JPH021724A - Epoxy resin composition and resin sealed type semiconductor device - Google Patents

Abstract

PURPOSE:To obtain the subject composition, containing a molten mixture, etc., of an epoxy resin with a curing agent for the epoxy resin and a polyamide elastomer, excellent in mechanical characteristics and low stress properties and suitable for sealing semiconductor chips. CONSTITUTION:The objective composition containing a molten, dissolved or reaction mixture of (A) an epoxy resin (e.g., bisphenol type epoxy resin) with (B) a curing agent for the epoxy resin (preferably having >=2 phenolic hydroxyl groups in one molecule, such as phenol novolak resin) and (C) a polyamide elastomer (which is a block copolymer of a polyamide constituted of hard segments of a straight-chain polyamide and soft segments of a straight-chain polyether). Furthermore, the amount of the blended component (C) is preferably 0.01-30wt.%.

Description

[Detailed Description of the Invention] [Object of the Invention] (Industrial Application Field) The present invention relates to an epoxy resin composition and a resin-encapsulated semiconductor device using the same, and particularly has excellent mechanical properties and low stress properties,
The present invention relates to a highly reliable epoxy resin composition and a resin-encapsulated semiconductor device using the same.

(Prior Art) Epoxy resin compositions are widely used to encapsulate integrated circuits (ICs), large-scale integrated circuits (LSIs), semiconductor components such as transistors, electronic components, and other components.

As described above, a sealing resin made of a cured product of an epoxy resin composition that seals semiconductor components, electronic components, etc. is required to withstand solder league when mounted on a printed circuit board. Regarding this soldering, methods of soldering by solder flow or reflow have become mainstream. Then, during soldering, the sealing resin is
Since they are exposed to temperatures of 00°C or higher, sometimes 300°C or higher, for short periods of time, it is necessary that these conditions do not cause cracks or other failures.

Conventionally, as epoxy resin compositions for the above-mentioned uses, those containing a cresol novolac type epoxy resin as a main component and a novolac type phenol resin containing H as a curing agent have been generally used.

However, the cured product of an epoxy resin composition having such a composition is brittle and has insufficient mechanical properties, so it is prone to cracking during solder flow or reflow, and there is a problem that sufficient reliability cannot be obtained. Ta.

Furthermore, the cured products of conventional epoxy resin compositions have a high elastic modulus, and therefore, when semiconductor chips etc. are sealed, the encapsulating resin has a high fA (e.g. 200°C) and a low temperature (e.g. -65°C).
℃), large thermal stress occurs between the encapsulating resin and the semiconductor chip sealed inside, which tends to cause cracks in the encapsulating resin and the chip, and also causes oxidation on the chip surface. This method had the drawback that cracks in the film and deformation of the aluminum wiring were likely to occur.

(Problems to be Solved by the Invention) As described above, the cured products of conventional epoxy resin compositions are brittle and have large thermal stress, and therefore the reliability of resin-sealed semiconductor devices obtained using the same is low. There was a point.

The present invention was made in view of the above problems.
An object of the present invention is to provide a low-stress and highly reliable epoxy resin composition and a resin-sealed semiconductor device using the same.

[Structure of the Invention] (Means for Solving the Problems) The epoxy resin composition of the present invention contains an epoxy resin, a curing agent for the epoxy resin, and a molten mixture, dissolved mixture, or reaction mixture of a polyamide elastomer. It is characterized by:

Moreover, the resin-sealed semiconductor device of the present invention is characterized in that a semiconductor device is sealed with the above-mentioned epoxy resin composition.

The present invention will be explained in more detail below.

The epoxy resin used in the present invention is commonly known and is not particularly limited. For example, bisphenol type epoxy resin, novolak type epoxy resin, tetrakis(glycidoxyphenyl)ethane, formula [1] (wherein, Q is a hydrocarbon group having 1 or more carbon atoms, and each R is independently hydrogen, halogen, carbon Glycidyl ester type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin , heterocyclic epoxy resin,
Examples include epoxy resins having two or more epoxy groups in one molecule, such as I\logenated epoxy resins. Among these, particularly preferred epoxy resins are novolac type epoxy resins, tetrakis(glycidoxyphenyl)ethane, and epoxy resins represented by the above formula [11]. These epoxy resins may be used alone or in a mixed system of two or more.

Note that the epoxy resin has a chlorine ion content of 1
Below Oppi, the content of hydrolyzable chlorine is 0.11m%
The following are desirable. This is because if more than 10 ppm of chlorine ions or more than 0.1% by weight of hydrolyzable chlorine is contained, the aluminum electrodes of the sealed semiconductor chip are likely to be corroded.

The curing agent for the epoxy resin used in the present invention is generally known and is not particularly limited. However, preferred curing agents are those having two or more phenolic hydroxyl groups in one molecule.

