the epoxy resin component.
The hydroxyl group in the modified phenolic resin component per equivalent is 0.7
To 1.3 equivalents, especially 0.8 to 1.
It is preferable to set to be 2 equivalents.

The silane coupling agent having a glycidoxy group (component C) used together with the above-mentioned components A and B is not particularly limited as long as it has a glycidoxy group. For example, γ-glycidoxypropyl Trimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltriethoxysilane and the like. These may be used alone or in combination of two or more. Among them, it is particularly preferable to use γ-glycidoxypropyltrimethoxysilane from the viewpoint of adhesive strength with the polyimide coating material.

The content of the silane coupling agent having a glycidoxy group (component C) is preferably set in the range of 0.01 to 1% by weight, particularly preferably 0.05 to 1% by weight, based on the whole epoxy resin composition. 0.5% by weight. That is, if it is too small, such as less than 0.01% by weight,
This is because the effect of improving the adhesive strength is small, and if it exceeds 1% by weight, the flowability of the epoxy resin composition tends to decrease.

The curing accelerator (component D) used together with the above components A to C is not particularly limited.
Conventionally known ones are used. Examples thereof include amines, imidazoles, phosphorus-based, boron-based, and phosphorus-boron-based curing accelerators. Specifically, alkyl-substituted guanidines such as ethylguanidine, trimethylguanidine, phenylguanidine, and diphenylguanidine;
(3,4-dichlorophenyl) -1,1-dimethylurea, 3-phenyl-1,1-dimethylurea, 3- (4-
3-substituted phenyl-1,1-dimethylureas such as (chlorophenyl) -1,1-dimethylurea, imidazolines such as 2-methylimidazoline, 2-phenylimidazoline, 2-undecylimidazoline and 2-heptadecylimidazoline; Monoaminopyridines such as 2-aminopyridine, amine imides such as N, N-dimethyl-N- (2-hydroxy-3-allyloxypropyl) amine-N'-lacimide, ethylphosphine, propylphosphine, butylphosphine , Phenylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, trioctylphosphine, triphenylphosphine, tricyclohexylphosphine, triphenylphosphine / triphenylborane complex, tetraphenylphosphonium tetra Organophosphorus compounds such Eniruboreto, 1,8-diazabicyclo (5,4,0) undecene-7, 1,5-diazabicyclo (4,3,0) nonene -
And 5 diazabicycloalkene compounds. Among them, organic phosphorus compounds such as triphenylphosphine and diazabicycloalkene compounds are preferably used. These may be used alone or in combination of two or more.

The content of the above-mentioned curing accelerator (component D) is preferably set so as to be in the range of 0.1 to 0.5% by weight, particularly preferably 0.1 to 0.5% by weight in the whole epoxy resin composition. ~ 0.3% by weight. That is, if the amount of the curing accelerator is too small, such as less than 0.1% by weight, it is difficult to obtain a sufficient curing promoting effect. This is because there is a tendency for the fluidity to decrease due to the shortening of the sintering time.

The inorganic filler (component E) used together with the components A to D is not particularly limited, and includes various conventionally known fillers, for example, quartz glass powder, talc, silica powder, and alumina powder. , Aluminum nitride powder, silicon nitride powder and the like. These may be used alone or in combination of two or more. Examples of the silica powder include a fused silica powder and a crystalline silica powder. Among them, it is preferable to use the above silica powder from the viewpoint that the coefficient of linear expansion of the obtained cured product can be reduced. Further, among the above silica powders, it is particularly preferable to use spherical fused silica powder from the viewpoint of high filling and high fluidity. Further, in the above-mentioned inorganic filler, the average particle diameter is preferably in the range of 10 to 40 μm, more preferably 15 to 30 μm. The average particle size is measured by a laser diffraction scattering type particle size distribution measuring device.

The amount of the inorganic filler (component E) is as follows:
It is preferably at least 75% by weight of the entire epoxy resin composition, more preferably in the range of 80 to 90% by weight, particularly preferably 85 to 90% by weight. That is, if the amount is too small, such as less than 75% by weight, the amount of moisture absorption of the sealing resin increases, and the resin strength decreases, so that cracks and peeling tend to occur easily during reflow of the semiconductor package. is there.

Further, in addition to the above-mentioned components A to E, the epoxy resin composition for encapsulating a semiconductor according to the present invention contains a flame retardant, a flame retardant auxiliary, a release agent, a pigment such as carbon black, a coloring agent, a low stress. Other additives such as an agent and a tackifier can be appropriately compounded.

Examples of the flame retardant include halogen-based flame retardants such as novolak type brominated epoxy resin, and diantimony trioxide and diantimony pentoxide are used as the flame retardant aid. These can be used alone or 2
Used in combination of more than one species.

