JPS6325012B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD 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, adhesive properties, moisture resistance, etc., compared to other thermosetting resins, and It has sufficient fluidity even at low pressure and maintains characteristics such as not deforming or damaging inserts, so it is used as a highly reliable electrical insulating material.
It is widely used for sealing and impregnating electronic components such as ICs, 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 Compared to epoxy resin molding materials that use other curing agents, it has the characteristics of being the best in terms of moisture resistance, reliability, moldability, etc., as well as being non-toxic and inexpensive. Widely used as a resin encapsulation material for semiconductor devices such as ICs, LSIs, diodes, and transistors. However, epoxy resin molding materials that use novolac-type phenolic resin as a curing agent have poor electrical properties at high temperatures, so using this material can reduce the operating temperature to 80°C.
When encapsulating a MOS type semiconductor device with the above characteristics,
This sealing device is used for chip wiring because leakage current flows between the electrodes, causing the chip to no longer exhibit normal semiconductor characteristics. It has disadvantages such as the aluminum wire corrodes over time and wire breakage occurs. 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 studied, but in addition, moisture resistance,
Epoxy resin compositions with excellent high-temperature electrical properties are desired. The present invention was made in view of the above circumstances, and an object of the present invention is to provide an epoxy resin composition having excellent moisture resistance and high-temperature electrical properties. Means and Effects for Solving the Problems The present inventors have conducted various studies to achieve the above object, and as a result, firstly, the moisture resistance observed when an epoxy resin composition is used for semiconductor encapsulation,
We considered the reasons for the poor high-temperature electrical characteristics as shown in A and B below. 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 sealing resin is in direct contact with the surface of the semiconductor element, but when an electric field is generated on the semiconductor element, the action of the electric field promotes the movement of ionic impurities and polar substances in the resin part that is in contact with the element. As a result, the characteristics of the resin deteriorate at the interface between the element and the resin. As a result, a leakage current occurs between the electrodes of the device, which in turn causes a shoot phenomenon, and eventually the device no longer exhibits normal semiconductor characteristics. (b) Causes of corrosion of aluminum wiring of IC left in a high temperature and high humidity atmosphere (i) If the adhesiveness between the encapsulating resin and the element and lead frame is poor, Moisture penetrates the interface between the two and reaches the element. This moisture causes trace amounts of water-soluble substances, such as ionic impurities such as chlorine, sodium, and organic acids, and unreacted substances with polar groups to be eluted from the cured product of the epoxy resin composition.
It reaches the surface of the semiconductor element and corrodes the aluminum wiring. (ii) 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, causing damage to the semiconductor device. reach the surface. below
Corrode the aluminum wiring in the same manner as in (i). Therefore, the present inventors have conducted extensive studies on epoxy resin compositions that eliminate as much as possible the causes of deterioration in moisture resistance and high-temperature electrical properties based on the above (a) and (b). To reduce polar impurities, in particular the amount of organic acids, chloride ions and hydrolyzable chlorine in the epoxy resin, especially the amount of hydrolyzable chlorine present as α,β-chlorohydrin groups and the phenolic resin. In addition, reducing the amount of organic acids and free Na, Cl, and the amount of free phenol in the epoxy resin, 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.
By adjusting the molar ratio (a/b) of the phenolic resin, adjusting the softening point of the phenolic resin, and further adjusting the blending amount of the curing accelerator and inorganic filler, the curing properties, electrical properties at high temperatures, This epoxy has excellent moisture resistance, and as a result, the aluminum wire will not corrode or break even if left in high temperature and high humidity conditions for long periods of time, and it also has excellent moldability and long-term storage stability. It was discovered that a resin composition could be obtained, and the present invention was completed. Therefore, the present invention provides: (1) The content of organic acids is 100 ppm or less, the content of chlorine ions is 2 ppm or less, the total content of hydrolyzable chlorine is 500 ppm or less, and the content is present as α,β-chlorohydrin groups. Hydrolyzable chlorine atoms
Cresol novolac epoxy resin with an epoxy equivalent of 180 to 230 or less, (2) a softening point of 80 to 120℃, and an organic acid content of 40 ppm or less.