Specific examples include phenol novolak resin, novolac type phenol resin such as cresol novolac resin, resol type phenol resin, polyparahydroxystyrene, phenol aralkyl resin, bisphenol A.
1 tetrakis(hydroxyphenyl)ethane, their halides.

Formula [■] HH (wherein, Q is a hydrocarbon group having 1 or more carbon atoms, each R independently represents hydrogen, halogen, a hydrocarbon group having 1 or more carbon atoms, or a halogenated hydrocarbon group, and n is 0 or (representing an integer of 1 or more). As curing agents other than those mentioned above, acid anhydride curing agents and amine curing agents can also be used. These curing agents may be used alone or in a mixed system of two or more.

Regarding the blending ratio of the curing agent and the epoxy resin, it is desirable to blend the curing agent and the epoxy resin so that the equivalent ratio of the phenolic hydroxyl group to the epoxy group is within the range of 0.5 to 1.5. this is,
This is because outside the above range, the reaction is difficult to occur sufficiently and the properties of the curing agent tend to deteriorate.

The polyamide elastomer used in the present invention is a block copolymer of polyamide, and is composed of a hard segment of linear polyamide and a soft segment of linear polyether. The outline of its structure is shown in formula [I11].

(In the formula, PA represents polyamide, PE represents polyether, and n represents an integer of 1 or more.) Specifically, FA is selected from nylon 6.66.612°11.12, etc., and PE is selected from nylon 6.66.612°11.12. Selected from polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc.

The blending amount of the polyamide elastomer is 0.0% of the total composition.
It is desirable that the amount is within the range of 0.01 to 30% by weight. This means that the effect of addition was not observed at less than o and oi weight%.
This is because if the amount exceeds 30% by weight, the properties of the composition will deteriorate.

The epoxy resin composition according to the present invention contains a molten mixture, a dissolved mixture, or a reaction mixture of the above-mentioned epoxy resin, a curing agent for the epoxy resin, and a polyamide elastomer.

A molten mixture or dissolved mixture of an epoxy resin, a curing agent for the epoxy resin, and a polyamide elastomer can be prepared as follows. First, a mixture of polyamide elastomer and epoxy resin or curing agent is prepared. In this case, the epoxy resin or curing agent and the polyamide elastomer are placed in the same container and the temperature is set to 100.
Either raise the temperature to ~300°C and stir and mix to make them compatible and prepare a uniform molten mixture, or dissolve the epoxy resin or curing agent and the polyamide elastomer in a solvent and mix them to make a uniform solution, and then A solid mixture is prepared by removing the solvent. Epoxy resin thus obtained/
The curable epoxy resin composition according to the invention can be prepared by mixing a polyamide elastomer mixture or a curing agent/polyamide elastomer mixture with a curing agent or an epoxy resin, respectively.

As a method other than the above-mentioned method, the epoxy resin, the curing agent, and the polyamide elastomer may be simultaneously melt-mixed or mixed using a solvent. Alternatively, a curable epoxy resin composition may be prepared by preparing a mixture of part of the epoxy resin and the polyamide elastomer, or a mixture of part of the curing agent and the polyamide elastomer, and then mixing it with the remaining resin components. good.

In addition, as a device for melt mixing, a heating mixing pot, a Nigoo roll, a kneading extruder, etc. are preferable.

Further, a reaction mixture of an epoxy resin, a curing agent for the epoxy resin, and a polyamide elastomer can be prepared as follows. In other words, carboxyl groups, hydroxyl groups, esters, etc. in the polyamide elastomer structure are
It can be reacted with epoxy resins and hardeners. Therefore, a reaction mixture can be prepared using this reaction.

A basic catalyst, such as triphenylphosphine, can be used to accelerate this reaction. By reacting polyamide elastomer with epoxy resin and curing agent in this way, polyamide elastomer can be incorporated into a three-dimensional network structure composed of epoxy resin and curing agent, and the phenomenon of polyamide elastomer bleeding onto the surface can be prevented. Not only can this be prevented, but the properties of the cured product can also be improved.

The above reaction may be carried out at any stage of the production. For example, the reaction may be carried out when the epoxy resin/polyamide elastomer mixture or the curing agent/polyamide elastomer mixture is prepared, or at the stage where the epoxy resin and the curing agent undergo a curing reaction.

The epoxy resin composition of the present invention may optionally contain a curing accelerator that promotes the reaction between the epoxy resin and the curing agent. Generally known curing accelerators can be used, but in order to obtain a highly reliable epoxy resin composition, it is desirable to use an organic phosphine, an organic phosphine oxyto, or a coordination compound of an organic phosphine.

