JPH0364532B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD The present invention relates to a method for producing a novel silicone-modified epoxy resin composition that can be suitably used for producing an epoxy resin composition for encapsulating semiconductor devices. Conventional techniques and problems to be solved by the invention Epoxy resins have been widely used in various molding materials, powder coating materials, electrical insulation materials, etc. as compositions containing hardening agents, inorganic fillers, etc. Especially recently, it has been used in large quantities as a material for encapsulating semiconductor devices. This is because epoxy resins generally have better moldability and better moldability than other thermosetting resins.
It takes advantage of its excellent adhesive properties, electrical properties, mechanical properties, moisture resistance, etc. However, since epoxy resins generally have a low elastic modulus and poor flexibility, they tend to crack when molded or processed into semiconductor devices or during heat cycle tests, and are susceptible to excessive stress. There are defects such as deformation of the element, which tends to reduce the function of the element and cause damage. In order to solve these problems, the applicant has developed an epoxy resin composition (Japanese Unexamined Patent Publication No. 129246/1989) in which organopolysiloxane is blended with a curable epoxy resin, and furthermore, an epoxy resin composition composed of an aromatic polymer and an organopolysiloxane. We proposed an epoxy resin composition containing a block copolymer (Japanese Patent Laid-Open No. 21417/1983), and improved the crack resistance of the epoxy resin composition. However, in recent years, the characteristics required for materials for encapsulating semiconductor devices have become increasingly strict, and therefore, epoxy resin compositions with further improved crack resistance are desired. The present invention was made in view of the above circumstances, and an object of the present invention is to provide a method for producing a novel silicone-modified epoxy resin that can be suitably used for epoxy resin compositions for encapsulating semiconductor devices. Means and Effects for Solving the Problems In order to achieve the above object, the present inventors conducted intensive studies and found that a specific organosilicon material having a ≡SiH group is used for epoxy resins containing an alkenyl group. Compound, i.e. the following formula (1) (However, in the formula, R ¹ represents a substituted or unsubstituted monovalent hydrocarbon group, hydroxyl group, alkoxy group, or alkenyloxy group, and a and b are 0.01≦a≦1, 1≦
It is a positive number satisfying b≦3, 1≦a+b≦4.
Further, the number of silicon atoms in one molecule is an integer of 1 to 400, and the number of hydrogen atoms directly bonded to silicon atoms in one molecule is an integer of 1 or more. ) It was discovered that a novel silicone-modified epoxy resin can be obtained by adding an organosilicon compound represented by the following. This silicone-modified epoxy resin is obtained by adding the ≡SiH group of the above organosilicon compound to the alkenyl group of the alkenyl group-containing epoxy resin component. By using such an addition reaction, the epoxy resin It is possible to easily obtain a silicone-modified epoxy resin that contains almost no free organosilicon compounds that are not bonded to the silicone, and the silicone-modified epoxy resin thus obtained can be used with conventionally known epoxy curing agents, catalysts, etc. When cured in the presence of a silicone curing catalyst such as an organotin compound, a low stress and strong cured product can be obtained, and when used in combination with a curable epoxy resin, excellent crack resistance can be obtained. It is possible to obtain a molded article of an epoxy resin composition which has a high glass transition temperature and also has a glass transition temperature improved by about 10°C. Therefore, the silicone-modified epoxy resin obtained by the present invention can be used as a component of an epoxy resin composition for encapsulating semiconductor devices. The inventors have discovered that the method is very useful as a method, and have come up with the present invention. The present invention will be explained in more detail below. The method for producing a silicone-modified epoxy resin of the present invention comprises using an alkenyl group-containing epoxy resin and the following formula (1). (However, in the formula, R ¹ represents a substituted or unsubstituted monovalent hydrocarbon group, hydroxyl group, alkoxy group, or alkenyloxy group, and a and b are 0.01≦a≦1, 1≦
It is a positive number satisfying b≦3, 1≦a+b≦4.
Further, the number of silicon atoms in one molecule is an integer of 1 to 400, and the number of hydrogen atoms directly bonded to silicon atoms in one molecule is an integer of 1 or more. ), and in this case, the ≡SiH group of the organosilicon compound is added to the alkenyl group of the epoxy resin. Here, the alkenyl group-containing epoxy resin component used in the present invention can be obtained by epoxidizing an alkenyl group-containing phenolic resin with epichlorohydrin, or by partially reacting a conventionally known epoxy resin with 2-allylphenol. It will be done. Specifically, the following formula (2) (However, in the formula, R is the same or different hydrogen atom, a halogen atom such as chlorine or bromine, or a carbon number of 1 to 8.
monovalent hydrocarbon group or

[Formula] represents a glycidyl ether group, and G is

[Example 1]

A four-necked flask with an internal volume of 1, equipped with a reflux condenser, a thermometer, a stirrer, and a dropping funnel, was used as a reaction device, and the following formula (i) was used in the four-necked flask. (However, G is