100 ppm or less, free Na, Cl is 2 ppm or less, free phenol is 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 phenolic resin is 0.8 to
a novolak type phenolic resin in a blending amount adjusted to a range of 1.5%, (3) a curing accelerator, and (4) an inorganic filler, and the curing accelerator is added in a total amount of 100 parts by weight of the epoxy resin and the phenolic resin. The present invention provides an epoxy resin composition containing 0.4 to 5 parts by weight per filler and 200 to 500 parts by weight of an inorganic filler. The present invention will be explained in more detail below. First, the epoxy resin (1) constituting the composition of the present invention has an average structural formula of This is a cresol novolak epoxy resin shown by In this case, the epoxy resin contains organic acid content of 100 ppm or less, more preferably 20 ppm or less, chlorine ion content of 2 ppm or less, more preferably 1 ppm or less, and hydrolyzable chlorine content of 500 ppm or less. The following, more preferably
It is necessary to use a material with an epoxy equivalent of 300 ppm or less and an epoxy equivalent of 180 to 230, more preferably 180 to 210. If even one of these conditions is not satisfied, the moisture resistance and high temperature electrical properties will deteriorate. In this case, the content of hydrolyzable chlorine should be kept below 500 ppm as mentioned above, but the amount of hydrolyzable chlorine atoms present as α,β-chlorohydrin groups is important;
It needs to be 40 ppm or less, more preferably 20 ppm or less. That is, the hydrolyzable chlorine atoms contained in the epoxy resin obtained by glycidylating a compound having a phenolic hydroxyl group with epichlorohydrin affect moisture resistance, but according to the results of the studies conducted by the present inventors, (i) to (iii) below, Among the chlorine atoms present in the form of chlorine atoms, it has been found that moisture resistance is significantly improved when the chlorine atoms present as α,β-chlorohydrin groups, which are most susceptible to hydrolysis, are reduced to 40 ppm or less. Therefore, among the hydrolyzable chlorine, α,
Reducing the amount of chlorine atoms present as β-chlorohydrin groups to 40 ppm or less is effective not only for cresol novolac epoxy resins but also for glycidylated products of various novolac resins such as phenol, bisphenol A, and bisphenol F in addition to cresol, and bisphenol. The use of epoxy resins having two or more epoxy groups in one molecule, such as the glycidylated product of A, is also highly recommended. Also, like this, α,
When using an epoxy resin in which the amount of chlorine atoms existing as β-chlorohydrin groups is 40 ppm or less,
In addition to organic phosphine compounds, other curing accelerators,
For example, curing accelerators such as various imidazole compounds and 1,8-diazabicyclo[5,4,0]undecene-7 can be effectively used. In addition, the above-mentioned cresol novolak type epoxy resin may be used with other epoxy resins, such as phenols other than cresol, bisphenol A,
It can be used in combination with various novolac resins such as bisphenol F, glycidyl ether type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, alicyclic epoxy resins, and these halogenated epoxy resins.
In this case, it is preferable to reduce the organic acid content and total chlorine content of these other epoxy resins as well. Further, the amount of these other epoxy resins used is preferably 50 parts by weight or less per 100 parts by weight of the novolak type epoxy resin. Furthermore, when using the above-mentioned component (1),
There is no problem in using a monoepoxy compound in combination as appropriate, and examples of the monoepoxy compound include styrene oxide, cyclohexene oxide, propylene oxide, methyl glycidyl ether, ethyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, octylene oxide, and dodecene. Examples include oxides. In addition, the novolak type phenolic resin (2) used as the curing agent of the present invention has an average structural formula of This novolak type phenolic resin is obtained by reacting the phenol represented by the formula with formalin using an acid catalyst.Similar to the above-mentioned cresol novolak epoxy resin, this novolak type phenolic resin is free Na,
Cl must be 2 ppm or less. In addition, if the monomer phenol contained in this composition, that is, the amount of free phenol, exceeds 1%, in addition to having a negative effect on the above-mentioned moisture resistance, when molded products are made with this composition, voids and unfilled molded products may occur. , defects such as whiskers occur, so the amount of free phenol is 1.
% or less. Furthermore, the amount of organic acids such as formic acid that remains during the production of this novolac type phenolic resin and is generated by the Cannitzaro reaction of a small amount of formaldehyde is also important from the viewpoint of moisture resistance of semiconductors.
Must be 100ppm or less. Furthermore, if the softening point of novolak type phenolic resin becomes less than 80℃,
The Tg becomes low, which causes poor heat resistance, and if the softening point exceeds 120°C, the melt viscosity of the epoxy resin composition increases, resulting in poor workability. The softening point of the type phenolic resin needs to be 80 to 120°C. In addition, free
