JP5573773B2 - Resin composition for sealing electronic components and electronic component device using the same - Google Patents

Description

  The present invention relates to an electronic component sealing resin composition excellent in long-term heat resistance and an electronic component device using the same.

  In recent years, there has been a demand for an electronic component device that can be used in a high-temperature atmosphere. For example, an electronic component device in which an electronic component is covered with a lid made of ceramics, metal, etc., and is sealed hollow. It is used. However, when the electronic component device thus hollow-sealed is used for an application in which vibration is generated, such as an automobile application, component malfunction such as short circuit of internal electrical connection due to external vibration is likely to occur. Therefore, in order to suppress the influence of vibration, a method of sealing an electronic component with a resin has been studied.

  Conventionally, an epoxy resin composition has been used as such a resin composition for encapsulating electronic components. And as what was excellent in the electronic component sealing use, for example, an epoxy resin containing a resin composition having a high glass transition temperature using a polyfunctional epoxy resin and a polyfunctional phenol resin in combination, or a bismaleimide resin or a benzoxazine resin Use of the composition is examined (see Patent Documents 1 to 3).

Japanese Patent No. 2587074 Japanese Patent No. 2825572 Japanese Patent No. 3900317

  However, since the resin composition disclosed in Patent Document 1 using a polyfunctional epoxy resin and a polyfunctional phenol resin in combination is not sufficient in terms of long-term heat resistance and adhesiveness, improvement thereof is required.

  In addition, the epoxy resin composition containing bismaleimide resin or benzoxazine resin disclosed in Patent Document 2 and Patent Document 3 has high heat resistance, but has a problem of poor moldability due to high viscosity. .

  The present invention has been made in view of such circumstances, and provides an electronic component sealing resin composition excellent in moldability, adhesiveness, etc., and excellent in long-term heat resistance, and an electronic component device using the same. For that purpose.

In order to achieve the above object, the present invention is an electronic component sealing resin composition containing the following components (C) to (F) together with the following components (A) and (B): (E) Let the content of a component be 5 weight% or more of the whole resin composition, and let the resin composition for electronic component sealing be the 1st summary.
(A) An epoxy resin having 3 or more epoxy groups in one molecule and having an epoxy equivalent of 160 to 180.
(B) A phenol resin having less than 2 methylene groups in one molecule, 3 or more phenolic hydroxyl groups, and a hydroxyl equivalent weight of 90 to 105.
(C) A curing accelerator.
(D) Carboxylic anhydride.
(E) Magnesium hydroxide.
(F) Inorganic filler excluding component (E).

  Moreover, this invention makes the 2nd summary the electronic component apparatus formed by sealing an electronic component using the said resin composition for electronic component sealing.

  That is, the present inventors have intensively studied to solve the above problems. As a result of the research, as described above, the polymer is a combination of a specific epoxy resin (A) with specified epoxy equivalents and a specific phenol resin (B) with specified hydroxyl equivalents. In addition to being excellent in moldability, adhesiveness, etc., since the amount of epoxy groups in the entire resin composition exceeds the amount of hydroxyl groups, self-polymerization by the excess epoxy groups proceeds, heat resistance, toughness, etc. It has been found that improvement is achieved. Furthermore, by including a carboxylic acid anhydride (D), a specific amount of magnesium hydroxide (E), etc. in the resin composition, the crosslinking density is increased, long-term heat resistance is improved, and the intended purpose is We have found that this can be achieved and have reached the present invention.

  As described above, the resin composition for sealing an electronic component of the present invention includes a specific epoxy resin (A), a specific phenol resin (B), a curing accelerator (C), and a carboxylic acid anhydride (D ), A specific amount of magnesium hydroxide (E), and an inorganic filler (F). Therefore, it is excellent in moldability, adhesiveness, etc., has a high glass transition temperature, and has excellent effects in long-term heat resistance. Moreover, when the resin composition for sealing an electronic component of the present invention is used, an electronic component device having high heat resistance reliability can be easily obtained.

  In particular, when the component (B) is contained so that the amount of the hydroxyl group of the component (B) is 0.7 to 0.9 equivalent with respect to 1 equivalent of the epoxy group in the component (A), the heat resistance In addition, the toughness becomes more excellent.

