JPS62141020A - Epoxy resin composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition excellent in moisture resistance, electrical properties, etc., and suitable for semiconductor sealing, by mixing a high-purity cresol novolak epoxy resin with a novolak phenolic resin, a specific cure accelerator and an inorganic filler. CONSTITUTION:A cresol novolak epoxy resin (A) of an organic acid content <=100ppm, a chloride ion content <=2ppm, a hydrolyzable chlorine content <=500ppm and an epoxy equivalent of 180-230 is mixed with a curing agent (B) comprising a novolak phenolic resin of a softening point of 75-120 deg.C, an organic acid content <=100ppm, free Na and Cl contents >=2ppm for each and a free phenol content <=1%, a cure accelerator (C) comprising an equimolar association product of a compound having both of a carboxyl group and an ester group in the molecule of the formula (wherein R is a 1-17C alkyl, phenyl or the like) with imidazole compound and an inorganic filler (D) at a molar ratio of the epoxy groups or component A to the phenolic hydroxyl groups of component B of 0.8-1.5.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to an epoxy resin composition particularly suitable for use in encapsulating semiconductor devices.

Problems to be Solved by the Prior Art and the Invention Epoxy resin molding materials generally have superior electrical properties, mechanical properties, adhesion, moisture resistance, etc., compared to other thermosetting resins, and are easy to mold. IC is a highly reliable electrical insulating material because it has sufficient fluidity even at extremely low pressures and maintains characteristics such as not deforming or damaging inserts.

It is widely used for sealing and impregnating electronic components such as LSIs, diodes, transistors, and resistors.

Conventionally, typical curing agents for this epoxy resin molding material include acid anhydrides, aromatic amines, novolac type phenolic resins, etc. Among these, epoxy resin molding materials using novolak type phenolic resin as a curing agent teeth,
Compared to epoxy resin molding materials that use other hardening agents, it has the best characteristics in terms of moisture resistance, reliability, moldability, etc., and is also non-toxic and inexpensive.
I.C.

It is widely used as a resin encapsulation material for semiconductor devices such as LSIs, diodes, and transistors.

However, epoxy resin molding materials using novolak type phenolic resin as a curing agent have poor thermal properties at high temperatures.
The platform that restrained the 8-type semiconductor device, this sealing device caused leakage current to flow between the electrodes and did not exhibit normal semiconductor characteristics.In addition, it was sealed with ICi resin and underwent a deterioration test under high temperature and high humidity. If this is done, the aluminum wires used for chip wiring will corrode in a short period of time, resulting in wire breaks.

For this reason, not only the epoxy resin and curing agent that make up the epoxy resin composition, but also various other components have been investigated, and some improvements have been made in the moisture resistance properties at high temperatures and high humidity and the electrical properties at high temperatures. However, epoxy resin compositions are not necessarily sufficient for use in semiconductors, and there is a need for epoxy resin compositions that have excellent moisture resistance and high-temperature electrical properties.

In addition, as semiconductor devices are required to be mass-produced at low cost, resin encapsulation of semiconductor devices has recently been replaced by transfer molding methods that can be mass-produced, especially advances in chip passivation technology and related peripheral technologies. Along with,
Resin sealing using low-pressure transfer molding has become mainstream, and molds for these molding methods have an increasing number of cavities and a tendency to become larger.In addition, unmanned production is progressing. ing. On the other hand, the materials for the frames of semiconductor devices have also been moving toward lower prices, and have changed from 4.270I to silver-plated copper plates, and then to nickel-plated copper plates.

In response to these trends, there is currently a need to improve the characteristics of resin compositions. That is, in response to the increase in the size of the above-mentioned molding molds, resin compositions are required to have even better fluidity and filling properties than conventional ones, and similarly, in response to the above-mentioned unmanned production, Better storage stability and wider workability are required so that production can be carried out without changing production conditions such as the composition of the resin composition and molding conditions. In addition, as a recent trend, resin compositions with a high content of inorganic fillers aimed at improving heat dissipation properties are not filled, without causing defects such as voids, and without causing disconnections in semiconductor devices. There is a growing demand for resin compositions that can produce expensive semiconductor devices without rejecting them and have sufficient fluidity at low pressure. It reflects the requirements 'ilI]. On the other hand, in response to changes in the materials of frames of semiconductor devices, resin compositions are required to have excellent adhesion to silver, nickel, etc. of 4.270, but phenol-curing epoxy resins have a rating of 4.2. Although it has excellent adhesion to alloys and silver, it has poor adhesion to nickel, so when semiconductor devices are encapsulated with phenol-curing epoxy resin, moisture resistance is poor, and the resin is thin (furan).) A? The rack has drawbacks such as flan formation due to poor adhesion between the frame and the resin.