Further, in addition to the halogen-based flame retardant, a polyhedral complex metal hydroxide represented by the following general formula (8) can be used. The composite metal hydroxide has a polyhedral crystal shape, and has a conventional hexagonal plate shape, or a so-called thin plate-like crystal shape such as a scale-like shape. Rather, crystal growth in the thickness direction (c-axis direction) is large both vertically and horizontally. For example, a plate-like crystal grows in the thickness direction (c-axis direction) to make it more three-dimensional and spherical. A composite metal hydroxide having a granular crystal shape, for example, a substantially dodecahedral, substantially octahedral, or substantially tetrahedral shape.

[0053]

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Regarding the composite metal hydroxide represented by the general formula (8), M representing the metal element in the formula (8) is Al, Mg, Ca, Ni, Co, Sn, Zn, C
u, Fe, Ti, B and the like.

Q representing another metal element in the composite metal hydroxide represented by the general formula (8) is IVa, Va, VIa, VIIa, VIII, Ib, IIb in the periodic table. Metals belonging to the group selected from For example, Fe, C
o, Ni, Pd, Cu, Zn, etc., and are selected alone or in combination of two or more.

The composite metal hydroxide having such a polyhedral crystal shape can be obtained, for example, by controlling various conditions in the production process of the composite metal hydroxide.
Obtaining a composite metal hydroxide having a desired polyhedral shape, such as a substantially dodecahedral, a substantially octahedral, or a substantially tetrahedral shape, in which crystal growth in the thickness direction (c-axis direction) is large both vertically and horizontally. And usually consists of these mixtures.

Specific representative examples of the composite metal hydroxide having the above-mentioned polyhedral shape include hydrates of magnesium oxide / nickel oxide, hydrates of magnesium oxide / zinc oxide, and hydrates of magnesium oxide / copper oxide. Japanese products.

The aspect ratio of the composite metal hydroxide having the polyhedral shape is usually 1 to 8, preferably 1 to 8.
To 7, particularly preferably 1 to 4. The term “aspect ratio” as used herein refers to the ratio of the major axis to the minor axis of the composite metal hydroxide. That is, when the aspect ratio exceeds 8, the effect of lowering the viscosity when the epoxy resin composition containing the composite metal hydroxide is melted becomes poor.

Examples of the release agent include compounds such as higher fatty acids, higher fatty acid esters and higher fatty acid calcium. For example, carnauba wax and polyethylene wax are used, and these may be used alone or in combination of two or more. Can be

Examples of the stress reducing agent include butadiene rubbers such as methyl acrylate-butadiene-styrene copolymer and methyl methacrylate-butadiene-styrene copolymer, and silicone compounds. Further, an ion trapping agent such as hydrotalcites and bismuth hydroxide may be blended for the purpose of improving the reliability in the moisture resistance reliability test.

The epoxy resin composition for semiconductor encapsulation of the present invention can be produced, for example, as follows.
First, as described above, a phenolic resin mixture comprising a phenolic resin represented by the general formula (2) and a phenolic resin represented by the general formula (3) is melt-reacted with a silane coupling agent having a mercapto group. To produce a modified phenolic resin curing agent (component B). Next, the modified phenolic resin curing agent (component B) and the remaining components,
An epoxy resin (A component) represented by the general formula (1),
Glycidoxy group-containing silane coupling agent (component C), curing accelerator (component D), inorganic filler (component E)
In addition, other additives are blended in a predetermined ratio. Next,
This mixture is melted and kneaded in a heated state using a kneading machine such as a mixing roll machine, and the mixture is cooled to room temperature. And
The desired epoxy resin composition for semiconductor encapsulation can be produced by a series of steps of pulverizing by a known means and tableting as necessary.

The method for encapsulating a semiconductor device using the epoxy resin composition for semiconductor encapsulation thus obtained is not particularly limited, and may be performed by a known molding method such as ordinary transfer molding. And a semiconductor device can be obtained.

In the semiconductor device of the present invention, the adhesiveness between the cured resin obtained by using the epoxy resin composition for semiconductor encapsulation and a semiconductor element is improved, and in particular, a polyimide coating layer is formed on the element surface. Adhesion to the surface of the semiconductor element thus obtained is remarkably improved, and excellent solder resistance is obtained.

Next, examples will be described together with comparative examples.

First, the following components were prepared.

