JPS62212417A - Epoxy resin composition - Google Patents

Abstract

PURPOSE:To obtain an epoxy resin composition excellent in cracking resistance and low in molding deformation, by incorporating a copolymer obtained by reacting an alkenyl group-containing epoxy resin with a specified or ganopolysiloxane. CONSTITUTION:An epoxy resin composition containing a copolymer obtained by reacting an alkenyl group-containing epoxy resin with an organopolysiloxane of the formula (wherein R is a substituted or unsubstituted monovalent hydrocarbon group, 0.01<=a<=1, 1<=b<=3 and 0.1<=a+b<4). Said alkenyl group-containing epoxy resin can be obtained by epoxidizing an alkenyl group-containing phenolic resin with epichlorohydrin or by partially reacting an epoxy resin with 2- allylphenol or the like. The copolymer incorporated can be obtained by reacting, said alkenyl group-containing epoxy resin with a -SiH group-containing organo- polysiloxane of the formula by heating in the presence of, e.g., a platinum catalyst such as chloroplatinic acid.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to an epoxy resin composition suitable for use as a molding material, a powder coating material, a semiconductor encapsulating material, and the like.

Epoxy resins and epoxy resin compositions containing inorganic fillers, etc., generally have better moldability, adhesion, electrical properties, mechanical properties, and moisture resistance than other thermosetting resins. Because it has excellent characteristics,
It is widely used as various molding materials, powder coating materials, electrical insulating materials, etc., and has recently attracted particular attention as a semiconductor encapsulating material.

However, conventional epoxy resin compositions often crack during curing, which impairs the appearance of molded and painted surfaces and causes defects in semiconductor devices and other devices. The present inventors previously proposed an epoxy resin composition with excellent crack resistance by adding a block copolymer consisting of an aromatic polymer and an organopolysiloxane to a curable epoxy resin ( JP-A No. 58-21417) has excellent crack resistance, a high glass transition point, a low expansion coefficient, and therefore a small amount of deformation during molding, and has excellent moldability, and has a bending strength of 1. There has been a desire for an epoxy resin composition that does not impair properties such as mechanical strength such as elastic modulus.

The present invention was developed in view of the above circumstances, and it has a low expansion coefficient, a high glass transition point, and excellent crack resistance without impairing the mechanical strength represented by bending strength and bending modulus. The object of the present invention is to provide an epoxy resin composition that has a small amount of deformation during molding.

In order to achieve the above object, the present inventors have developed an epoxy resin composition containing a curable epoxy resin and a curing agent as main components to further improve crack resistance. As a result of extensive research into block copolymer components that bring about excellent effects, we have found that a copolymer obtained by adding an organopolysiloxane containing a mi5i-H group to an epoxy resin containing an alkenyl group has been developed as an epoxy resin. It has been found that it has excellent properties as a compounding agent in compositions. That is, this copolymer contains almost no free organopolysiloxane that is not bonded to the epoxy resin through the addition reaction between the alkenyl group and the -SiH group. When blended with the copolymer, an epoxy resin composition not only does not lower the glass transition point but also has a low expansion coefficient that is improved by about 10°C. It was discovered that because it contains segments, it has a high affinity for curable epoxy resins, thus enabling micro-dispersion, and dramatically improving crank resistance, leading to the completion of the present invention.

Therefore, the present invention provides an epoxy resin composition containing an alkenyl group-containing epoxy resin and the following formula (1)% formula (1) (wherein R is a substituted or unsubstituted monovalent hydrocarbon group,
a is 0.01≦a≦1, b is 1≦b≦3.1.01≦a
+b<4. ) The present invention provides an epoxy resin composition containing a copolymer obtained by an addition reaction with an organopolysiloxane represented by the following.

The present invention will be explained in more detail below.

The copolymer blended into the epoxy resin composition of the present invention is an alkenyl group-containing epoxy resin and the following formula (1) (wherein R is a substituted or unsubstituted monovalent hydrocarbon group, and a is 0.0
1≦a≦1, b is 1≦b≦3゜1.01≦a + b
<4. ) is a reaction product obtained by an addition reaction with an organopolysiloxane represented by

Here, the alkenyl group-containing epoxy resin can be obtained by epoxidizing an alkenyl group-containing phenol resin with shrimp glorohydrin, or by partially reacting a conventionally known epoxy resin with 2-allylphenol, etc. Specific examples include compounds of the following formula.