The present invention was made in view of the above circumstances, and provides an epoxy resin composition that not only has excellent moisture resistance and high-temperature electrical properties, but also has excellent storage stability, such as adhesion to nickel, etc., and high fluidity retention. The purpose is to provide

Means and Effects for Solving the Problems In order to achieve the above object, the present inventors have conducted various studies, and as a result, firstly, the moisture resistance, which is observed when an epoxy resin composition is used for semiconductor encapsulation, The following 41 reasons were considered for the poor high-temperature electrical characteristics.

B. Cause of poor high-temperature electrical properties for semiconductor encapsulation If the encapsulation resin contains trace amounts of ionic impurities or polar substances, these become active and move easily in a high-temperature atmosphere. Furthermore, the encapsulating resin is in direct contact with the surface of the semiconductor element, but when an electric field is generated in the semiconductor element, ionic impurities and polar substances can easily move in the resin part that is in contact with the element due to the action of the electric field. This accelerates the deterioration of resin properties at the interface between the element and the resin. For this reason, a leakage current occurs between the electrodes of the device, which in turn causes a short circuit phenomenon, and eventually the device no longer exhibits normal semiconductor characteristics.

(Causes of corrosion of aluminum wiring of IC (i)) If the adhesiveness between the sealing resin, the element, and the lead frame is poor, the element may be left in a high temperature and high humidity atmosphere. Moisture penetrates the interface between the lead frame and the lead frame and reaches the device.This moisture removes trace amounts of water-soluble substances from the cured epoxy resin composition, such as ionic impurities such as chlorine, sodium, and organic acids, and polar Unreacted substances with groups are eluted,
It reaches the surface of the semiconductor element and corrodes the aluminum wiring.

Gi) Since the cured product of the epoxy resin composition for semiconductor devices has hygroscopicity and water permeability, moisture from the outside penetrates into the interior through the cured product in a high-temperature, high-humidity atmosphere, and the surface of the semiconductor element. reach. Corrode the aluminum wiring in the same manner as described below.

Therefore, the present inventors have made use of the excellent advantages found in conventional epoxy resin compositions by using a novolac type phenolic resin as a curing agent. As a result of intensive research into epoxy resin compositions that eliminate as much as possible the causes of decreases in Amounts of acids, chloride ions and hydrolyzable chlorine and organic acids and free Na in phenolic resins.

In addition, the epoxy equivalent of the epoxy resin, the epoxy group (a) of the epoxy resin and the phenolic hydroxyl group (b) of the phenolic resin are reduced.
) to adjust the softening point of phenol translocation by adjusting the molar ratio Ca/b) of phenol, and furthermore, calcium is added to the above-mentioned engineered oil xy resin and phenol resin in specific molecules as a curing accelerator.
By adding and using an aggregate of a compound having both a xyl group and an ester group and an imidabul compound, it has excellent curing properties, drowsiness properties at high temperatures, and moisture resistance properties, and as a result, it can be used for a long time under high temperature and high humidity. The aluminum wire does not corrode or break even when left unused, and it also has excellent adhesion to nickel, etc., excellent molding workability, and high fluidity retention.
It was discovered that an epoxy resin composition with excellent long-term storage stability can be obtained, and the present invention was completed.

Therefore, the present invention provides (1) a cresol resin having an organic acid content of 100 ppm or less, a chlorine ion content of 2 ppm or less, a hydrolyzable salt content of 500 ppm or less, and an epoxy equivalent of 180 to 230; Lac epoxy resin, (2) has a softening point of 75 to 120°C, an organic acid content of 100 ppm or less, free Na and Cl of 2 ppm or less, free phenol of 1% or less, and the epoxy of the above epoxy resin. group (,) and phenolic hydroxyl group (b) of phenolic resin
(3) Nodelac type phenol resin with a blending amount adjusted to a molar ratio (a/b) in the range of 0.8 to 1.5, (3) the following formula (1) (However, in the formula, R is a carbon number of 1 to 1. 17 alkyl group.