A more preferable range for Na and Cl is 2 ppm or less, a more preferable range for the amount of free phenol is 0.3% or less, a more preferable range for the amount of organic acid is 30 ppm or less, and a more preferable range for the softening point of the novolak type phenolic resin is 90%. ~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 novolak type phenolic resin of the present invention, phenol-furfural resin, resorcinol-formaldehyde resin, these organopolysiloxane-modified phenolic resins, natural resin-modified phenolic resins, oil-modified phenolic resins, etc. may be used in combination as appropriate. do not have. As the curing accelerator used in the present invention, organic phosphine compounds, various imidazole compounds, 1,8
-diazabicyclo[5,4,0]undecene-7
However, it is particularly desirable to use tertiary organic phosphine compounds with small particle sizes that are solid at room temperature, especially those with an average particle size of 20 μm or less and a maximum particle size of 150 μm or less. By using a tertiary organic phosphine compound with fine particles, it is not only effective for the purpose of the present invention, but also the phenol-curable epoxy resin composition can be used as a transfer molding material for ICs, diodes,
When semiconductor devices such as transistors are sealed,
This has the effect of reducing transparent bleed, which has a high resin content, and occurs in the frame legs of ICs, the lead wires of diodes, and the heat sinks of transistors. On the other hand, those with an average particle size exceeding 20μm and those with a maximum particle size of
If the diameter exceeds 150 μm, bleeding may occur frequently. Examples of the tertiary organic phosphine compounds include triphenylphosphine, tricyclohexylphosphine, methyldiphenylphosphine, triparatolylphosphine, and the like.
One or more of these may be used. Among these, triphenylphosphine and triparatolylphosphine are particularly desirable for the purpose of the present invention.
The amount of these curing accelerators used should be 0.4 to 5 parts by weight, more preferably 0.8 to 2 parts by weight, per 100 parts by weight of the epoxy resin in (1) and the phenol resin in (2) above. If the amount is too small, the curability will be poor, and if the amount is too large, the storage stability, electrical properties at high temperatures, and moisture resistance properties of the epoxy resin composition will be poor. In addition, the more preferable range of the average particle diameter of the organic phosphine compound according to the present invention is 10 μm.
Hereinafter, a more preferable range of the maximum particle diameter is 50 μm or less. Although there are no particular restrictions on the method for producing a curing accelerator that satisfies the above-mentioned particle size, the following method can be suitably employed. That is, for an organic phosphine compound having a high melting point, the desired pulverized product can be obtained by repeatedly pulverizing it by conventional hammer pulverization or ball mill pulverization. However, some organic phosphine compounds that are effective as hardening accelerators have relatively low melting points.
The organic phosphine compound may melt and the desired particle size may not be obtained. For this purpose, the organic phosphine compound and the inorganic filler, especially quartz powder, are thoroughly mixed in advance using a mixer such as a Henschel mixer or a V blender, and then subjected to a mechanical crusher or ball mill until the desired level is obtained. Alternatively, the organic phosphine compound is dissolved in a solvent such as tetrahydrofuran, acetone, toluene, etc., and then the average particle size is determined.
Inorganic filler with a maximum particle size of 20μm or less, 150μm or less,
In particular, there is a method in which quartz powder is placed in this solution, thoroughly stirred, the vacuum is stopped, the solvent is removed, and the resulting inorganic filler adsorbing the organic phosphine compound is sieved until it reaches the desired particle size. can be suitably adopted. Examples of the inorganic filler (4) used in the present invention include quartz powder, alumina powder, talc, glass fiber, antimony trioxide, and among these, quartz powder is preferred. This quartz powder may be either amorphous or crystalline, or a mixture thereof, and may be natural or synthetic. When using equipment to protect against alpha rays, it is preferable to use powdered or spherical synthetic quartz with a low content of uranium, thorium, etc.
Crystalline material with a SiO ₂ content of 98% or more or fused quartz in which SiO ₂ is once melted is preferable. When using quartz powder as an inorganic filler, the preferred average particle diameter range of the quartz powder is 5 to 30 μm;