(However, in the above formula, -P+ q is usually 1 × p × 10
, 1 < q < 3) On the other hand, as the organopolysiloxane represented by the above formula (1), 1
It has at least one =SiH group in the molecule, and R1 is a monovalent hydrocarbon group such as a methyl group, an ethyl group, a vinyl group, a phenyl group, a benzyl group, or a chloroprobyl group.

Substituted-valent hydrocarbon groups such as chlorobomethyl group, glycidylprobyl group, hydroxyl group, and methoxy group.

It represents the same or different groups selected from alkoxy groups such as ethoxy groups, and alkenyloxy groups such as impropenyloxy groups and imbutenyloxy groups, and a is 0
．． 01≦a (4, b is 1≦b≦3. a+b is 1.01≦
a + b < 4. Particularly suitable organopolysiloxanes are hydrodiene methyl polysiloxane at both ends, hydrodiene methylphenyl polysiloxane at both ends, and hydrodiene methyl (2-trimethoxysilylethyl) polysiloxane at both ends. Specifically, the following compounds may be mentioned.

e ■ H-8itonM e )3. H-si(OEt)
z +n≦20-200 CH3CH.

15i〇-S　i　-CH.

HCH3 ((cH3)zsi○)3 (CH3H5iO)! [
C, H, Si0,2]5 The copolymer to be blended into the epoxy resin composition of the present invention is obtained by combining the above-mentioned alkenyl-containing epoxy resin and the -SiH group-containing organopolysiloxane of formula (1) using a conventionally known addition catalyst. 1 can be obtained by carrying out a heating reaction in the presence of a platinum-based catalyst such as chloroplatinic acid.

This addition reaction is carried out in an inert solvent such as benzene, toluene, or methyl isobutyl ketone at 60-120"C.
In the composition of the present invention, the molar ratio of alkenyl group/ES i H group is preferably 1.0 or more, preferably 1.5 to 5.0 during the addition reaction. As a result, a silicone-modified epoxy resin containing an alkenyl group can be obtained, and a polymerization reaction between the alkenyl groups or an addition reaction to various polyfunctional mercaptans can be used as a means to thicken and harden the composition. I can do it. In addition, silicone-modified epoxy resins obtained by addition-reacting an organosilicon compound having a hydrolyzable group bonded to a silicon atom to an epoxy resin containing an alkenyl group can be thickened in the presence of water, or
It can be hardened. Furthermore, it is also possible to use a silicone resin having a silanol group or a hydrolyzable group.

Depending on the type of silicone-modified epoxy resin and the selection of the curing agent used as necessary, the composition of the present invention can be produced by a method based on reaction of epoxy groups, a method based on reaction of alkenyl groups, and a method based on reaction of hydration bonded to silicon atoms. The viscosity can be increased or cured by three methods, including the reaction of decomposable groups, or by a combination of these curing reactions.

The copolymer of the present invention is used by adding it to a curable epoxy resin, and this curable epoxy resin is an epoxy resin having two or more epoxy groups in one molecule; There is no particular restriction on the molecular structure, molecular weight, etc., as long as it can be cured with various curing agents as described below, and various conventionally known substances can be used. For example, epichlorohydrin and bisphenol are used. Examples include epoxy resins synthesized from various novolak resins, such as epoxy resins, alicyclic epoxy resins, and epoxy resins into which halogen atoms such as chlorine and bromine atoms are introduced.

In addition, when using the above-mentioned epoxy resin, there is no problem in using a monoepoxy compound in combination as appropriate, and examples of this monoepoxy compound include styrene oxide, cyclohexene oxide, propylene oxide, methyl glycidyl ether, ethyl glycidyl ether, phenyl glycidyl ether, and allyl. Examples include glycidyl ether, octylene oxide, and dodecene oxide. The above-mentioned epoxy resins are not necessarily limited to the use of only one type, but may be used in combination of two or more types.

