JPS6148544B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an epoxy resin composition that has excellent mechanical properties, electrical properties, and water resistance properties, and can provide a cured product with improved Krazok resistance without lowering the glass transition point. Especially for electronic and electrical parts (packaging)
The object of the present invention is to provide a basic composition suitable for obtaining an epoxy resin compound that has excellent thermal conductivity (heat dissipation) required for the invention, low stress, and excellent crack resistance. Resins used for packaging electronic and electrical parts include thermosetting resins such as epoxy resins, silicone resins, polybutadiene, polyurethane, and phenol resins, as well as various thermoplastic resins, depending on the use and purpose. A wide variety of types are known. Among these, epoxy resins are used most widely and in large quantities because of their excellent mechanical properties, electrical properties, heat resistance, adhesive properties, moldability, etc. In particular, its position as a resin encapsulation material for semiconductor elements such as diodes, transistors, ICs, and LSIs, which have seen rapid technological growth in recent years, is overwhelming due to its excellent properties. However, with the recent trend towards thinner layers, miniaturization, and increased integration of electronic components, the characteristics required of packaging materials are becoming even more stringent, and conventional materials of this type are no longer sufficient. I am in a situation where I cannot be satisfied. In other words, these characteristics include higher purity, advanced electrical properties, shorter molding cycles to improve productivity, high thermal conductivity to dissipate heat, and to reduce physical stress on elements. It has low stress and excellent crack resistance that can withstand severe thermal cycles and impacts.In particular, it has high thermal conductivity and excellent crack resistance (low stress ) is extremely difficult to achieve. At present, no material has been obtained that has all of the above-mentioned properties. Most of the epoxy resin materials known today for encapsulating semiconductor devices are made by filling a bisphenol type epoxy resin or novolac type epoxy resin with a large amount of amorphous or crystalline silica powder, which acts as a crosslinking agent and a curing agent. It is then thermally cured. Various materials are known that can individually satisfy the required properties as described above, but all of them have to sacrifice some or most of the other physical properties. It is judged that it is no longer possible to satisfy many, especially contradictory, characteristics at the same time by extending the conventional technology. For example, to improve low stress and crack resistance, various flexibilizers (1,4-butanediol,
Polyoxyalkylene ether glycol, glycerin, polysulfide polymer, polyoxyalkylene glycidyl ether, etc.) are blended or products that are blended with these may have a decrease in glass transition point, water resistance, heat resistance, etc. Large amounts of crystalline silica alone are used to improve conductivity, but this has the problem of decreasing crack resistance and increasing stress or expansion coefficient. In short, in order to achieve both high thermal conductivity and crack resistance, which are currently the main objectives of the present inventors, the above-mentioned drawbacks have more or less appeared in the conventional techniques, and it has been extremely difficult to solve them. In order to solve these difficult problems, the inventors of the present invention have conducted extensive research and have found that block copolymers with various molecular structures consisting of aromatic polymers and organopolysiloxanes can be used as epoxy resins. It has been found that dispersion or dispersion co-crosslinking is extremely effective, and in fact, the initial objective can be reliably achieved by this method, leading to the completion of the present invention. Generally, the siloxane bond energy that forms the skeleton of organopolysiloxane is 106Kca/mo
It has extremely high heat resistance, and the free rotation of siloxane bonds not only provides excellent flexibility but also increases the volume occupied by space and has excellent interfacial properties. Moreover, linear organopolysiloxane has stable properties over a wide temperature range, and can be expected to be effective as a flexibility imparting agent for epoxy resins. (See patent application No. 33601, 1983). Another example is that, unlike conventionally known flexibilizing agents, organopolysiloxanes do not melt into epoxy resins much even at high temperatures, and this causes the glass transition observed in other flexibilizing agents. This is the reason why it has the feature that it does not cause a decrease in points. However, if organopolysiloxane is used as it is, it is difficult to obtain a sea-island structure with excellent dispersibility, and the sea-island structure is likely to change, resulting in problems such as a decrease in mechanical strength and easy moisture permeation. However, since siloxane bonds have much better bonding properties to the silica surface than other organic polymers, it is quite possible to obtain results that can be put to practical use. In order to more effectively utilize the excellent properties of organopolysiloxanes, the present inventors have conducted various improvement studies and found that block polymers of aromatic polymers and organopolysiloxanes have excellent dispersibility and mechanical strength. There is almost no decrease in
We achieved this goal by developing an excellent modifier that maintains moisture permeability. That is, the present invention comprises (a) curable epoxy resin 100 parts by weight (b) aromatic polymer and the formula [R ¹ aSiO4-a/2] _o ... (i) (in the formula, R ¹ is a hydrogen atom or 1 valent organic group,
a is a positive number with an average value of 1.8 to 2.7), and n is an integer of 3 to 200.
The present invention relates to a curable epoxy resin composition comprising 5 to 100 parts by weight and (c) an inorganic filler of 0 to 1000 parts by weight, particularly for electronic components that simultaneously have high thermal conductivity, crack resistance, and low stress properties. The present invention provides a composition suitable for packaging. The organopolysiloxane-containing block copolymer that achieves the object of the present invention desirably has at least one functional group capable of reacting with an epoxy resin and a crosslinking agent in its molecule, and further improves the stability of the copolymer. The bond between both segments is particularly susceptible to hydrolysis for long-term moisture resistance

