JP2727888B2 - Silicone-modified aralkyl resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel silicone-modified aralkyl resin which can be suitably used as a component of an epoxy resin composition for encapsulating semiconductor devices.

[0002]

2. Description of the Related Art
Epoxy resins are widely used in various molding materials, powder coating materials, electric insulating materials, and the like as a composition obtained by adding a curing agent and an inorganic filler to the resin. Particularly in recent years, diodes, transistors, ICs, LSIs, It is widely used as a resin-sealing-type semiconductor device sealing material such as a super LSI. This is based on the fact that epoxy resins are generally superior to other thermosetting resins in terms of moldability, adhesiveness, electrical properties, mechanical properties, moisture resistance, and the like.

In recent years, the degree of integration of these semiconductor devices has been increasing, and the chip size has been increasing accordingly. However, the external dimensions of the package are required to reduce the size and weight of electronic devices. It is becoming smaller and thinner. Further, in a method of attaching a semiconductor component to a circuit board, surface mounting of the semiconductor component is performed to increase the density of components on the board and to reduce the thickness of the board.

However, when a semiconductor device is surface-mounted on a circuit board, it is common to immerse the entire semiconductor device in a solder bath or pass the semiconductor device through a high-temperature zone in which the solder melts. As a result, there is a problem that cracks occur in the sealing resin layer, and separation 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 of the surface mounting.However, in the actual working process, the moisture absorption of the sealing resin layer Inevitably, the reliability of the semiconductor device sealed with the epoxy resin composition after mounting may be greatly impaired.

Therefore, development of a high quality epoxy resin composition for a semiconductor device capable of providing a highly reliable semiconductor device after surface mounting on a circuit board has been desired.

The present invention has been made in view of the above circumstances,
An object of the present invention is to provide a novel silicone-modified aralkyl resin that can be suitably used as a component of an epoxy resin composition for a surface mount semiconductor device.

[0007]

The present inventors have made intensive studies to achieve the above object, and as a result, have found that aralkyl resins containing an alkenyl group selected from structural formulas (2) to (7) described below. On the other hand, the number of silicon atoms in one molecule represented by the following composition formula (1) having a ≡SiH group is 1 to 40
By adding an organic silicon compound which is 0, a silicone-modified aralkyl resin containing almost no free organic silicon compound not bonded to an alkenyl group in the alkenyl group-containing aralkyl resin can be industrially advantageously obtained. Depending on whether it is a phenolic resin or an epoxy resin, this silicone-modified aralkyl resin can be used as a curing agent for an epoxy resin in the same manner as a conventionally known phenolic resin or epoxy resin, or cured together with an epoxy curing agent and a catalyst. It can also be cured in the presence of a curing catalyst for silicone such as an organotin compound, if necessary, to give a low-stress, tough cured product, and when used together with a curable epoxy resin as a resin component. Is an epoxy resin with excellent crack resistance and improved glass transition point by about 10 ° C. Providing a molded product of the resin composition,
Therefore, they have found that the silicone-modified aralkyl resin obtained in the present invention is very useful as a component of an epoxy resin composition for semiconductor encapsulation, and have accomplished the present invention.

[0008]

Embedded image (Where R ¹ is a methyl group, an ethyl group, a phenyl group,
A benzyl group, a chloromethyl group, a chloropropyl group, a monovalent group selected from alkoxy groups having 1 to 5 carbon atoms,
a and b are 0.01 ≦ a ≦ 1, 1 ≦ b ≦ 3, 1 ≦ a + b ≦
It is a positive number that satisfies 4. )

Accordingly, the present invention provides a compound represented by the following structural formula (2):
To the alkenyl group of the alkenyl group-containing aralkyl resin selected from (7) to (7), a ≡SiH group of an organosilicon compound having 1 to 400 silicon atoms in one molecule represented by the composition formula (1) is added. And a silicone-modified aralkyl resin.

Hereinafter, the present invention will be described in more detail. The silicone-modified aralkyl resin of the present invention is obtained by adding the following alkenyl group of an alkenyl group-containing aralkyl resin selected from structural formulas (2) to (7) described below to the following composition formula ( It is a polymer obtained by adding a ≡SiH group of an organosilicon compound having 1 to 400 silicon atoms in one molecule shown in 1).