In addition, as a curing agent, an amine curing agent represented by diaminodiphenylmethane, diaminodiphenylsulfone, metaphenylene diamine, etc., an acid anhydride curing agent such as phthalic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, or Examples include phenol novolak curing agents having two or more hydroxyl groups in one molecule, such as phenol novolak and cresol novolak.

Furthermore, in the present invention, various curing accelerators 1 such as imidazole or its derivatives, tertiary amine derivatives,
There is no problem in using phosphine derivatives, cycloamidine derivatives, etc. in combination.

In addition, the amount of the curing agent used is the amount normally used,
The amount of the curing accelerator can also be within a normal range.

When using an inorganic filler in the present invention.

If the total amount of epoxy resin and curing agent is less than 100 parts by weight, the resulting epoxy resin composition may have low stress, and satisfactory results may not be obtained in terms of physical properties such as crack resistance. On the other hand, if it exceeds 1,000 parts by weight, the fluidity may deteriorate and it may be difficult to disperse the inorganic filler, so it is preferably 100 to 1,000 parts by weight. Alternatively, there is no limit to the combination of two or more types of silica, and natural silica such as crystalline silica, amorphous silica, etc. may be selected as appropriate depending on the intended use of the epoxy resin composition.

Synthetic high-purity silica, synthetic spherical silica, talc, mica,
One or more selected from silicon nitride, boron nitride, alumina, etc. can be used.

The amount of the above-mentioned copolymer in the epoxy resin composition is
If the amount is less than 1 part by weight based on the total amount of epoxy resin and curing agent of 100 parts by weight, the effect of improving the glass transition point of the epoxy resin composition, improving crack resistance, suppressing aluminum wiring movement, etc. will be insufficient. There is also 10
If the amount exceeds 0 parts by weight, the mechanical strength of the epoxy resin composition tends to decrease.
The amount is preferably 60 parts by weight.

The composition of the present invention may further contain various additives depending on its purpose, use, etc., if necessary. For example, waxes, fatty acids such as stearic acid, mold release agents such as metal salts thereof, pigments such as carbon black, dyes, antioxidants, flame retardants, surface treatment agents (r-glycidoxypropyltrimethoxysilane etc.), and other additives may be added.

The composition of the present invention can be obtained by a method such as uniformly stirring and mixing predetermined amounts of the above-mentioned components, mixing with a kneader, roll, extruder, etc. at 70 to 95°C, cooling, and pulverizing. . Note that there is no particular restriction on the order of blending the components.

The epoxy resin composition of the present invention can be suitably used as a molding material and a powder coating material, and is also effective for sealing semiconductor devices such as IC1LSI, transistors, thyristors, and diodes, and for manufacturing printed circuit boards. Can be used for

As explained above, the present invention uses a curable epoxy resin,
In addition to the curing agent and the inorganic filler, a copolymer obtained by an addition reaction between an alkenyl group-containing epoxy resin and an organopolysiloxane with a 15iH structure having a specific degree of polymerization is blended, resulting in a 1 bending strength of 1 bending strength. It does not reduce mechanical strength such as elasticity, has a low coefficient of expansion, has a high glass transition temperature, and has excellent crack resistance.The amount of deformation of the aluminum electrode is small, making it suitable for molding materials, powder coating materials, and semiconductor sealing. An epoxy resin composition suitable for use as a sealing material etc. is obtained.

Reference examples are shown next. Reference examples 1.2 are examples of producing a copolymer used in the present invention, and Reference example 3 is an example of producing a copolymer used as a comparative product.

[Reference example]

300 g of an epoxidized phenol novolak resin (epoxy equivalent: 195) with a softening point of 80°C was put into a four-bottle flask with an internal volume of 112 and equipped with a reflux condenser, a thermometer, a stirrer, and a dropping funnel, and the mixture was heated to 110°C without stirring. - A mixture of 32 g of allylphenol and 1 g of tributylamine was added dropwise over a period of 10 minutes, and stirring was continued for 2 hours at a temperature of 110°C. Unreacted 2-allylphenol and tributylamine were distilled off from the resulting contents under reduced pressure to obtain an allyl group-containing epoxy resin (allyl equivalent: 1490, epoxy equivalent: 235).

