JPH05132539A - Epoxy resin composition - Google Patents

Abstract

PURPOSE:To obtain an epoxy resin composition which can give a cured product excellent in heat resistance, flexibility, hydrophobicity, etc., by mixing an epoxy resin with a specified polyallylphenol and a specified polyphenol. CONSTITUTION:100 pts.wt. epoxy resin as a base resin is mixed with 5-200 pts.wt. polyallylphenol containing two or more structural units of formula I in the molecule [e.g. formula II (wherein (m) is 1-6)] and 5-200 pts.wt. polyphenyl of formula III (wherein (n) is 1-6) to obtain the objective epoxy resin composition. This composition has excellent curability and can give a cured product excellent in heat resistance, hydrophobicity, flexibility and cracking resistance. Therefore, it is useful for multi-ply laminated resins, conductive pastes, protective films for electronic elements, sealing materials, adhesives, coating materials and molding materials used in electronic and electrical equipments, transportation machines, etc.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an epoxy resin composition. More specifically, the present invention relates to an epoxy resin composition which is particularly excellent in heat resistance, flexibility, crack resistance, hydrophobicity and curability. The epoxy resin composition of the present invention having such excellent properties is used in various fields, particularly in the fields of resins for multi-layer lamination, conductive pastes, electronic element protective films, adhesives, paints, encapsulating materials and molding materials. Therefore, it can be advantageously used.

[0002]

2. Description of the Related Art In recent years, electronic and electrical equipment, transportation equipment, etc. have been made smaller and lighter and have higher performance, and resin materials used for these have been excellent in heat resistance, hydrophobicity and flexibility. What is desired is also desired, and one having good moldability is desired.

A polyimide resin is generally known as a heat resistant resin. Epoxy resin is widely known as a resin having good moldability.

[0004]

Since the polyimide resin known as a heat-resistant resin is a dehydration condensation type, voids are easily generated in the cured product due to condensed water generated by the reaction, and the reliability of the cured product is high. Is reduced. Moreover, since the polyimide itself is insoluble and infusible, it is difficult to mold this resin.

Bismaleimide resin is known as a polyimide resin having improved molding processability.
It requires a high temperature above ℃, and the workability is poor. In addition, the bismaleimide resin is poor in hydrophobicity, which significantly reduces the reliability of the cured product. Also, the bismaleimide resin is
Since the cured product has a high crosslink density, it is poor in flexibility and cracks easily occur in the molded product.

The epoxy resin, which is a resin having excellent moldability, does not have the disadvantages found in the above-mentioned polyimide resin and bismaleimide resin. However, in epoxy resins, amines, acid anhydrides, phenols and the like are usually used as a curing agent, and the obtained cured products are rather poor in heat resistance. For example, the glass transition temperature of a cured product of an epoxy / phenol curing system is usually 140-
It is about 170 ° C., and it is desired to raise this.

The present invention eliminates the above-mentioned drawbacks of the prior art, in other words, is a resin composition having an epoxy resin as a base resin and having excellent curability, and having heat resistance and flexibility. An object of the present invention is to provide a resin composition which can form a cured product having excellent hydrophobicity and crack resistance and can be advantageously used in various fields.

[0008]

The resin composition of the present invention for attaining this object has the following formula with respect to 100 parts by weight of an epoxy resin which is a base resin.

[0009]

[Chemical 5]

5 to 200 parts by weight of polyallylphenol having a plurality of constitutional units represented by the following formula in the molecule, and the following formula:

[0011]

[Chemical 6]

An epoxy resin composition comprising 5 to 200 parts by weight of a polyphenol represented by

Any epoxy resin may be used as the base resin in the composition of the present invention. That said, examples of epoxy resins that can be advantageously used in the compositions of the present invention include bisphenol A type epoxy resins, cresol novolac type epoxy resins, phenol novolac type epoxy resins, biphenyl type epoxy resins. And epoxy resins having two or more epoxy groups in one molecule, such as glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin and halogenated epoxy resin.

Among the epoxy resins, more preferable in the present invention is a biphenyl type epoxy resin.
This is because the composition of the present invention containing a biphenyl type epoxy resin as a base resin gives a cured product having improved heat resistance and moisture resistance.