[0011]

Embedded image (Where R ¹ is a methyl group, an ethyl group, a phenyl group,
A benzyl group, a chloromethyl group, a chloropropyl group, a monovalent group selected from alkoxy groups having 1 to 5 carbon atoms,
a and b are 0.01 ≦ a ≦ 1, 1 ≦ b ≦ 3, 1 ≦ a + b ≦
It is a positive number that satisfies 4. )

The alkenyl group-containing aralkyl resin component used in the present invention is represented by the following structural formula (2):
Use one selected from (7). Of these, those of the formulas (2) and (3) are particularly preferably used.

[0013]

[0014]

Embedded image

[0015]

Wherein R is a hydrogen atom, a halogen atom, a methyl group, an ethyl group, a butyl group or An alkenyl group selected from an acryloxy group, and at least G in the molecule Glycidyl ether group. Further, n, p, and q are integers of 0 to 20, respectively. )

The content of the alkenyl group in the alkenyl group-containing aralkyl resin may be at least one in one molecule, but may be 0.01 to 0.4 with respect to all hydroxyl groups or all glycidyl ether groups. The number is preferably, and more preferably 0.03 to 0.3 .

Next, the organosilicon compound added to the alkenyl group-containing aralkyl resin has at least one ≡SiH group in one molecule and is represented by the following composition formula (1) as described above. It is what is done.

[0018]

Embedded image (Where R ¹ is a methyl group, an ethyl group, a phenyl group,
A benzyl group, a chloromethyl group, a chloropropyl group, a monovalent group selected from alkoxy groups having 1 to 5 carbon atoms,
a and b are 0.01 ≦ a ≦ 1, 1 ≦ b ≦ 3, 1 ≦ a + b ≦
It is a positive number that satisfies 4. )

In the above formula (1), R ¹ is a methyl group,
It is selected from an ethyl group, a phenyl group, a benzyl group, a chloropropyl group, a chloromethyl group, and an alkoxy group having 1 to 5 carbon atoms (such as a methoxy group and an ethoxy group).

The organosilicon compound of the above formula (1) is
The number of silicon atoms in one molecule is from 1 to 400, preferably 20
And the number of hydrogen atoms directly connected to silicon atoms in one molecule is 1 or more, preferably an integer of 1 to 10.

The silicone-modified aralkyl resin of the present invention is obtained by subjecting the above-mentioned alkenyl group-containing aralkyl resin to an addition reaction with the organosilicon compound of the above formula (1).

In this case, the alkenyl group-containing aralkyl resin and the organosilicon compound of the above formula (1) may be used alone or in combination of two or more. Where A is the equivalent of the alkenyl group and B is the equivalent of the ≡SiH group in the organosilicon compound, the ratio is 0.1 ≦ B / A ≦ 2, particularly 0.2 ≦ B / A ≦ 1. It is preferred to react. If B / A is less than 0.1, the yield of the target compound may be low, which may be industrially disadvantageous. If B / A is more than 2, gelation may occur.

In addition reaction, it is preferable to use a conventionally known addition catalyst, for example, a platinum catalyst such as chloroplatinic acid. In addition, the addition amount of the additional catalyst can be a normal amount.

The above addition reaction is preferably carried out in an organic solvent. As the organic solvent, it is preferable to use an inert solvent such as benzene, toluene and methyl isobutyl ketone.

The conditions of the addition reaction are not particularly limited, but the reaction is preferably carried out at 60 to 120 ° C. for 30 minutes to 10 hours.

After completion of the reaction, the desired silicone-modified aralkyl resin can be obtained by post-treatment and purification by a usual method.

The silicone-modified aralkyl resin of the present invention may be used as a curing agent for an epoxy resin in the same manner as a conventionally known phenol resin or epoxy resin, or may be used together with an epoxy curing agent and a catalyst, depending on whether the resin is a phenol resin or an epoxy resin. It can be cured, and in some cases, can be cured in the presence of a curing catalyst for silicone such as an organotin compound, thereby giving a low-stress and tough cured product. When used in combination with a curable epoxy resin, a cured product having excellent crack resistance and a glass transition point improved by about 10 ° C. is provided. Therefore, the silicone-modified aralkyl resin of the present invention is suitably used as a component of an epoxy resin composition for encapsulating a semiconductor device.

When the silicone-modified aralkyl resin of the present invention is used for encapsulating a semiconductor device, other components are the same as those of the conventional epoxy resin composition. For example, this silicone-modified aralkyl resin (phenol type) is used as a curing agent. Used alone or in combination with a usual curing agent, blended with a curable epoxy resin, curing accelerator, filler, etc., or used a silicone-modified aralkyl resin (epoxidized product) as a resin component It is possible to produce an epoxy resin composition for semiconductor device encapsulation by using it alone or in combination with a usual curable epoxy resin, and adding a curing agent, a curing accelerator, a filler, and the like thereto. it can.