It is a monovalent organic group selected from phenyl, benzyl, and cyclohexyl groups. ) in the molecule indicated by Cal?
An equimolar aggregate of a compound having both a xyl group and an ester group and an imidazole compound, and (4) a compound containing an inorganic filler. The present invention provides a xylene resin composition.

The present invention will be explained in more detail below.

First, the epoxy resin (1) constituting the composition of the present invention is a cresol novolac epoxy resin represented by the average structural formula.

In this case, the epoxy resin contains organic acid content of 100 ppm or less, preferably 20 ppm or less, chlorine ion content of 2 ppm or less, preferably 1 ppm or less, and hydrolyzable chlorine. The content of 500 ppm or less, more preferably a o o ppm
It is necessary to use a material having an epoxy equivalent of 180 to 230, preferably 180 to 210. If even one of these conditions is not satisfied, the moisture resistance will decrease.

In addition, the above-mentioned No? Lac-type epoxy resin is necessary, but it can be used in combination with other epoxy resins such as glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, alicyclic epoxy resin, and these halodanized epoxy resins. can do. In this case, these other epoxy resins also have their organic acid content,
It is preferable to reduce the total amount of chlorine. In addition, the amount of these other epoxy resins used is Noblak type epoxy resin 1
The amount is preferably 50 parts by weight or less relative to 00 parts by weight.

In addition, when using the above-mentioned component (1), there is no problem in using a monoepoxy compound as appropriate, and examples of this monoepoxy compound include styrene oxide, cyclohexene oxide, propylene oxide, methyl glycidyl ether, ethyl glycidyl ether, and phenyl glycidyl. Examples include ether, allyl glycidyl ether, octerene oxide, and dodecene oxide.

In addition, the novolac type phenolic resin (2) used as the curing agent of the present invention is a novolac type phenolic resin obtained by reacting a phenol represented by the average structural formula (% formula %) with formalin using an acid catalyst. However, like the above-mentioned cresol novolac epoxy resin, free Na in this noblack type phenol resin is limited from the viewpoint of moisture resistance of semiconductors.

It is necessary to keep Cl f 2 ppm or less. In addition, if the amount of monomer phenol contained in this composition exceeds 1%, it will not only have a negative effect on the moisture resistance mentioned above, but also when molded products are made with this composition. To? Since defects such as hydration, unfilling, whiskers, etc. occur, the amount of free phenol needs to be 1% or less. Furthermore, the amount of organic acids such as hexalic acid produced by the cannibal reaction of trace amounts of formaldehyde remaining during the production of the novolac type phenolic resin must also be kept at 100 ppm or less in view of the moisture resistance of the semiconductor. Furthermore, when the softening point of Noblak type phenolic resin reaches 75℃, T
g becomes low, resulting in poor heat resistance.Also, when the softening point exceeds 120°C, the melt viscosity of the epoxy resin 1 group acid increases, resulting in poor workability, and in both cases, moisture resistance decreases. Therefore, the softening point of novolac type phenolic resin is 7.
It is necessary to set it as 5-120 degreeC.

In addition, free Na in the novolac type phenolic resin,
A more preferable range for Cl is 2 ppm or less, a more preferable range for the amount of free phenol is 0.3 ppm or less, a more preferable range for the amount of organic acid is 30 ppm or less, and a more preferable range for the amount of free phenol is 30 ppm or less. A preferred range is 90 to 110°C, and by adjusting the temperature within the above range, the object of the present invention can be more reliably achieved.

Furthermore, in addition to the novolac type phenolic resin of the present invention,
Phenol-furfural resin, resorcinol-formaldehyde resin, these organopolysiloxane-modified phenol resins, natural resin-modified phenol resins, oil-modified phenol resins, and the like may be used in combination as appropriate.

In the present invention, by adding the above-mentioned aggregate of a compound having both a carboxyl group and an ester group in the specific molecule and an imidazole compound to the epoxy resin composition containing the above-mentioned epoxy resin or phenol resin, Moisture resistance is improved, and adhesion to nickel etc. and storage stability are significantly improved. However, the aggregate used in the present invention has a carboxyl group and an ester group in the above-mentioned specific molecules. As long as it is an aggregate of the compound and the imidazole compound, there are no particular restrictions on its type or production method. However, for the purpose of the present invention, such as reliably exhibiting the above effects, an aggregate having a structure represented by the following formula (2) is preferable. The method for producing these aggregates is not particularly limited, but includes dissolving two types of compounds constituting the aggregates.

