JPS61163923A - Epoxy resin composition - Google Patents

Abstract

PURPOSE:The titled composition excellent in reliability of moisture resistance, heat resistance and ion exchange capacity, obtained by mixing an inorganic ion exchanger formed of a specified metal oxide surface-treated with a coupling agent or a resin with an epoxy resin. CONSTITUTION:A treated inorganic ion exchanger is obtained either by surface- treating an inorganic ion exchanger obtained by melt-mixing and crystallizing at least one metal oxide of the formula (wherein M and M' are each a trivalent to pertavalent metal such as Sb and Bi and n is 0-2) with a silane coupling agent (e.g., epoxysilane) or by mixing said exchanger with a molten resin (e.g., epoxy resin), melting the mixture, cooling the melt, grinding the solid into an ion exchanger powder surface-coated with the resin. The titled composition is obtained by mixing 100pts.wt. epoxy resin with 1-30pts.wt. said treated inorganic ion exchanger, an inorganic filler, a curing agent and, optionally, wax, colorant, coupling agent, flame retardant, etc., kneading the obtained mixture by heating and cooling and grinding the product.

Description

[Detailed description of the invention]

[Technical Field] The present invention relates to an epoxy resin composition with improved moisture resistance reliability, particularly to an epoxy resin composition for semiconductor encapsulation.

[Background technology]