[Epoxy resin A] An epoxy resin represented by the following formula (a) (epoxy equivalent: 208, melting point: 135)
C] [in the formula (a), a mixture of an epoxy resin in which R is a methyl group (M) and an epoxy resin in which R is a tert-butyl group (B) (molar ratio M: B = 6: 4)]

[0067]

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[Epoxy resin B] A biphenyl-based epoxy resin represented by the following formula (b) (epoxy equivalent: 195;
(Melting point 107 ° C)

[0069]

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[Epoxy resin C] An epoxy resin represented by the following formula (c) (epoxy equivalent 168, softening point 58
℃)

[0071]

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[Phenol resin A] A phenol resin represented by the following formula (d) (having a hydroxyl equivalent of 154 and a softening point of 78)
℃)

[0073]

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[Phenol resin B] A phenol resin represented by the following formula (e) (having a hydroxyl equivalent of 170 and a softening point of 83
℃)

[0075]

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[Curing accelerator] Triphenylphosphine

[Silane Coupling Agent A] γ-glycidoxypropyltrimethoxysilane

[Silane Coupling Agent B] γ-Mercaptopropyltrimethoxysilane

[Silica Powder] Spherical fused silica powder (average particle size 30 μm)

[Inorganic Flame Retardant] Composition Formula MgO.ZnO.H
₂ O polyhedral crystal composite metal hydroxide (average particle size 1.7 μm, maximum particle size 3.7 μm, specific surface area 3.5 m ²
/ G)

[Preparation of Modified Phenolic Resin Curing Agent] The components shown in Table 1 below were blended in the proportions shown in the table, melt-mixed in a melting pot (at 175 ° C.) for 1 hour, and then cooled and solidified. . Thereafter, the resultant was pulverized to prepare a modified phenol resin curing agent which was a target pre-reaction product.

[0082]

[Table 1]

[0083]

Examples 1 to 8 and Comparative Examples 1 to 5 The respective raw materials shown in the following Tables 2 and 3 were blended in the proportions shown in the same table, and were melted and kneaded by a roll kneader (10 minutes) heated to 80 ° C. . Next, the melt was cooled, pulverized, and further tableted to obtain an epoxy resin composition for semiconductor encapsulation.

[0084]

[Table 2]

[0085]

[Table 3]

Using the thus obtained epoxy resin compositions of Examples and Comparative Examples, the following method was used.
The spiral flow value, flow tester viscosity, moisture absorption, adhesiveness, and solder resistance were measured and evaluated. The results are shown in Tables 4 to 6 below.

[Spiral Flow Value] Using a mold for measuring spiral flow, EMMI 1-6 at 175 ± 5 ° C.
The spiral flow value was measured according to 6.

[Flow tester viscosity] 2 g of each of the above epoxy resin compositions was precisely weighed and molded into tablets. Then, put this in the pot of the Koka type flow tester,
The measurement was performed with a load of 0 kg. The melt viscosity of the sample was determined from the moving speed of the piston when the molten epoxy resin composition was extruded through a die hole (diameter 1.0 mm × 10 mm).

[Hygroscopicity] Using the epoxy resin compositions obtained in the above Examples and Comparative Examples, a diameter of 50 mm and a thickness of 1
mm-shaped disk-shaped cured product (molding conditions: 175 ° C. ×
2 minutes + post-curing 175 ° C x 5 hours). 85 ° C /
Moisture was absorbed in 85% RH for 24 hours. Furthermore, it was made to absorb moisture for a total of 168 hours at 85 ° C./85% RH. The moisture absorption was calculated from the weight before and after moisture absorption at this time.

[Adhesiveness] Using each of the above-mentioned epoxy resin compositions and a metal frame plate, as shown in FIG. 1, an adhesive in which a frustoconical resin cured body 15 is provided on the left end surface of a metal frame plate 13. Transfer measurement method (175 ° C x 2 minutes, 175 ° C x 5 hours post-curing)
(The area of the bonded portion was 10 mm ² ). Using this, as shown in FIG. 2, the resin cured body 15 is sandwiched by the measuring jig 16, the end of the measuring jig 16 is fixed by the chuck 17 of the autograph device, and the metal of the measuring sample is fixed. The end portion of the frame plate 13 is fixed with the chuck 18 of another autograph device, and the shearing force when the cured resin 15 on the surface of the metal frame plate 13 peels off from the metal frame plate 13 while applying a load in the direction of the arrow is measured. This value was taken as the adhesive strength. The metal frame plate 13
Were measured using two kinds of alloys, namely, 42 alloy alloy (42 nickel-iron alloy) and copper. Further, a silicon chip having a polyimide coating layer (thickness: 10 μm, photosensitive polyimide film) is used instead of the metal frame plate 13, and the silicon chip having the polyimide coating layer and the cured resin are formed in the same manner as described above. The adhesion was measured.

