JPH1053588A - Amine compound modified with trimellitic anhydride - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound good in storage stability and flowability and useful as a curing catalyst for curable epoxy resins, etc., by reacting trimellitic anhydride with 1,8-diazabicyclo(5.4.0)undecene-7. SOLUTION: A new trimellitic anhydride-modified amine compound of formula I obtained by reacting trimellitic acid with 1,8-diazabicyclo(5.4.0)undecene-7. The compound is useful as a curing catalyst for curable epoxy resin compositions, is good in storage stability and flowability, can give cured products excellent in characteristics such as moldability, moisture resistance and adhesivity, and is advantageous for giving epoxy resin composition effective for sealing semiconductor devices such as IC, LSI, transistors, thyristors and diodes. The compound is obtained by reacting 1,8-diazabicyclo(5.4.0)undecene-7 of formula II with trimellitic anhydride of formula III in acetone under heating.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention is particularly useful as a curing catalyst for a curable epoxy resin composition, has good storage stability and fluidity, and has excellent properties such as moldability, moisture resistance and adhesiveness. The present invention relates to a trimellitic anhydride-modified amine compound capable of obtaining an epoxy resin composition giving a cured product.

[0002]

2. Description of the Related Art
In the semiconductor industry, resin-sealed diodes, transistors, ICs, LSIs, and super LSIs have become mainstream,
Above all, a curable epoxy resin composition containing an epoxy resin, a curing agent and various additives is generally excellent in moldability, adhesiveness, electrical properties, mechanical properties, moisture resistance, etc. as compared with other thermosetting resins. Therefore, semiconductor devices are often sealed with a cured product of an epoxy resin composition. However, recently, the degree of integration of these semiconductor devices has been increasing, and the chip size has been increasing accordingly. On the other hand, package external dimensions have been reduced in size and thickness in response to demands for smaller and lighter electronic devices. Furthermore, in the method of attaching a semiconductor component to a circuit board, surface mounting of the semiconductor component has been widely performed in order to increase the density of components on the board.

However, when a semiconductor device is surface-mounted, it is common to immerse the entire semiconductor device in a solder bath or to pass the semiconductor device through a high-temperature zone in which the solder melts. Cracks occur in the layer, and peeling occurs at the interface between the lead frame or chip and the sealing resin. Such cracks and peeling become more remarkable when the sealing resin layer of the semiconductor device absorbs moisture before the thermal shock at the time of surface mounting. Therefore, the reliability of the semiconductor device sealed with the epoxy resin composition after mounting may be greatly impaired.

[0004] Therefore, as a countermeasure against such popcorn, a method of reducing the moisture absorption by filling a high amount of a filler has hitherto been performed. Also, the use of a fast-curing catalyst has been studied for the purpose of reducing the viscosity of the epoxy resin composition in order to improve the moldability of a thin package and to improve the molding cycle in order to further improve the productivity.

However, when a conventional curing catalyst such as a tertiary amine compound, a tertiary phosphine compound or a derivative thereof is used, there is a problem that the viscosity of the composition increases during kneading. Was.

On the other hand, there has been a proposal to use an imidazole derivative as a curing catalyst, as disclosed in JP-A-58-76420.
JP-A-58-103525, JP-A-57-100128 and JP-B-6-18853 use an epoxy resin curing agent obtained by the reaction of 2-methylimidazole with pyromellitic anhydride and trimellitic anhydride. Describes that an epoxy resin composition which gives a cured product having good storage stability and excellent moisture resistance is obtained. However, this imidazole-based derivative has poor electrical properties, tends to have a high failure rate in a reliability test, and has a drawback that the storage stability of the composition is reduced.

[0007] As described above, using the conventional curing agent and further simply using the curing accelerator together with the conventional curing agent results in storage stability,
It has been difficult to obtain an epoxy resin composition which gives a cured product having good fluidity and excellent properties such as moisture resistance and adhesiveness.

The present invention has been made in view of the above circumstances, and particularly relates to an epoxy resin composition which has excellent storage stability and fluidity and provides a cured product having excellent properties such as moldability, moisture resistance and adhesiveness. An object of the present invention is to provide a novel trimellitic anhydride-modified amine compound which can be suitably used as a curing accelerator for obtaining the same.

