JPS58198526A - Heat-resistant epoxy resin composition - Google Patents

Abstract

PURPOSE:An epoxy resin composition of high heat resistance, consisting essentially of a triglycidyl ether of a trisphenol as an epoxy resin and a trisphenol as a curing agent. CONSTITUTION:The titled composition consisting essentially of a triglycidyl ether of a trisphenol of formula I (wherein R1 is a lower alkyl residue), e.g., tris(4-glycidoxyphenyl)methane, as an epoxy resin, and a trisphenol of formula II(wherein R2 is a lower alkyl residue), e.g., tris(4-hydroxyphenyl)methane, as a curing agent. Combination of the resin with the curing agent can provide a composition having heat resistance for higher than that of conventional heat- resistant epoxy resin compositions.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an epoxy resin composition, and an object thereof is to provide a composition having high heat resistance.

Epoxy resin exhibits excellent properties such as adhesiveness, chemical resistance, and electrical properties, so it is used in a wide range of applications such as adhesives, paints, and electrical insulation materials. However, in recent years, the conditions of use have become increasingly harsh. Therefore, it is becoming increasingly difficult to use conventional epoxy resin compositions.

One of the usage conditions that is becoming increasingly severe is heat resistance, and there is a demand for products such as adhesives, paints, and electrically insulating materials that have even higher heat resistance than 4M.

The present inventors have completed the present invention as a result of intensive research in order to obtain a composition that does not lose the excellent properties of the epoxy resin and has heat resistance that is 19 times higher than that of the present inventors. It is something.

Epoxy resins are usually cured using a combination of amines, acid anhydrides, and phenols, which are generally called curing agents, but in terms of chemical resistance, the bonds formed during the curing reaction are highly polar. The cured product of phenol I'iK is chemically more stable and has better texture than the cured product of ``7j'' and acid anhydrides, which give a chemically active structure. investigated the use of phenols, which have excellent chemical resistance, as a curing agent to improve the heat resistance of epoxy resins.

Among compositions for curing epoxy resins with 7 enols, those with excellent heat resistance use a novolac type polyfunctional epoxy resin as the epoxy resin and a polyfunctional phenol phenol novolac as a curing agent. is widely known. By using a polyfunctional epoxy resin, it is possible to obtain higher heat resistance than a composition using general-purpose bisphenol A diglycidyl ether; however, when the composition is cured, the glass transition temperature Fi160°C 11 degrees Kt is not reached.

Therefore, in order to further improve the heat resistance of phenol-cured epoxy resin compositions that have excellent chemical resistance, the present inventors investigated various combinations of epoxy resins and phenols, and found that conventionally known heat-resistant epoxy resin compositions The present invention was completed by discovering a single product that has much higher heat resistance than other products.

That is, the present invention provides (a) a triglycidyl ether of trisphenol represented by the following general formula [I] as an epoxy resin, (bL) a fuming agent, and a trisphenol triglycidyl ether represented by the following general formula [I] as an epoxy resin;
11] is a heat-resistant epoxy resin composition containing trisphenol as an essential component.

General formula (I) General formula (n) (R1 and R1 in the above formulas (1) and (H) represent lower alkyl residues) As the spinning epoxy resin of the present invention represented by the general formula (1), , tris(4-chrysitoquinphenyl)methane, 1,1,2-tris(4-glycidoxyphenyl)
Examples include ethane, 1,1.3-)lis(4-glycidoxyphenyl)furopane, and the general formula (II)
Examples of the curing agent represented by: tris(4-hydroquinphenyl)methane, 1,1,2-)lis(4-hydroxyphenyl)ethane, 1,1,3-1-IIs(4-hydroxyphenyl) An example is fluoropane, but depending on the purpose, other epoxy compounds or other curing agents may be used in combination without impairing Fi and properties.

From the viewpoint of heat resistance, the ratio of the epoxy resin to the phenolic water group used in the present invention is preferably 0.5 to 2, more preferably 0.8 to 1. The value is 2, and the most preferred value is 1.

When curing the heat-resistant epoxy resin of the present invention,
Catalysts such as imidanols, tertiary amines, and boron fluoride compounds can generally be used to accelerate the curing rate. Depending on the purpose, etc., conventionally known reinforcing materials, fillers, mold release agents, flame release agents, dyes and pigments, coupling agents, etc. can be used as appropriate. Examples of inorganic reinforcing materials or fillers include inorganic powders such as silica, quartz glass powder, alumina, calcium silicate, calcium carbonate, talc, and kaolin, inorganic edge wires such as glass fiber and carbon fiber, glass balloons, and glass balloons. Hollow spheres are exemplified, and silica and quartz glass powders are particularly preferred from the viewpoint of electrical properties. The ratio L of the inorganic filler used is preferably 50 to 500 parts by weight per 100 parts by weight of the epoxy resin and curing agent, and particularly preferably 100 to 3011 parts. The combined use of an inorganic filler improves the strength, and also improves the coefficient of thermal expansion, thermal conductivity, etc., making it not only suitable for heat-resistant mechanical parts but also easy to use for electrical PI#s. When used for electrical insulation, among inorganic fillers, those mainly composed of silica powder and quartz glass powder, which have excellent electrical properties, are particularly suitable.
As heat resistance becomes more important in urban areas due to higher integration and higher power, it has become a very suitable composition for semiconductor encapsulation resins and is useful as a encapsulation material.