Suitable biphenyl type epoxy resins include 4,4'-bis (2,3-epoxypropoxy) biphenyl and 4,4'-, as described in, for example, JP-A-63-251419. Bis (2,3-epoxypropoxy) -3,3 ', 5,5'-tetramethylbiphenyl, 4,4'-bis (2,3-epoxypropoxy) -3,3', 5,5'-tetra Methyl-2-chlorobiphenyl, 4,4'-bis (2,3-epoxypropoxy) -3,3 ', 5,5'-tetramethyl-2-bromobiphenyl, 4,4'-bis (2,3 -Epoxypropoxy) -3,3 ', 5,5'-tetraethylbiphenyl, 4,4'-bis (2,3-epoxypropoxy)-
3,3 ', 5,5'-tetrabutylbiphenyl and the like can be mentioned. The general formula of such an epoxy resin is as follows.

[0016]

[Chemical 7]

In the above formula, R and R'each represent an epoxy functional group, and R ^{1 to} R ⁸ each represent a hydrogen atom, a C _{1 to} C ₄ lower alkyl group or a halogen atom. A representative example of epoxy functional groups R and R'is the 2,3-epoxypropoxy group. Preferred examples of R ^{1 to} R ⁸ include a hydrogen atom, a methyl group, an ethyl group, a propyl group,
A butyl group, a chlorine atom, a bromine atom, etc. can be mentioned. Such epoxy groups are commercially available,
For example, YX-4000H manufactured by Yuka Shell Epoxy Co., Ltd. can be advantageously used.

Of course, the epoxy resins may be used alone or in a mixture of two or more kinds.

The polyallylphenol used in the epoxy resin composition of the present invention functions as a curing agent. Examples of preferred polyallylphenol include:

[0020]

[Chemical 8]

Those represented by can be mentioned. M in these formulas is 1-6. The larger the value of m, the higher the viscosity, the better the workability,
It is understood that the heat resistance is also good. Such polyallylphenol may be synthesized according to known techniques,
Alternatively, for example, commercially available products may be used, including SH-150AR (trade name) sample-shipped by Mitsubishi Petrochemical Co., Ltd.

The polyallylphenol used as a curing agent raises the glass transition temperature of the cured product to improve the heat resistance and further improves the hydrophobicity. The compounding amount of polyallylphenol is 100% epoxy resin as the base resin.
It is preferably 5 to 200 parts by weight with respect to parts by weight.
If it is less than 5 parts by weight, a sufficient curing reaction cannot be expected, and if it exceeds 200 parts by weight, the glass transition temperature of the cured product is lowered and the heat resistance is impaired. A more preferable blending amount of polyallylphenol is 50 to 100 parts by weight with respect to 100 parts by weight of the epoxy resin.

The polyphenol added to the composition of the present invention acts as a curing aid and is particularly effective in simultaneously improving curability and mechanical strength. This polyphenol

[0024]

[Chemical 9]

## EQU2 ## where n is 1 to 6. Such a polyphenol may be synthesized by a known technique, or a commercially available product may be used, for example, a product commercially available as SH-180 (trade name) from Mitsubishi Petrochemical Co., Ltd.

The polyphenol used as a curing aid can be used in various compounding amounts in the composition of the present invention depending on the desired effect of addition, and the compounding amount can usually be changed within a wide range. it can. However, it is generally preferable that the compounding amount be 5 to 200 parts by weight with respect to 100 parts by weight of the epoxy resin. If the amount is less than 5 parts by weight, the effect of the addition is not sufficiently exhibited. If the amount exceeds 200 parts by weight, the polyphenol is a brittle substance, so that the properties such as toughness of the cured product deteriorate.
A more preferable blending amount of the polyphenol is 30 to 100 parts by weight with respect to 100 parts by weight of the epoxy resin.

To the composition of the present invention, one or more of the following flexibility-imparting agents are added, if necessary, in order to impart appropriate flexibility to the resulting cured product. can do.

(A) Polystyrene / polybutadiene / polystyrene end block copolymer (b) Ethylene / propylene copolymer (c) Ethylene / α-olefin copolymer (d) Epoxy functional silicone rubber powder (e ) Silicon modified epoxy resin

Among the above-mentioned flexibility-imparting agents, ethylene / propylene copolymers are ternary copolymers containing dicyclopentadiene or ethylidene norbornene as a third component monomer in addition to ethylene monomer and propylene monomer. Polymers are preferred.