The organic phosphine compound has the formula [IV] (where R, -R, are hydrogen or a hydrocarbon group, and a part of the hydrocarbon group may be substituted with a substituent containing another atom. (Excluding cases where R1-R9 are all hydrogen.) This is a compound represented by the following. Specific examples include triphenylphosphine, tris(methylphenyl)phosphine, tris(methoxyphenyl)phosphine, tributylphosphine, tricyclohexylphosphine, methyldiphenylphosphine, butylphenylphosphine, diphenylphosphine, phenylphosphine, and the like. R
Examples of organic phosphine compounds in which 3 is an organic group containing an organic phosphine include 1,2-bis(diphenylphosphino)ethane, bis(diphenylphosphino)methane, and the like. Among these, arylphosphine compounds are preferred, and triphenylphosphine, tris(methylphenyl)phosphine, tris(methoxyphenyl)phosphine, and the like are particularly preferred.

Organic phosphine oxyto has the formula [V,] (wherein R1-
R1 is hydrogen or a hydrocarbon group, and a portion of the hydrocarbon group may be substituted with a substituent containing another atom. In addition, R1
-Except when R1 is entirely hydrogen. ) is a compound represented by Specifically, triphenylphosphine oxyto, tris(methylphenyl-phosphine oxyto, tribenzylphosphine oxyto, trioctylphosphine oxyto, tonocyclohexylphosphine oxyto, diphenylethylphosphine oxyto,
Examples include phenyldimethylphosphine oxide, diphenylphosphine oxide, dihexylphosphine oxide, tris(chlorophenyl)phosphine oxide, tris(hydroxyphenyl)phosphine oxide, tris(methoxyphenyl)phosphine oxide, and the like.

Among these, triarylphosphine oxyto such as triphenylphosphine oxyto is preferred.

The coordination compound of organic phosphine has the formula [VI] (wherein R1
-R6 is hydrogen, halogen, or a hydrocarbon group, and a portion of the hydrocarbon group may be substituted with a substituent containing another atom. Note that at least one of R1 to R3 is a hydrocarbon group. M is a boron or aluminum atom. ) is a compound represented by organic phosphine and MR4R8R6
It can be easily obtained by reacting with.

The organic bosphine constituting the coordination compound of organic phosphine includes triphenylphosphine, tris(methylphenyl)phosphine, tribenzylphosphine, trioctylphosphine, tricyclohexylphosphine, diphenylethylphosphine, phenyldimethylphosphine, diphenylphosphine, Examples include dihequinulfosphine, phenylphosphine, decylphosphine, tris(chlorophenyl)phosphine, tris(hydroxyphenyl)phosphine, tris(methoxyphenyl)phosphine, and the like. Among these, triarylphosphines such as triphenylphosphine are preferred.

tVIR4R5 constituting an organic phosphine coordination compound
Examples of the compound represented by R6 include boron hydride, aluminum hydride, boron halide, /% aluminum halide, organoboron, and organoaluminum.

(HIa boron compounds include triphenylboron,
Tris (ethylphenyl) boron, tribenzyl boron, trioctyl boron, tricyclohexyl boron, diphenylmethyl boron, phenyl dibutyl boron, diphenyl boron, phenyl dibutyl boron, diphenyl boron, dioctyl boron, phenyl boron, cyclohexyl boron, Examples include tris(chlorophenyl)boron.

Examples of the a-organic aluminum compound include aluminum compounds corresponding to the above-mentioned boron compounds, such as triphenylaluminum.

Among these organic boron and organic aluminum compounds, triaryl compounds are preferred.

In the present invention, at least one type or a combination of two or more types of the above organic phosphine, organic phosphine oxyto, and organic phosphine coordination compounds can be used. These amounts are o, oot to 10 of the entire composition.
A weight percent range is preferred.

The epoxy resin composition of the present invention may further contain an inorganic filler, a mold release agent, a flame retardant, a blue agent, a surface treatment agent for the filler, a stress imparting agent, etc., if necessary.

Inorganic fillers include fused silica, crystalline silica, glass fiber, talc, alumina, calcium silicate, calcium carbonate, barium sulfate, magnesia, silicon nitride,
Generally known materials such as boron nitride can be used.

Examples of mold release agents include natural waxes, synthetic waxes, metal salts of straight chain fatty acids, acid amides, esters, and paraffins. Flame retardants include chlorinated paraffins, bromotoluene, hexabromobenzene, and Antimony oxide or the like, carbon black or the like as a coloring agent, and a run-coupling agent as a filler surface treatment agent can be used.

When preparing an epoxy resin T11 composition containing various additives as described above as a molding material, - For boat fishing, the raw materials are blended in a fixed composition ratio, mixed thoroughly with a mixer, for example, and then heated with a hot roll. 6 Melt mixing treatment or mixing treatment using a kneader or the like is performed.