[Formula] The bond must be removed. This is presumed to be suitable for semiconductor device packaging materials, etc., which require extremely high reliability over long periods of time even under high humidity conditions. The composition according to the present invention will be explained in detail below. First, the curable epoxy resin as component (a) used in the present invention is a curable epoxy resin consisting of two or more epoxy resins and various curing agents in one molecule, and this epoxy resin will be described later. As long as it can be cured with various curing agents such as Examples include epoxy resins synthesized from various novolak resins including phenol, alicyclic epoxy resins, and epoxy resins into which halogen atoms such as chlorine and bromine atoms are introduced. In addition, when using the above-mentioned component (a), 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, phenyl glycidyl ether,
Examples include allyl glycidyl ether, octylene oxide, and dodecene oxide. When using component (a), it is not necessarily limited to only one type, and two or more types may be used in combination. In addition, as curing agents, amine curing agents such as diaminodiphenylmethane, diaminodiphenyl sulfone, metaphenylene diamine, etc., acid anhydrides such as phthalic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, etc. Examples include phenol novolac curing agents having two or more hydroxyl groups in one molecule, such as phenol novolak, cresol novolak, and the like. Furthermore, in the present invention, various curing accelerators such as imidazole or its derivatives, tertiary amine derivatives, phosphine derivatives,
There is no problem in using cycloamidine derivatives etc. in combination. It goes without saying that it is essential to use the curing agent in an amount necessary to cure the epoxy resin. Next, the block copolymer as the component (b) used in the present invention has a remarkable effect on improving crack resistance, which is the greatest objective of the present invention. It consists of a polymer and an organopolysiloxane represented by the above formula (i). Regarding the improvement of crack resistance, a considerable effect is expected by adding and blending a block copolymer of a non-aromatic polymer and an organopolysiloxane. Due to poor compatibility, it has the disadvantage that it tends to gradually migrate to the surface of the molded product over time. On the other hand, the block copolymer which is the component (b) in the present invention has the feature that the compatibility with the epoxy resin is appropriately controlled because it uses an aromatic polymer. Examples of aromatic polymers constituting the block copolymer of component (b) include those represented by the general formula Z-Q-[Z-Q-] _x -Z...(ii) can. Z in this formula is a mono- to tetravalent group derived from a benzene ring represented by the formula C ₆ HpVqR ² rXs ...(iii) or a formula or It is a mono- to divalent organic group containing a monovalent group derived from a benzene ring represented by In formulas (iii) to (v), R ² is a substituted or unsubstituted monovalent organic group having 1 to 6 carbon atoms (however, this
R ₂ does not contain an oxygen atom, a sulfur atom, a silicon atom, or a nitrogen atom), and specifically, R ² includes a methyl group, an ethyl group, a propyl group, a t-butyl group, a vinyl group, and an allyl group. Examples include a phenyl group, a cyclohexyl group, and the like. R ³ represents a hydrogen atom or a substituted or unsubstituted monovalent organic group having 1 to 6 carbon atoms, and examples of this organic group include the same groups as those exemplified for R ₂ above. V is a monovalent organic group containing an oxygen atom, a sulfur atom, a silicon atom, or a nitrogen atom, such as an alkoxy group such as a methoxy group or an ethoxy group, (-CR ³ ₂ ) _-u OH, ( −CR ³ ₂ ) − _u SH,

【formula】,

【formula】

【formula】,

【formula】

【formula】,

【formula】

【formula】,

[Formula] etc. can be given. In the above formula, R ¹ , R ² and R ³ each represent the same meaning as above, and W is a hydroxyl group, an alkoxy group,
It is an acyloxy group, etc., and u is an integer of 0 to 6. X is a halogen atom such as a chlorine atom, a bromine atom, or an iodine atom. p, q, r, s, p', q', r', s' are each 0
An integer of ~5, where p+q+r+s=2~5,
p′+q′+r′+s′=5. Q is (-CR ³ ₂ ) - _t (here R ³ is the same as above, t is an integer from 1 to 6), -O-, -S-, -SO ₂ -,