[0009]

Means for Solving the Problems and Embodiments of the Invention The present inventors have made intensive studies in order to achieve the above object, and as a result, first, as shown in the following reaction formula A, trimellitic anhydride and And 1,8-diazabicyclo (5.4.0) undecene-7 to give the following formula (1)
When a novel trimellitic anhydride-modified amine compound represented by is obtained, and this trimellitic anhydride-modified amine compound is blended in an epoxy resin composition as a curing catalyst, the storage stability and fluidity are good, and The present inventors have found that a cured product having excellent properties such as water resistance, moisture resistance, and adhesiveness and having good electric characteristics can be obtained, and have accomplished the present invention.

Accordingly, the present invention provides a trimellitic anhydride represented by the following formula (1) obtained by reacting trimellitic anhydride with 1,8-diazabicyclo (5.4.0) undecene-7. A modified amine compound is provided.

[0011]

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Hereinafter, the present invention will be described in more detail. The trimellitic anhydride-modified amine compound of the present invention comprises:
Trimellitic anhydride and 1,8-diazabicyclo (5.
4.0) A compound represented by the following formula (1), which is obtained by reacting with undecene-7.

[0013]

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In this case, to obtain the trimellitic anhydride-modified amine compound of the formula (1), 1,8-diazabicyclo (5.4.0) undecene-7 is usually added to 152 parts by weight (1 mol) of the compound. , Trimellitic anhydride 173 ~
230 parts by weight (0.9 to 1.2 times mol), preferably 1 part
It is recommended that 92 parts by weight (1 mol) be mixed and reacted. Here, when the use amount of trimellitic anhydride is larger than the above range, the acid component becomes excessive, and when added to the epoxy resin composition, the storage stability of the epoxy resin composition is deteriorated, and If the amount is less than the above range, the amine component may remain and cause insufficient adhesion in the epoxy resin composition.

The reaction of the above trimellitic anhydride with 1,8-diazabicyclo (5.4.0) undecene-7 is preferably carried out in the presence of a reaction solvent. Specific examples of the reaction solvent include lower ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, (poly) ethers such as methyl cellosolve and diethylene glycol, and organic polar solvents such as dimethyl sulfoxide, dimethyl formamide and pyridine. These can be used alone or in combination of two or more. A particularly preferred solvent is acetone, but other solvents can be used in combination with acetone. When acetone is used as a reaction solvent, the amount used is 100 parts by weight with respect to 152 parts by weight (1 mol) of 1,8-diazabicyclo (5.4.0) undecene-7.
2,000 parts by weight, especially 1,300 parts by weight, is suitable.
If the amount is less than 100 parts by weight, the reaction does not proceed uniformly, and the yield of the reaction product may be deteriorated.
If the amount is more than 00 parts by weight, the workability of removing acetone may decrease.

The reaction temperature is 10 to 60 ° C., preferably 15 to 25.
C is preferred. The reaction time is usually 1-2 hours.

After the above-mentioned reaction, the solvent is removed. At this time, it is important to carry out the operation so that moisture is not absorbed. When water is absorbed, the reaction product represented by the above formula (1) is opened to form a dicarboxylic acid derivative. When the dicarboxylic acid derivative is used as a curing accelerator for an epoxy resin composition, the ring is opened. It may be difficult to use the dicarboxylic acid derivative because it is not compatible with other components in the composition. Therefore, it is generally recommended that the solvent be removed at 90 to 130 ° C, particularly 100 to 120 ° C. If the temperature is lower than 90 ° C., the reaction product may not be able to be taken out in a molten state. If the temperature exceeds 130 ° C., workability and work environment may be deteriorated.

Further, as a method of purifying the obtained reaction product, recrystallization is effective. The obtained reaction product is dissolved in a small amount of acetone, and then a large excess of toluene, xylene, n-hexane, etc. It can be purified by precipitation in a solvent.