Examples include a method in which an aggregate is produced by a reaction, or a method in which the entire aggregate is produced by heating and dissolving both of the above two types of compounds in a solvent such as acetone, and then cooling and removing the solvent. A combination can be produced.

The blending amount of these aggregates used in the present invention is as described above (1
0.5 to 30 parts by weight, preferably 1 to 30 parts by weight per 100 parts by weight of the epoxy resin (1) and the phenol resin (2)
If the amount is less than 0.5 parts by weight, the curability will be poor, and if it exceeds 30 parts by weight, the molding workability and storage stability of the epoxy resin composition will be poor, thus achieving the object of the present invention. I can't.

The epoxy resin composition of the present invention may further contain curing accelerators other than the above-mentioned aggregates, and these curing accelerators include triphenylphosphine, tricyclohexylphosphine, tributylphosphine, methyldiphenylphosphine, 1 .2-Bis(diphenylphosphino)ethane, bis(diphenylphosphino)methaneto organic phosphine compounds, 1.8-noazabicyclo(5
, 4,0) tertiary amines such as undecene-7, imidazoles, etc., and these may be used alone or in combination of two or more as long as the object of the present invention is not impaired.

As the inorganic filler (4) used in the present invention,
For example, quartz powder, alumina powder, talc, glass fiber,
Examples of quartz powder include antimony trioxide.
The epoxy resin composition may be either amorphous or crystalline, or a mixture thereof, and may be natural or synthetic. When using it for countermeasures, it is preferable to use powdered or spherical synthetic quartz that has a small amount of uranium, thorium, etc. In addition to the above, it is preferable to use quartz with a high heat dissipation property due to its pyrothermic conductivity. If you want to improve it,
Crystalline or SiO2 with S r 02 content of 98% or more
It is preferable to use fused quartz, etc., which have been melted once, with a high light filling rate, and crystalline silica is particularly preferable.

The preferred average particle diameter range of the inorganic filler is 5 to 30.6.
m, a more preferable range is 5 to 20 μm, and the blending amount is 9,200 to 9,200 parts per 00 parts by weight of the above-mentioned epoxy resin and (2) (1) phenol resin.
It is desirable that the amount is 500 parts by weight, especially 230 to 500 parts by weight. In this case, in order to obtain an epoxy resin composition with high thermal conductivity, the above-mentioned crystalline silica is used as an inorganic filler, and the total amount is The epoxy resin of (1) above and (2)
) 400 per 100 parts of total weight with phenolic resin
~550: ffi'Ji parts, particularly preferably 450 to 500 parts by weight.

Furthermore, in order to increase the thermal conductivity of the epoxy resin composition,
In addition to the inorganic filler of the present invention, boron hydride such as (BH)x, aluminum nitride, alumina, magnesium oxide,
An inorganic filler with high thermal conductivity such as silicon carbide can be used in combination as appropriate.

The composition of the present invention may further contain various additives depending on its purpose, use, etc., if necessary. For example, waxes, mold release agents such as fatty acids such as stearic acid and their metal salts, pigments such as carden black, dyes, flame retardants, and surface treatment agents (γ-glycidoxypropyltrimethoxysilane, etc.) , antioxidants, silicone-based sinterability agents, and other additives may be blended.

Among the above additives, when carnauba wax is used as a mold release agent in combination with the aggregate according to the present invention, the adhesiveness of the epoxy resin composition of the present invention is improved to a large extent. It is preferable to add carnauba wax to the resin composition to improve adhesiveness.

The composition of the present invention can be obtained by stirring and mixing the above-mentioned components uniformly, heating the mixture to 70 to 95°C, kneading with a roll, kneader, etc., cooling, and pulverizing. I can do it. Note that there is no particular restriction on the order of blending the components.

The epoxy resin composition of the present invention is applicable to IC, LSI.

