JPH04174545A - Semiconductor device, semiconductor sealing epoxy resin composition used for the same and its manufacture - Google Patents

Abstract

PURPOSE:To obtain excellent reservation stability, by sealing a semiconductor element by using epoxy resin composition which contains epoxy resin, hardner, inorganic filler, diazabicycloalkane component, and boric acid component. CONSTITUTION:Epoxy resin A, hardner B, inorganic filler C, diazabicycloalkane component D, and boric acid component E are used in epoxy resin composition, which is usually in the state of powder or its tablet. Further, in addition to A-E, organopolysiloxane F is used. When E is used together with D, curing is accelerated. Component of D is set within 1.5% of the sum amount of A and B, and preferably, in the range of 0.5-1.5%. Compound amount of E is set to be 0.5-5 in the mixed mol ratio to D, and preferably, in the range of 1-3. Thereby a highly reliable semiconductor device sealed by using epoxy resin composition excellent in reservation stability can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to semiconductor devices etc. that are resin-sealed with an epoxy resin composition having excellent storage stability and have high moisture resistance reliability and solder resistance reliability. It is.

[Prior Art] Ceramic or plastic packages are usually used to seal semiconductor elements such as transistors, ICs, and LSIs. The above ceramic package is resistant to temperature and humidity because the constituent material itself has heat resistance and excellent moisture resistance.Furthermore, since it is a hollow package, it has high mechanical strength and can be sealed with high reliability. It is. However, the above-mentioned ceramic package has the disadvantage that it is relatively expensive and is not suitable for mass production, so recently, sealing using plastic has become mainstream. Epoxy resin compositions have traditionally been used for this type of resin sealing.
He has achieved good results.

In particular, the epoxy resin composition includes an epoxy resin, a phenol resin as a hardening agent, an inorganic filler,
Products composed of imidazoles as curing accelerators, various rubbers as elasticity reducing agents in some cases, silicone oil, etc. are considered to have excellent sealing workability (especially workability during transfer molding). It is used for awards.

[Problem to be Solved by the Invention I] However, recently, from the viewpoint of emphasizing workability, there has been a demand for fast-curing epoxy resins, and various curing accelerators have been added to these epoxy resins. As an example,
Examples include bicycloalkenes such as 1,8-diazabicycloalkene. However, in fast-curing epoxy resin compositions for sealing that contain such curing accelerators, the curing reaction progresses during storage, making it difficult to perform sealing molding operations during the manufacture of semiconductor devices. Even if molded, the adhesion between the encapsulating resin and the lead frame will deteriorate, and the viscosity will increase, causing the gold wire of the semiconductor element to break, reducing the reliability of the resulting semiconductor device. A problem arises. This tendency is remarkable when the melting point of the molten mixture of epoxy resin and curing agent is low, especially when the melting point is 40° C. or lower. The above melting point is
For example, it is measured using a differential scanning calorimetry (DSC) device, such as DSC (manufactured by Rigaku Denki Co., Ltd.).

TAS-200), the heating rate is 5°C/sin, and the temperature at which endotherm starts is taken as the melting point of the epoxy resin composition.

That is, as shown in the figure, the baseline X and the endothermic curve Y
The intersection point A with the tangent line (-dotted chain line Z) is defined as the melting point. For this reason, when storing the above-mentioned epoxy resin composition for sealing for a long period of time, it is usually stored frozen, but this is quite time-consuming and complicated, and there is a need for improvement. Therefore, it is desired to develop a technique that can provide a highly reliable semiconductor device without freezing during long-term storage as described above.

On the other hand, recently, low viscosity holes made of epoxy resins and phenolic resins have been used. This suppresses expansion during resin sealing by heating by blending a large amount of inorganic filler. However, when such a large amount of inorganic filler is added, the storage stability of the epoxy resin composition deteriorates.

The present invention was made in view of the above circumstances, and provides a semiconductor device that is resin-sealed with an epoxy resin composition that has excellent storage stability and has excellent reliability, and an epoxy resin composition for semiconductor encapsulation used therein. Its purpose is to provide products and their manufacturing methods.

[Means to solve the problem]

In order to achieve the above object, the present invention provides the following (A) to
The first gist is a semiconductor device in which a semiconductor element is sealed using an epoxy resin composition containing (E) (A) an epoxy resin.

(B) Hardening agent.

(C) Inorganic filler.

CD) diazabicycloalkene component.

(E) Boric acid component.

In addition to the above (A) to (E), the second aspect is a semiconductor device in which a semiconductor element is sealed using an epoxy resin composition containing the following (F): (F) organopolysiloxane.

The third aspect is an epoxy resin composition for semiconductor encapsulation containing the following (A) to (E): (A) an epoxy resin;

(B) Hardening agent.

(C) Inorganic filler.

(D) Diazabicycloalkene component.

(E) Boric acid component.