These flexibility-imparting agents can have various structures and are actually commercially available in various forms. As an example, polystyrene / polybutadiene / polystyrene end block copolymer is Kraton G-
1652 (Shell Chemical Co., Ltd.), ethylene / propylene copolymer as JSR 57P (Japan Synthetic Rubber Co., Ltd.), ethylene / α-olefin copolymer as Tuffmer PP.
-0280 (Mitsui Petrochemical Co., Ltd.) is a silicone rubber powder containing an epoxy functional group, which is Trefil E601.
(Toray Dow Corning Co., Ltd.), a silicone-modified epoxy resin is available as SIN-620 (Dainippon Ink and Chemicals, Inc.).

The above-mentioned flexibility-imparting agent is effective in improving the flexibility and toughness of the cured product and improving the crack resistance. Further, these flexibility imparting agents also have an effect of improving the moisture resistance of the cured product. Any of the flexibility-imparting agents was added to 5 parts by weight of 100 parts by weight of the epoxy resin as the base resin.
It is desirable to add ˜80 parts by weight. If it is less than 5 parts by weight, the effect of addition does not appear, and if it exceeds 80 parts by weight, the heat resistance of the cured product decreases.

The epoxy resin composition of the present invention may contain a powdered inorganic filler in order to improve the mechanical strength of the cured product. Examples of inorganic fillers include fused silica, crystalline silica, alumina, calcium carbonate and the like. The amount of these fillers added is preferably in the range of 20 to 85% by weight of the total composition. Two
If the addition amount is less than 0% by weight, the desired effect cannot be expected, and if it is more than 85% by weight, the flowability of the composition is lowered and the workability is lowered, and the cured product is apt to crack. ..

Further, the following components can be optionally added to the composition of the present invention.

(1) A curing accelerator for promoting a curing reaction between an epoxy resin as a base resin, a polyallylphenol as a curing agent and a polyphenol as a curing aid. Examples of the curing accelerator include imidazole compounds such as 2-methylimidazole, phosphine compounds such as triphenylphosphine, and DBU compounds such as diazabicycloundecene (DBU) phenolic salts.

(2) A coupling agent for improving the compatibility with the resin when an inorganic filler is added. For example, a silane coupling agent such as 3-aminopropyltriethoxysilane or a titanium coupling agent such as tetraoctylbis (phosphite) titanate can be used. The addition amount of the coupling agent depends on the type and amount of the inorganic filler used, the specific surface area and the minimum coating area of the coupling agent, but is preferably about 0.1 to 15 parts by weight in the present invention.

(3) Releasing aids (eg carnauba wax, stearic acid and its metal salts, montan wax, etc.). (4) Flame retardant (for example, brominated epoxy resin, antimony trioxide, etc.). (5) Pigments (for example, carbon black). (6) Colorant (for example, titanium dioxide).

The epoxy resin composition of the present invention can be prepared by heating its constituent components at a temperature of about 60 to 120 ° C. by using an appropriate means such as a roll, a kneader or an extruder. Alternatively, it may be prepared by employing a solvent mixing method in which a suitable organic solvent such as acetone or toluene is dissolved and mixed.

In addition, in the composition of the present invention, it is desirable to perform after-cure after the molding process in order to complete the curing reaction of the uncured epoxy resin in the cured product. The after-curing after the molding process may be such that the heat treatment is performed for a predetermined time in a constant temperature bath at a temperature approximately the same as the temperature during the molding process.

[0039]

The polyallylphenol compounded as a curing agent in the epoxy resin composition of the present invention raises the glass transition temperature of the cured product to improve heat resistance, and is a representative of conventional heat resistant resins. It is effective in improving hydrophobicity, flexibility, and crack resistance as compared with a certain polyimide resin. The polyphenol added as a curing aid improves not only the curability of the composition of the present invention but also the mechanical strength of the cured product.

The flexibility-imparting agent, which is optionally added to the epoxy resin composition of the present invention, is effective for improving the flexibility of the cured product and, as a result, improving the crack resistance of the cured product. To work. Further, the inorganic filler added to the composition of the present invention improves the mechanical strength of the cured product.

[0041]

EXAMPLES Next, the present invention will be described in more detail with reference to Examples and Comparative Examples. In the following examples, the number of parts means "parts by weight" unless otherwise specified. The cresol novolac type epoxy resin used in each of the following examples is EOCN-1025 manufactured by Nippon Kayaku Co., Ltd., and the biphenyl type epoxy resin is YX-400 manufactured by Yuka Shell Epoxy Co., Ltd.
0H, polyallylphenol is SH manufactured by Mitsubishi Petrochemical Co., Ltd.
It was -150 AR and the polyphenol was SH-180 also manufactured by Mitsubishi Petrochemical Co., Ltd.