[0029]

The silicone-modified aralkyl resin of the present invention, when used as a resin component for encapsulating a semiconductor device, gives a cured product having very low hygroscopicity and low elasticity and excellent in various properties. It is useful as a resin component.

[0030]

EXAMPLES The present invention will be specifically described below with reference to Examples and Formulation Examples, but the present invention is not limited to the following Examples.

[Example 1] A reflux condenser,
In a 3 liter four-necked flask equipped with a thermometer, a stirrer, and a dropping funnel, 600 g of toluene, 600 g of methyl isobutyl ketone (MIBK), and a phenol aralkyl resin represented by the following formula (8) (phenol equivalent: 170)
Add 340 g, heat and dissolve while stirring, and add 50% KO
2.25 g of an H aqueous solution was added, and the mixture was dehydrated under reflux.

[0032]

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Allyl glycidyl ether (AGE) 1
After 1.4 g of the solution was added dropwise thereto, the mixture was reacted under reflux for 8 hours. After neutralizing with concentrated hydrochloric acid, washing with water and distilling off the solvent under reduced pressure, 335 g of a mixture (compound A) of the AGE phenol aralkyl resin and the raw material of the formula (8) (yield 9)
5.3%, phenol equivalent 185.3, allyl equivalent 35
13.1) was obtained.

[0034]

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Next, 100 g of the compound A (allyl group-containing phenol aralkyl resin) obtained above and 370 g of MIBK were placed in a four-necked flask of the same reactor as above.
0.39 g of a 2-ethylhexanol-modified chloroplatinic acid solution having a platinum concentration of 0.5% was added thereto, Compound A was dissolved under heating and stirring, azeotropically dehydrated for 1 hour, and further represented by the following formula (9) under reflux. 45.77 g of the resulting organosilicon compound was added dropwise using a dropping funnel. After the dropwise addition, the mixture was reacted for 6 hours while further refluxing. After washing with water and distilling off the solvent,
A crude reaction product was obtained.

[0036]

Embedded image

143 g of the crude reaction product was added to acetone 40
0 g, dissolved in 150 g of water and left to stand, to obtain a solution in which two layers were separated. After discarding the upper layer of this solution, 200 g of acetone was again added and mixed, and 50 g of water was added thereto. I left it. The lower layer was collected from the resulting two-layer separation solution, and acetone and water were distilled off under reduced pressure to obtain 43 g of the desired silicone-modified aralkyl resin (compound B below).

[0038]

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Example 2 140.56 g of compound A, 417.4 g of epichlorohydrin and 0.1 ml of cetyltrimethylammonium were placed in a four-necked flask having the same reaction apparatus as described above.
4 g was added and the mixture was stirred under reflux for 3 hours. Then NaOH
(50% aqueous solution) 67 g under reduced pressure (80-90 ° C / 10
(0 to 130 mmHg). After completion of the dropwise addition, the mixture was aged for 3 hours, then filtered and the solvent was removed.
% Aqueous solution) to remove hydrolyzable chlorine and wash with water.
170.5 g of a mixture of the epoxidized AGE phenol aralkyl resin and the epoxidized material of the formula (8) (compound C below) (yield 92%, epoxy equivalent 245.
3, allyl equivalent 4660.7).

[0040]

Embedded image

Next, the compound C100 was prepared in the same manner as in Example 1.
g, 370 g of toluene and 0.39 g of a platinum catalyst were dissolved by heating with stirring, and the organosilicon compound of the formula (9) was dissolved in the same manner as described above.
8 g was added dropwise, and after-treatment and purification, the following compound D
19.6 g were obtained.

[0042]

Embedded image

Example 3 327 g of a phenol aralkyl resin of the following formula (10) (phenol equivalent 218),
The reaction was carried out in the same manner as in Example 1 using 8.56 g of GE. As a result, 322 g of a mixture (E) of the AGE phenol aralkyl resin having the following structure and the raw material of the formula (10) was obtained (96% yield, 235 phenol equivalent). .5, allyl equivalent 447
4.5) was obtained.

[0044]

Embedded image

Then, Compound E100 was prepared in the same manner as in Example 1.
g, 370 g of MIBK and 0.39 g of a platinum catalyst were dissolved under heating with stirring, and 35.1 g of the organosilicon compound of the formula (9) was added dropwise. After post-treatment and purification, the compound of the following formula F34.
5 g were obtained.