  In addition, when the content of the component (D) is in the range of 1 to 5 parts by weight with respect to 100 parts by weight of the total amount of the components (A) and (B), moisture resistance reliability, long-term heat resistance, etc. Become better.

  Moreover, when the inorganic filler of the said (F) component is a silica powder, it will become excellent by the reduction effect of the thermal linear expansion coefficient of the hardening body of the resin composition for electronic component sealing.

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

As described above, the resin composition for sealing an electronic component of the present invention contains the following components (C) to (F) together with the following components (A) and (B). The content of the component is 5% by weight or more of the entire resin composition.
(A) An epoxy resin having 3 or more epoxy groups in one molecule and having an epoxy equivalent of 160 to 180.
(B) A phenol resin having less than 2 methylene groups in one molecule, 3 or more phenolic hydroxyl groups, and a hydroxyl equivalent weight of 90 to 105.
(C) A curing accelerator.
(D) Carboxylic anhydride.
(E) Magnesium hydroxide.
(F) Inorganic filler excluding component (E).

  As the epoxy resin of the component (A), as described above, an epoxy resin having 3 or more epoxy groups in one molecule and having an epoxy equivalent of 160 to 180 is used. The number of epoxy groups in one molecule is preferably 3-4.

  The epoxy resin of component (A) is specifically a triphenolmethane type epoxy resin represented by the following general formula (1), tetraglycidyl ether of bis (naphthalenediol) methane (the following chemical formula ( 2)) 1,1,2,2-tetrakis (hydroxyphenyl) ethane tetraglycidyl ether (the following chemical formula (3)) and the like. These may be used alone or in combination of two or more. Among these, from the viewpoint of heat resistance, a triphenolmethane type epoxy resin represented by the following general formula (1) is preferably used.

  The content of the component (A) in the resin composition for sealing an electronic component of the present invention is preferably 5 to 15% by weight of the entire resin composition.

  In addition, in the resin composition for sealing an electronic component of the present invention, an epoxy resin other than the component (A) may be used in combination with the component (A). From the viewpoint of heat resistance, it is preferable to use at least% by weight as the component (A).

  As described above, the phenol resin of the component (B) used together with the epoxy resin of the component (A) has less than 2 methylene groups and 3 or more phenolic hydroxyl groups in one molecule. A phenol resin having a hydroxyl group equivalent of 90 to 105 is used. Here, the term “less than 2 methylene groups in one molecule” means that, when a plurality of types of the phenol resin of the component (B) are used in combination, an average of less than 2 methylene groups in one molecule It also means that the number of methylene groups in one molecule is zero. The number of phenolic hydroxyl groups in one molecule is preferably 3-4.

  And the phenol resin of the said (B) component will not be specifically limited if the said prescription is satisfy | filled, For example, a triphenol methane type phenol resin, tetrakis (hydroxyphenyl) ethane, a phenol novolak resin, etc. can give. These may be used alone or in combination of two or more. Among these, from the viewpoint of heat resistance, a triphenolmethane type phenol resin that satisfies the above-mentioned regulations is preferably used.

  The content of the component (B) in the resin composition for sealing an electronic component of the present invention is preferably such that the hydroxyl group content of the component (B) is 0.7 per 1 equivalent of the epoxy group in the component (A). The component (B) is preferably contained so as to be -0.9 equivalent, and particularly preferably 0.75-0.85 equivalent. That is, by setting the content in this way, the amount of epoxy groups in the entire resin composition exceeds the amount of hydroxyl groups, self-polymerization by the excess epoxy groups proceeds, and a cured product that is superior in heat resistance and toughness It is because it can obtain.

  In the electronic component sealing resin composition of the present invention, a phenol resin other than the component (B) may be used in combination with the component (B). From the viewpoint of heat resistance, it is preferable to use at least% by weight as the component (B).

  In addition, as described above, when an epoxy resin other than the component (A) is used in combination or a phenol resin other than the component (B) is used in combination, an epoxy resin including an epoxy resin other than the component (A) The ratio of the entire epoxy group and the phenolic hydroxyl group of the whole phenol resin including the phenol resin other than the component (B) is 0.7 to 0.9 equivalent of the hydroxyl group with respect to 1 equivalent of the epoxy group. Thus, it is preferable to set the blending ratio, and it is particularly preferable to set the blending ratio so that the amount of hydroxyl group is 0.75 to 0.85 equivalent to 1 equivalent of epoxy group.

