JPH0625370A - Silicone-modified aralkyl resin - Google Patents

Abstract

PURPOSE:To obtain the subject new resin useful as a resin component for sealing a semiconductor device, providing a cured material having extremely low water absorption and low elasticity by adding a specific organosilicon compound to an alkenyl group of an aralkyl resin containing an alkenyl group. CONSTITUTION:Three Si groups of an organosilicon compound of formula I (R<1> is monofunctional hydrocarbon, OH, etc.; (a) and (b) are integers satisfying 0.01<=a<=1, 1<=b<=3, 1<=a+b<=4) are added to an alkenyl group of an aralkyl resin containing an alkenyl group to give the objective resin. The resin is preferably obtained by adding the compound of formula I to the aralkyl resin containing an alkenyl group in the presence of a platinum catalyst such as chloroplatinic acid in an inert organic solvent such as benzene at 60-120 deg.C for 30 minutes to 10 hours. A resin of formula II (R is H, Cl, etc.; G is OH, glycidyl ether, etc.; (n) is 0-20) etc., is preferable as the aralkyl resin containing an alkenyl group.

Description

Detailed Description of the Invention

[0001]

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 a semiconductor device.

[0002]

2. Description of the Related Art Conventionally, the problems to be solved by the invention
Epoxy resin is widely used as a composition obtained by adding a curing agent and an inorganic filler to various molding materials, powder coating materials, electrical insulating materials, and the like. Recently, in particular, diodes, transistors, ICs, LSIs, It is used in large quantities as a resin-encapsulation type semiconductor device encapsulation material such as VLSI. This utilizes the characteristics that the epoxy resin is generally superior to other thermosetting resins in moldability, adhesiveness, electrical characteristics, mechanical characteristics, moisture resistance and the like.

In recent years, the degree of integration of these semiconductor devices has increased, and the chip size has been correspondingly increased. On the other hand, the package external dimensions are required to reduce the size and weight of electronic equipment. Along with this, miniaturization and thinning are progressing. Further, also in the method of mounting a semiconductor component on a circuit board, surface mounting of the semiconductor component is performed in order to increase the density of components on the substrate and to reduce the thickness of the substrate.

However, when the semiconductor device is surface-mounted on a circuit board, a method of immersing the entire semiconductor device in a solder bath or passing through a high temperature zone where the solder melts is generally used, but thermal shock at that time is used. As a result, there is a problem in that a crack is generated in the sealing resin layer or peeling occurs at the interface between the lead frame or the chip and the sealing resin. Such cracks and peeling become more noticeable when the sealing resin layer of the semiconductor device absorbs moisture before the thermal shock of surface mounting, but in the actual working process, the moisture absorption of the sealing resin layer does not occur. This is unavoidable, and thus the reliability of the semiconductor device encapsulated with the epoxy resin composition after mounting may be greatly impaired.

Therefore, it has been desired to develop a high quality epoxy resin composition for a semiconductor device which can provide a highly reliable semiconductor device after surface mounting on a circuit board.

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 surface-mount semiconductor devices.

[0007]

Means for Solving the Problems The present inventors have conducted extensive studies to achieve the above-mentioned object, and as a result, for the aralkyl resin containing an alkenyl group, the following composition formula (1) having an ≡SiH group was used. It is possible to industrially advantageously obtain a silicone-modified aralkyl resin containing almost no free organosilicon compound that is not bonded to an alkenyl group in an alkenyl group-containing aralkyl resin by adding the organosilicon compound shown. The silicone-modified aralkyl resin can be used as a curing agent for an epoxy resin like a conventionally known phenol resin or epoxy resin, or can be cured together with an epoxy curing agent or a catalyst, depending on whether it is a phenol resin or an epoxy resin. Can be cured in the presence of a curing catalyst for silicone such as organotin compounds, if necessary This gives an epoxy resin having a low stress and toughness, and when used in combination with a curable epoxy resin as a resin component, it has excellent crack resistance and has an improved glass transition point of about 10 ° C. It was found that a silicone-modified aralkyl resin obtained by the present invention is very useful as a component of an epoxy resin composition for semiconductor encapsulation, and thus the present invention is completed. It is a thing.

[0008]

[Chemical 2] (In the formula, R ¹ represents a substituted or unsubstituted monovalent hydrocarbon group, a hydroxyl group or an alkoxy group, and a and b are 0.01
It is a positive number that satisfies ≦ a ≦ 1, 1 ≦ b ≦ 3, 1 ≦ a + b ≦ 4. )

Accordingly, the present invention provides a silicone-modified aralkyl resin obtained by adding the ≡SiH group of the organosilicon compound represented by the above composition formula (1) to the alkenyl group of the alkenyl group-containing aralkyl resin.