The fourth aspect is an epoxy resin composition for semiconductor encapsulation containing the following (F) in addition to the above (A) to (E): (F) organopolysiloxane.

The fifth method for producing an epoxy resin composition is to knead the ingredients having the following (A) to (E) in a heated state to form a semi-cured state.
(A) Epoxy resin.

(B) Hardening agent.

(C) Inorganic filler.

(D) Diazabicycloalkene component.

(E) Boric acid component.

The sixth gist is a method for producing an epoxy resin composition in which the above (A) to (E) plus the following (F) are kneaded in a heated state to form a semi-cured epoxy resin composition.

(F) Organopolysiloxane.

The diazabicycloalkene component CD) and the boric acid component (E) include individual compounds of diazabicycloalkene and boric acid, as well as diazabicycloalkene and boric acid reacted in advance. Contains borates of diazabicycloalkenes. Therefore, in the present invention, the diazabicycloalkene component (D) and the boric acid component (E) may be combined to form the diazabicycloalkene component (D). Even if the diazabicycloalkene component and the boric acid component (E) are described separately, the boric acid component (E) may not be substantially present. However, the present invention is intended to include such aspects as well.

[Effect]

The present inventors have conducted a series of studies in order to obtain an epoxy resin composition for semiconductor encapsulation that has excellent storage stability without impairing its properties. As a result, it was discovered that rather than using diazabicycloalkene alone, which has traditionally been used as a curing accelerator, extremely large effects can be obtained by converting it into a borate form or using it in combination with boric acid. Ta. Furthermore, it was discovered that even more excellent reliability could be obtained by adding organopolysiloxane in addition to the boric acid component, and the present invention was achieved.

Next, the present invention provides diazabicycloalkene component (D)
and a boric acid component (E), and as mentioned earlier, both of the above components include not only a single compound of diazabicycloalkene and boric acid, but also a reaction product of both. Also included. Therefore, in the present invention, the combinations of the diazabicycloalkene component and the boric acid component are enumerated as follows.

First Embodiment A diazabicycloalkene component (D) and a boric acid component (E) are combined, and a diazabicycloalkene borate is used as the combined component.

Second embodiment: The diazabicycloalkene borate and diazabicycloalkene are used together.

Third Embodiment A diazabicycloalkene and boric acid are used together.

Fourth aspect A diazabicycloalkene borate salt, diazabicycloalkene, and boric acid are used together.

Fifth aspect A diazabicycloalkene borate and boric acid are used together.

Furthermore, in the above embodiment, the melting point of the molten mixture of the epoxy resin (A) and the curing agent (B), and in some cases organopolysiloxane (F) is added to both the epoxy resin and the curing agent. If the temperature is below 40°C, add the inorganic filler (C) and then directly add the diazabicycloalkene to form the epoxy resin composition (
When made into a compound), storage stability deteriorates. For example, the epoxy resin (A) and the curing agent (B) react with each other over time, and the viscosity of the compound changes.

Therefore, even if a semiconductor element is sealed using this, reliability becomes unstable. In the course of the series of research mentioned above, the present inventors found that when the melting point of the mixture of epoxy resin (A) and curing agent (B) is 40°C or lower, diazabicycloalkene cannot be used as it is. Instead, the inventors have found that the above disadvantages can be eliminated by using diazabicycloalkene as a borate salt, which is also a major feature of the present invention.

The epoxy resin composition used in the present invention comprises an epoxy resin ylri (A), a curing agent (B), an inorganic photo-tJE agent (C), a diazabicycloalkene component (D), and a boric acid component (E ), and is usually in powder form or tablet form. In some cases, it may also be in the form of a solution. Furthermore, in addition to the above A to E, organopolysiloxane (F) is used.

Examples of the epoxy resin (A) include commonly used epoxy resins, such as novolak epoxy resins, particularly cresol novolac epoxy resins. As a novolac type epoxy resin, the epoxy equivalent is 160~
250°C and a softening point of 35 to 130°C are generally used. As the Talesol novolac type epoxy resin, those having an epoxy equivalent of 180 to 210 and a softening point of 35 to 110'c are generally used.

The curing agent (B) acts as a curing agent for the epoxy resin (A), and a phenol resin is usually used. Examples of the above phenolic resin include phenol novolak, 0-talesol novolak, m-cresol novolak, P-talesol novolak, 0-talesol novolac,
Ethylphenol novolak, m-ethylphenol novolak, p-ethylphenol novolak, etc. are preferably used. It is preferable to use these novolac resins having a softening point of 50 to 110 degrees and a 1 hydroxyl equivalent of 100 to 150. Further, as a curing agent (component B), imidazole or the like may be used in combination with the above phenol resin. In this case, the blending ratio of both of the above is preferably set within 3 parts of imidazole per 100 parts by weight (hereinafter abbreviated as "parts") of the phenol resin, and particularly preferably 1.5 to 2.5 parts by weight of imidazole. Department. The blending amount of these curing agents (B) is 5% based on the entire epoxy resin composition.
It is preferable to set it within the range of ~25% by weight (hereinafter abbreviated as "r%"). In terms of equivalent ratio, the amount of phenol resin is 0.6 to 1.0 per 1 epoxy equivalent of epoxy resin.
Generally, they are blended in a proportion of pentahydroxyl equivalents.