In recent years, there has been a remarkable increase in the integration and density of semiconductor elements, and the demands on epoxy resin compositions for semiconductor encapsulation have become even more severe. The fields of application of the epoxy resin composition include not only transistors and ICs, but also LSIs, as well as 64KDRAM and 256KDRAM.
In recent years, the epoxy resin composition described above has also been used to seal ll1LSIs such as those typified by the following. However, a disadvantage of resin sealing, typified by epoxy resin compositions, is its moisture resistance reliability, which is currently inferior to ceramic sealing. The decrease in temperature resistance in resin encapsulation causes the ionization of ionic components, especially halogens and alkalis, contained in the encapsulation resin composition, causing the problem of corrosion of aluminum, which is the wiring material for semiconductor elements. It is coming. In order to solve the above problem, conventional methods have been attempted to reduce ions. One method is to reduce hydrolyzable ions, especially chloride ions, which are produced as by-products during base resin synthesis. That is, this method purifies the epoxy resin, but although this method is somewhat effective, there is a limit to the reduction of chlorine ions at the resin synthesis stage, and it cannot be said to be sufficient. Another method is to incorporate into the base resin an ion exchange resin that exchanges ionizing ions for harmless ions. however,
In this method, not only the exchange capacity of the ion exchange resin is low, but also there is a problem with the purity of the ion exchange resin, and the heat resistance is not good, so when subjected to thermal shock such as solder shock, the ion exchange capacity decreases and eventually disappears. Due to these problems, the current situation is that sufficient effects have not been obtained. [Objective of the Invention 1] The present invention has been made in view of the above-mentioned points. The object of the present invention is to provide an epoxy resin composition that can reduce moisture and sodium ions and improve moisture resistance reliability. [Disclosure of the Invention 1 That is, the epoxy resin composition of the present invention has the general formula M
An inorganic ion exchanger formed of one or more metal oxides represented by xOs'M'205'nHzo (M, M' are trivalent to pentavalent transition metals, n is 0 to 2), It is characterized by a treated inorganic ion exchanger whose surface is treated with a coupling agent or resin and is blended with an epoxy resin, and the above object is achieved by adding this treated inorganic ion exchanger. It is. The present invention will be described in detail below.
f7'gf*i!・-f&x ”′.°°“'205”
It is composed of one or more metal oxides represented by 1n H20 (M%M' is a trivalent to pentavalent transition metal, n is 0 to 2), and these metal oxides are melted and mixed. , is crystallized. Here, M or M' includes, for example, antimony, bismuth, etc.
M and M' may be the same metal or different metals. Also, n is not necessarily an integer, for example 0.5.
The general formula of a preferable inorganic ion exchanger, which may be 1.5, is S b203・Bizo s・0.5H
,O. Observation of the surface state of this inorganic ion exchanger shows that it partially has the structure of M-OH, and this M-O
H plays an important role in ion exchange. That is, for halogen ions, M-OH+H"+CI-→M-CI+H" OH→M
-CI+8.0 Also, for alkali ions, M OH+ Na" -*M-Na +OH-+
H"→M -Na 10Hz O M-Na after ion exchange in this way. M-CI is stable and there is no risk of secondary decomposition. Also, the H+ generated after the exchange or OH- is H
20, and does not corrode aluminum, which is the wiring material for semiconductor elements. The product after ion exchange is also very stable and has characteristics not seen in conventional ion exchange resins, as well as the ability to trap and exchange both cations and anions with a single substance. Also, this jltfl
The ion exchanger is stable up to 400 to 450°C, and its exchange ability does not decrease even when subjected to thermal shock such as soldering. Treated with a p&bi ion exchanger coupling agent having such properties, or treated with an epoxy resin, 7
A treated jiff ion exchanger is created by surface treatment with a resin such as enol resin. Here, as the coupling agent, silane coupling agents such as epoxysilane, amide/silane, and alicyclic epoxysilane can be used, and epoxysilane is particularly preferred. Further, the pretreatment of the coupling agent and the inorganic ion exchanger can be carried out by a known method. When treating an inorganic ion exchanger with a resin to create a treated inorganic ion exchanger, for example, 120~
It is possible to use a product obtained by adding 1 to 30 parts by weight of an inorganic ion exchanger to 100 parts by weight of an epoxy resin melted at 170°C, followed by melt-mixing for 5 to 60 minutes, followed by cooling and pulverization. If the inorganic ion exchanger is melt-mixed with the resin in this way, the surface of the inorganic ion exchanger will be completely coated with the resin, resulting in very good compatibility with other resins.
Moreover, the dispersibility of the treated inorganic ion exchanger is improved, and the ion exchange capacity is further increased. This treated inorganic ion exchanger is added to an epoxy resin or an epoxy resin such as a modified epoxy resin, mixed, an inorganic filler such as silica, a curing agent such as a phenol novolac resin, wax, a coloring agent, etc. as necessary, A coupling agent, a flame retardant, etc. are added, the mixture is heated and kneaded, and then cooled and pulverized to obtain an epoxy resin composition. The amount of the treated inorganic ion exchanger added to the resin composition is as follows:
It can be added in an amount of 1 to 30 parts by weight per 00 parts by weight. If the amount added is less than 1 part by weight, the effect of the addition is poor, and even if the amount added exceeds 30 parts by weight, the ion exchange ability will not improve and it will be uneconomical. In addition, the particle size of the treated inorganic ion exchanger is preferably 200μ or less, 20