  The curing accelerator for the component (C) used together with the component (A) and the component (B) is not particularly determined as long as the curing of the epoxy resin and the phenol resin proceeds. From the viewpoint of heat resistance, it is preferable to use an imidazole compound. Especially, it is more preferable to use the imidazole compound which has an alkylol group at the point which accelerates | stimulates the self-polymerization of an epoxy group, and it is still more preferable to use the imidazole shown by following Chemical formula (4). And it is preferable that content of these (C) component shall be 0.02-0.2 weight% of the whole resin composition for electronic component sealing from the point of sclerosis | hardenability and preservability.

  Examples of the carboxylic acid anhydride of the component (D) used together with the components (A) to (C) include phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, anhydrous Examples thereof include nadic acid, methyl nadic anhydride, succinic anhydride, trimellitic anhydride, and pyromellitic anhydride. Especially, it is preferable to use trimellitic anhydride from the point which can produce | generate three carboxyl groups at the time of hardening reaction, and can raise the crosslinking density of the resin composition for electronic component sealing. The content of the component (D) is preferably in the range of 1 to 5 parts by weight with respect to 100 parts by weight of the total amount of the components (A) and (B). That is, when the content of the component (D) is less than the above range, it becomes difficult to obtain an effect of increasing the crosslinking density. Conversely, when the content exceeds the above range, the moisture resistance reliability of the resin composition for encapsulating an electronic component is difficult. This is because a tendency to decrease is observed.

  The magnesium hydroxide of the (E) component used together with the above components (A) to (D) is effective to increase the crosslink density of the resin composition for sealing electronic components, like the carboxylic acid anhydride of the (D) component. In particular, it has the effect of improving long-term heat resistance. In this invention, in order to acquire the said effect, it needs to set so that content of (E) component may be 5 weight% or more of the whole resin composition for electronic component sealing of this invention.

  And it is preferable that content of the said (E) component is 5 to 15 weight% of the whole resin composition for electronic component sealing of this invention. That is, when the content of the component (E) is less than the above range, it is difficult to obtain the effect of increasing the crosslinking density. Conversely, when the content exceeds the above range, the moisture resistance reliability of the electronic component sealing resin composition is lowered. It is because the tendency to do is seen.

  Examples of the inorganic filler of the component (F) used together with the components (A) to (E) include quartz glass, talc, silica (such as fused silica and crystalline silica), alumina, aluminum nitride, silicon nitride, and the like. Powder. These may be used alone or in combination of two or more. Among them, silica powder is used because the internal stress is reduced by reducing the thermal linear expansion coefficient of the cured body of the resin composition for encapsulating electronic components, and as a result, the warpage of the substrate after sealing can be suppressed. It is preferable to use a fused silica powder among the silica powders. Examples of the fused silica powder include a spherical fused silica powder and a crushed fused silica powder. From the viewpoint of fluidity, it is particularly preferable to use a spherical fused silica powder.

  The content of the component (F) is preferably 60 to 80% by weight, more preferably 70 to 80% by weight based on the entire resin composition for sealing an electronic component of the present invention. That is, when the content of the component (F) is less than the above range, since the linear expansion coefficient of the cured body of the resin composition for encapsulating an electronic component is increased, the curvature of the cured body tends to increase. On the other hand, if the above range is exceeded, the fluidity of the resin composition for encapsulating electronic components deteriorates, and the adhesiveness to electronic components and substrates tends to decrease.

  In addition to the components (A) to (F), various additives can be added to the resin composition for sealing an electronic component of the present invention as long as the function of the resin composition for sealing an electronic component is not impaired. . As such additives, for example, adhesion imparting agent, conductivity imparting agent for static electricity countermeasures, flame retardant, ion scavenger, antioxidant, low stress agent, mold release agent, fluidity imparting agent, Examples thereof include a hygroscopic agent and a coloring agent.

  As the adhesion-imparting agent, polyorganosiloxane is preferable, and among them, the polyorganosiloxane represented by the following general formula (5) has adhesion imparting property to the lead frame while maintaining mold releasability. Particularly preferred in terms. The polyorganosiloxane represented by the following general formula (5) is commercially available, for example, X-22-4741, KF-1002 (above, manufactured by Shin-Etsu Silicone), FZ-3736, SF-8421, BY16- 876 (manufactured by Toray Dow Corning Co., Ltd.) is available.