In order to confirm the trimellitic anhydride-modified amine compound of the formula (1) of the present invention, measurement of the melting point is effective.
The melting point is usually in the range of 90 to 110 ° C, preferably 95 ° C.
-100 ° C. If the melting point is less than 90 ° C,
An unreacted amine component may remain, and when the melting point exceeds 110 ° C., it is considered that the reaction product is further changed to another structure.

The trimellitic anhydride-modified amine compound of the present invention can be suitably compounded in an epoxy resin composition as a curing accelerator. Hereinafter, this point will be described in more detail. As the epoxy resin used in the epoxy resin composition, a known epoxy resin can be mentioned.
There is no particular limitation as long as it has at least two epoxy groups in the molecule. For example, mention may be made of bisphenol A type epoxy resin, novolak type epoxy resin, alicyclic epoxy resin, glycidyl type epoxy resin, biphenyl type epoxy resin, naphthalene ring containing epoxy resin, cyclopentadiene containing epoxy resin, polyfunctional epoxy resin and the like. These can be used alone or in combination of two or more. Especially,
It is preferable to use a biphenyl type epoxy resin or a naphthalene ring-containing epoxy resin to highly fill the inorganic filler, and to use a brominated epoxy resin to improve flame retardancy. The epoxy resin has a softening point of 50 to 100.
It is preferable to use one having an epoxy equivalent of 100 to 400 ° C.

As the curing agent used in the epoxy resin composition, known curing agents can be used, for example, phenol novolak resin, triphenol methane resin, phenol aralkyl resin, naphthalene ring-containing phenol resin,
Phenolic resins having two or more phenolic hydroxyl groups, such as cyclopentadiene-containing phenolic resins and terpene ring-containing phenolic resins, can be mentioned. in this case,
A phenol resin having a softening point of 60 to 120 ° C,
It is preferable to use one having a hydroxyl equivalent of 90 to 150.

The amount of the curing agent used is the same as in the prior art.
For example, when a phenolic resin is used, the amount of the phenolic resin used is preferably appropriately adjusted and used in such an amount that the equivalent ratio of the epoxy group of the epoxy resin to the hydroxyl group of the phenolic resin is in the range of 0.5 to 2, Usually epoxy resin 1
30 to 100 parts by weight, preferably 4 parts by weight, per 100 parts by weight
It is recommended to use 0 to 70 parts by weight. If the phenolic resin is less than 30 parts by weight, sufficient strength may not be obtained. On the other hand, if the phenolic resin exceeds 100 parts by weight, unreacted phenolic resin may remain and cause a decrease in moisture resistance. .

The trimellitic anhydride-modified amine compound of the present invention is blended with the epoxy resin composition containing the above-mentioned epoxy resin and curing agent as a curing accelerator. A method in which the trimellitic acid-modified amine compound is used in the form of a fine powder in advance or a method in which the amine compound is dispersed in a phenol resin and used may be employed.

The compounding amount of the trimellitic anhydride-modified amine compound of the present invention is 10% in total of the epoxy resin and the curing agent.
0.1 to 10 parts by weight, especially 0.3 to 5 parts by weight with respect to 0 parts by weight
Parts by weight are preferred. If the amount is less than 0.1 part by weight, it may not be possible to cure in a short time. If the amount exceeds 10 parts by weight, the curing speed is too fast to obtain a good molded product, and the storage stability is lowered. In some cases, the amount of extracted water chlorine in the cured product increases, and the electrical characteristics may deteriorate.

In addition to the trimellitic anhydride-modified amine compound, other curing accelerators may be used in combination, for example, imidazole or a derivative thereof, triphenylphosphine, tris-p-methoxyphenylphosphine, tricyclohexyl. Phosphine derivatives such as phosphine,
1,8-diazabicyclo (5.4.0) undecene-7
Cycloamidine derivatives such as (DBU) can be used in combination.

The epoxy resin composition preferably contains an inorganic filler. The addition of the inorganic filler is effective in reducing the expansion coefficient of the sealing material and reducing the stress applied to the semiconductor element. It is. Specific examples of the inorganic filler include crushed and spherical fused silica and crystalline silica. Besides, alumina, silicon nitride, aluminum nitride and the like can also be used.