【formula】,

【formula】,

【formula】,

【formula】

【formula】,

【formula】

(where R ³ and t are the same as above) and

[Formula] (wherein R ² , X, r and s are the same as above), etc. x in formula (ii) is an integer from 0 to 30. In addition, in the above, formula (ii) is used as an aromatic polymer.
In the present invention, the formula Z-Q-...-Q-Z, Z-Z-...-Z-
Z,

[Formula] or

It goes without saying that those represented by the formula are also included, and Z and Q may be the same group, but this does not go beyond the scope of the present invention. That is, when formula (ii) is expressed as Z-Qα-[Z-Qβ-] _x -Z, when Z and Q are the same, α and β
are each 0. Examples of such aromatic polymers include those shown below. In each of the above formulas, R ² , R ³ , V, X, p, q, r, s
and x have the same meanings as above. On the other hand, the organopolysiloxane constituting the block copolymer of component (2) is represented by the average composition formula (i) above, in which R ¹ is the same or different monovalent organic group. There is a methyl group,
Unsubstituted-valent hydrocarbon groups such as ethyl group, propyl group, butyl group, vinyl group, allyl group, phenyl group,
The hydrogen atoms of these groups are partially halogen atoms, alkyl groups, mercapto groups, amino groups,
Groups substituted with aminoalkyl groups, hydroxyl groups, etc., such as -CH ₂ OH, -CH ₂ NHCH ₂ CH ₂ NH ₂ , -CH ₂ CH ₂ CH ₂ NH ₂ , -CH ₂ CH ₂ SH, -CH ₂ CH ₂ CH ₂ SH etc., hydroxyl group, methoxy group, alkoxy group such as ethoxy group, etc., and (-CH ₂ )- ₃ C≡N,

【formula】

etc. are exemplified. a is a number having an average value of 1.8 to 2.7. In the present invention, the degree of polymerization of this siloxane is required to be in the range of 3 to 200. This is because block copolymers obtained using polymerization degrees of less than 3 have difficulty imparting sufficient crack resistance, while siloxanes with polymerization degrees of more than 200 have aromatic polymers. This is because the reactivity with the copolymer becomes poor and it becomes difficult to obtain a uniform reaction product (block copolymer). If component (b) is used to provide other properties, such as sufficient flexibility, it is preferable that the siloxane be linear, but it is preferable that the siloxane be branched to some extent. There is no problem even if this happens. There is no particular limitation on the bonding mode between the aromatic polymer and the organopolysiloxane described above, but when reactivity and the like are taken into consideration, the following reaction modes can be mentioned. (W: halogen atom or hydrolyzable group such as alkoxy group, acyloxy group, amino group, amide group, etc.) The reaction examples listed here are merely examples of reactive groups and bonding modes for obtaining a copolymer of an aromatic polymer and an organopolysiloxane, and are not intended to be limiting. In addition, since the copolymer having the type of bond shown in reaction example (1) has the disadvantage of being weak (unstable) against moisture, in the present invention, the aromatic polymer and the organopolysiloxane are teeth

It is desirable that they are bonded in a bonding manner other than [Formula]. The block copolymers obtained here include those having the structures shown below. However, in the following formula, A is an aromatic polymer and B is a siloxane. A-B-A,

【formula】 (-A-B-A)-, B-A-B,

【formula】

【formula】

【formula】 [-A-B-]