[Example 2]

As an organosilicon compound, the following formula (v) A silicone-modified epoxy resin having the following properties was produced in the same manner as in Example 1, except that the resin shown below was used. Appearance: White-yellow opaque solid Melt viscosity: 760 cp (150°C) Loss on heating: 0.56% (150°C, 1 h) The obtained silicone-modified epoxy resin has the following formula in formula (iv):

[Formula] is

[Example 3]

As an organosilicon compound, the following formula (vi) A silicone-modified epoxy resin having the following properties was produced in the same manner as in Example 1, except that the resin shown below was used. Appearance: White-yellow opaque solid Melt viscosity: 890 cp (150°C) Loss on heating: 0.45% (150°C, 1 h) The obtained silicone-modified epoxy resin has the following formula (iv):

[Formula] is

They have the same structural formula except that the formula is changed to [Formula]. [Example 4, 5] Using the same reaction apparatus as in Example 1, 200 g of phenol novolac resin (allyl equivalent: 1100, OH equivalent: 125) with a softening point of 100°C, 800 g of chloromethyl oxirane, and cetyl were placed in a four-necked flask. Add 0.6g of trimethylammonium bromide and heat at 110°C.
The mixture was heated and stirred for hours. Thereafter, the four-necked flask was cooled to bring the temperature of the contents to 70°C, and 128 g of a 50% aqueous solution of sodium hydroxide was added dropwise over 3 hours under reduced pressure of 160 mmHg while performing azeotropic dehydration. The solvent was distilled off under reduced pressure from the product thus obtained, and then 300 g of methyl isobutyl ketone and 300 g of acetone were added.
After dissolving it in a mixed solvent of g, it was washed with water. The solvent was distilled off under reduced pressure to obtain an allyl group-containing epoxy resin represented by the following formula (vii) (allyl equivalent: 1590, epoxy equivalent: 190). Next, the allyl group-containing epoxy resin obtained above was placed in a four-necked flask of the same reactor as above.
150g, methyl isobutyl ketone 100g, toluene
Add 200g of platinum and 0.04g of a 2-ethylhexanol-modified chloroplatinic acid solution with a platinum concentration of 2%, completely dissolve the allyl group-containing epoxy resin under heating and stirring, perform azeotropic dehydration for 1 hour, and then heat at reflux temperature. 1st
50 g of the organosilicon compound shown in the table was added dropwise over 30 minutes using a dropping funnel. After the dropwise addition, stirring was continued for 4 hours while maintaining the reflux temperature to obtain a silicone-modified epoxy resin (structural formula) having the properties shown in Table 1.

[Example 6]

Using the same reaction apparatus as in Example 1, 300 g of epoxidized cresol novolac resin (epoxy equivalent: 204) with a softening point of 70°C was placed in the four-necked flask.
While stirring with a stirrer, a mixture of 67 g of 2-allylphenol and 1 g of tributylamine was added dropwise using a dropping funnel at a temperature of 110° C. over 10 minutes, and the temperature was further maintained and stirring was continued for 2 hours. Unreacted 2-allylphenol, tributylamine and the solvent were distilled off from the obtained product under reduced pressure to obtain an allyl group-containing epoxy resin represented by the following formula (ix) (allyl equivalent: 651, epoxy equivalent: 332). Ta. Next, 200 g of the obtained allyl group-containing epoxy resin was placed in a four-necked flask of the same reaction apparatus as above.
Methyl isobutyl ketone 200g, 2-ethylhexanol modified chloroplatinic acid solution with platinum concentration 2% 0.04
g to completely dissolve the allyl group-containing epoxy resin under heating and stirring, and after azeotropic dehydration for 1 hour, the following formula (x) was added at reflux temperature. Methyldipropenyloxysilane 31.2
g was added dropwise over 30 minutes using a dropping funnel. After the dropwise addition, stirring was continued for 4 hours while maintaining the reflux temperature, and the solvent was distilled off under reduced pressure to obtain a silicone-modified epoxy resin (allyl equivalent: 3100) with the following properties.
221.4g was obtained (structural formula ()). Appearance: Light brown transparent solid Melt viscosity: 530cp (150℃) Loss on heating: 1.25% (150℃, 1h) Table 2 shows the results of elemental analysis, NMR analysis, and IR analysis of the silicone-modified epoxy resins of Examples 1 to 6 above.