The present invention will be described in more detail below. In the silicone-modified aralkyl resin of the present invention, the ≡SiH group of the organosilicon compound represented by the following composition formula (1) is added to the alkenyl group of the alkenyl group-containing aralkyl resin. It is a polymer composed of

[0011]

[Chemical 3] (In the formula, R ¹ represents a substituted or unsubstituted monovalent hydrocarbon group, a hydroxyl group or an alkoxy group, and a and b are 0.01
It is a positive number that satisfies ≦ a ≦ 1, 1 ≦ b ≦ 3, 1 ≦ a + b ≦ 4. )

Here, as the alkenyl group-containing aralkyl resin component used in the present invention, phenol aralkyl resin to which allyl glycidyl ether or the like is added, or phenol aralkyl resin allyl etherified by reacting allyl halide, Alternatively, those obtained by epoxidizing this type of alkenyl group-containing phenol aralkyl resin with epichlorohydrin or partially reacting the epoxidized phenol aralkyl resin with 2-allylphenol or the like can be used.

Specific examples of such an alkenyl group-containing aralkyl resin include those represented by the following structural formulas (2) to (7), and those of the formulas (2) and (3) are particularly preferable. Used for.

[0014]

[Chemical 4]

[0015]

[Chemical 5]

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

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]

[Chemical 6] (In the formula, R ¹ represents a substituted or unsubstituted monovalent hydrocarbon group, a hydroxyl group or an alkoxy group, and a and b are 0.01
It is a positive number that satisfies ≦ a ≦ 1, 1 ≦ b ≦ 3, 1 ≦ a + b ≦ 4. )

In the above formula (1), R ¹ is a substituted or unsubstituted monovalent hydrocarbon group, a hydroxyl group or an alkoxy group, and the unsubstituted monovalent hydrocarbon group has 1 to 2 carbon atoms.
0, especially 1 to 10, such as methyl group, ethyl group,
Examples thereof include a phenyl group, a benzyl group, a vinyl group, an allyl group, an acryloxy group, an isopropenyloxy group and an isobutenyloxy group. Examples of the substituted monovalent hydrocarbon group include a chloropropyl group, a chloromethyl group and a glycidylpropyl group. And the like, and the alkoxy group has 1 to 1 carbon atoms.
Examples thereof include 0, particularly 1 to 5, such as methoxy group and ethoxy group.

The organosilicon compound of the above formula (1) is
The number of silicon atoms in one molecule is 1 to 400, preferably 20.
The number of hydrogen atoms directly bonded to a silicon atom in one molecule is 1 or more, preferably 1 to 10.

The silicone-modified aralkyl resin of the present invention can be obtained by addition-reacting the above-mentioned alkenyl group-containing aralkyl resin 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 kinds. 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 preferable to react. If B / A is smaller than 0.1, the yield of the target compound may be small, which may be industrially disadvantageous, and if B / A is larger than 2, gelation may occur.

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

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

The addition reaction conditions are not particularly limited, but it is usually preferable to carry out the reaction 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 conventional method.

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

When the silicone-modified aralkyl resin of the present invention is used for encapsulating a semiconductor device, the other components are the same as in the conventional epoxy resin composition. For example, this silicone-modified aralkyl resin (phenol type) is used as a curing agent. As a resin component, a curable epoxy resin, a curing accelerator, a filler or the like is blended, or a silicone-modified aralkyl resin (epoxidized product) is used 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 to it. it can.

[0029]

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

[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] 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), a phenol aralkyl resin represented by the following formula (8) (phenol equivalent 170)
Add 340g, dissolve with heating with stirring, 50% KO
2.25 g of H aqueous solution was added and dehydrated under reflux.

[0032]

[Chemical 7]

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

[0034]

[Chemical 8]

Then, in a four-necked flask of the same reaction apparatus as described above, 100 g of the above-obtained compound A (allyl group-containing phenol aralkyl resin), 370 g of MIBK,
0.39 g of a 2-ethylhexanol-modified chloroplatinic acid solution having a platinum concentration of 0.5% was added, the compound A was dissolved under heating and stirring, azeotropic dehydration was carried out for 1 hour, and further represented by the following formula (9) under reflux. 45.77 g of the organosilicon compound to be prepared was added dropwise with a dropping funnel. After the dropping, the mixture was reacted for 6 hours while further refluxing. Then, after washing with water and distilling off the solvent,
A crude reaction product was obtained.

[0036]

[Chemical 9]

143 g of this crude reaction product was added to 40 parts of acetone.
It was dissolved in 0 g, and 150 g of water was added thereto and left to stand to obtain a solution having two layers 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 obtained solution for two-layer separation, 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]

[Chemical 10]

Example 2 In a four-necked flask having the same reaction apparatus as described above, 140.56 g of Compound A, 417.4 g of epichlorohydrin, 0.10 g of cetyltrimethylammonium were added.
4 g was added, and the mixture was stirred under reflux for 3 hours. Then NaOH
67 g (50% aqueous solution) under reduced pressure (80 to 90 ° C./10
It was added dropwise at 0 to 130 mmHg). After completion of the dropping, the mixture was aged for 3 hours, then filtered, the solvent was removed, and further NaOH (10
% 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 raw material of the formula (8) (compound C below) (yield 92%, epoxy equivalent 245.
3, an allyl equivalent of 4660.7) was obtained.