[Formula] [-B-A-B-] Furthermore, in order to further prevent the transfer of this copolymer to the surface of the molded product, at least one or more reactive functional group is introduced into the copolymer. Preferably, this reactive functional group can be any type without any restriction as long as it can react with the epoxy resin, amine type, phenolic type, or acid anhydride curing agent. The siloxane content of the copolymer varies depending on the degree of polymerization of the siloxane and the blending ratio of the aromatic polymer and organopolysiloxane, but generally
It is said to be in the range of 15-80%. Such copolymers can be obtained in various forms, from resin-like to rubber-like, depending on the degree of polymerization of siloxane and the content of siloxane. It is essential to use this copolymer in an amount of 5 to 100 parts by weight per 100 parts by weight of the curable epoxy resin as component (a). This is because if the amount of copolymer used is less than 5 parts by weight, it is difficult to provide crack resistance and low stress properties, whereas if the amount is 100 parts by weight or more, crack resistance and low stress properties are not satisfied. However, on the other hand, the mechanical strength decreases. Representative examples of the inorganic filler that is component (c) include crystalline or non-crystalline silica, including Aerosil (manufactured by Degutsusa) and Cab-O-sil (manufactured by Cabobot). , Ultrasil
Ultrafine powdered silica (usually having an average particle size of 1 to 30 μm) commercially available under trade names such as (manufactured by Degutsa), Celite (manufactured by John Manville), Imsil
(manufactured by Illinois Minerals), crystalline or amorphous quartz powder (usually having an average particle size of 1 to 30 μm) is exemplified. Generally, ultrafine powdered silica has excellent reinforcing properties, but its thickening significantly impedes fluidity, making it unsuitable for casting or molding. It is preferable to selectively use powders, which can impart excellent properties. Furthermore, fillers other than silica-based fillers may be used depending on the use and purpose of the composition of the present invention, such as talc, mica, clay, kaolin, calcium carbonate, alumina, zinc white, and baryta. , glass balloon, glass fiber, aluminum hydroxide, calcium hydroxide, asbestos, titanium oxide, iron oxide, etc. It goes without saying that these fillers are not limited to being used alone, but two or more types may be used in combination. The siloxane bond in the component (b) above has a high bonding property with the surface of these fillers, especially silica fillers, and not only helps in making it hydrophobic, but also has the function of improving dispersibility, so if it is blended in large quantities. The present invention is particularly effective in highly filled silica filler systems because it has a positive effect on improving various physical properties of compounds. The amount of the inorganic filler, which is component (iii), is 1,000 parts by weight or less per 100 parts by weight of component (i), preferably 150 to 100 parts by weight per 100 parts by weight of the total amount of components (a) and (b).
It is preferable to use it in a range of 400 parts by weight. this is
This is because if an amount exceeding 500 parts by weight is used, not only will dispersion become difficult, but also satisfactory results will not be obtained in terms of properties such as workability, low stress, and crack resistance. Incidentally, since the addition and blending of component (B) to achieve the object of the present invention shows a remarkable effect even in a curing blend consisting only of a polymer, the use of component (C) is not necessarily essential. Various additives may be added to the composition according to the present invention depending on the use, purpose, etc., within a range that does not impede the purpose of the present invention, such as carbon black, graphite, wollastonite, etc. fillers, fatty acids, mold release agents such as waxes, coloring agents such as carbon black, coupling agents such as epoxy silane, vinyl silane, boron compounds, alkyl titanates, and flame retardants such as antimony compounds. can. The composition can be uniformly mixed by dry kneading, melt kneading, or solution method using a roll, kneader, screw type continuous kneader, etc., and this composition is suitable for compression, transfer, and injection molding. It can be used in a wide range of molding methods and applications, such as so-called molding compounds, liquid, solution or powder coating materials, and potting materials. Molded products obtained from the composition of the present invention have good crack resistance and excellent electrical properties, heat resistance, and moisture resistance. It can be widely applied to molds, general molding, electrical insulation, lamination, etc. Next, examples of the present invention will be given, and all parts in each example indicate parts by weight. However, all characters marked with Me are CH ₃ -. Reference example 1 Reflux condenser, thermometer, stirring bar,
and phenolic novolac resin containing allylphenol in the proportions shown in (b) of Table 1 below in a 4-neck flask with an internal volume of 500 ml equipped with a dropping funnel.
Add 50g of 2% 2-ethylhexanol-modified chloroplatinic acid solution (abbreviated as P-1) and 200g of methyl isobutyl ketone, completely dissolve the novolak resin, and perform azeotropic dehydration for 1 hour. , at reflux temperature

[Formula] 50g was added dropwise from the dropping funnel over a period of 20 minutes. After the completion of the dropwise addition, the reaction was continued for another 2 hours, and the desired product (block copolymer) was obtained by washing with water and distilling off the solvent. (Silicone-modified novolak resin No. 5 in Table 1). Block copolymers were obtained in the same manner using the novolac resins shown in Tables 1 and 2 below.

【table】

[Table] Reference example 2 In a 3-necked flask with an internal volume of 300 ml equipped with a thermometer, nitrogen gas inlet tube, and stirring bar, Epoxy cresol novolak resin (EOCN-
102 (manufactured by Nippon Kayaku), 0.4 g of triethylamine and 50 g of N,N-dimethylformamide as catalysts, and heated at 80°C under a nitrogen gas atmosphere.
The reaction was allowed to take place for 30 minutes. After the reaction was completed, the solvent was distilled off to obtain a transparent high viscosity fluid (copolymer No. 12). In addition, the solution viscosity of 50% methyl ethyl ketone is
It was 23cS (25℃). Reference Example 3 Using the same reaction apparatus as Reference Example 1, Epoxy cresol novolak resin (EOCN-
102), 5 g of methanol, and 80 g of N,N-dimethylformamide were placed in a reaction vessel, and after reacting at 100°C for 5 hours, the solvent was distilled off to obtain a light brown transparent solid (copolymer Combined No. 13). The 50% methyl ethyl ketone solution viscosity of this product was 35 cS (25°C). Reference Example 4 Using the same reaction apparatus as Reference Example 1, Epoxy cresol novolak resin (EOCN-
102) 53g was reacted in N,N-dimethylformamide at 130°C for 5 hours under a nitrogen atmosphere, and the solvent was distilled off to obtain a pale yellow translucent resin (copolymer No. 14). The solution viscosity of this 50% methyl ethyl ketone solution was 25 cS (25°C). Reference Example 5 Various block copolymers were obtained by using various aminosiloxanes as shown in Table 3 and reacting them with epoxy cresol novolak resin.