It is used as a sealant for semiconductor devices such as transistors, thyristors, and diodes, and in the production of printed circuit boards. Note that when sealing the semiconductor device, conventionally employed molding methods such as transfer molding, injection molding, and casting methods can be employed. In this case, the molding temperature of the epoxy resin composition is 150~
180'C, post cure at 150-180'C
It is preferable to carry out the treatment for 16 hours.

DETAILED DESCRIPTION OF THE INVENTION As described in detail, the present invention provides an epoxy resin composition containing an epoxy resin, a phenol resin as a curing agent, and an inorganic filler, wherein the epoxy resin has an organic acid content of 100 ppm or less, chlorine The content of ions is 2
ppm or less, hydrolyzable chlorine content is 500 ppm
Hereinafter, a cresol black epoxy resin with an epoxy equivalent of 180 to 230 is used, and as a phenol resin, a softening point is 80 to 120 °C and an organic acid content of 100 pp.
m or less, free Na, C2 is 2 ppm or less, free phenol is 1 H or less, and the epoxy M (
a) and the phenolic hydroxyl group (b) of the phenolic resin
Adjust the molar ratio (a/b) of the two to a range of 0.8 to 1.5, and further add an aggregate of an imidazole compound and a compound in which Cal has both a xyl group and an ester group in a specific molecule. As a result, an epoxy resin composition can be obtained which has excellent moisture resistance, high-temperature electrical properties, adhesion to nickel, etc., and storage stability, and is suitably used for encapsulating semiconductor devices.

EXAMPLES Hereinafter, the present invention will be specifically explained by showing examples and comparative examples, but the present invention is not limited to the following examples.

[Examples 1 to 4. Comparative Example 1.2] Cresol novolak epoxy resin with epoxy equivalent weight 196 (chloride ion' ppm l hydrolyzable chlorine 300
ppm, organic acid content 20 ppm), and phenolic novolac resin with a softening point of 100°C (organic acid content 10 ppm h Na ion, Ct ion each 1
ppm.

The blending ratios of free phenol (0.1%) are shown in Table 1, and the total i 100 parts include 30 parts by weight of antimony trioxide, 230 MW parts of fused quartz, 1 part by weight of carnauba wax, and 1 part by weight of carnauba wax. Black l = Satobe,
An equimolar association of γ-glycidoxyprobyltrimethoxysilane monomer, a compound having both carboxyl and ester groups in the molecule represented by the above formula (2) as a curing accelerator, and an imidazole compound. (Hereinafter, referred to as aggregate A) After thoroughly mixing the composition to which 0.5 to 30 parts by weight was added, the mixture was kneaded with a heating roll, cooled, and then ground to form an epoxy resin composition (Example 1). ~4° Comparative Example 1
, 2) was obtained.

Using these epoxy resin compositions, the secondary transition temperature Tg
, and the following measurements A-E were performed.

A. A mold conforming to the spiral flow EMMI standard was filled with epoxy resin, and measurements were taken under the conditions of a molding temperature of 175° C. and a molding pressure of 0 φ value.

B. Molding temperature of Percoll hardness epoxy resin 175℃, molding pressure cuff 0'
Kg/cm2. The molding time was 90 seconds, and after dismantling the mold, the hardness of the molded product was measured at a Percoll hardness of 935.

Measurement of C0 body-like resistivity Molding temperature 160°C, molding pressure cuff 0 kg/m2. For a test piece that was molded under conditions of 2 minutes of molding time to make a disk with a diameter of 6 cm and a thickness of 2 m, and post-cured at 180°C for 4 hours, the body 4'lil resistivity at 150°C was determined by JIS- -6911.

D. Measurement of moisture resistance properties Test pieces obtained under the same molding conditions and post-key conditions as in A above were held in water vapor at 121°C for 500 hours, and then the dielectric constant and dielectric loss tangent at 60Hz were measured according to JIS-6911. It was measured.

E. At corrosion test: 100 14-bin ICs with At placement on the chip were molded using transfer molding material, and 180 molded products were obtained.
C. for 4 hours, and then left in water vapor at 121.degree. C. for 500 hours. Ifrii of the aluminum wiring was detected and determined to be defective.

The results of the above tests are shown in Table 1.

From the results in Table g41, the molar ratio (epoxy group/phenol group) between the epoxy group of the cresol novolak epoxy resin and the phenol group of the novolac type phenol resin is outside the range of the present invention, that is, when it is less than 0.8 or 1.5. If it exceeds At
Although corrosion becomes noticeable, it was confirmed that when the range of the present invention is satisfied, an epoxy resin composition having excellent volume resistivity, moisture resistance, and a good At corrosion rate can be obtained.