Inorganic fillers (C) used together with the epoxy resin (A) and curing agent (B) include silica, alumina, calcium carbonate, quartz glass, silica, talc, clay, and zirconium oxide.

Powdered materials such as zirconium silicate and beryllium oxide can be used. Then, the inorganic filler (C
It is preferable that the blending amount of component) is set within the range of 30 to 90% based on the total epoxy resin composition.

The diazabicycloalkene component (D) used together with the epoxy resin (A), curing agent (B) and inorganic filler (C) is a diazabicycloalkene or a borate thereof, and can be used alone or in combination. It will be done. These act as curing accelerators. And diazabicycloalkene is represented by the following general formula.

[In the formula, n is an integer of 2 to 6. ] Specifically, 1 is expressed by the following formula assuming that n is 2.
, 5-diazabicyclo(4,2,0)octene-5, represented by the following formula when n is 3, 1,5-diazabicyclo(4,3,O)nonene-5, when n is 4 l,5-diazabicyclo(4,4
,0) Decene-5, represented by the following formula when n is 5, 1,8-diazabicyclo(5,4,0)undecene-7, 1 represented by the following formula when n is 6 , 9-
Examples include diazabicyclo(6,4,O) dodecene-8. Such a diazabicycloalkene component (D)
The amount of the diazabicycloalkene component is appropriately selected and blended depending on the purpose of use, but whether used alone or in combination, the diazabicycloalkene component is the total amount of the epoxy resin (A) and the curing agent (B). It is desirable to set the content within 1.5%, preferably within a range of about 0.5 to 1.5%. Examples of the diazabicycloalkene borates include orthoborate, pyroborate, metaborate, and various other polyborates of the diazabicycloalkene (D). Among them, 1,8-diazabicyclo(5,4,
O) undecene-7,1,5-diazabicyclo(4,3
, O) Nonene-5 borate is preferably used. These borates are usually in solution form.

Boric acid component (E
) include orthoboric acid, pyroboric acid, metaboric acid, and various other polyboric acids. These compounds are used not only in the form of individual compounds, but also in the form of borates obtained by reacting with diazabicycloalkenes in advance. When used in this state, the boric acid component (E) should be replaced with the diazabicycloalkene component (
D). The blending amount of these boric acid components (E) is as follows:
When used in combination with D), it is desirable to set the mixing molar ratio with the diazabicycloalkene component to about 0.5 to 5, preferably about 1 to 3.

Furthermore, an organopolysiloxane (F) is used together with the epoxy resin (A), curing agent (B), inorganic filler (C), diazabicycloalkene component (D), and boric acid component (E). The above organopolysiloxane (F
) is preferably one having a polysiloxane skeleton represented by the following general formulas (I) and (If). These may be used alone or in combination.

In the above formula (1), R2 is preferably a propyl group, and R3 is a phenyl group or a monovalent organic group having a functional group reactive with an aralkyl group. As the above-mentioned monovalent organic group having a reactive organic group, a group having an epoxy group via a propyl group (glycidyl ether) is preferably mentioned. Such an organopolysiloxane, an epoxy resin (A) and a curing agent (
By reacting with at least one of B), good results for low stress properties can be obtained. Such an organopolysiloxane has a molecular weight of -500
It is preferable to use one having a molecular weight of 500 to 40,000, particularly preferably 500 to 30,000. That is, if the molecular weight is less than 500, the resulting sealing resin will have insufficient low stress properties, and if it exceeds 40,000, there will be a tendency for the reactivity with at least the above-mentioned epoxy resin (A) to decrease.

The amount of the organopolysiloxane blended is set in the range of 3 to 40 parts per 100 parts of at least one of the epoxy resin (A) and the curing agent (B), from the viewpoint of low stress properties of the cured product. preferable.

In addition, in addition to the above-mentioned components (A to F), a release agent may be appropriately added to the epoxy resin composition used in the present invention, if necessary.

As the mold release agent, conventionally known long-chain carboxylic acids such as stearic acid and barmitic acid, metal salts of long-chain carboxylic acids such as zinc stearate and calcium stearate, and waxes such as carnauba wax and montan wax are used. be able to.

Furthermore, in addition to the above mold release agent, a coupling agent.

Commonly used additives such as flame retardant 2 colorants can also be added.