The average particle size and shape of these inorganic fillers are not particularly limited, but the average particle size is 5 to 40 μm, especially 10 to 40 μm.
It is preferably 30 μm, and a spherical one is preferably used in order to increase the packing and reduce the stress on the chip surface. In order to increase the bonding strength between the resin and its surface, it is preferable to use an inorganic filler which has been previously surface-treated with a silane coupling agent or the like.

The above-mentioned inorganic fillers may be used alone or in combination of two or more. The amount of the inorganic filler is not particularly limited, but is preferably 200 to 900 parts by weight based on the total amount of the resin components. If it is less than 200 parts by weight, the expansion coefficient increases and the stress applied to the semiconductor device increases, which may cause deterioration of device characteristics. In some cases, the moldability becomes high and the moldability deteriorates.

Further, in addition to the above-mentioned components, as a silicone-based flexibility-imparting agent for reducing stress, for example, silicone rubber powder, silicone gel, a block polymer of an organic resin and a silicone polymer (for example, an alkenyl group-containing polymer) And an epoxy resin or a phenol resin and a copolymer obtained by a hydrosilylation reaction of an organohydrogenpolysiloxane. In addition,
Instead of adding such a flexibility-imparting agent, the surface of the inorganic filler may be treated with a two-pack type silicone rubber or silicone gel.

The amount of use of the above-mentioned flexibility-imparting agent is preferably 0.5 to 10% by weight, especially 1 to 5% by weight of the whole composition. In some cases, sufficient impact resistance may not be provided, and when it exceeds 10% by weight, mechanical strength may be insufficient.

Further, if necessary, other optional components can be blended as long as the effects of the present invention are not impaired. Examples of such optional components include release agents such as carnauba wax, higher fatty acids, and synthetic waxes, thermoplastic resins such as MBS resin, silane coupling agents, antimony oxide, and phosphorus compounds.

Further, the method for producing the epoxy resin composition is as follows:
There is no particular limitation, and a method of uniformly stirring and mixing a predetermined amount of the above-mentioned components, kneading with a kneader, a roll, an extruder or the like which has been heated to 70 to 95 ° C. in advance, cooling, pulverizing, and the like. Can be obtained at here,
There is no particular limitation on the order of compounding the components.

The epoxy resin composition thus obtained can be effectively used for sealing semiconductor devices such as ICs, LSIs, transistors, thyristors, and diodes, and for producing printed circuit boards. it can. In this case, molding can be carried out by employing a conventionally employed molding method, for example, transfer molding, injection molding, casting method and the like. The molding temperature of the epoxy resin composition is 150 to 180 ° C., 30 to 180 seconds,
Post curing is preferably performed at 150 to 180 ° C. for 2 to 16 hours.

[0034]

The trimellitic anhydride-modified amine compound of the present invention has good storage stability and fluidity, and has good adhesion, moisture resistance, etc., when incorporated into an epoxy resin composition as a curing accelerator. A cured product with excellent properties can be obtained, and ICs, LSIs, transistors, thyristors,
This is advantageous for obtaining an epoxy resin composition effective for sealing a semiconductor device such as a diode.

[0035]

EXAMPLES The present invention will be described in detail below with reference to Examples and Reference Examples, but the present invention is not limited to the following Examples. All parts in each example are parts by weight.

Example 1 A 4-liter four-necked flask equipped with a thermometer, a stirrer and a reflux condenser was charged with 1,8-diazabicyclo (5.4.0) undecene-7 (hereinafter referred to as DBU).
152 parts) and 400 parts of acetone were added, and DBU was dissolved in acetone. After heating and dissolving, a solution of 192 parts of trimellitic anhydride dissolved in 900 parts of acetone was dropped from a dropping funnel. After completion of the dropwise addition, the mixture was reacted at 20 ° C. for 1 hour, and then the acetone was stripped under reduced pressure.
Tap the reactant in the molten state while heating to 120 ° C,
A brown solid was obtained.

100 parts of the obtained brown solid was mixed with 5 parts of acetone.
After dissolving in 0 parts, a further 1000 parts of toluene was added to precipitate a salt, and the salt was filtered off and dried to obtain a reaction product A (yield 92%).