Next, in order to check the moldability, especially the incidence of bleeding,
A 14-pin IC mold with 0 cavity was filled with the epoxy resin compositions of Example 3 and Comparative Example 1, and the mold temperature was 175°C.
100 pieces of 14-pin ICi were made under the conditions of a molding time of 2.5 minutes and an injection pressure cuff of 0 kg and 7 cm2, and the incidence of bleeding was observed. In this case, a case where one or more bleeds appeared from the legs of the IC was counted as a defect. As a result of measuring the occurrence rate of bleeding 1r, Example 3 had a defective rate of 0.1%, but Comparative Example 1 had a defective rate of 18%.

[Example 5, 6. Comparative Examples 3 to 9] The same additives, blending ratio, and manufacturing conditions as in Example 3 were used, except that the purity of the cresol novolac epoxy resin and novolac type phenol resin used in Example 3 was as shown in Table 2. Epoxy resin composition (Examples 5 and 6)
and Comparative Examples 3 to 9) were prepared and subjected to the At corrosion test in E above and the molding defect rate test in F below.

F. Measurement of molding defect rate 14 PINIC with 100 pieces in transfer molding machine
Ten shots were molded using the mold, and the appearance defect rate (defects such as defects, unfilled, snake eyes, etc.) was measured.

The above measurement results of E and F are shown in Table 2.

From the results in Table 2, the hydrolyzable chlorine, chlorine ion, and organic acid content of cresol novolac epoxy resin, or the organic acid content, Na, and C2 of novolak type phenolic resin
-, if free phenol exceeds the scope of the present invention, At
Corrosion of wiring occurs, especially when the content of organic acids is high, the defective rate of At corrosion increases extremely, and if free phenol such as novolak-type phenol exceeds the scope of the present invention, molded products may be damaged. It was confirmed that the defective rate increased.

[Examples 7-9. Comparative Example 10.111 (used in Example 3)? An epoxy resin composition (Execution ftl 7~
9. Comparative Example 10.11) was prepared and used to measure Tg and the above A and F.

The results are shown in Table 3.

Table 3 From the results in Table 3, as the softening point of the Noblak type phenolic resin increases or decreases, the Tg increases or decreases, and when the softening point becomes 80°C or lower, the sulfur 4 yral flow becomes shorter, and conversely, when the softening point decreases to 120°C, the Tg increases or decreases. It was confirmed that molding workability deteriorates when the temperature exceeds .degree. C., and when the temperature exceeds the range of the present invention, the defective rate of molded products increases.

[Examples 10-14. Comparative Examples 12 to 14] Cresol novolak epoxy resin (EOCN-10 manufactured by Nippon Kakei Co., Ltd.)
2*Epoxy equivalent weight 215. Chlorine ion 2 ppm, hydrolyzable chlorine 500 ppm, organic acid content 100
ppm) 60 parts, brominated epoxy resin (BREN manufactured by Nippon Kakei Co., Ltd.: Epoxy equivalent 280. Chlorine ion 2 p
pm + hydrolyzable chlorine 450 ppm, organic acid content 20 ppm) 10 parts, phenolic novolac resin (TD-2093 manufactured by Inu Nippon Inc., softening point 93°C
, organic acid containing fit 20 ppm m Nm ions,
(2 ppm or less each of ct ions, 1% or less of free phenol), 30 parts of crystalline silica 6 (Crystallite 5 manufactured by Taramori; 5IO2 content 98 short), 475 parts of γ-glycidoxytrimethoxysilane 1.5 parts , 1 part of carbine black, 5 parts of antimony trioxide, a curing accelerator of the type and amount shown in Table 4, and carnauba wax of the amount shown in Table 4 were thoroughly mixed, and then heated and heated. Knead with a niegu and mixing roller under pressure,
The mixture was then cooled and pulverized to obtain epoxy resin compositions (Examples 10 to 14 and Comparative Examples 12 to 14).

Using these epoxy resin compositions, the above-mentioned A.