The epoxy resin composition used in the present invention can be produced, for example, as follows. That is, the above-mentioned raw materials are kneaded in a heated state by passing through a mixer such as a mixing roll machine to produce a semi-cured resin composition. and,
The desired epoxy resin composition can be produced through a series of steps of cooling this to room temperature, pulverizing it by known means, and tableting if necessary. Furthermore, when organopolysiloxane (F) is used, it is reacted with at least one of the epoxy resin (A) and the curing agent (B) in advance. Next, this reaction product and the remaining raw materials are kneaded in a heating state using an FF11 machine such as a mixing roll machine to produce a semi-cured resin composition. After that, the desired epoxy resin composition can be manufactured by going through the same steps as above.

The encapsulation of a semiconductor element using such an epoxy resin composition is not particularly limited, and can be performed by a conventional method, for example, a known molding method such as transfer molding.

The semiconductor device obtained in this way has high reliability (moisture resistance reliability) as shown in the examples below.

(solder resistance reliability). This is thought to be due to the fact that the adhesion between the lead frame, etc. of the semiconductor element and the sealing resin is improved, and corrosion of the lead frame, etc. due to poor adhesion is prevented.

[Effects of the Invention] As described above, the semiconductor device of the present invention is constructed by sealing a semiconductor element using the above-mentioned special epoxy resin composition, and the epoxy resin composition itself has storage stability. It has excellent reliability, especially moisture resistance and solder resistance. In particular, the above-mentioned epoxy resin composition does not need to be stored frozen and can be stored at room temperature, resulting in a significant improvement in workability. Moreover, according to the manufacturing method of the present invention, a semi-cured epoxy resin composition can be easily manufactured.

Next, examples will be described together with comparative examples.

First, diazabicycloalkenes as curing accelerators shown in Table 1 below were prepared. In addition, in Table 1,
DBU is 1,8-diazabicyclo(5,4,0)undecene-7 and DBN is 1,5-diazabicyclo(4
,3,0) nonene-5.

(Hereinafter in the margin) Table 11''-11 Next, examples of the above-mentioned first aspect will be described together with comparative examples.

[Examples 1 to 8, Comparative Example 1.2] The raw materials shown in Table 2 below were blended in the proportions shown in the same table, and kneaded for 1°5 minutes using a mixing roll machine (temperature 110°C) to form a semi-cured product. A resin composition was prepared. Then, this was cooled to room temperature and then pulverized to obtain a powdered epoxy resin composition for semiconductor encapsulation.

(The following is a blank space) Spiral flow (SF) was measured for the powdered epoxy resin compositions obtained in the above Examples and Comparative Examples, and the retention rate of the epoxy resin compositions was characterized. The results are shown in Table 3 below. The above retention rate is calculated by the following 2.

Then, SF is obtained as follows. First, a powdered epoxy resin composition is prepared in the form of a tablet (diameter 24mm).
5 mm x thickness 20 mm).

This tablet is preheated to a specified temperature (155±5° C.) and placed deep into the pot of a spiral SF mold, and the mold is clamped to increase the clamping pressure to 210±10 kg/mm 2 . And the mold clamping pressure is 210±10kg/m
2, and at the same time the injection pressure cuff reaches 60 ± 5 kg/m+" (total pressure), apply injection pressure for 1 minute and 50 seconds. Next, release the pressure from the plunger of the transfer molding machine, and then release the above mold clamping pressure. The mold is opened and the SF value is obtained by measuring the spiral length of the mold to 2.5 m (1 in).

(Left below) In addition, what was obtained from the above examples and comparative examples,
A semiconductor device was produced by molding a semiconductor element by transfer molding using a powdered epoxy resin composition that had been stored at 25° C. for 25 days. The semiconductor device thus obtained was subjected to a 2000-hour reliability test in a pressure cooker under voltage application (
(hereinafter abbreviated as "PCBT test"), and 215℃ x 90
sec paper phase soldering (VPS) was performed, and a pressure puller test (rPCT test hereinafter) was performed at 150° C. for 300 hours, and the number of defective pieces was counted to evaluate the reliability. The results are shown in Table 4 below.

(The following is a blank space) Otoko-1"L--1 From the results in Tables 3 and 4 above, it can be seen that the epoxy resin compositions obtained in Examples have better storage stability than those in Comparative Examples. . In addition, the number of defective semiconductor devices that were resin-sealed using the epoxy resin composition of the example was much smaller than that of the comparison side hole. From these facts, the epoxy resin compositions obtained in the Examples have excellent storage stability, and the Example products resin-sealed with these epoxy resin compositions have excellent moisture resistance and solder resistance. You can see that

Next, an example of the second aspect described above will be described together with a comparative example.

(Examples 9 to 17) The raw materials shown in Table 5 below were blended in the proportions shown in the same table, and kneaded for 1.5 minutes using a mixing roll machine (temperature 110°C) to produce a semi-cured resin composition. did.

