JPH0372522A - Epoxy resin composition - Google Patents

Abstract

PURPOSE:To prepare a metal powder-contg. epoxy resin compsn. useful for a coating material, adhesive, molding material, etc., and excellent in the heat resistance, water resistance, and heat dissipation properties by compounding a liq. epoxy resin, a specific mixed curing agent, and a metal power as essential components. CONSTITUTION:An epoxy resin compsn. useful, e.g. for adhering a semiconductor device to a least frame is prepd. by compounding, as essential components, 100 pts.wt. liq. epoxy resin (e.g. bisphenol A epoxy resin, bisphenol F epoxy resin, tetraglycidylcyclohexylamine, or triglycidylaminophenol); 15-45 pts.wt. curing agent [a mixture of 10-75wt.% diaminodiphenylmethane with 90-25wt.% bis(4-amino-3-methylcyclohexyl)methane or bis(4-aminocyclohexyl)methane; and 50-800 pts.wt. metal powder (e.g. Al, Fe, Cu).

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a metal powder-containing epoxy resin composition that is useful for paints, adhesives, molding materials, etc. and has excellent heat resistance, water resistance, and heat dissipation properties. It is.

In particular, the present invention is an epoxy resin composition that has excellent heat resistance, water resistance, and heat dissipation properties, and can be used as paints applied to exterior materials such as various electrical products, adhesives for electrical parts, and The present invention provides an epoxy resin composition suitable for use as a molding material.

(Prior Art) Epoxy resins have excellent adhesive properties, mechanical strength, and chemical resistance, and are used in a wide range of applications such as electrical insulation materials, paints, and civil engineering and construction materials.

Among these applications, there are cases where the temperatures of the two adherends via the adhesive are different and the adhesive is used for the purpose of dissipating a large amount of heat from the high temperature adherend to the low temperature adherend. Adhesives with good thermal conductivity are used to bond semiconductor elements such as ICs to metal lead frames, quickly transmitting the heat generated from the elements to the lead frame, and suppressing the rise in temperature of the elements. .

-I'312, for this purpose, a eutectic alloy of gold and silicon or a conductive epoxy resin adhesive containing 60 to 80% by weight of silver is used.

In particular, epoxy resin adhesives are being used in a wide range of applications due to their high adhesive strength and low cost.

The performance required of this epoxy resin adhesive includes reactivity that cures within a few minutes at 200°C, heat resistance that can withstand the temperature during wire bonding, water resistance, and adhesiveness at high temperatures. In particular, there is a need for adhesives that react in a short time at low temperatures.

Additionally, some semiconductor devices require electrical insulation and high heat dissipation properties, which conventional adhesives cannot meet.

(Problems to be Solved by the Invention) Thus, there has been a desire for a material that has high heat dissipation while maintaining low-temperature, short-time reactivity and electrical insulation.

(Means for Solving the Problem) The present inventors have tackled this problem and as a result of intensive research, have achieved a high electrical The inventors have discovered that it is possible to obtain a resin composition that has low-temperature, short-time reactivity and high heat dissipation properties while maintaining insulation properties, and has completed the present invention.

That is, the present invention includes: (1) 100 parts by weight of liquid epoxy resin; (2) 10 to 75% by weight of diaminodiphenylmethane; and 90% by weight of bis(4-ano-3-methylcyclohexyl)methane or bis(4-a[nocyclohexyl)methane ~
15 to 45 parts by weight of a mixed curing agent consisting of 25% by weight, and (1) 90 to 800 parts by weight of (aminocyclohexyl)methane selected from aluminum powder, iron powder and copper powder.

The liquid epoxy resin used in the present invention is an epoxy resin that is liquid at room temperature.

For epoxy resins that are liquid at room temperature, see Figure 1 on page 8 of "Introductory Epoxy Resins" (published by Kobunshi Publishing Association in 1988).
．． Various epoxy resins illustrated in No. 5 can be used.

Typical examples include polyphenol polyglycidyl ethers such as bisphenol A epoxy resin, bisphenol F epoxy resin, and bisphenol AD epoxy resin, tetraglycidyldiaminodiphenylmethane, tetraglycidyl-bis(4-aminocyclohexyl)methane, and tetraglycidyl xylene diamine,
Tetraglycidylcyclohexyldimethyleneamine, triglycidylaminophenols; for example, triglycidyl-methanopentaphenophenol, triglycidyl-para-aminophenol, triglycidylmethaminoalkylphenol, triglycidylvalaminoalkylphenol, and the like. Preferred are bisphenol A epoxy resins and triglycidylaminophenols.

The curing agent used in the present invention is a mixed curing agent of cyanodiphenylmethane (hereinafter referred to as DDM) and bis(3-methylcyclohexyl)methane or bis(4-aminocyclohexyl)methane. Alicyclic polyamine bis(4-amino-3-methylcyclohexyl)methane or bis(4-aminocyclohexyl)methane alone has a problem of short pot life. especially,
Bis(4-aminocyclohexyl)methane has a short pot life.As a means to solve this problem, it has become possible to extend the pot life by mixing aromatic polyamine (DDM).