A more preferable range is 5 to 20 μm, and the amount of quartz powder blended is 200 to 500 parts by weight, more preferably 230 parts by weight, per 100 parts by weight of the total amount of the epoxy resin (1) and the phenol resin (2). It should be ~400 parts by weight. Quartz powder having the above particle size distribution can be obtained by crushing and classifying silica or fused silica, and spherical silica can be obtained by crushing silica or synthetic quartz and treating it in an oxyhydrogen flame. The particle size can be adjusted by classification if necessary. In addition, antimony trioxide can be blended as a flame retardant aid, but when blending antimony trioxide, it must have a softening point of 50°C to 120°C and contain less impurities such as hydrolyzable chlorine and chlorine ions. It is preferable to use a glycidyl ether type halogen compound in combination with a reduced halogen content. In other words, various studies have been made to make resin compositions non-flammable, but when it comes to epoxy resins, it is generally done today by using a combination of halides, especially Br compounds, and antimony trioxide. It is. However, if a semiconductor device sealed with an epoxy resin composition containing a halide is left in a high-temperature atmosphere of 200° C. or higher, phenomena such as a loss of necessary characteristics occur. This is because in halogen compounds, the bond energy between halogen and carbon is smaller than the bond energy between carbon and carbon, and the bond energy between carbon and carbon, so when the temperature exceeds 180℃, the bond between halogen and carbon breaks, and the halogen atom This is thought to be due to the fact that it allows the body to move freely. However, according to the results of various studies conducted by the present inventors, when the above-mentioned glycidyl ether type halogen compound is used in a reduced amount and used in combination with antimony trioxide of high purity and small particle size,
It has been discovered that an epoxy resin composition that is flame retardant and has excellent moisture resistance and high-temperature electrical properties can be obtained. Here, as the glycidyl ether type halogen compound, epoxy group-attached, that is, glycidyl ether type Br and Cl compounds are preferable in terms of dispersibility and electrical properties at high temperatures, and among them,
Although Br compounds are effective, from the viewpoint of moisture resistance of semiconductors, tetrabromobisphenol A-diglycidyl ether having the following structural formula (iv) or structural formula
Glycidyl ether of brominated phenol novolak type epoxy resin (v) is particularly preferred. In this case, the glycidyl ether type halogen compound contains hydrolyzable chlorine.
It is preferable to use a glycidyl ether type halogen compound containing chlorine ions of 500 ppm or less, and 5 ppm or less of chlorine ions.In order to ensure reliability at high temperatures, the halogen content in the glycidyl ether type halogen compound should be reduced to 100 ppm or less of the total resin component.
0.2 to 2 parts by weight per part by weight, preferably 0.2 to 1 part by weight, and when producing the epoxy resin composition by heating and kneading it at 50° to 120°C with a roll or extrusion material, the glycidyl ether type halogen compound In order to disperse the glycidyl ether type halogen compound well in the resin composition, the softening point of the glycidyl ether type halogen compound is
The temperature is preferably 50 to 120°C, preferably 60 to 100°C. If the softening point is lower than 50°C, the dispersibility will be good, but the viscosity of the epoxy resin composition will be low, which may cause voids or burrs to occur during molding, resulting in a high molding failure rate. ,120℃
If it is higher than this, the dispersibility deteriorates, and a large amount of the glycidyl ether type halogen compound is required for the flame retardant effect, which may result in poor electrical properties at high temperatures. In addition, in order to improve dispersibility, it is preferable to use the glycidyl ether type halogen compound in the form of fine powder. In addition, antimony trioxide has a purity of 98% or more, preferably 99% or more, and an extracted water conductivity of 5 μ/cm ² or less, preferably 2 μ /cm ² or less is preferably used. Furthermore, when used in combination with the above-mentioned glycidyl ether type halogen compound, it effectively exhibits the effect as a flame retardant aid in a small amount, so it is preferable to use one with good dispersibility. 5 μm
Hereinafter, it is more effective to set the particle size to 0.5 to 3 μm from the viewpoint of preventing secondary aggregation between particles, which occurs when the particle size becomes fine. The amount of antimony trioxide used is 3 to 100 parts by weight of all resin components.
It is preferably 20 parts by weight, particularly 5 to 15 parts by weight. In addition, as antimony trioxide, in order to improve its dispersibility, it is preferable to use antimony trioxide that has been surface-treated in advance with a silane compound with a functional group used in quartz powder, etc. Among these, as the silane compound Preference is given to using γ-glycidoxypropyltrimethoxysilane. Therefore, in this way, a glycidyl ether type halogen compound having a softening point of 50 to 120°C, an amount of hydrolyzable chlorine of 500 ppm or less, and a chlorine ion content of 5 ppm or less is combined with the glycidyl ether type halogen compound, the epoxy resin, and the like. The total amount with the phenol resin, that is, the amount equivalent to 0.2 to 2 parts by weight of the halogen component in the glycidyl ether type halogen compound per 100 parts by weight of the total resin component, and as a flame retardant aid, an average particle size of 5 μm or less, By using 5 to 20 parts by weight of antimony trioxide with a purity of 98% or more and an extracted water conductivity of 5μ/cm2 ^{or less} per 100 parts by weight of the total resin component, the amount of halogen compounds in the resin composition can be reduced compared to conventional methods. However, it has flame retardancy even if it is extremely reduced, and it also contains chlorine ions, which are ionic or polar impurities.