[Table] Reference Example 6 A sodium salt was synthesized by melting 53 g of brominated phenol novolak resin in 100 ml of methyl ethyl ketone and reacting with 11.5 g of NaOH. The solvent was then replaced with 200 ml of dimethylformamide, the mixture was kept at 130°C, and the addition funnel was added with stirring. 88 g was added dropwise over 30 minutes. Then increase the temperature to 150
The reaction was carried out at ℃ for 8 hours. After the reaction, the precipitate was separated and washed with water to neutralize the block copolymer (No.
19) was obtained. The resulting product was a brown, transparent, rubbery substance. The 50% methyl ethyl ketone solution viscosity of this product was 16.5 cS (25°C). Reference Example 7 53 g of brominated phenol novolak resin was dissolved in 200 ml of methyl ethyl ketone, and the mixture was stirred at the reflux temperature of methyl ethyl ketone.
From the dropping funnel 85g was added dropwise over a period of 0 minutes, after which methyl ethyl ketone was distilled off, the temperature was raised to 150℃, and the temperature was increased to 30℃.
The reaction was carried out for 5 hours under reduced pressure of mmHg. After the reaction is complete and methyl ethyl ketone is added,
By washing with water and neutralizing it, a dry, translucent, rubbery block copolymer (No. 20) was obtained. Reference example 8 Phenol novolak resin (phenol/O-allylphenol = 9 mol/1 mol)
120g, P-1 0.2g, methyl isobutyl ketone
Pour 400g into a flask and heat under reflux temperature. 82g was dropped. After the dropwise addition was completed, the reaction was continued for another 2 hours, and the solvent was distilled off to obtain a block copolymer (No. 21). The viscosity of a 50% methyl isobutyl ketone solution of this product was 42 cS (25°C). Example 1 67.9 parts of epoxy cresol novolak resin (EOCN-102, manufactured by Nippon Kayaku) with an epoxy equivalent of 220,
32.1 parts of phenol novolak resin (MP-120, manufactured by Gunei Chemical), 25 parts each of block copolymers No. 1 to 11 synthesized in Reference Example 1, 1.6 parts of silane coupling agent (KBM403, manufactured by Shin-Etsu Chemical) , crystalline quartz powder
After uniformly mixing 375 parts of carbon black, 12 parts of carbon black, 1.2 parts of carnauba wax, and 1.3 parts of C ₁₁ z azine (manufactured by Shikoku Kasei) as a curing accelerator, the mixture was kneaded with two heated rolls at 80 to 95°C to form the product. Material No.1~
Comparative Example 1 67 parts of epoxy cresol novolak resin (EOCN-102, manufactured by Nippon Kayaku) with an epoxy equivalent weight of 220, phenol novolak resin (MP-120, manufactured by Gunei Chemical Co., Ltd.) 33 parts, silane coupling agent (KBM403)
1.3 parts, 300 parts of crystalline quartz powder, 1 part of carbon black
1 part carnauba wax, as a curing accelerator
Molding material No. 12 was obtained by mixing 1.0 part of C ₁₁ z azine and kneading with two heated rolls at 80 to 90°C (control product). Molding material No. obtained in Example 1 and Comparative Example 1 above.
A thermal cycle test and general physical property measurements were conducted on samples Nos. 1 to 12 as described below, and the results are shown in Table 4 below. <Cold/heat cycle test> 0.35mm thick silicon wafer 16mm x 4.5mm
The pieces were cut into rectangles and glued to a 14-pin IC frame (42 alloy), and then transfer molded using the molding materials obtained above at 160℃ for 2 minutes, and then at 180℃ for 4 hours. Post-cure, then cool this material at -55℃ for 30 minutes,
We conducted a so-called cold-heat cycle, which involves heating at 150℃ for 30 minutes, to reduce the defective rate due to cracks in the molded resin.
The number of cycles until it reached 50% was measured. <General Properties> Each of the molding materials obtained above was subjected to transfer molding at a temperature of 160° C. and a pressure of 70 Kg/cm ² in order to measure the bending strength, expansion coefficient, glass transition point, water absorption rate, and resin stress. The results were as shown in the table. However, the measurement conditions for each physical property are as shown below. Measurement of mechanical strength (bending strength): According to JIS K6911, molding temperature 160℃, molding pressure
70Kg/cm ² , molding time 3 minutes, width 10mm, length
A 100mm and 4mm thick bar was molded and then after-cured for 4 hours in a thermostat at 180°C for measurement as a test piece. Measurement of linear expansion coefficient: ASTM using the bending strength measurement test piece mentioned above.
Measured according to D696. Measurement of glass transition point Cut out a 5 mm square and 20 mm long prism from a test piece for bending strength measurement, and measure the bending point of linear expansion when the temperature is raised at a rate of 5 degrees Celsius per minute using a vacuum science and engineering dictometer. was taken as the glass transition point. Measurement of water absorption rate: After molding a disc with a thickness of 2 mm and a diameter of 70 mm under the conditions of molding temperature of 160℃, molding pressure of 70Kg/cm ² and molding time of 3 minutes, it was after-cured for 4 hours in a constant temperature bath at 180℃. was used as a test piece, and the sample was taken out after being subjected to a pressure checker test at 121°C, 2 atm, for 500 hours, and the weight increase from the initial stage was taken as the water absorption rate. Measurement of resin stress: 3mm piezoresistance whose resistance value changes due to stress
Die-bond the square semiconductor chip diffused onto a 14-pin IC frame, wire-bond it with Au wire,
The initial resistance value (R ₀ ) of the element connected to the external electrode was measured, and the element was heated at 160℃, 70Kg/cm ² , and molded for 3 hours.
The resistance value (R) after resin sealing was measured under molding conditions of minutes, and (R-R ₀ )/R ₀ was defined as the resin stress.