Then, this was cooled to room temperature and then pulverized to obtain a powdered epoxy resin composition for semiconductor encapsulation. In addition, the molar ratio value in the column of curing accelerator in Table 5 below indicates the molar mixing ratio of diazabicycloalkene and diazabicycloalkene borate, and (diazabicycloalkene)= (borate of diazabicycloalkene).

(The following is a blank space) Using the powdered epoxy resin compositions obtained in the above examples and comparative examples, the retention rate of the epoxy resin compositions was characterized in the same manner as in the examples of the first aspect. The results are shown in Table 6 below.

(Left below) In addition, using the powdered epoxy resin compositions obtained in the above Examples and Comparative Examples, a PCT test was performed in the same manner as in the first embodiment, and the number of defective pieces was counted. was evaluated.

The results are shown in Table 7.

(Leaving space below) Tables 12 and 11 From the results in Tables 6 and 7 above, it can be seen that the epoxy resin compositions obtained in Examples have better storage stability than those in Comparative Examples. . Moreover, the number of defective semiconductor devices resin-sealed using the epoxy resin composition of the example and the actual height measurement was significantly smaller than that of the comparison side hole. From these facts, the epoxy resin assemblies obtained in the examples have excellent storage stability, and the holes on the implementation side resin-sealed with these epoxy resin compositions have excellent moisture resistance and solder resistance reliability. You can see that

Next, an example of the third aspect described above will be described together with a comparative example.

[Examples 18 to 25] The raw materials shown in Table 8 below were blended in the proportions shown in the same table, and kneaded for 1.5 minutes using a mixing roll machine (temperature 110°C) to produce a semi-cured resin composition. did.

Then, this was cooled to room temperature and then pulverized to obtain a powdered epoxy resin composition for semiconductor encapsulation.

(The following is a blank space) Using the powdered epoxy resin compositions obtained in the above examples and comparative examples, the retention rate of the epoxy resin compositions was characterized in the same manner as in the examples of the first aspect. The results are shown in Table 9 below.

(Hereinafter, blank spaces) Further, using the products obtained in the above Examples and Comparative Examples, a PCT test was performed in the same manner as in the Example of the first aspect, and the reliability was evaluated by counting the number of defective products. The results are shown in Table 10.

(The following is a blank space) Table 10-11 From the results in Tables 9 and 10 above, it can be seen that the epoxy resin compositions obtained in Examples have better storage stability than those in Comparative Examples. Moreover, the number of defective semiconductor devices in which the holes on the implementation side were resin-sealed using the epoxy resin composition of the example was significantly smaller than that in the holes on the comparison side. From these facts, the epoxy resin compositions obtained in the examples have excellent storage stability, and the actual height measurements resin-sealed with these epoxy resin compositions have excellent moisture resistance reliability and solder reliability. I know that there is.

Next, examples of the fourth and fifth aspects described above will be described together with comparative examples.

[Examples 26 to 31] The raw materials shown in Table 11 below were blended in the proportions shown in the same table,
A semi-cured resin composition was prepared by kneading for 1.5 minutes using a mixing roll machine (temperature: 110°C). Then, this was cooled to room temperature and then pulverized to obtain a powdered epoxy resin composition for semiconductor encapsulation.

(The following is a blank space) Using the powdered epoxy resin compositions obtained in the above examples and comparative examples, the retention rate of the epoxy resin compositions was characterized in the same manner as in the examples of the first aspect. The results are shown in Table 12 below.

(Left below) In addition, using the products obtained in the above Examples and Comparative Examples, a PCT test was conducted in the same manner as in the Example of the first aspect, and the reliability was evaluated by counting the number of defective pieces. . The results are shown in Table 13.

(The following is a blank space) Male-f Table From the results in Tables 12 and 13 above, it can be seen that the epoxy resin compositions obtained in the Examples have better storage stability than those in the Comparative Examples.

In addition, the number of defective semiconductor devices that were resin-sealed using the epoxy resin composition of the example was significantly smaller than that of the comparative example. From these facts, the epoxy resin compositions obtained in the Examples have excellent storage stability, and the Example products resin-sealed with these epoxy resin compositions have excellent moisture resistance and solder resistance. You can see that

Next, examples in which the melting point of the molten mixture of the epoxy resin (A) and the curing agent (B) is 40° C. or lower will be described together with comparative examples.

[Examples 32 to 45, Comparative Examples 3 and 4] The raw materials shown in Table 14 below were prepared, and first an epoxy resin and a phenol resin as a hardening agent were melt-mixed. At this time, the melting point of the molten mixture was measured and is also shown in Table 14 below. Then, the above molten mixture and the remaining raw materials were blended, and 1.
A semi-cured resin composition was prepared by kneading for 5 minutes. Then, this was cooled to room temperature and then pulverized to obtain a powdered epoxy resin composition for semiconductor encapsulation.