  The resin composition for sealing an electronic component of the present invention can be produced, for example, as follows. That is, the components (A) to (F) and other additives as necessary are blended at a predetermined ratio according to a conventional method, and melt-kneaded in a heated state using a kneader such as a mixing roll. Thereafter, it is cooled and solidified at room temperature. Thereafter, the solidified product as described above is pulverized by known means, and subjected to a series of steps of tableting as necessary, whereby the intended resin composition for sealing an electronic component of the present invention is obtained. Can be manufactured.

  The method for sealing an electronic component using the thus obtained resin composition for sealing an electronic component of the present invention is not particularly limited, and is performed by a known molding method such as normal transfer molding. be able to. Moreover, it is also possible to apply the granular powder to the compression molding method without going through the tableting process.

  And the electronic component apparatus of this invention formed by sealing an electronic component using the said resin composition for electronic component sealing WHEREIN: The said resin composition for electronic component sealing is excellent in a moldability, adhesiveness, etc. In addition, since the glass transition temperature is high and the long-term heat resistance is excellent, an electronic component device having high heat resistance reliability is obtained. Examples of the electronic component device thus obtained include electronic component devices such as IC and LSI.

  Next, examples will be described together with comparative examples. However, the present invention is not limited to these examples.

  First, prior to Examples and Comparative Examples, the following materials were prepared.

[Epoxy resin E1 (component A)]
Triphenolmethane type epoxy resin represented by the general formula (1) (epoxy equivalent 170) (Nippon Kayaku Co., Ltd., EPPN-501HY)

[Epoxy resin E2 (component A)]
Bis (naphthalenediol) methane type epoxy resin (epoxy equivalent 165) represented by the chemical formula (2) (manufactured by Dainippon Ink & Chemicals, HP-4700)

[Epoxy resin E3 (component A)]
1,1,2,2-tetrakis (hydroxyphenyl) ethane type epoxy resin represented by the chemical formula (3) (epoxy equivalent 172) (manufactured by Nippon Kayaku Co., Ltd., GTR-180)

[Epoxy resin E4 (Epoxy resin other than component A)]
Orthocresol novolac type epoxy resin (epoxy equivalent 197) (manufactured by Nippon Kayaku Co., Ltd., EOCN-1020)

[Phenolic resin P1 (component B)]
Triphenolmethane type phenolic resin (hydroxyl equivalent 97) (Maywa Kasei Co., Ltd., MEH-7500)

[Phenolic resin P2 (component B)]
Phenol novolac resin (hydroxyl equivalent 105) (Maywa Kasei Co., Ltd., H-4)

[Phenolic resin P3 (phenolic resin other than component B)]
Phenol biphenylene type phenol resin (hydroxyl equivalent: 206) (Maywa Kasei Co., Ltd., MEH-7851S)

[Curing accelerator (component C)]
2-Phenyl-4-methyl-5-hydroxymethylimidazole

[Strength rubonic acid anhydride (component D)]
Trimellitic anhydride

[Metal hydroxide M1 (E component)]
Magnesium hydroxide, average particle size 5μm

[Metal hydroxide M2 (Metal hydroxide other than E component)]
Aluminum hydroxide, average particle size 5μm

[Inorganic filler (F component)]
Fused spherical silica, average particle size 25μm

[Pigment]
Carbon black

[Coupling agent]
γ-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-803)

〔Release agent〕
Oxidized polyethylene wax

[Polyorganosiloxane]
Epoxy polyether modified silicone oil (manufactured by Shin-Etsu Silicone, KF-1002)

[Examples 1 to 12, Comparative Examples 1 to 6]
After blending the above components in the proportions shown in Tables 1 to 3 below, the resin components were melted and kneaded in a roll kneader heated to 80 to 120 ° C. over 5 minutes. The molten mixture thus obtained was cooled and solidified, and further pulverized to obtain a target powdery epoxy resin composition. In addition, the amount of hydroxyl groups (hydroxyl group / epoxy group) with respect to 1 equivalent of epoxy groups in the resin composition thus obtained and the amount of metal hydroxide (% by weight) in the resin composition are also shown in the same table. It was.

  Using the thus obtained powdered epoxy resin compositions of Examples and Comparative Examples, and tablets obtained by tableting them, each property was evaluated according to the following criteria. The results are shown in Tables 1 to 3 below.