[0040]

[Chemical 11]

Then, the compound C100 was prepared in the same manner as in Example 1.
g, toluene 370 g, and platinum catalyst 0.39 g are heated and dissolved under stirring, and the organosilicon compound of the formula (9) 19.
After 8 g was added dropwise and after-treatment and purification, the following compound D
19.6 g was obtained.

[0042]

[Chemical 12]

Example 3 327 g of phenol aralkyl resin (phenol equivalent 218) of the following formula (10), A
When GE 8.56 g was used and reacted in the same manner as in Example 1, 322 g (yield 96%, phenol equivalent 235) of a mixture (E) of the AGEd phenol aralkyl resin having the following structure and the raw material of the formula (10) was obtained. .5, allyl equivalent 447
4.5) was obtained.

[0044]

[Chemical 13]

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

[0046]

[Chemical 14]

Example 4 Using 161.6 g of compound E, 365.2 g of epichlorohydrin, and 0.35 g of cetyltrimethylammonium, an epoxidation was carried out in the same manner as in Example 2. As a result, compound E and the epoxy as the raw material of formula (10) were obtained. 182 g (yield 91%, epoxy equivalent 293.5, allyl equivalent 5576.5) of a mixture (G) with a compound was obtained.

[0048]

[Chemical 15]

Then, similarly, 100 g of compound G, 370 g of toluene, and 0.39 g of platinum catalyst were heated and dissolved with stirring, and 19.8 g of the organosilicon compound of formula (9) was added dropwise to the solution, which was post-treated.
Upon purification, 19.9 g of the following compound H was obtained.

[0050]

[Chemical 16]

1 to 4 show the silicone-modified aralkyl resins (compound (B), obtained in Examples 1 to 4).
The infrared absorption spectra of (D), (F), and (H) are shown. Further, the nuclear magnetic resonance spectra (attribution of NMR peaks) of the compounds (B), (D), (F) and (H) were as follows.

[0052]

[Chemical 17]

[Compounding Examples 1 to 5] The silicone-modified aralkyl resin obtained in the examples, a curable epoxy resin, a curing agent, a curing catalyst, quartz powder, a flame retardant, etc. were used in the compounding amounts shown in Table 1, The resulting blend was uniformly melt-mixed with two heat rolls to produce five types of thermosetting resin compositions (however, since the silicone-modified aralkyl resin improves the kneading property, the crude reaction before purification is performed). The product was used).

Here, as the curable epoxy resin and the curing agent, the epoxidized product of ortho-cresol novolac resin (Compound J) and the phenol novolac resin shown below (Compound K) were used.

[0055]

[Chemical 18]

The following 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 (bending strength and bending elastic modulus) 180 ° C, 70 kg / cm according to JISK-6911
^{2. A} bending bar having a size of 10 × 4 × 100 mm was molded under the condition of a molding time of 2 minutes, and post-cured at 180 ° C. for 4 hours. (C) 5 under the conditions of expansion coefficient, glass transition temperature 180 ° C., 70 kg / cm ² , molding time 2 minutes
A test piece of × 5 × 15 mm was molded, post-cured at 180 ° C. for 4 hours, and the value when the temperature was raised at 5 ° C./min was measured by a dilatometer. (D) Water absorption rate: 180 ° C., 70 kg / cm ² , molding time: 2 minutes 5
A 0φ × 3 mm disk was molded, 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. The above results are shown in Table 1.
Also described in.

[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 gives a cured product having a very low water absorption rate and a low elastic modulus.

[Brief description of 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).

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] October 1, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0016

[Correction method] Change

[Correction content]

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

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0057

[Correction method] Change

[Correction content]

[0057]

[Table 1]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kuji Shimizu 1 Hitomi, Oita, Matsuida-cho, Usui-gun, Gunma 10 Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory

Claims (1)

[Claims] 1. A silicone-modified aralkyl resin obtained by adding an ≡SiH group of an organosilicon compound represented by the following composition formula (1) to an alkenyl group of an alkenyl group-containing aralkyl resin. [Chemical 1] (In the formula, R ¹ represents a substituted or unsubstituted monovalent hydrocarbon group, a hydroxyl group or an alkoxy group, and a and b are 0.01
It is a positive number that satisfies ≦ a ≦ 1, 1 ≦ b ≦ 3, 1 ≦ a + b ≦ 4. )