(The following is a blank space) Using the powdered epoxy resin compositions obtained in the above examples and comparative examples, the retention rate of the epoxy resin compositions was characterized in the same manner as in the examples of the first aspect. The results are shown in Table 15 below.

(The following is a blank space) (9A) Furthermore, using the samples obtained in the above Examples and Comparative Examples, the number of days the samples were left in the 25° C. atmosphere was changed to 10 days. Other than that, reliability was evaluated by performing a PCT test in the same manner as in the example of the first aspect and counting the number of defective pieces. The results are shown in Table 16.

(Hereinafter, blank spaces) Table M From the results in Tables 15 and 16 above, it can be seen that the epoxy resin compositions obtained in Examples have better storage stability than those in Comparative Examples.

Moreover, the number of defective semiconductor devices resin-sealed using the epoxy resin composition of the example and the actual height measurement was significantly smaller than that of the comparison side hole. From these facts, the epoxy resin compositions obtained in the examples have excellent storage stability, and the actual height measurements resin-sealed with these epoxy resin compositions have excellent moisture resistance and solder resistance reliability. I know that there is.

Next, examples using organopolysiloxane in the first embodiment described above will be described together with comparative examples.

First, four types of organopolysiloxanes A to D shown in Table 17 below were prepared.

(Left below) [Examples 46 to 61, Comparative Examples 5 to 8] The raw materials shown in Table 18 below were blended in the proportions shown in the table,
A semi-cured resin composition was prepared by kneading for 1.5 minutes using a mixing roll machine (temperature: 110°C). Then, this was cooled to room temperature and then pulverized to obtain a powdered epoxy resin composition for semiconductor encapsulation.

(Hereinafter, blank spaces) Using the powdered epoxy resin compositions obtained in the above Examples and Comparative Examples, the retention rate of the epoxy resin compositions was evaluated in the same manner as in the Examples of the first aspect. The results are shown in Table 19 below.

(Left below) In addition, using the powdered epoxy resin compositions obtained in the above Examples and Comparative Examples, PCT tests were conducted in the same manner as in the first aspect, and the number of defective pieces was counted. evaluated. The results are shown in Table 20 below.

1--lny-1 (part 1) Star--Iny (part 2) From the results in Tables 19 and 20 above, the epoxy resin compositions obtained in the examples are more stable in storage than those in the comparative examples. It turns out that he has excellent sex.

Furthermore, the semiconductor devices that were resin-sealed using the epoxy resin compositions of the examples and which were tested had a significantly smaller number of defects than the comparative products. From these facts, the epoxy resin compositions obtained in the examples have excellent storage stability, and the actual height measurements resin-sealed with these epoxy resin compositions have excellent moisture resistance and solder resistance. You can see that

Next, examples using organopolysiloxane in addition to the second embodiment described above will be described together with comparative examples.

[Examples 62 to 70] The raw materials shown in Table 21 below were blended in the proportions shown in the same table,
A semi-cured resin composition was prepared by kneading it for 1.5 minutes using a mixing roll machine (temperature: 0"C). This was then cooled to room temperature and then pulverized to form a powder for semiconductor encapsulation. An epoxy resin composition was obtained.
The molar ratio value in the column of curing accelerator in Table 1 indicates the molar mixing ratio of diazabicycloalkene and diazabicycloalkene borate, (diazabicycloalkene): (diazabicycloalkene). borate).

(The following is a blank space) Using the powdered epoxy resin compositions obtained in the above examples and comparative examples, the retention rate of the epoxy resin compositions was characterized in the same manner as in the examples of the first aspect. The results are shown in Table 22 below.

(Margin below)! -X- Table (%) In addition, using the powdered epoxy resin compositions obtained in the above Examples and Comparative Examples, a PCT test was performed in the same manner as in the first embodiment, and the number of defective pieces was counted. Reliability was evaluated.

The results are shown in Table 23.

From the results shown in Tables 22 and 23 above, it can be seen that the epoxy resin compositions obtained in Examples have better storage stability than those in Comparative Examples.

In addition, the number of defective semiconductor devices that were resin-sealed using the epoxy resin composition of the example was much smaller than that of the comparison side hole. From these facts, the epoxy resin compositions obtained in the Examples have excellent storage stability, and the Example products resin-sealed with these epoxy resin compositions have excellent moisture resistance and solder resistance. I can see that...

Next, an example using organopolysiloxane in addition to the third embodiment described above will be described together with a comparative example.

[Examples 71 to 78] The raw materials shown in Table 24 below were blended in the proportions shown in the same table,
A semi-cured resin composition was prepared by kneading for 1.5 minutes using a mixing roll machine (temperature: 110°C). Then, this was cooled to room temperature and then pulverized to obtain a powdered epoxy resin composition for semiconductor encapsulation.