An epoxy resin composition in which the amount of hydrolyzable chlorine and the like is properly controlled, has excellent moisture resistance and high-temperature electrical properties, and is suitable for use in encapsulating semiconductor devices and the like can be obtained. The composition of the present invention may further contain various additives depending on its purpose, use, etc., if necessary. For example, waxes, fatty acids such as steering acid and mold release agents such as their metal salts, pigments such as carbon black, dyes, flame retardants, surface treatment agents (γ-glycidoxypropyltrimethoxysilane, etc.), aging There is no problem in blending an inhibitor, a silicone-based flexibility imparting agent, and other additives. The composition of the present invention can be obtained by a method such as uniformly stirring and mixing the required amounts of the above-mentioned components, kneading with a roll or kneader preheated to 70 to 95°C, cooling, and pulverizing. can. Note that there is no particular restriction on the order of blending the components. The epoxy resin composition of the present invention is used for sealing semiconductor devices such as ICs, LSIs, transistors, thyristors, and diodes, and for manufacturing printed circuit boards. In the case of sealing the semiconductor device, conventionally used molding methods such as transfer molding, injection molding, and casting can be used. In this case, the molding temperature of the epoxy resin composition is preferably 150 to 180°C, and the post-curing is preferably carried out at 150 to 180°C for 2 to 16 hours. Effects of the Invention As explained above, the present invention provides an epoxy resin composition containing an epoxy resin, a phenolic resin as a curing agent, a curing accelerator, and an inorganic filler, in which the content of organic acid as the epoxy resin is reduced.
100ppm or less, chlorine ion content 2ppm or less,
The total content of hydrolyzable chlorine is 500 ppm or less, the content of hydrolyzable chlorine existing as α,β-chlorohydrin group is 40 ppm or less, and the epoxy equivalent is
Uses 180-230 cresol novolac epoxy resin, with a softening point of 80-120 as a phenolic resin.
°C, organic acid content less than 100ppm, free Na,
A novolac-type phenolic resin containing 2 ppm or less of Cl and 1% or less of free phenol is used, and the molar ratio (a/
b) is adjusted to a range of 0.8 to 1.5, and further, 0.4 to 5 parts by weight of a curing accelerator and an inorganic filler per 100 parts by weight of the total amount of the epoxy resin and the phenol resin.
By using 200 to 500 parts by weight, an epoxy resin composition can be obtained which has excellent moisture resistance and high temperature electrical properties and is suitable for use in 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 Examples 1 to 3] Cresol novolak epoxy resin with an epoxy equivalent of 196 (chlorine ion 1 ppm, hydrolyzable chlorine
300ppm, hydrolyzable chlorine present as α,β-chlorohydrin groups 20ppm, organic acid content
20ppm), and phenolic novolak resin with a softening point of 100℃ (organic acid content 10ppm, Na ion, Cl
The blending ratios of 1 ppm each and 0.1% free phenol are shown in Table 1, and 30 parts by weight of antimony trioxide and 100 parts by weight of the total amount of these are shown in Table 1.
230 parts by weight of fused quartz, 1 part by weight of carnauba wax,
Thoroughly mix a composition containing 1 part by weight of carbon black, 1 part by weight of γ-glycidoxypropyltrimethoxysilane, and 0.75 part by weight of triparatolylphosphine with an average particle size of 5 μ and a maximum particle size of 100 μ as a curing accelerator. After that, knead with heated rolls,
The mixture was then cooled and pulverized to obtain epoxy resin compositions (Examples 1 to 4, Comparative Examples 1 and 2). Using these epoxy resin compositions, the secondary transition temperature Tg and the following measurements of A to E were performed. A Spiral Flow A mold conforming to the EMMI standard was filled with epoxy resin, and measurements were taken under conditions of a molding temperature of 160°C and a molding pressure of 70 kg/cm ² . B Barcol hardness Molding temperature of epoxy resin 160℃, molding pressure 70
Kg/cm ² , molded in 2 minutes, Barcol hardness
The hardness during molding was measured using 935. C Measurement of volume resistivity A test in which a disk with a diameter of 6 cm and a thickness of 2 mm was made by molding at a molding temperature of 160°C, a molding pressure of 70 Kg/cm ² , and a molding time of 2 minutes, and this was post-cured at 180°C for 4 hours. The value of the piece when heated at 150°C was measured according to JIS-K16911. D. Measurement of moisture resistance properties A test piece obtained under the same molding conditions and post-cure conditions as in A above was held in steam at 120°C for 500 hours, and then the dielectric constant and dielectric loss tangent were measured at 60Hz in accordance with JIS K 6911. E Al corrosion test 100 14-pin ICs with Al wiring on the chip were molded using transfer molding material, the molded products were post-cured at 180℃ for 4 hours, and then left in steam at 120℃ for 500 hours. , a failure was determined by detecting a break in the aluminum wiring. The results of the above tests are shown in Table 1.