〔Glass-transition temperature〕
The loss elastic modulus of the epoxy resin composition is measured by a dynamic viscoelasticity measuring device (DMA), and the temperature (° C.) at the peak value of the tan δ curve derived from the loss elastic modulus is obtained as the glass transition temperature (Tg). It was.

[Ni adhesive strength]
A columnar molded product was produced on a copper alloy lead frame on which nickel plating was applied on the entire surface by transfer molding of a tablet of the resin composition. Thereafter, at 260 ° C., the maximum force until the molded product is peeled from the nickel-plated surface by pressing the side surface of the molded product is measured with a universal bond tester series 4000 (manufactured by Daisy). The value (N / cm ² ) divided by the bottom area of the molded product was evaluated as “Ni adhesive strength”.

〔Heat-resistant〕
A test piece for evaluation was prepared by transfer molding of a tablet of the resin composition, and this was dried for 500 hours with a dryer at 200 ° C. And the weight change rate (%) before and behind drying was measured. Further, the case where the change rate was 0.5% or less was evaluated as ◯, and the case where the change rate was greater than 0.5% was evaluated as ×.

[PCBT]
A DIP-16 pin package was produced by transfer molding of a tablet of the resin composition. Using this package, a pressure cooker bias test (PCBT) was performed under the conditions of 130 ° C., 85% RH, and 2.3 atm as a moisture resistance reliability test. Then, after the PCBT was performed for 500 hours, a package having a defective rate of less than 50% was evaluated as ◯, a defective rate of 50 to 80% as Δ, and a defective rate higher than 80% as ×.

  From the result of the said table | surface, since the epoxy resin composition of an Example has high glass transition temperature and Ni adhesive force is also high, it is excellent in the electronic component sealing use. Moreover, in all the examples, since the rate of change in weight is small even after the heat test, it is excellent in long-term heat resistance, and furthermore, good results are obtained also in PCBT, so high moisture resistance reliability It can be seen that

  On the other hand, in Comparative Example 1, a phenol resin other than the component (B) in the present invention is used as the phenol resin, and in Comparative Example 2, an epoxy resin other than the component (A) in the present invention is used as the epoxy resin. Is used, the glass transition temperature is low and the Ni adhesive strength is also low. Furthermore, in Comparative Example 1 and Comparative Example 2, the weight change rate after the heat resistance test was large, and the results were inferior in long-term heat resistance as compared with the Examples. In Comparative Example 3, no carboxylic acid anhydride was contained, and as a result, the long-term heat resistance was inferior to that of the Example. In Comparative Example 4, the metal hydroxide is not contained, in Comparative Example 5, the content of the metal hydroxide is too small, and in Comparative Example 6, the metal hydroxide is contained in a predetermined amount. However, the metal hydroxide is not magnesium hydroxide. Therefore, in Comparative Examples 4-6, the rate of weight change after the heat test was large, and from this, Comparative Examples 4-6 resulted in inferior long-term heat resistance compared to the Examples.

Claims (5)

An electronic component sealing resin composition containing the following components (C) to (F) together with the following components (A) and (B), wherein the content of the component (E) is the entire resin composition: 5% by weight or more of a resin composition for encapsulating electronic parts.
(A) An epoxy resin having 3 or more epoxy groups in one molecule and having an epoxy equivalent of 160 to 180.
(B) A phenol resin having less than 2 methylene groups in one molecule, 3 or more phenolic hydroxyl groups, and a hydroxyl equivalent weight of 90 to 105.
(C) A curing accelerator.
(D) Carboxylic anhydride.
(E) Magnesium hydroxide.
(F) Inorganic filler excluding component (E).   The said (B) component is contained so that the amount of hydroxyl groups of (B) component may be 0.7-0.9 equivalent with respect to 1 equivalent of epoxy groups in (A) component. Resin composition for sealing electronic parts.   The resin for sealing an electronic component according to claim 1 or 2, wherein the content of the component (D) is in the range of 1 to 5 parts by weight with respect to 100 parts by weight of the total amount of the components (A) and (B). Composition.   The resin composition for electronic component sealing as described in any one of Claims 1-3 whose inorganic filler of the said (F) component is a silica powder.   The electronic component apparatus formed by sealing an electronic component using the resin composition for electronic component sealing as described in any one of Claims 1-4.