(Margin) Using the powdered epoxy resin compositions obtained in the above Examples and Comparative Examples, the retention rates of the epoxy resin compositions were evaluated in the same manner as in the Examples of the first aspect. The results are shown in Table 25 below.

(Left below) In addition, using the products obtained in the above examples and comparative examples, a PCT test was conducted in the same manner as in the example of the first aspect, and the reliability was evaluated by counting the number of defective pieces. . The results are shown in Table 26.

From the results in Tables 25 and 26 above, it can be seen that the epoxy resin compositions obtained in Examples have better storage stability than those in Comparative Examples.

In addition, the number of defective semiconductor devices that were resin-sealed using the epoxy resin composition of the example was much smaller than that of the comparison side hole. From these facts, the epoxy resin compositions obtained in the Examples have excellent storage stability, and the Example products resin-sealed with these epoxy resin compositions have excellent moisture resistance and solder resistance. You can see that

Next, examples using organopolysiloxane in addition to the fourth and fifth embodiments described above will be described together with comparative examples.

[Examples 79 to 84] The raw materials shown in Table 27 below were blended in the proportions shown in the same table,
A semi-cured resin composition was prepared by kneading for 1.5 minutes using a mixing roll machine (temperature: 110°C). Then, this was cooled to room temperature and then pulverized to obtain a powdered epoxy resin composition for semiconductor encapsulation.

(The following is a blank space) Using the powdered epoxy resin compositions obtained in the above examples and comparative examples, the retention rate of the epoxy resin compositions was characterized in the same manner as in the examples of the first aspect. The results are shown in Table 28 below.

(Hereinafter, blank spaces) Further, using the products obtained in the above Examples and Comparative Examples, a PCT test was performed in the same manner as in the Example of the first aspect, and the reliability was evaluated by counting the number of defective products. The results are shown in Table 29.

From the results in Tables 28 and 29 above, it can be seen that the epoxy resin compositions obtained in Examples have better storage stability than those in Comparative Examples.

Moreover, the number of defective semiconductor devices resin-sealed using the epoxy resin composition of the example and the actual height measurement was significantly smaller than that of the comparative example hole. From these facts, the epoxy resin compositions obtained in the examples have excellent storage stability, and the actual height measurements resin-sealed with these epoxy resin compositions have excellent moisture resistance and solder resistance reliability. I know that there is.

Next, examples in which the melting point of the molten mixture of the epoxy resin (A), the curing agent (B) and the organopolysiloxane (D) is 40°C or lower will be described together with comparative examples.

[Examples 85 to 98, Comparative Examples 9.10] The raw materials shown in Table 30 below were prepared, and first, epoxy resin, phenol resin, and organopolysiloxane A to D were melt-mixed.

At this time, the melting point of the above molten mixture was measured, and the following
It is also shown in Table 0. Then, the above molten mixture and the remaining raw materials were blended and kneaded for 1.5 minutes using a mixing roll machine (temperature: 110°C) to produce a semi-cured resin composition.

Then, this was cooled to room temperature and then pulverized to obtain a powdered epoxy resin composition for semiconductor encapsulation.

Using the powdered epoxy resin compositions obtained in the above Examples and Comparative Examples, the retention rate of the epoxy resin compositions was characterized in the same manner as in the Examples of the first aspect. The results are shown in Table 31 below.

(Hereinafter, blank space) Furthermore, using the samples obtained in the above Examples and Comparative Examples, the number of days the samples were left in an atmosphere at 25° C. was changed to 10 days. Other than that, reliability was evaluated by performing a PCT test in the same manner as in the example of the first aspect and counting the number of defective pieces. The results are shown in Table 32.

(Left blank below) Table 12-32 From the results in Tables 31 and 32 above, it can be seen that the epoxy resin compositions obtained in Examples have better storage stability than those in Comparative Examples. .

In addition, the number of defects in semiconductor devices with the example hole resin-sealed using the epoxy resin composition of the example was significantly smaller than that with the comparative hole. Based on these facts, the epoxy resin compositions obtained in the examples have excellent storage stability, and the example holes sealed with the epoxy resin compositions have excellent moisture resistance and solder resistance. You can see that

[Brief explanation of drawings]

The drawing is a DSC melting curve. Patent applicant: Nitto Denko Corporation Agent: Patent Attorney Yukihiko Nishifuji

Claims (22)