[Example 7]

In a four-necked flask of the same reaction apparatus as in Example 1, 200 g of the allyl group-containing epoxy resin obtained in Example 6, 400 g of methyl isobutyl ketone, and 0.1 g of a 2-ethylhexanol-modified chloroplatinic acid solution with a platinum concentration of 2% were placed. was added, the allyl group-containing epoxy resin was completely dissolved under heating and stirring, and after azeotropic dehydration for 1 hour, the following formula (iii) was added at a temperature of 110°C. 50g of the organopolysiloxane shown is added dropwise over 30 minutes using a dropping funnel, and then trimethoxysilane (HSi(OMe) ₃ ) is further added at a temperature of 60°C.
12.2 g was added dropwise over 30 minutes using a dropping funnel.
After dropping, stirring was continued for 4 hours at a temperature of 110°C for aging, and the solvent was distilled off under reduced pressure to obtain 256.7 g of a silicone-modified epoxy resin (allyl equivalent: 1800) with the following properties (structural formula (d)). Appearance: Pale yellow transparent solid Melt viscosity: 920cp (150℃) Loss on heating: 1.48% (150℃, 1h) [Example 8] In a four-neck flask of the same reaction apparatus as in Example 1, 150 g of the allyl group-containing epoxy resin of formula (ii) obtained in Example 1, 250 g of methyl isobutyl ketone,
Add 0.04 g of a 2-ethylhexanol-modified chloroplatinic acid solution with a platinum concentration of 2%, heat and stir to completely dissolve the allyl group-containing epoxy resin, perform azeotropic dehydration for 1 hour, and then reduce the following average at reflux temperature. 45 g of an organosilicon compound with a number average molecular weight of _{980 and a ≡SiH equivalent of 492 shown by the composition formula () (Me 2 SiO) 0.3 (MeHSiO) 0.2 ( PhSiO 3/2 ) 0.5 ...} () It was added dropwise over 30 minutes using a dropping funnel. After that, stirring was continued for 4 more times at reflux temperature.
After a period of time, the solvent was distilled off under reduced pressure to obtain 191.3 g of a silicone-modified epoxy resin having the following properties. Appearance: Light brown transparent solid Melt viscosity: 2140 cp (150°C) Loss on heating: 0.87% (150°C, 1 h) [Example 9] Using the same reaction apparatus as in Example 1, epoxy equivalent was placed in the four-necked flask. 945 Epibis type epoxy resin (Epicoat manufactured by Shell Chemical)
1004) and 500 g of toluene were added and stirred at a temperature of 60°C to uniformly dissolve the mixture.Furthermore, 4 ml of a 2.0 mol/l methanol solution of sodium methylate was mixed with stirring under heating. Thereafter, 70 g of allyl acrylate was added dropwise over 20 minutes using a dropping funnel, and stirring was continued for 4 hours while maintaining the temperature at 60°C. Next, after aeration with carbon dioxide gas,
The solvent was distilled off from the resulting cake under reduced pressure to obtain an allyl group-containing epoxy resin having an allyl equivalent of 514 and an epoxy equivalent of 1120 (structural formula ()). Next, 102.8 g of the allyl group-containing epoxy resin thus obtained, 300 g of toluene, and a platinum concentration of 2% were placed in a four-necked flask of the same reaction apparatus as above.
2-ethylhexanol modified chloroplatinic acid solution of
0.04g of the allyl group-containing epoxy resin was completely dissolved under heating and stirring, and after azeotropic dehydration for 1 hour, trimethoxysilane (HSi) was added at 80°C.
12.2 g of (OMe) ₃ ) was added dropwise over 30 minutes using a dropping funnel. After the dropwise addition, stirring was further performed for 4 hours at a temperature of 110°C, and the solvent was distilled off under reduced pressure to obtain a silicone-modified epoxy resin (allyl equivalent
995) 113.2 g was obtained (structural formula ()). Appearance: Pale yellow transparent solid Melt viscosity: 1470cp (150℃) Loss on heating: 1.45% (150℃, 1h)

Claims (1)

[Claims] 1. Alkenyl group-containing epoxy resin component and the following formula
(1) (However, in the formula, R ¹ represents a substituted or unsubstituted monovalent carbon hydrogen group, hydroxyl group, alkoxy group, or alkenyloxy group, and a and b are 0.01≦a≦1, 1≦
It is a positive number satisfying b≦3, 1≦a+b≦4.
Further, the number of silicon atoms in one molecule is an integer of 1 to 400, and the number of hydrogen atoms directly bonded to silicon atoms in one molecule is an integer of 1 or more. ) to produce a silicone-modified epoxy resin in which a ≡SiH group of the organosilicon compound is added to the alkenyl group of the alkenyl group-containing epoxy resin. A method for producing silicone-modified epoxy resin. 2 The alkenyl group-containing epoxy resin component has the following formula:
(2) (However, in the formula, R represents the same or different hydrogen atom, a halogen atom, a monovalent hydrocarbon group having 1 to 8 carbon atoms, or a glycidyl ether group represented by [formula], and G represents a glycidyl ether group represented by [formula]) ether group, p is an integer of 0 to 20, q is an integer of 1 to 20, and t is 0 or 1). Method.