[0046]

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Example 4 Epoxidation was carried out in the same manner as in Example 2 using 161.6 g of compound E, 365.2 g of epichlorohydrin, and 0.35 g of cetyltrimethylammonium. 182 g (yield 91%, epoxy equivalent 293.5, allyl equivalent 5576.5) of a mixture (G) with a compound was obtained.

[0048]

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Next, similarly, 100 g of the compound G, 370 g of toluene and 0.39 g of a platinum catalyst were dissolved under heating with stirring, and 19.8 g of the organosilicon compound of the formula (9) was added dropwise.
After purification, 19.9 g of the following compound H was obtained.

[0050]

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FIGS. 1 to 4 show the silicone-modified aralkyl resins (compound (B),
(D), (F), (H)) shows the infrared absorption spectrum. The nuclear magnetic resonance spectra (assignment of NMR peaks) of compounds (B), (D), (F) and (H) were as follows.

[0052]

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[Formulation Examples 1 to 5] The silicone-modified aralkyl resin obtained in the examples, the curable epoxy resin, the curing agent, the curing catalyst, the quartz powder, the flame retardant, etc. were used in the amounts shown in Table 1, The resulting blend was uniformly melted and mixed with two hot rolls to produce five types of thermosetting resin compositions (however, the silicone-modified aralkyl resin has a crude reaction before purification in order to improve kneading properties). The product was used).

Here, epoxidized orthocresol novolak resin (compound J) and phenol novolak resin (compound K) shown below were used as the curable epoxy resin and the curing agent, respectively.

[0055]

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The following various tests (a) to (d) were conducted on these thermosetting resin compositions. (A) Spiral flow value Using a mold conforming to the EMMI standard, 175 ° C, 70
It was measured under the condition of kg / cm ² . (B) Mechanical strength (flexural strength and flexural modulus) 180 ° C, 70 kg / cm according to JIS K-6911
^{2. A} bending rod of 10 × 4 × 100 mm was molded under the conditions of a molding time of 2 minutes, and post-cured at 180 ° C. for 4 hours. (C) Expansion coefficient, glass transition temperature 180 ° C., 70 kg / cm ² , molding time 2 minutes 5
A test piece of × 5 × 15 mm was molded and post-cured at 180 ° C. for 4 hours, and the value when the temperature was raised at 5 ° C./min by a dilatometer was measured. (D) Water absorption rate: 180 ° C., 70 kg / cm ² , molding time 2 min.
A disk of 0φ × 3 mm was formed, post-cured at 180 ° C. for 4 hours, and left in an atmosphere of 121 ° C./100% RH for 24 hours to measure the water absorption. Table 1 shows the above results.
It is described together.

[0057]

[Table 1]

From the results shown in Table 1, it was found that the thermosetting resin composition containing the silicone-modified aralkyl resin of the present invention gave a cured product having a very low water absorption and a low elastic modulus.

[Brief description of the drawings]

FIG. 1 is a graph showing an IR spectrum of compound (B).

FIG. 2 is a graph showing an IR spectrum of compound (D).

FIG. 3 is a graph showing an IR spectrum of compound (F).

FIG. 4 is a graph showing an IR spectrum of compound (H).

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Hisashi Shimizu 1-10 Hitomi, Matsuida-cho, Usui-gun, Gunma Prefecture Inside the Silicone Electronic Materials Research Laboratory, Shin-Etsu Chemical Co., Ltd. (56) References JP-A-5-97949 ( JP, A) JP-A-5-59175 (JP, A) JP-A-4-73795 (JP, A) JP-A-62-212417 (JP, A) JP-A-2-180952 (JP, A) JP 63-56515 (JP, A)

Claims (1)

(57) [Claims] 1. An alkenyl group of an alkenyl group-containing aralkyl resin selected from the group consisting of the following structural formulas (2) to (7), wherein the number of silicon atoms in one molecule represented by the following composition formula (1) is 1 to A silicone-modified aralkyl resin obtained by adding a ≡SiH group of an organosilicon compound having a molecular weight of 400. Embedded image Wherein R is a hydrogen atom, a halogen atom,
Methyl, ethyl, butyl or An alkenyl group selected from an acryloxy group, and at least G in the molecule Glycidyl ether group. Further, n, p, and q are integers of 0 to 20, respectively. ) (Where R ¹ is a methyl group, an ethyl group, a phenyl group,
A benzyl group, a chloromethyl group, a chloropropyl group, a monovalent group selected from alkoxy groups having 1 to 5 carbon atoms,
a and b are 0.01 ≦ a ≦ 1, 1 ≦ b ≦ 3, 1 ≦ a + b ≦
It is a positive number that satisfies 4. )