【table】

[Examples 5 and 6, Comparative Examples 3 to 9]

Example 3 except that the purity of the cresol novolak epoxy resin and novolak type phenol resin used in Example 3 was as shown in Table 2.
Epoxy resin compositions (Examples 5 and 6 and Comparative Examples 3 to 9) using the same additives, blending ratio, and manufacturing conditions as
The aluminum corrosion test (E) above and the molding failure rate test (F) below were conducted. F Measurement of molding defect rate 14PIN IC made of 100 pieces with transfer molding machine
Ten shots were molded using the mold, and the appearance defect rate (defects such as voids, unfilling, snake eyes, etc.) was measured. The above measurement results of E and F are shown in Table 2.

【table】

[Examples 7 to 9, Comparative Examples 10 and 11]

Epoxy resin compositions (Examples 7 to 9, Comparative Examples 10, 11 ) was used to measure Tg and the above A and F measurements. The results are shown in Table 3.

[Examples 10-12, Comparative Example 12]

Epoxy resin compositions (Examples 10-
12, Comparative Example 12) was prepared, and the aforementioned measurements of A, B, E, and F were performed, and the results shown in Table 4 were obtained.

[Examples 13 to 16]

An epoxy resin composition was prepared in the same manner as in Example 3, except that the average particle size and maximum particle size of triparatolylphosphine were as shown in Table 5, and the rate of occurrence of bleeding was the same as in Example 3. Measured using the method. The results are shown in Table 5.

[Example 17]

Triphenylphosphine 10 in a 500ml flask
Add gr and 200gr of toluene, and then adjust the average particle size.
100g of quartz powder with a particle size of 3 μm and a maximum particle size of 100 μm was added, and the mixture was stirred at room temperature for 2.0 hours. Thereafter, toluene was completely removed under reduced pressure to obtain 110 gr of free-flowing quartz powder adsorbed with triphenylphosphine. When this was passed through a 325 mesh sieve five times and the particle size of what passed through the sieve was measured, the average particle size was 3 μm and the maximum particle size was 100 μm, which was almost the same as the quartz powder used. Example 1 average particle size 5 μm, maximum particle size 100 μm
Instead of triphenylphosphine, 7.5% of the above triphenylphosphine adsorbed quartz powder was used.
An epoxy resin composition was prepared in the same manner as in Example 1 except that parts by weight were used. When E and F were measured using the above composition, the Al corrosion occurrence rate was 0%, and the bleeding occurrence rate at IC was 0%.
It was 1.0%. [Example 18] Triphenylphosphine in a Henshil mixer
Add 200gr and 2000gr of quartz powder with an average particle size of 10μm and a maximum particle size of 150μm, and rotate at 360rpm for 5 minutes.
After stirring for a minute and taking out the contents, pulverize with a sample mill equipped with a 0.5 mm sieve.
1200g of ground material was obtained. This pulverized material was passed through a 325 mesh sieve five times, and what passed through the sieve was a white powder with an average particle size of 10 μm and a maximum particle size of 100 μm. Example 1 average particle size 5 μm, maximum particle size 100 μm
An epoxy resin composition was prepared in the same manner as in Example 1, except that 7.5 parts by weight of the above white powder was used in place of triparatolylphosphine. When E and F were measured using the above composition, the Al corrosion occurrence rate was 0%, and the IC bleed occurrence rate was 0.5%. [Examples 19 to 22, Comparative Example 13] Cresol novolac epoxy resin with epoxy equivalent, total amount of hydrolyzable chlorine, and amount of hydrolyzable chlorine present as α,β-chlorohydrin groups as shown in Table 6. (chloride ion 1ppm, organic acid content 20ppm) 62 parts, phenol equivalent 110, softening point
Novolac type phenolic resin at 100℃ (organic acid content 10ppm, Na ion, Cl ion each 1ppm, free phenol 0.1%) 35 parts, epoxy equivalent 280
3 parts of brominated phenol novolak type epoxy resin (bromine content 36%), 250 parts of fused silica (average particle size 13 μm), 1 part of triphenylphosphine,
1 part carnauba wax, 1 part carbon black,
A composition consisting of 10 parts of antimony trioxide with a purity of 99.5% and 2 parts of γ-glycidoxypropyltrimethoxysilane was thoroughly mixed, kneaded with heated rolls, and then cooled and ground to form an epoxy resin composition (Example). 19-22 and Comparative Example 13) were obtained. Regarding these epoxy resin compositions, the above C,
Tests D and E were conducted. The results of the above tests are shown in Table 6.