If it exceeds 0μ, not only will moldability problems such as date clogging occur, but also the surface area per unit weight will become smaller, leading to a problem of lower exchangeability. Therefore, the particle size of the treated inorganic ion exchanger is more preferably 100 microns or less. However, the general formula M 20 z ・M ' 209
・nH20 (M, M' are trivalent to pentavalent transition metals, n is θ~
By blending a treated inorganic ion exchanger in which a jllllfl ion exchanger composed of one or more metal oxides shown in 2) is treated with a coupling agent or a resin into an epoxy resin, the resin composition can be changed. Hydrogen ions and monohydroxide ions are released by exchanging each ion such as halogen ion and sodium ion present in the object, and the hydrogen ions and hydroxide ions recombine to become water, which corrodes aluminum, which is the wiring material. Therefore, moisture resistance reliability can be improved. Specifically, the amount of extracted ions is less than half of the conventional amount,
Moisture resistance reliability has also been improved by more than twice that of conventional products. Moreover, j
As mentioned above, the lfi ion exchanger has a high exchange capacity,
In addition, since it is a metal oxide, it has excellent heat resistance, so even if it is subjected to thermal shock such as solder shock, its ion exchange ability will not decrease, improving composite reliability, and it is also highly pure. . In addition, the surface state of the inorganic ion exchanger is M-OH, and the surface state of silica used as a filler! It is relatively similar to 1siOH, and this M
The OH group of -OH partially undergoes hydrolysis with the methoxy group contained in the coupling agent, resulting in the structure M-0-R (R is the coupling agent). It will adhere more closely to the epoxy resin,
As a result, moisture resistance reliability can be further improved. The present invention will be specifically described below based on examples. uLL Using a treated inorganic ion exchanger surface-treated with epoxy silane, after uniformly dispersing and mixing the ingredients shown in Table 1,
The mixture was melt-kneaded, cooled, and pulverized to obtain an epoxy resin composition for use with semiconductors. Using a treated inorganic ion exchanger created by melt-mixing an inorganic ion exchanger and an epoxy resin, the ingredients shown in Table 1 are uniformly dispersed and mixed, then melt-kneaded, cooled, and then pulverized to produce semiconductor encapsulation. A stopper epoxy resin composition was obtained. An inorganic ion exchanger without surface treatment was used as it was, and the ingredients shown in Table 1 were uniformly dispersed and mixed, melt-kneaded, and then cooled and crushed to obtain an epoxy resin composition for semiconductor encapsulation. . After uniformly dispersing and mixing the ingredients shown in Table 1 without adding an inorganic ion exchanger, the mixture was melt-kneaded, and then cooled and crushed to obtain an epoxy resin composition for semiconductor encapsulation.Next The moisture resistance of the obtained tree N composition was measured.The moisture resistance test was carried out by sealing a TEG with aluminum wiring on a 16p DIP, and subjecting this sealed product to PCT (151℃・10
0%RH) conditions and (/PCBT (133℃・100%
Corrosion of aluminum was visually observed after being left under conditions of (RH, B = 20 V), and was expressed as the time until 50% of the sealed products became defective. The results are shown in Table 2. From the results in Table 2, it is confirmed that the addition of an untreated inorganic ion exchanger as in Comparative Example 1 has a slight effect on improving moisture resistance, but it is not sufficient. The sealed products of Examples 1 and 2 had an extremely high moisture resistance of 1.・B l 20 s・0.5H2O Table 2 [Effect of the invention 1 As described above, the present invention has the general formula M2O, ・M′20,
・nHzo (M, M' are trivalent to pentavalent transition metals, n is θ~
1 or 2 of the metal oxides shown in 2)! A treated inorganic ion exchanger formed by above a, which is surface-treated with a coupling agent or resin, is blended with the epoxy resin, so it is an inorganic ion exchanger. exchanges with ions such as halogen ions and sodium ions that are present in the street fat compound and releases hydrogen ions and monohydroxide ions that are harmless to aluminum, so it does not corrode aluminum, which is the wiring material. , moisture resistance reliability can be improved. Moreover, this inorganic ion exchanger has a high exchange capacity, and since it is a metal oxide, it also has excellent heat resistance, so even if it is subjected to thermal shock such as solder shock, the ion exchange capacity does not decrease, and the composite The reliability can be improved and the purity is also high. In addition, this inorganic ion exchanger is blended with a treated inorganic ion exchanger treated with a coupling agent or IfjlF, which improves compatibility and dispersibility with the epoxy resin, resulting in extremely moisture resistance. An excellent sealing resin composition can be obtained. Agent Patent Attorney Ishi 1) Chief Seven Procedures Amendment (Voluntary) April 8, 1985

Claims (3)

[Claims] (1) General formula M_2O_3・M'_2O_5・nH_2
An inorganic ion exchanger formed of one or more metal oxides represented by O (M, M' are trivalent to pentavalent transition metals, n is 0 to 2) is combined with a coupling agent or resin. An epoxy resin composition comprising a surface-treated inorganic ion exchanger blended with an epoxy resin. (2) The epoxy resin composition according to claim 1, wherein the coupling agent is a silane coupling agent. (3) As a treated inorganic ion exchanger, 120 to 170°C
The epoxy resin composition according to claim 1, wherein the epoxy resin composition is obtained by adding an inorganic ion exchanger to the epoxy resin, melt-mixing the epoxy resin, and then cooling and pulverizing the mixture.