Rounding of the Preparation of the Composition of the Invention Various methods can be used to mix the components depending on the purpose, including solution mixing using a solvent, melt mixing using a hot roll, etc.
Conventionally known methods such as powder mixing using a ball mill can be used.

The present invention will be explained in detail by showing Examples and Comparative Examples below.

Fruit #fFl11 Tris (4-glycidoxyphenylene A) methane (epoxy equivalent 166) 1001 m, tris (4-hydroxyphenyl) methane (OH equivalent 98) 59 parts and 2
-7 Enylimidazole 195 parts were heat-melted and mixed in a kneader, then cooled 1 and pulverized.

This resin composition was applied at a mold temperature of 170°C and a curing time of 2.
The resulting molded piece was post-cured at 175° C. for 5 hours. The thermal expansion of this molded piece was measured using a quartz tube diotometer under the condition of a heating rate of 2 short erosions, and the thermal expansion coefficient and secondary transition temperature (glass transition temperature Tg) of the glass mold were determined.

The results are shown in Table 1.

Example 2 1.1.3-) Lis(4-glycidoxyphenyl)propane (softening point 60°C, epoxy equivalent 180) 10
0 parts, tris(4-hydroquinphenyl)methane 5
411S and 1.5 parts of 2-fegolimidazole were heated and mixed, cooled and pulverized, molded and post-cured in the same manner as in Example 1, and measured in the same manner. 1st page of results
K showed.

Comparative Example 1 In real [Fl I, phenol novolac (softening point 8
The same procedure was followed except that 63 parts of OH equivalent (105) were used at 5°C. The results are shown in Table 1.

Comparative Example 2 In Example I, instead of tris(4-glycidoxyphenyl)methane and tris(4-hydroxyphenyl)methane, klenorucborac type epoxy resin (softening point 70''C-, epoxy equivalent) was used. , 11 21
5) 100 parts phenol novolac (softening point 8
The same procedure was followed except that 5°C and 49 parts of OH equivalent (105) were used. The results are shown in Table 1.

Example 3 Tris(4-glycidoxyphenyl) methane 100M
, ) 59 parts of lith (4-hydroxyphenyl)methane and 1.5 parts of 2-7 enylimidazole were heated and melted and mixed in a kneader, then cooled and pulverized.

To 160.5 parts of this resin powder, 380 parts of silica powder, 2 parts of calcium stearin, and 2 parts of γ-glycidoxypropyltrimethoxine were added, mixed with pre-mix, heated and kneaded with a hot roll, and cooled. , and crushed to obtain a molding material.

Using this molding material, the mold temperature was 170℃, and the crushing time was
A test piece was obtained by transfer molding in 2 minutes, and this was
Post-cure was performed at 5°C for 5 hours.

Using this test piece, the same thermal expansion measurement as in Example 1,
Initial volume resistivity, pressurized steam (121'C12 atm)
The volume resistivity and bending strength after pressure curdling (PCT) were measured. The results are shown in Table 2.

Comparative Example 3 Cresol novolac type epoxy resin (softening point 70°C,
Epoxy weight 215) 100% 1-phenol novolak (softening point 85°C, 014% 11105) 49
1 part and 1.5 parts of 2-7 enylimidazole were heated and melted and mixed in a Nigu, then cooled and pulverized.

To 150.5 parts of this resin powder, 36011 silica powder,
A molding material was obtained in the same manner as in Example 3 by adding 2 parts of calcium stearate and 2 parts of γ-glycidoxypropyl trimethochynesilane.

The results were shown in the second barley using the same method as in Example 3 except that this molding material was used.

Table 2

Claims (1)

[Claims] 1.L The epoxy resin is a triglycidyl ether of trisphenol represented by the following general formula (I) (in the formula, R5 is a lower alkyl residue), and the curing agent is the following general formula (tn) ( R2 in the formula is a lower alkyl residue) Heat-resistant epoxy resin composition 2 containing trisphenol represented by the following as an essential component: A curing agent for the epoxy group of the epoxy resin (a)
The epoxy resin composition according to claim 1, wherein the proportion of phenolic hydroxyl groups in b) is 0.5 to 2.