[Table] Example 2 Molding materials were prepared in the same manner using the same composition as molding material No. 5 of Example 1 except that the amount of block copolymer used was changed to 5.0, 50 or 100 parts. Nos. 13 to 15 were obtained (all products of the present invention). Example 3 64.5 parts of epoxy cresol novolak resin (EOCN-102, manufactured by Nippon Kayaku) with an epoxy equivalent of 220,
35.5 parts of tetrahydrophthalic anhydride, 25 parts of block copolymer No. 5, silane coupling agent (KBM
-403, manufactured by Shin-Etsu Chemical) 1.6 parts, crystalline quartz powder 375
1.2 parts, carbon black, carnauba wax
After uniformly mixing 1.0 part of stearic acid, 1.5 parts of stearic acid, and 1.0 part of C ₁₁ z azine, the mixture was kneaded with two rolls heated at 90 to 100°C to obtain molding material No. 16 (product of the present invention). Comparative Example 2 64.5 parts of epoxy cresol novolak resin (EOCN-102, manufactured by Nippon Kayaku) with an epoxy equivalent of 220,
35.5 parts of latrahydrophthalic anhydride, 1.3 parts of silane coupling agent (KBM403, manufactured by Shin-Etsu Chemical), 300 parts of crystalline quartz powder, 1 part of carbon black, 1 part of carnauba wax, 1.5 parts of stearic acid, and C ₁₁ z
0.8 parts of azine was treated in the same manner as in Example 3 to obtain molding material No. 17 (product of the present invention). Example 4 80 parts of epoxy cresol novolak resin (EOCN-102, manufactured by Nippon Kayaku) with an epoxy equivalent weight of 220, 20 parts of diaminodiphenylmethane, and block copolymer
No. 5, 25 parts, silane coupling agent (KBM403,
(manufactured by Shin-Etsu Chemical), 230 parts of crystalline quartz powder, and 2 parts of stearic acid were thoroughly kneaded using two heated rolls to obtain molding material No. 18 (product of the present invention). Comparative Example 3 100 parts of epoxy cresol novolac resin (EOCN-102, manufactured by Nippon Kayaku) with an epoxy equivalent weight of 220, 25 parts of diaminodiphenylmethane, 1 part of silane coupling agent (KBM403, manufactured by Shin-Etsu Chemical), crystalline quartz powder 230 parts and 2 parts of stearic acid were treated in the same manner as in Example 4 to obtain molding material No. 19 (control product). The molding materials obtained in Examples 2 to 4 and Comparative Examples 2 to 3 were subjected to a thermal cycle test using the method described above, and the results are shown in Table 5 below.