Next, 120 g of the allyl group-containing epoxy resin obtained by the above method, 200 g of toluene, and 0.0 g of a 2-ethylhexanol-modified chloroplatinic acid solution with a platinum concentration of 2% were placed in a four-bottle flask similar to the above. 04
After 1 hour of azeotropic dehydration, 80 g of organopolysiloxane shown in Table 1 was added dropwise at reflux temperature for 30 minutes, and the mixture was further stirred at the same temperature for 4 hours to react. , and wash the obtained contents with water.

By distilling off the solvent under reduced pressure, reaction products (copolymers i, n, m) shown in Table 1 were obtained.

Chapter 1 Table (Note 1) Compound A; (Note 2) Compound B; (Note 3) Compound C; CH, CH, Si (OMe).

[Reference Example 2] Using a four-loaf flask similar to Reference Example 1, a phenol novolak resin with a softening point of 100°C modified with allyl glycidyl ether (phenol equivalent: 125, allyl equivalent: 1 liter, 100), 200° chloromethyl Oki9ji52
800° C. and stirred and mixed for 3 hours at a temperature of 110°C.
This was cooled to a temperature of 70°C, the pressure was reduced to 160 ■Hg, and 12% of a 50% aqueous solution of sodium hydroxide was added to the mixture.
8 g was added dropwise over 3 hours while performing azeotropic dehydration. The obtained contents were distilled off under reduced pressure to remove the solvent, then dissolved in a mixed solvent of 300 g of methyl isobutyl ketone and 300 g of acetone, washed with water, and the solvent was distilled off under reduced pressure to obtain an allyl group-containing compound. An epoxy resin (allyl equivalent: 1590, epoxy equivalent: 190) was obtained. Using the organopolysiloxane shown in Table 2, the reaction products (copolymers rV, V) shown in Table 2 were obtained in the same manner as in Reference Example 1.

Table 2 [Reference Example 3] In place of the aryl group-containing epoxy resin of Reference Example 1, a phenol novolac resin containing allylphenol (phenol equivalent: 125, allyl equivalent: 1100, and an organopolysiloxane of the type shown in Table 3) was used. In the same manner as in Reference Example 1, the reaction products (copolymers 1 and 2) shown in Table 3 were obtained.

Table 3 [Reference Example 4] 200 g of the allyl group-containing epoxy resin obtained by the method of Reference Example 1 was added to the same reaction apparatus as described above. After adding 400 g of methyl isobutyl ketone and 0.1 g of a 2-ditylhexanol-modified chloroplatinic acid solution with a platinum concentration of 2% and performing azeotropic dehydration for 1 hour, 50 g of the organopolysiloxane represented by formula 1 was added at a temperature of 110°C. It took 30 minutes to drip from the dropping funnel. After that, further trimethoxysilane H5i (OME) 31
2.2 g was added dropwise from the dropping funnel at a temperature of 60° C. over a period of 30 minutes.

After aging at 110°C for 4 hours, the solvent was distilled off under reduced pressure to obtain the reaction product (copolymer ■) 256 shown below.
．． I got 7g.

Appearance: Pale yellow transparent solid Melt viscosity (CP, 150°C): 920 Loss on heating (%, 150°C, 1 hr): l, 48 Allyl equivalent: 2450 Examples and comparative examples are shown below, and 1. The present invention is specifically explained. However, the present invention is not limited to the following examples, and in the following examples, parts indicate parts by weight. (Left below) [Example 1] 180 parts of the copolymer obtained in [Reference Example 4], 17 parts of methyltetrahydrophthalic anhydride, 6.5 parts of mercapto group-containing siloxane xane represented by the formula, 1.0 part of benzophenone , triphenylphosphine 1
．． Blend 0 parts into a gate mixer.

By mixing for 10 minutes at a temperature of 90°C, a composition with a viscosity of 960 voids at 25°C was obtained. The physical properties of the composition obtained by heating and curing are shown below.