The resin-sealed semiconductor device according to the present invention can be easily manufactured by sealing a semiconductor chip using the above-mentioned epoxy resin composition. Sealing is most commonly performed by low pressure transfer molding, but sealing by injection molding, compression molding, casting, etc. is also possible. The epoxy resin composition is cured by heating during sealing, and a resin-sealed semiconductor device is finally obtained which is sealed with a cured product of this composition. It is particularly desirable to heat to 150° C. or higher during curing. Further, by performing post-curing at 150 to 300°C for several hours to several tens of hours, properties such as heat resistance of the cured product can be improved. The post cure temperature is preferably 170°C or higher, more preferably 200°C or higher, and the post cure time is preferably 3 to 30°C.
It is 16 hours.

(Example) Hereinafter, the present invention will be explained in more detail based on examples.

First, mixtures AC of polyamide elastomer and epoxy resin or curing agent were prepared.

Mixture A: 100 parts of polyamide elastomer (block copolymer of nylon 66 and polyethylene glycol), 50 parts of cresol novolac yupoxy resin with an epoxy equivalent of 20 units.
0 part was placed in a flask, heated to 200° C. under nitrogen atmosphere, and stirred. When the mixture became compatible and homogeneous, heating was stopped and mixture A was obtained by cooling.

Mixture B 100 parts of a polyamide elastomer (block copolymer of nylon 12 and polypropylene glycol) and 400 parts of a phenol novolak resin with a softening point of 100°C were placed in a flask, and a mixture B was obtained in the same manner as above.

Mixture C 100 parts of polyamide elastomer (block copolymer of nylon 6 and polytetramethylene glycol), 200 parts of tris(glycidoxyphenyl)methane of 162 epoxy metal, and 0.2 part of triphenylphosphine were placed in a flask. Mixture C was obtained in the same manner as above.

Examples 1 to 7 and Comparative Examples 1 to 4 The raw materials shown below were blended in the composition (parts by weight) shown in Table 1, mixed with a mixer, and then kneaded for 3 minutes with heated rolls at 100 ° C. Epoxy resin compositions for transfer molding of Examples 1 to 7 and Comparative Examples 1 to 4 were prepared.

Mixture A-C Polyamide elastomer used in mixture A Cresol novolak type epoxy resin with epoxy equivalent of 200 (epoxy resin A) Tris(glycidoxyphenyl)methane (epoxy resin B) with epoxy equivalent of 162 m Phenol novolac resin (curing agent A) Tris(hydroxyphenyl)methane with a hydroxyl equivalent of 97 (curing agent B) Triphenylphosphine (curing accelerator A) Triphenylphosphine oxyto (curing accelerator B) Fused silica powder (filler ) Antimony trioxide (flame retardant) Carbon black (coloring agent) Carnauba wax (mold release agent) γ-glycidoxypropyltrimethoxysilane (silane coupling agent) Each epoxy resin composition prepared as described above A molded cured product was produced by transfer molding. Further, using each epoxy resin composition, an MO3 type integrated circuit was resin-sealed by transfer molding to produce a resin-sealed semiconductor device.

Here, transfer molding was performed by molding an epoxy resin composition heated to 90°C with a high-frequency preheater at 170°C for 2 minutes, and further post-curing at 200°C for 8 hours. Also, the size of the sealed semiconductor chip is 1
010X12+, the molded resin package has a thickness of 2
It is a flat package type.

In particular, the following evaluation tests were conducted on each molded cured product and each resin-sealed semiconductor device.

(a) The bending strength of the molded cured product was measured at 25°C.

(b) The flexural modulus of the molded cured product was measured at 25°C.

(e) A bending fracture test was conducted on the molded cured product at 25° C., and the maximum amount of deflection until fracture was measured.

(d) 65°C for 20 resin-sealed semiconductor devices
A thermal cycle test was conducted by exposing the sample to 200° C. 100 times alternately for 30 minutes each time. After the test, the package was cut to see if there were any resin cracks inside.

(8) Reflow soldering was performed on 20 resin-sealed semiconductor devices at 215° C. using the vapor phase (VPS) method, and it was examined whether resin cracks were observed in the package appearance.

(1') Name of resin-sealed semiconductor device after PS completion 2
About 0 pieces! A moisture resistance test was conducted using a pressure compression method at 21'C and 12 atmospheres, and the occurrence of corrosion defects in the semiconductor chip after 200 hours was investigated.

These evaluation results are also listed in Table 1.

[Effects of the Invention] As is clear from the above results, the epoxy resin X compound of the present invention has excellent mechanical properties, and the resin J' obtained by sealing a semiconductor chip with it is Positive semiconductor devices have high reliability and therefore have great industrial value.

Claims (2)

[Claims] (1) An epoxy resin composition comprising an epoxy resin, a curing agent for the epoxy resin, and a melted mixture, dissolved mixture, or reaction mixture of a polyamide elastomer. (2) A resin-sealed semiconductor device, characterized in that a semiconductor chip is sealed with the epoxy resin composition according to claim (1).