【table】

[Examples 23-25, Comparative Examples 14-16]

Novolac type phenolic resin with phenol equivalent weight 110 and softening point 90℃ (organic acid content 8ppm, Na ion, Cl ion each 1ppm, free phenol 0.1
%) 32 parts and the total amount of hydrolyzable chlorine shown in Table 7, the amount of hydrolyzable chlorine present as α,β-chlorohydrin groups of cresol novolac epoxy resin (epoxy equivalent 200, chlorine ion 1 ppm, organic acid To 61 parts (content 20 ppm) was added a curing accelerator of the type and amount shown in Table 7, and an epoxy equivalent of 280
2 parts of brominated epoxidized phenolic novolac resin, 5 parts of phenol-functional silicone oil (40% siloxane, 190 phenol equivalent), 270 parts of fused silica (average particle size 5μ), 0.7 parts of carnauba wax, carbon black. After adding 1 part of γ-glycidoxypropyltrimethoxysilane and 1.5 parts of γ-glycidoxypropyltrimethoxysilane, epoxy compositions (Examples 23 to 25, Comparative Examples 14 to 16) were obtained in the same manner as Examples 19 to 22. Regarding these epoxy resin compositions, the above A,
Tests E and F were conducted. The results of the above tests are shown in Table 7.

【table】

[Example 26-29]

Cresol novolac epoxy resin with epoxy equivalent weight 196 (1 ppm chlorine ion, hydrolyzable chlorine
300ppm, hydrolyzable chlorine present as α,β-chlorohydrin groups 20ppm, organic acid content
20ppm), novolac type phenolic resin with a softening point of 100℃ (organic acid content 10ppm, Na ion, Cl ion each 1ppm, free phenol 0.1%) and glycidyl ether of brominated novolac type phenolic resin (softening point 70℃, hydrated) Degradable chlorine 100ppm,
The amount of bromine in the glycidyl ether compound relative to the total amount of the epoxy resin, phenol resin, and glycidyl ether compound (hereinafter referred to as Br content), purity 99.5 % of antimony trioxide (extracted water electrical conductivity 3 μ/cm), the average particle diameter and blending amount are as shown in Table 8, and the purity is 99.9.
% triphenylphosphine (extract water electrical conductivity
1 μ/cm), 230 parts of fused quartz, 1 part of carnauba wax, 1 part of carbon black, and 1 part of γ-glycidoxypropyltrimethoxysilane were thoroughly mixed, and then mixed with a heating roll. The mixture was kneaded, then cooled and pulverized to obtain an epoxy resin composition. These epoxy resin compositions were subjected to spiral flow tests in A above and various tests in G and H below. G. Insulation test 100 14-pin ICs with Al wiring on the chip were molded using transfer molding material, the molded products were post-cured at 180℃ for 4 hours, and then left in an atmosphere at 250℃ for 1000 hours. ICs in which the aluminum wiring was disconnected and the leakage current increased 10 times were counted as defective, and the defective rate was measured. H Flame retardant test According to UV standards, molded products with a thickness of 1 mm are
-V-O was determined. The results of the above tests are shown in Table 8.