Further, the semiconductor element is subjected to transfer molding (conditions: 175 ° C. × 2 minutes) using the epoxy resin compositions obtained in the above Examples and Comparative Examples, and post-cured at 175 ° C. × 5 hours to obtain a semiconductor device. The device was obtained. This semiconductor device is an LQFP-144 (die pad size: 7.5).
× 7.5 mm, copper frame).

[Solder Resistance] Number of Cracks Generated Using the above semiconductor device, 168 in 85 ° C./85% RH.
Infrared (IR) at 240 ° C x 10 seconds after moisture absorption for a time
A solder evaluation test was performed by reflow. Then, the packages in which cracks occurred were counted. In addition, the analysis of the crack of the package used the ultrasonic microscope.

Peeling of Interface of Semiconductor Element Using the above-described semiconductor device, 168 in 85 ° C./85% RH was used.
Infrared (IR) at 240 ° C x 10 seconds after moisture absorption for a time
A solder evaluation test was performed by reflow. Then, those in which peeling occurred at the interface between the semiconductor element and the sealing resin layer (cured body) were evaluated as ○, and those in which no peeling occurred were evaluated as x.
The analysis of interface separation was performed using an ultrasonic microscope.

Separation of Lead Frame Interface Using the above-described semiconductor device, 168 in 85 ° C./85% RH.
Infrared (IR) at 240 ° C x 10 seconds after moisture absorption for a time
A solder evaluation test was performed by reflow. Then, the case where peeling occurred at the interface between the lead frame and the sealing resin layer (cured body) was evaluated as ○, and the case where peeling did not occur was evaluated as x. The analysis of interface separation was performed using an ultrasonic microscope.

[0095]

[Table 4]

[0096]

[Table 5]

[0097]

[Table 6]

[0098] In Tables 4 to 6, the products of Examples had good values of the spiral flow value and the gel time. In addition, it has a low moisture absorption, has excellent adhesiveness, and has an excellent evaluation result in a soldering resistance test, indicating that a highly reliable semiconductor device has been obtained. On the other hand, since the comparative example product had high hygroscopicity or low adhesiveness, it had low reliability such as cracks and interfacial peeling in the solder resistance test.

[0099]

As described above, the present invention relates to an epoxy resin (component A) represented by the general formula (1), a phenol resin represented by the general formula (2) and a phenol resin represented by the general formula (3).
A modified phenolic resin curing agent (component (B)) obtained by melt-mixing and reacting a mixture of a phenolic resin represented by the formula (1) with a silane coupling agent having a mercapto group, and a silane coupling agent (component (C)) having a glycidoxy group. An epoxy resin composition for semiconductor encapsulation. For this reason, the adhesiveness with the semiconductor element is improved, and a semiconductor device having excellent solder resistance can be obtained by sealing the semiconductor element using this. In particular, the adhesiveness to the semiconductor element surface using a polyimide coating agent on the element surface is remarkably improved, and the cured sealing resin has excellent low moisture absorption and toughness. Obtainable.

[Brief description of the drawings]

FIG. 1 is a perspective view showing an adhesive force measurement sample used when evaluating the adhesiveness of a cured resin body made of an epoxy resin composition.

FIG. 2 is an explanatory diagram showing a method for measuring a shearing force between a cured resin body and a frame.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09K 3/10 C09K 3/10 Q C08K 5/54 E H01L 23/29 H01L 23/30 R 23 / 31F Term (Reference) 4H017 AA04 AA22 AA27 AA29 AA31 AB08 AB17 AD06 AE05 4J002 CC072 CD045 CD051 CD055 CD065 CD121 CD125 DE148 DF018 DJ008 DJ018 DJ048 EQ017 ER027 ET017 EU017 EU047 EU117 EW137 EW177 EX066 A02 FD130G02A AD01 AD04 AD05 AD07 AD08 AD10 AF01 AF06 AF08 DA02 DA05 DC02 DC05 DC26 DC34 DC39 DC40 DC42 DC44 DD07 FA03 FA04 FA05 FA11 FA13 FB08 JA07 KA05 4M109 AA01 BA01 CA21 EA03 EA06 EB03 EB04 EB06 EB12 EC01 EC03 EC05 EC09

Claims (2)

[Claims] 1. An epoxy resin composition for semiconductor encapsulation, comprising the following components (A) to (E). (A) An epoxy resin represented by the following general formula (1). Embedded image (B) Melt reaction of a phenolic resin mixture comprising a phenolic resin represented by the following general formula (2) and a phenolic resin represented by the following general formula (3) with a silane coupling agent having a mercapto group. Modified phenolic resin curing agent. Embedded image Embedded image (C) a silane coupling agent having a glycidoxy group. (D) a curing accelerator. (E) an inorganic filler. 2. A semiconductor device obtained by resin-sealing a semiconductor element using the epoxy resin composition for semiconductor encapsulation according to claim 1.