B, E, F measurements and the following G, H measurements were taken O G, adhesiveness 6w width x 11w length x 200μ made of the material shown in Table 4
Two metal pieces having a thickness of m were used, and as shown in FIGS. 1 and 2, these metal pieces were sealed in an m*me epoxy resin composition n. In this case, both metal pieces m, m were sealed in an epoxy resin composition n so that their tips 6mn faced each other. In addition, the epoxy resin composition was molded and sealed with resin at a molding temperature of 180°C, a molding pressure of 0 kg/17n2, and a molding time of 2 minutes, and this was post-cured at 180°C for 16 hours to obtain a measurement sample. .

The adhesion strength was measured by pulling the left and right gold pieces of the standard sample on a tensile tester with 1 added to 6 (1).

H. Storage stability After the epoxy resin composition was left in an atmosphere at a temperature of 40°C for 24 hours, the spiral flow resistance of the above A was measured, and the spiral flow resistance was determined based on the spiral flow value and the initial value of the spiral flow. Storage stability was evaluated by determining the retention rate.

Table 4 shows the results of the 1xll-/7'Ipo) 1ushinort evaluation.

From the results in Table 4, it can be seen that even if the amount of curing accelerator in the epoxy resin composition is the same, a compound having both a carboxyl group and an ester group in the molecule within the scope of the present invention as a curing accelerator and an imidazole compound are the same. When a molar aggregate is used, the Atk food test form defective rate,
It has much better adhesion and storage stability with the metal material used on the surface of the semiconductor frame, and its spiral flow and Percoll hardness values are also at least the same.

Furthermore, even if a curing accelerator that falls within the scope of the present invention 'ft' 7N4 is used, if the amount of the curing accelerator does not satisfy the scope of non-invention and is less than 0.5 parts, the crosslinking density If the amount exceeds 30 parts, the reactivity is high, resulting in a large amount of scaly semi-cured material during production, and the flowability is low. However, by adding an amount of curing accelerator that satisfies the scope of the present invention, moldability and
The properties such as electrical properties, humidity, physical properties, and storage stability were sufficiently good, and from the above, the effects of the present invention were confirmed.

[Brief explanation of drawings]

1 and 2 show an epoxy resin composition sample in which a metal piece is sealed for evaluating the adhesive strength of the epoxy resin composition, FIG. 1 is a plan view, and FIG. 2 is a front view. m...Metal piece, n...Epoxy resin composition. Source: Shin-Etsu Chemical Co., Ltd.

Claims (1)

[Claims] 1. An epoxy resin, a phenol resin as a hardening agent,
In an epoxy resin composition containing an inorganic filler,
As an epoxy resin, the content of organic acids is 100 ppm or less, the content of chlorine ions is 2 ppm or less, the content of hydrolyzable chlorine is 500 ppm or less, and the epoxy equivalent is 180 ~
Using 230 cresol novolac epoxy resin,
As a phenolic resin, the softening point is 75-120°C, the content of organic acid is 100 ppm or less, and free Na and Cl are 2 parts.
pm or less and a novolac type phenolic resin with free phenol of 1% or less, and the molar ratio (a/b) of the epoxy group (a) of the epoxy resin and the phenolic hydroxyl group (b) of the phenol resin. The curing accelerator is adjusted to a range of 0.8 to 1.5, and the following formula (1) ▲ Numerical formula, chemical formula, table, etc. is available ▼... (1) (However, in the formula, R is a carbon number of 1 to 17. A monovalent organic group selected from an alkyl group, a phenyl group, a benzyl group, and a cyclohexyl group.) An equimolar aggregate of a compound having both a carboxyl group and an ester group in the molecule and an imidazole compound is added. An epoxy resin composition characterized by: 2. The epoxy resin composition according to claim 1, wherein the equimolar aggregate is added in an amount of 0.5 to 30 parts by weight per 100 parts by weight of the total amount of epoxy resin and phenol resin. 3. The epoxy resin composition according to claim 1 or 2, wherein the inorganic filler is blended in an amount of 200 to 500 parts by weight per 100 parts by weight of the total amount of the epoxy resin and the phenol resin. 4. Crystalline silica as an inorganic filler per 100 parts by weight of the total amount of all resin components constituting the epoxy resin composition.
The epoxy resin composition according to claim 3, which is used in an amount of 0 to 500 parts by weight. 5. The epoxy resin composition according to any one of claims 1 to 4, wherein the imidazole compound is 2-phenylimidazole.