Bending strength; 8,5 kg/rrm2 Flexural modulus;
280kg/m" Crack resistance (Method A): 0% When the composition was poured into a 20x100x100+m (7) shaped mold and irradiated with ultraviolet rays for 5 minutes using a high-pressure mercury lamp, it showed rubber-like elasticity with the following physical properties. A hard body was obtained.(Measurement was based on JISK6301.)
32 (JIS) Tensile strength: 8.4 kg/aj Elongation: 180% On the other hand, the composition that was sealed and stored in an aluminum tube immediately after mixing retained its fluidity even after being left at 20°C for 6 months. Was.

[Examples 2 to 1o, Comparative Examples 1 to 2] Epoxidized cresol novolak resin with epoxy equivalent of 200 (curable epoxy resin), phenol novolak resin with phenol equivalent of 110, methyltetrahydrophthalic anhydride, copolymer obtained in Reference Example Polymer, P-)22-diamine, triphenylphosphine (TPP), and benzyldimethylamine (BDMA) were used in the amounts shown in Table 4, and the resulting mixture was uniformly heated with two rolls. Melt-mixed 11 types of epoxy resin compositions (Example 2~
9. Comparative Examples 1-2) were manufactured.

Regarding these epoxy resin compositions, the following (a) to (
e) various tests were conducted.

175℃ using a mold that complies with EMMI standards.

70) Measured under the conditions of cg/ad.

(b) Mechanical elastic modulus) JISK
A 110X4Xloo anti-socket was molded under the conditions of 175°C, 70kg/ad, and 2 minutes of molding time in accordance with 6911 Ni.
Measurements were made after post-curing at 180°C for 4 hours.

(c) Using a glass test piece of 4 mm x 15 mm, the value was measured using a diradometer when the temperature was raised at a rate of 5° C. per minute.

(d) Mukuni-ness.

9. Glue a silicone chip with a size of OX4.5x0.5m to a 14PIN-IC frame (4270I), mold an epoxy resin composition on it under molding conditions of 180℃ x 2 minutes, and post-process at 180℃ for 4 hours. -19 after curing
A heat cycle of 6° C. x 1 minute to 260° C. x 30 seconds was repeatedly applied, and the resin crack occurrence rate after 50 cycles was measured.

(e) Amount of aluminum electrode: One deformation measuring element with an aluminum electrode deposited on a silicon chip with a size of 3.4 x 10.2 x 0.3 + m.
Bonded to the 4-pin IC frame (4270),
An epoxy resin composition was molded onto this under molding conditions of 180°C x 2 minutes, and after post-curing at 180°C for 4 hours, -1
A heat cycle of 96° C. x 1 minute to 260° C. x 30 seconds was repeatedly applied, and the amount of deformation of the aluminum electrode after 200 cycles was examined.

The results of the above tests are also listed in Table 4.

[Examples 11 to 18, Comparative Example 3] Epoxidized cresol novolak resin with epoxy equivalent weight 200 (curable epoxy resin I 1. Phenol equivalent weight 11
0 phenol novolak resin, copolymer obtained in reference example, triphenylphosphine (TPP), 1.8-
Diazabicycloundecene-7 (DBU) was used in the amounts shown in Table 4, and 10 parts of brominated epoxy novolak resin, 260 parts of 1 part of brominated epoxy novolac resin, and 1 part of 3-glycidoxypropyltrimethoxysilane were used. .5 parts, wax E1
．． 5 parts of carbon black and 1.0 part of carbon black were uniformly melted and mixed using two heated rolls to produce 11 types of epoxy resin compositions (Examples 11 to 18° and Comparative Example 3). .

The same tests (a) to (e) as in Example 2 were conducted on these epoxy resin compositions.

Claims (1)

[Claims] 1. Alkenyl group-containing epoxy resin and the following formula (1) H_
aR_bSiO_[_4_-_(_a_+_b_)_]
___/_2...(1) (wherein R is a substituted or unsubstituted monovalent hydrocarbon group, a is 0.01≦a≦1, and b is 1≦
b≦3, 1.01≦a+b<4. ) An epoxy resin composition comprising a copolymer obtained by reaction with an organopolysiloxane represented by the following.