[Claims] (1) A semiconductor device in which a semiconductor element is sealed using an epoxy resin composition containing the following (A) to (E). (A) Epoxy resin. (B) Hardening agent. (C) Inorganic filler. (D) Diazabicycloalkene component. (E) Boric acid component. (2) A semiconductor device in which a semiconductor element is sealed using an epoxy resin composition containing the following (F) in addition to (A) to (E) according to claim (1). (F) Organopolysiloxane. (3) A claim in which the organopolysiloxane (F) is represented by the following general formula (I) and has reacted with at least one of the epoxy resin (A) and the curing agent (B). (2) The semiconductor device as described. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) [In the above formula (I), X is a divalent group derived from a reactive functional group such as an amino group, carxyl group, hydroxyl group, or epoxy group. In the group, R_1 is H or a monovalent organic group, R_2 is a divalent organic group, R_3 is a methyl group, a phenyl group, an aralkyl group, or a monovalent organic group having a reactive functional group, m+n is an integer from 5 to 200, m
/n is 3 or more. (However, if R_3 is a methyl group, the above m/n = 3 or more does not apply.)] (4) The organopolysiloxane (F) is represented by the following general formula (II), and is reacted with at least one of the epoxy resin (A) and the curing agent (B) ( 2) The semiconductor device described. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(II) [In the above formula (II), R_1 is a monovalent organic group, R_
2 is a divalent organic group, R_3 is a phenyl group or an aralkyl group, m+n is an integer of 5 to 200, and m/n is 3 to 20. ] (5) Claim (1) wherein the diazabicycloalkene component (D) and the boric acid component (E) are diazabicycloalkene borate obtained by reacting the diazabicycloalkene and boric acid in advance. ) to (4). (6) Claims (1) to (4) wherein the diazabicycloalkene component (D) and the boric acid component (E) are a borate of a diazabicycloalkene and a diazabicycloalkene.
The semiconductor device according to any one of the above. (7) The semiconductor according to any one of claims (1) to (4), wherein the diazabicycloalkene component (D) and the boric acid component (E) are a diazabicycloalkene and boric acid. Device. (8) Claim (1) wherein the diazabicycloalkene component (D) and the boric acid component (E) are a diazabicycloalkene borate, a diazabicycloalkene, and boric acid.
The semiconductor device according to any one of (4) to (4). (9) Any one of claims (1) to (4), wherein the diazabicycloalkene component (D) and the boric acid component (E) are a diazabicycloalkene borate and boric acid. The semiconductor device described in . (10) Claims (5) and (6) wherein the melting point of the molten mixture of the epoxy resin (A) and the curing agent (B) is 40°C or less.
, (8), and (9). (11) Claims (5), (6), and (8) wherein the melting point of the three-component melt mixture of (A) the epoxy resin, (B) the curing agent, and (F) the organopolysiloxane is 40°C or less.
), (9). (12) An epoxy resin composition for semiconductor encapsulation containing the following (A) to (E). (A) Epoxy resin. (B) Hardening agent. (C) Inorganic filler. (D) Diazabicycloalkene component. (E) Boric acid component. (13) An epoxy resin composition for semiconductor encapsulation, which contains the following (F) in (A) to (E) according to claim (12). (F) Organopolysiloxane. (14) The diazabicycloalkene component of (D) and (E)
The epoxy resin composition for semiconductor encapsulation according to claim 12 or 13, wherein the boric acid component is a diazabicycloalkene borate obtained by reacting a diazabicycloalkene with boric acid in advance. (15) The diazabicycloalkene component of (D) and (E)
The epoxy resin composition for semiconductor encapsulation according to claim 12 or 13, wherein the boric acid component is a diazabicycloalkene borate and a diazabicycloalkene. (16) The diazabicycloalkene component of (D) and (E)
The epoxy resin composition for semiconductor encapsulation according to claim 12 or 13, wherein the boric acid component is diazabicycloalkene and boric acid. (17) The diazabicycloalkene component of (D) and (E)
Claim (12) wherein the boric acid component is a borate of a diazabicycloalkene, a diazabicycloalkene, and boric acid.
) or the epoxy resin composition for semiconductor encapsulation according to (13). (18) The diazabicycloalkene component of (D) and (E)
The epoxy resin composition for semiconductor encapsulation according to claim 12 or 13, wherein the boric acid component is a diazabicycloalkene borate and boric acid. (19) Claims (14) and (1) wherein the melting point of the molten mixture of the epoxy resin (A) and the curing agent (B) is 40°C or lower.
The epoxy resin composition for semiconductor encapsulation according to any one of 5), (17), and (18). (20) Claims (14), (15), wherein the melting point of the three-component melt mixture of (A) epoxy resin, (B) curing agent, and (F) organopolysiloxane is 40°C or less;
The epoxy resin composition for semiconductor encapsulation according to any one of (17) and (18). (21) A method for producing an epoxy resin composition, which comprises kneading ingredients having the following (A) to (E) in a heated state to form a semi-cured state. (A) Epoxy resin. (B) Hardening agent. (C) Inorganic filler. (D) Diazabicycloalkene component. (E) Boric acid component. (22) An epoxy resin composition characterized in that the ingredients (A) to (E) according to claim (21) are mixed with the following (F) in a semi-cured state by kneading in a heated state. Manufacturing method. (F) Organopolysiloxane.