The properties of the compositions prepared in the following examples and their cured products were evaluated according to the methods described below.・ Glass transition temperature Measured with a thermomechanical analyzer (vacuum physics). -Bending strength According to JIS K6911. Bending elastic modulus According to JIS K6911.・ Crack Sample after cooling (10 × 5 ×
30mm) cross section evaluated with a microscope. -Water absorption rate According to JIS K6911. -Moisture resistance The aluminum wiring simulation element was used to evaluate defects after PCT treatment (125 ° C / 2.3 atm).・ Package crack Molded 84-pin QFP, 12
After moisture absorption treatment at 1 ° C and 100% relative humidity for 24 hours, 26
Investigate the occurrence of cracks when immersed in solder at 0 ° C. Gel time Measure the curing time on a hot plate (180 ° C). -By viscosity flow tester method.

Examples 1 to 39 and Comparative Example 1 listed below
In Examples 16 to 16, a cresol novolac type resin is used as the epoxy resin of the base resin, and Example 40 to
In 78 and Comparative Examples 17 to 32, a biphenyl type epoxy resin was used.

Examples 1 to 9 and Comparative Examples 1 to 4 Cresol novolac type epoxy resin, polyallylphenol and polyphenol were kneaded together by a pressure kneader to prepare compositions having the compounding amounts shown in Table 1.

Then, the obtained composition was made into a powder of 8 mesh pass, transferred to a press mold, and compression molded at 200 ° C. and 80 kg / cm ² for 20 minutes, and after-cured at 200 ° C. for 8 hours. Then, a test piece was prepared. Using these test pieces, various properties were measured according to the methods described above. The obtained results are shown in Table 1 and FIG.

[0046]

[Table 1]

From Table 1, for 100 parts of epoxy resin,
It can be seen that by using 5 to 200 parts of polyallylphenol as the curing agent, an epoxy resin composition having excellent heat resistance of the cured product (high glass transition temperature) can be obtained. It can be seen that the cured product has excellent hydrophobicity as judged by the water absorption. Further, by using 5 to 200 parts of polyphenol as a curing aid, an epoxy resin composition having good curability could be obtained.

It is clear from FIG. 1, which is a graph of the results of the PCT test showing the moisture resistance of the cured product, that the composition of the present invention gives a cured product having much better moisture resistance than the composition of the comparative example. become.

As described above, from the epoxy resin composition of the present invention in which the polyallylphenol curing agent and the polyphenol curing aid are blended, a resin for multi-layer lamination, a conductive paste, which is used in electronic / electrical devices, transportation machines and the like, It has been found that a cured product having useful properties as an electronic element protective film, a sealing material, a molding material, etc. can be obtained. That said,
As the evaluation result about the package crack shows,
The compositions of Examples 1 to 9 have the special harsh P content as described above.
It was found that some package cracks were generated under the solder immersion conditions after the CT treatment.

Examples 10 to 14 and Comparative Examples 5 and 6 In these examples, a mixture of cresol novolac type epoxy resin, polyallylphenol and polyphenol was further used as a flexibility-imparting agent by using polystyrene / polybutadiene / polystyrene end block copolymerization. Coal (Clayton G-1652 manufactured by Shell Chemical Co., Ltd.) was added, and these were kneaded together with a pressure kneader to prepare a composition having the compounding amount shown in Table 2.

Specimens were made from each of the resulting compositions according to the procedure described in Example 1, and cured products were similarly characterized. The results are shown in Table 2 and FIG.

[0052]

[Table 2]

From Table 2, for 100 parts of epoxy resin,
Polystyrene / polybutadiene / as flexibility imparting agent
It can be seen that the addition of 5 to 80 parts of the polystyrene end block copolymer improved the flexibility of the cured product and suppressed the occurrence of package cracks. Further, it can be seen from FIG. 2 that cured products having better moisture resistance than the cured products obtained from the compositions of Examples 1 to 9 were obtained.

Examples 15 to 19 and Comparative Examples 7 and 8 Examples 10 to 14 except that an ethylene / propylene copolymer (JSR 57P manufactured by Japan Synthetic Rubber Co., Ltd.) was used as the flexibility-imparting agent. In the same manner, the compositional amounts of the compositions shown in Table 3 were prepared and the cured test pieces were characterized. The results are shown in Table 3 and FIG.