The melting point of the obtained reaction product A was 94 ° C., and the element analysis and the IR absorption spectrum were measured. The results are shown in Table 1 and FIG.

[0039]

[Table 1]

Example 2 A reaction product B was obtained in the same manner as in Example 1 except that methyl isobutyl ketone was used instead of acetone. The melting point of this reactant B is 94 ° C.
And the yield was 86%.

Example 3 A reaction product C was obtained in the same manner as in Example 1 except that methyl ethyl ketone was used instead of acetone. Reactant C has a melting point of 95 ° C.
The yield was 85%.

REFERENCE EXAMPLE As shown in Table 2, the epoxy resin, the phenol resin, and the reactant A obtained in Example 1 were used.
And 1.5 parts of wax E, 1 part of carbon black, 6 parts of brominated epoxy resin, 7 parts of antimony trioxide
Parts, 500 parts of fused quartz powder and 2 parts of γ-glycidoxypropyltrimethoxysilane were uniformly melt-mixed with a hot two roll, cooled and pulverized to prepare an epoxy resin composition. The physical properties of the obtained epoxy resin composition and the cured product were tested by the following methods. Table 2 shows the results. (A) Spiral flow 175 ° C, 70k using a mold conforming to EMMI standard
g / cm ² . (B) Hot hardness A 10 × 4 × 100 mm bending bar was formed under the conditions of 175 ° C., 70 kg / cm ² , and a molding time of 90 seconds. (C) Storage stability The number of days when the spiral flow value became 80% of the initial value when each material was left at 25 ° C. was shown. (D) Gelation time The gelation time of the composition was measured at 175 ° C. (E) Melting temperature 17 using a Koka type flow tester (manufactured by Shimadzu Corporation).
It was measured at 5 ° C. (F) Adhesion A cylindrical molded product having a diameter of 15 mm and a height of 5 mm was molded on a copper plate and a nickel plate under the conditions of 175 ° C., 70 kg / cm ² , and a molding time of 2 minutes, and post-cured at 180 ° C. for 4 hours. The peeling amount between the molded product and the copper plate or nickel plate was measured with a push-pull gauge.

Epoxy resin A: Epoxidized cresol novolak resin (softening point 55 ° C., epoxy equivalent 200, ECON1020-55 manufactured by Nippon Kayaku Co., Ltd.) Epoxy resin B: biphenyl type epoxy resin (softening point 1
Epoxy resin C: Epoxidized triphenolmethane (softening point 60 ° C, epoxy equivalent 172, EPP manufactured by Nippon Kayaku Co., Ltd.)
N501H) Phenol resin A: Phenol novolak resin (softening point: 80 ° C., hydroxyl equivalent: 110, TD21 manufactured by Dainippon Ink and Chemicals, Inc.)
31) Phenol resin B: phenol aralkyl resin (softening point 70 ° C., hydroxyl equivalent 170, Millex X manufactured by Mitsui Toatsu Co., Ltd.)
L-225-3L)

[0044]

[Table 2]

From the results shown in Table 2, trimellitic anhydride and 1,8-diazabicyclo (5.4.0) were used as curing accelerators.
The epoxy resin composition using the reactant A (the product of the present invention) obtained by reacting undecene-7 with undecene-7 has an unreacted 1,8
-A cured product having less increase in viscosity during kneading, good fluidity and storage stability, and excellent adhesion and the like, as compared with an epoxy resin composition containing diazabicyclo (5.4.0) undecene-7. It was confirmed that.

[Brief description of the drawings]

FIG. 1 is a chart showing an IR absorption spectrum of a reactant A of Example 1.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Masachika Yoshino 1-10 Hitomi, Matsuida-machi, Usui-gun, Gunma Prefecture Inside Silicone Electronic Materials Research Laboratory, Shin-Etsu Chemical Co., Ltd. Hitomi 1-10, Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Technology Laboratory

Claims (1)

[Claims] 1. A trimellitic anhydride-modified amine compound represented by the following formula (1) obtained by reacting trimellitic anhydride with 1,8-diazabicyclo (5.4.0) undecene-7. Embedded image