[Table] [Example 30] Cresol novolac epoxy resin with an epoxy equivalent of 196 (chlorine ion 1 ppm, hydrolyzable chlorine
200ppm, hydrolyzable chlorine present as α,β-chlorohydrin groups 20ppm, organic acid content
10ppm) 66 parts, novolak type phenolic resin with a softening point of 110°C (organic acid content 10ppm, Na and Cl ions each 1ppm, free phenol 0.1%) 33 parts,
1 part of tetrabromobisphenol A-diglycidyl ether with an epoxy equivalent of 340, antimony trioxide with a purity of 99.5% (average particle size) surface treated with γ-glycidoxypropyltrimethoxysilane
1.0μm, extracted water electrical conductivity 3μ/cm) 15 parts, purity
After thoroughly mixing a composition consisting of 0.75 parts of 99.9% triphenylphosphine, 230 parts of fused silica, 1.0 parts of carnauba wax, 1.0 parts of carbon black, and 1.0 parts of γ-glycidoxypropyltrimethoxysilane, the mixture was heated with a heated roll. The mixture was kneaded, then cooled and pulverized to obtain an epoxy resin composition. Using this epoxy resin composition, the G, H
When the test was carried out, the defect rate in the heat resistance test was 0, and in the flame retardant test, it was equivalent to V-O and nonflammable, and as in Examples 29 to 32, both heat resistance and flame retardance were excellent. An epoxy resin composition was obtained.

Claims (1)

[Scope of Claims] 1. An epoxy resin composition containing an epoxy resin, a phenolic resin as a curing agent, a curing accelerator, and an inorganic filler, wherein the epoxy resin has an organic acid content of 100 ppm or less and a chlorine ion content. The total content of hydrolyzable chlorine is 2ppm or less.
500ppm or less, and the content of hydrolyzable chlorine present as α,β-chlorohydrin group is 40ppm
Below, a cresol novolac epoxy resin with an epoxy equivalent of 180 to 230 is used, and a phenolic resin with a softening point of 80 to 120℃ and an organic acid content of
Use a novolac type phenolic resin with 100 ppm or less, free Na and Cl 2 ppm or less, and 1% or less free phenol, and the molar ratio of the epoxy group a of the epoxy resin to the phenolic hydroxyl group b of the phenolic resin ( a/b) in the range of 0.8 to 1.5, and further add a curing accelerator of 0.4 to 5 parts per 100 parts by weight of the epoxy resin and the phenolic resin.
An epoxy resin composition comprising 200 to 500 parts by weight of an inorganic filler. 2. A glycidyl ether type halogen compound with a softening point of 50 to 120°C, a total hydrolyzable chlorine content of 500 ppm or less, and a chlorine ion content of 5 ppm or less per 100 parts by weight of the total resin component in the glycidyl ether type halogen compound. As a halogen component of 0.2 to 2
In addition to blending within the range of parts by weight, the average particle size is 5 μm.
The epoxy resin composition according to claim 1, further comprising 5 to 20 parts by weight of antimony trioxide having a purity of 98% or more and an extracted water conductivity of 5 μ/cm ² or less per 100 parts by weight of the total resin components. 3. The epoxy resin composition according to claim 2, wherein tetrabromobisphenol A-diglycidyl ether or diglycidyl ether of a brominated phenol novolac type epoxy resin is used as the glycidyl ether type halogen compound. 4. The epoxy resin composition according to claim 2, wherein the antimony trioxide is antimony trioxide whose surface has been previously treated with a silane compound having a functional group. 5. The epoxy resin composition according to claim 4, wherein γ-glycidoxypropyltrimethoxysilane is used as the silane compound. 6 As a curing accelerator, the average particle size is 20 μm or less,
The epoxy resin composition according to any one of claims 1 to 6, which uses a tertiary organic phosphine compound that is solid at room temperature and has a maximum particle size of 150 μm or less. 7. The epoxy resin composition according to claim 6, which uses triphenylphosphine or triphenylphosphine or triphenylphosphine as the organic phosphine compound. 8. The epoxy resin composition according to claim 6 or 7, which uses a pulverized product obtained by mixing and pulverizing an inorganic filler powder and a tertiary organic phosphine compound. 9 Claim 6 using an organic phosphine compound adsorbed in advance on inorganic filler powder
The epoxy resin composition according to item 1 or item 7.