[0055]

[Table 3]

From Table 3, for 100 parts of the epoxy resin,
It can be seen that by adding 5 to 80 parts of the ethylene-propylene copolymer as the flexibility-imparting agent, the flexibility of the cured product was improved and the generation of package cracks was suppressed. Further, it can be seen from FIG. 3 that cured products having better moisture resistance than the cured products obtained from the compositions of Examples 1 to 9 were obtained.

Examples 20 to 24 and Comparative Examples 9 and 10 Example 10 was repeated except that an ethylene / α-olefin copolymer (Tufmer PP-0280 manufactured by Mitsui Petrochemical Co., Ltd.) was used as the flexibility-imparting agent. ~ 4 as in Table 4
A composition having the compounding amount shown in Table 1 was prepared and the cured test piece was characterized. The results are shown in Table 4 and FIG.

[0058]

[Table 4]

From Table 4, for 100 parts of the epoxy resin,
It can be seen that by adding 5 to 80 parts of the ethylene / α-olefin copolymer as the flexibility-imparting agent, the flexibility of the cured product was improved and the generation of package cracks was suppressed. Further, it can be seen from FIG. 4 that cured products having better moisture resistance than the cured products obtained from the compositions of Examples 1 to 9 were obtained.

Examples 25 to 29 and Comparative Examples 11 and 12 Epoxy functional group-containing silicone powder (Trefil E-60 manufactured by Toray Dow Corning Co., Ltd.) as a flexibility imparting agent.
As in Examples 10-14, except that 1) was used, the compositional amounts of the compositions shown in Table 5 were prepared and the cured test pieces were characterized. The results are shown in Table 5 and FIG.

[0061]

[Table 5]

From Table 5, for 100 parts of epoxy resin,
It can be seen that by adding 5 to 80 parts of the epoxy functional group-containing silicone powder as the flexibility imparting agent, the flexibility of the cured product was improved and the generation of package cracks was suppressed. Further, it can be seen from FIG. 5 that cured products having better moisture resistance than the cured products obtained from the compositions of Examples 1 to 9 were obtained.

Examples 30 to 34 and Comparative Examples 13 and 14 Same as Examples 10 to 14 except that a silicon-modified epoxy resin (SIN-620 manufactured by Dainippon Ink and Chemicals, Inc.) was used as the flexibility imparting agent. The formulations were prepared as shown in Table 6 and the cured test pieces were characterized. The results are shown in Table 6 and FIG.

[0064]

[Table 6]

From Table 6, for 100 parts of the epoxy resin,
Silicon-modified epoxy resin as a flexibility-imparting agent
It can be seen that the addition of 80 parts improved the flexibility of the cured product and suppressed the generation of package cracks. Further, it can be seen from FIG. 6 that cured products having better moisture resistance than the cured products obtained from the compositions of Examples 1 to 9 were obtained.

Examples 35 to 39 and Comparative Examples 15 and 16 In these examples, a mixture of cresol novolac type epoxy resin, polyallylphenol and polyphenol, and powdery silica (RD-Tatsumori Co., Ltd.) as an inorganic filler were used. 8) was added, and these were kneaded together with a pressure kneader to prepare compositions having the compounding amounts shown in Table 7.

Test pieces were prepared from each of the obtained compositions according to the procedure described in Examples 1 to 9 and cured products were similarly characterized. The results are shown in Table 7 and FIG. Table 7
In addition, the viscosity of the prepared composition is also described.

[0068]

[Table 7]

From Table 7, 20-85% by weight of the total composition
It can be seen that the addition of the inorganic filler can advantageously improve the mechanical strength of the cured product without significantly reducing the flowability of the composition. Further, it can be seen from FIG. 7 that the cured product also has good moisture resistance.

Examples 40 to 48 and Comparative Examples 17 to 20 Examples 1 to 1 except that a biphenyl type epoxy resin was used in place of the cresol novolac type epoxy resin.
Compositions were prepared in the same manner as in No. 9, and various properties of cured test pieces obtained from these compositions were evaluated. The prepared composition was as shown in Table 8. The obtained results are shown in Table 8 and FIG.

[0071]

[Table 8]

From Table 8, it can be seen that the heat resistance was further improved by changing the base resin to the biphenyl type epoxy resin. Further, from FIG. 8, a significant improvement in moisture resistance is recognized. However, the compositions of Examples 40-48, like the compositions of Examples 1-9, caused some package cracking under solder immersion conditions after the particularly severe PCT treatment.