[Table] Example 5 67 parts of epoxy cresol novolak (EOCN-102, manufactured by Nippon Kayaku) with an epoxy equivalent weight of 220, 33 parts of phenol novolak resin (MP-120, manufactured by Gunei Chemical)
25 parts each of the block copolymers (No. 12 to 18) synthesized in Reference Examples 2 to 5, 1.6 parts of a silane coupling agent (KBM-403, manufactured by Shin-Etsu Chemical), 375 parts of crystalline quartz powder, Mix well 1.2 parts of Carbon Black, 1.2 parts of Carna Power Mix, and 1.0 part of 2-phenylimidazole as a curing accelerator, and heat to 80-95℃.
By kneading with two heated rolls, molding resins (No. 20 to No. 26) were obtained (all products of the present invention). Comparative Example 4 67 parts of epoxy cresol novolak resin (EOCN-102, manufactured by Nippon Kayaku) with an epoxy equivalent of 220, 33 parts of phenol novolak resin (MP-120, manufactured by Gunei Chemical), silane coupling agent (KBM-403) (manufactured by Shin-Etsu Chemical), 300 parts of crystalline quartz powder, 1 part of carbon black, 1.0 part of Carnapower Mix, and 0.8 part of 2-phenylimidazole as a hardening accelerator were thoroughly mixed, and heated at 80 to 95℃. By kneading with this roll, molding material No. 27 was obtained (control product). Example 6 67 parts of epoxy cresol novolak (EOCN-102, manufactured by Nippon Kayaku) with an epoxy equivalent weight of 220, 33 parts of phenol novolak resin (MP-120, manufactured by Gunei Chemical)
part, block copolymer (No. 13) 5.3 parts, silane coupling agent (KBM-403, manufactured by Shin-Etsu Chemical) 1.4 parts
1 part, 316 parts of crystalline quartz powder, 1 part of carbon black
1 part of Carna Power Mix and 0.8 part of 2-phenylimidazole as a curing accelerator were thoroughly mixed and kneaded with two heated rolls at 80 to 95°C to obtain molding material No. 28 (the present invention). product). Example 7 62 parts of epoxy cresol novolak resin (EOCN-102, manufactured by Nippon Kayaku) with an epoxy equivalent weight of 220, 38 parts of phenol novolak resin (MP-120, manufactured by Gunei Chemical), block copolymer (No. 13) ) 43.3 parts, silane coupling agent (KBM-403, manufactured by Shin-Etsu Chemical)
1.9 parts, crystalline quartz powder 430 parts, carbon black
Molding material No. 29 was obtained by kneading 1.4 parts of Carnapower Mix, 1.4 parts of Carnapower Mix, and 1.1 parts of 2-phenylimidazole in the same manner as in Example 6 (product of the present invention). Example 8 75.6 parts of epoxy cresol novolak resin (EOCN-102, manufactured by Nippon Kayaku) with an epoxy equivalent of 220,
24.4 parts of phenol novolak resin (MP-120, manufactured by Gunei Chemical Co., Ltd.), 100 parts of block copolymer (No. 13),
2.6 parts of a silane coupling agent (KBM-403, manufactured by Shin-Etsu Chemical), 600 parts of crystalline quartz powder, 2 parts of carbon black, 2 parts of Carnapower Wax, and 1.6 parts of 2-phenylimidazole are kneaded in the same manner as in Example 6. As a result, molding material No. 30 was obtained (product of the present invention).

[Table] Example 9 The block copolymer of Example 5 was changed to the block copolymer (No. 19) synthesized in Reference Example 6.
Molding materials were manufactured with exactly the same composition. As a result of conducting a thermal cycle test on this molding material, the number of cycles at which a 50% defective rate occurred was 280 cycles. Example 10 The block copolymer of Example 5 was replaced with the block copolymer (No. 20) synthesized in Reference Example 7.
Molding materials were obtained with exactly the same composition. When this molding material was subjected to a thermal cycle test, the number of cycles at which a 50% defective rate was achieved was 250 cycles. Example 11 Epoxy cresol novolak resin (EOCN-
102, Nippon Kayaku) 66 parts, phenol novolac resin (MP-120, Gunei Chemical) 22 parts, brominated epoxy resin (XD-8094, Dow Chemical) 12
25 parts of block copolymer (No. 21), 400 parts of crystalline silica, 6.5 parts of antimony trioxide, 1.7 parts of silane coupling agent (KBM-403, manufactured by Shin-Etsu Chemical), 1 part of carbon black, 1.3 parts of Carna Power Wax ,
A molding material was obtained by thoroughly kneading 1.0 part of 2-phenylimidazole using two heated rolls. The properties of this molding material are as follows. 1 Linear expansion coefficient 2.5×10 ^-5 1/℃ (room temperature ~ 120
℃) 2 Bending strength (room temperature) 12Kg/mm ² 〓 (150℃) 6Kg/mm ² 3 Glass transition temperature 175℃ 4 Cooling and heating cycle test (until 50% failure occurs)
Example 12 Epoxy cresol novolak resin (EOCN-
102, manufactured by Nippon Kayaku) 67 parts, 32 parts of phenol novolak resin (MP-120, manufactured by Gunei Chemical), 20 parts of a block copolymer represented by the following formula, A molding material was obtained by thoroughly kneading 350 parts of crystalline quartz powder, 1.2 parts of carbon black, 1.2 parts of Carna Power Wax, and 1.3 parts of C ₁₁ z amine (manufactured by Shikoku Kasei). In a thermal cycle test of this molding material, the number of cycles until 50% failure occurred was 200 cycles. Example 13 Epoxy cresol novolak (EOCN-
102, manufactured by Nippon Kayaku) 67 parts, phenol novolak resin (MP-120, manufactured by Gunei Chemical) 33 parts, block copolymer represented by the following formula 20 parts, A molding material was obtained by thoroughly kneading 350 parts of crystalline quartz powder, 1.5 parts of OP-wax, and 1.0 part of 2-phenylimidazole. This molding material reached a 50% defective rate in 150 cycles in a thermal cycle test.