Examples 49 to 53 and Comparative Examples 21 and 22 A mixture of a biphenyl type epoxy resin, polyallylphenol and polyphenol, and a polystyrene / polybutadiene / polystyrene end block copolymer (made by Shell Chemical Co.) as a flexibility-imparting agent. Clayton G-165
Example 4 except that 2) was added to prepare the composition.
The procedure of 0-48 was repeated. The prepared composition is as shown in Table 9, and the obtained results are shown in Table 9 and FIG.

[0074]

[Table 9]

From Table 9, for 100 parts of epoxy resin,
Polystyrene / polybutadiene / as flexibility imparting agent
It can be seen that the addition of 5 to 80 parts of the polystyrene end block copolymer improved the flexibility of the cured product and suppressed the occurrence of package cracks. Further, it can be seen from FIG. 9 that cured products having extremely excellent moisture resistance were obtained as compared with the cured products obtained from the compositions of Examples 40 to 48.

Examples 54 to 58 and Comparative Examples 23 and 24 Examples 49 to 53 except that an ethylene / propylene copolymer (JSR 57P manufactured by Japan Synthetic Rubber Co., Ltd.) was used as the flexibility-imparting agent. In the same manner, the compositional amounts of the compositions shown in Table 10 were prepared and the cured test pieces were characterized. The results are shown in Table 10 and FIG.

[0077]

[Table 10]

From Table 10, by adding 5 to 80 parts of the ethylene / propylene copolymer as a flexibility-imparting agent to 100 parts of the epoxy resin, the flexibility of the cured product is improved and the package cracks are prevented. It can be seen that the occurrence was suppressed. Further, it can be seen from FIG. 10 that cured products having extremely excellent moisture resistance were obtained as compared with the cured products obtained from the compositions of Examples 40 to 48.

Examples 59 to 63 and Comparative Examples 25 and 26 Example 49 except that an ethylene / α-olefin copolymer ( Tuffmer PP-0280 manufactured by Mitsui Petrochemical Co., Ltd.) was used as the flexibility-imparting agent. ~ 53 as in Table 1
The compositions were prepared in the amounts shown in 1 and the cured test pieces were characterized. The results are shown in Table 11 and FIG.

[0080]

[Table 11]

From Table 11, by adding 5 to 80 parts of ethylene / α-olefin copolymer as a flexibility-imparting agent to 100 parts of epoxy resin, the flexibility of the cured product is improved and the package crack It can be seen that the occurrence of is suppressed. Further, it can be seen from FIG. 11 that cured products having extremely excellent moisture resistance were obtained as compared with the cured products obtained from the compositions of Examples 40 to 48.

Examples 64 to 68 and Comparative Examples 27 and 28 Epoxy functional group-containing silicone powder (Toray Dow Corning Trefil E-60 as a flexibility imparting agent).
As in Examples 49 to 53, except that 1) was used, the compositional amounts of the compositions shown in Table 12 were prepared and the cured test pieces were characterized. The results are shown in Table 12 and FIG.
Shown in.

[0083]

[Table 12]

From Table 12, by adding 5 to 80 parts of the epoxy functional group-containing silicone powder as a flexibility-imparting agent to 100 parts of the epoxy resin, the flexibility of the cured product is improved and package cracking occurs. It turns out that was suppressed. Moreover, from FIG. 12, Examples 40-48
It can be seen that a cured product having extremely excellent moisture resistance was obtained as compared with the cured product obtained from the composition of.

Examples 69 to 73 and Comparative Examples 29 and 30 Same as Examples 49 to 53 except that a silicon-modified epoxy resin (SIN-620 manufactured by Dainippon Ink and Chemicals, Inc.) was used as the flexibility-imparting agent. The compositions in the amounts shown in Table 13 were prepared and the cured test pieces were characterized as follows. The results are shown in Table 13 and FIG.

[0086]

[Table 13]

From Table 13, by adding 5 to 80 parts of a silicone-modified epoxy resin as a flexibility-imparting agent to 100 parts of the epoxy resin, the flexibility of the cured product is improved and the occurrence of package cracks is suppressed. I know what was done. Further, from FIG. 13, it can be seen that a cured product having extremely excellent moisture resistance was obtained as compared with the cured products obtained from the compositions of Examples 40 to 48.

Examples 74 to 78 and Comparative Examples 31 and 32 In these examples, a mixture of biphenyl type epoxy resin, polyallylphenol and polyphenol, and powdered silica (RD-8 manufactured by Tatsumori Co., Ltd.) as an inorganic filler. ) Was added and kneaded together with a pressure kneader to prepare a composition having a compounding amount shown in Table 14.

Specimens were prepared from the obtained compositions according to the procedures described in Examples 1 to 9 and cured products were similarly characterized. The results are shown in Table 14 and FIG.
Table 14 also shows the viscosity of the prepared composition.

[0090]

[Table 14]

From Table 14, it can be seen that by adding 20 to 85% by weight of the total amount of the inorganic filler, the mechanical strength of the cured product can be advantageously improved without significantly reducing the flowability of the composition. I understand. Further, it can be seen from FIG. 14 that the moisture resistance of the cured product is also very good.

[0092]

As described above, the epoxy resin composition of the present invention comprising an epoxy resin as a base resin and a polyallylphenol curing agent and a polyphenol curing aid has excellent curability and heat resistance, A cured product having excellent hydrophobicity, flexibility and crack resistance can be produced. Therefore, it is very useful as a multi-layer laminated resin, a conductive paste, an electronic element protective film, a sealing material, an adhesive, a coating material, and a molding material used in electronic / electrical devices, transportation machines and the like.

Furthermore, the epoxy resin composition of the present invention, which additionally contains a flexibility-imparting agent, is a cured product having sufficient flexibility that exhibits better crack resistance even under severe conditions. Can be generated. Moreover, the epoxy resin composition of the present invention to which the inorganic filler is added can produce a cured product having excellent mechanical strength.

[Brief description of drawings]

FIG. 1 is a graph showing a relationship between a PCT treatment time of a cured product and a defective rate.

FIG. 2 is a graph showing a relationship between a PCT treatment time of a cured product and a defective rate.

FIG. 3 is a graph showing a relationship between a PCT treatment time of a cured product and a defective rate.

FIG. 4 is a graph showing a relationship between a PCT treatment time of a cured product and a defective rate.

FIG. 5 is a graph showing a relationship between a PCT treatment time of a cured product and a defective rate.

FIG. 6 is a graph showing a relationship between a PCT treatment time of a cured product and a defective rate.

FIG. 7 is a graph showing a relationship between a PCT treatment time of a cured product and a defective rate.

FIG. 8 is a graph showing a relationship between a PCT treatment time of a cured product and a defective rate.

FIG. 9 is a graph showing a relationship between a PCT treatment time of a cured product and a defective rate.

FIG. 10 is a graph showing the relationship between the PCT treatment time of the cured product and the defect rate.

FIG. 11 is a graph showing the relationship between the PCT treatment time of the cured product and the defect rate.

FIG. 12 is a graph showing the relationship between the PCT treatment time of the cured product and the defect rate.

FIG. 13 is a graph showing the relationship between the PCT treatment time of the cured product and the defect rate.

FIG. 14 is a graph showing a relationship between a PCT treatment time of a cured product and a defective rate.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Norio Saruwatari 1015 Kamiodanaka, Nakahara-ku, Kawasaki-shi, Kanagawa Fujitsu Limited

Claims (5)

[Claims] 1. With respect to 100 parts by weight of an epoxy resin which is a base resin, the following formula: 5 to 200 parts by weight of polyallylphenol having a plurality of structural units represented by the following formula in the molecule, and the following formula: An epoxy resin composition comprising 5 to 200 parts by weight of a polyphenol represented by: 2. The composition according to claim 1, wherein the epoxy resin is a cresol novolac type epoxy resin or a biphenyl type epoxy resin. 3. The polyallylphenol is: Or The composition according to claim 1 or 2, which is represented by: 4. A polystyrene / as a flexibility-imparting agent.
Polybutadiene / polystyrene end block copolymer,
At least one selected from the group consisting of an ethylene / propylene copolymer, an ethylene / α-olefin copolymer, a silicone rubber powder containing an epoxy functional group, and a silicone-modified epoxy resin, and the epoxy resin 10 described above.
The composition according to claim 1 or 2, which comprises 5 to 80 parts by weight with respect to 0 parts by weight. 5. The composition according to claim 1, which comprises 20 to 85% by weight of the total composition of the powdered inorganic filler.