Claims (1)

[Claims] 1 (a) 100 parts by weight of curable epoxy resin, (b) aromatic polymer and formula [R ¹ aSiO4-a/2] _o (wherein R ¹ is a hydrogen atom or a monovalent organic group,
a is a positive number with an average value of 1.8 to 2.7), and n is an integer of 3 to 200.
Curable epoxy resin composition 2 comprising 5 to 100 parts by weight and (c) 0 to 1000 parts by weight of an inorganic filler.Claim 1, wherein the epoxy resin is a novolac type epoxy resin and/or a bisphenol type epoxy resin. Curable epoxy resin composition powder 3 described in 3 The aromatic polymer constituting the block copolymer has the general formula Z-Q-[Z-Q-] _x -Z [wherein Z is the formula C ₆ HpVqR ² rXs (where R ₂ is a substituted or unsubstituted monovalent organic group having 1 to 6 carbon atoms, V is a monovalent organic group containing an oxygen atom, sulfur atom, silicon atom, or nitrogen atom, and X is Halogen atoms, p, q, r and s are each integers of 0 to 5, provided that p+q+r+
C ₆ Hp′Vq′R ² r′Xs′ [Formula] or C ₆ Hp′Vq′R ² r'Xs' [Formula] (Here, R ₂ , V and X have the same meanings as above, and R ³ is a hydrogen atom or has 1 to 6 carbon atoms.
substituted or unsubstituted monovalent organic group, p′, q′,
r' and s' are each integers from 0 to 5, provided that
p′+q′+r′+s′=5), Q is a monovalent or divalent organic group containing one bridge group derived from a benzene ring, Q is (−CR ³ ₂ ) _−t R ₃ is the same as above, t is an integer from 1 to 6), -O-, -S
―, ―SO ₂ ―, [formula], [formula], [formula] [formula], [formula] (wherein R ³ and t are the same as above) and [Formula] (wherein R ₂ , X, r and s are the same as above), x is an integer from 0 to 3] The curable epoxy resin composition according to claim 1 or 2, wherein the aromatic polymer constituting the block copolymer is a substituted or unsubstituted phenol novolak. Curable epoxy resin composition 5 according to claim 1 or 2.Claim 5, wherein the aromatic polymer constituting the block copolymer is a substituted or unsubstituted epoxy novolak. Curable epoxy resin composition 6 according to item 1 or 2.Claims 1, 2, 3, and 2, wherein the organopolysiloxane constituting the block copolymer is dimethylpolysiloxane. Curable epoxy resin composition 7 according to item 4 or item 5 The organopolysiloxane constituting the block copolymer is a copolymer consisting of dimethylpolysiloxane units and methylphenylsiloxane and/or diphenylsiloxane units. Curable epoxy resin composition 8 according to claim 1, 2, 3, 4 or 5, wherein the aromatic polymer and organopolysiloxane in the block copolymer are , [Formula] The curable epoxy resin composition 9 according to claim 1, wherein the block copolymer has a functional group capable of reacting with component (a) in its molecule. Claims 1, 2, and 3, which are copolymers having at least one
Curable epoxy resin composition 10 according to item 4, 5, 6, 7 or 8. Claim 1, wherein the block copolymer is a multi-block copolymer. Curable epoxy resin composition 11 The curable epoxy resin composition according to claim 1, wherein the inorganic filler is fused (amorphous) silica or crystalline silica.