In addition, the mixing ratio of DDM in the mixed curing agent was 75% by weight.
If above, the pot life will be extended, but it will be DD at room temperature.
There is a problem that M precipitates.

Furthermore, if the DDM content is less than 10% by weight, there is little effect on extending the pot life.

When the mixed curing agent is blended into the epoxy resin, the active hydrogen group of the mixed curing agent may be used in a range of 0.5 to 1.5 equivalents per 1 equivalent of epoxy groups in the epoxy resin.

Metal powders that can be used in the present invention are selected from aluminum, iron and copper powders. Preferably, aluminum powder is used, and the weight of the epoxy resin and its cured product can be kept relatively low.

These metal powders can be pulverized by various methods. The most widely used manufacturing method is the atomization method, and because it is nearly spherical, it is said to suppress the increase in internal stress when it is highly filled in a compounded product. The average particle diameter of the metal powder is not particularly limited, but is 30
~40μ is preferred. The amount of metal powder added is 50 to 800 parts by weight per 100 parts by weight of the epoxy resin.

The purpose of adding metal powder is to improve thermal conductivity, reduce the coefficient of thermal expansion, and reduce costs. In particular, the improvement in thermal conductivity due to the addition of metal powder cannot be expected with other fillers such as inorganic fillers such as silica and alumina. If the amount is less than 50 parts by weight, the desired improvement in thermal conductivity cannot be achieved. On the other hand, if it exceeds 800 parts by weight, the viscosity of the compounded product becomes too high, resulting in an extremely low workability and a problem in that electrical insulation properties are impaired.

In addition, in the &ll Kaimono Hobo of the present invention, as the coupling agent, one or two coupling agents selected from silane-based, titanium-based, and aluminum-based coupling agents are used.
10 parts by weight may be added.

Preferred are titanium-based coupling agents.

Coupling agents are effective in reducing the viscosity of compounded products and improving the dispersibility of metal powder.

By adding the coupling agent in an amount of 0.1 to 5 parts by weight per 1.0 parts by weight of the epoxy resin, the viscosity of the compounded product can be reduced and workability can be improved. If 5 parts by weight or more of the coupling agent is added, the crosslinking density of the cured product will be inhibited, leading to a decrease in heat resistance, preferably 0.5 to 5 parts by weight.
It is 3 parts by weight.

Various additives such as a diluent for reducing the viscosity of the compounded product, various fillers as thickeners, and antifoaming agents can be used in the composition of the present invention.

As the diluent, for example, glycidyl ether compounds such as monoglycidyl ether and polyglycidyl ether, and in some cases, plasticizers such as dioctyl phthalate can be used.

Examples of the filler include inorganic fillers such as silica, alkali, barium sulfate, and calcium carbonate, glass fiber,
A fibrous filler such as carbon fiber can be used.

Describing the method for preparing the composition of the present invention, (1) epoxy resin and (2) metal powder are uniformly mixed in advance using a mixer, roll, etc., and (3) a mixed curing agent prepared separately is added to the mixture. Just add and mix.

If the viscosity of the composition is too high, the composition may be heated to reduce the viscosity. However, since heating shortens the pot life of the composition, excessive heating must be avoided.

The composition of the present invention can be used by using various coating methods such as brushing and roll coating, various bonding methods using a dispenser or injection machine, and various molding methods such as pouring. After shaping, store at room temperature ~15
A cured product can be obtained by leaving it for several minutes to several hours in an atmosphere at 0°C.

Hereinafter, a more specific explanation will be given using Examples, but these are not intended to limit the scope of the present invention.

Example I 100 parts by weight of AER-331 (manufactured by Asahi Kaei, bisphenol A type epoxy resin, epoxy equivalent: 189), 200 parts by weight of aluminum powder with an average particle size of 35μ, and titanium canopring agent KR-46B (manufactured by Ajinomoto). )1
Mix the weight parts using a universal mixer (manufactured by Sanei Seisakusho).
A base material A1 was prepared by uniformly mixing.

Separately, 15 parts by weight of diaminodiphenylmethane and bis(4 parts by weight)
-amino-3-methylcyclohexyl) was heated and melted to prepare a curing agent B1.

Mix 130 parts by weight of hardening agent B with 301 parts by weight of main ingredient A1, mix to f, pour into a specified mold, and heat at 60°
A molded article was obtained by heating at C for 15 hours and at 180°C for 8 hours. The physical properties of the molded product were measured according to JIS-6911 and ASTM D64B-56. The results are shown in Table-1.

Table 1 (Examples 2 to 4) Using the base material A1 used in Example 1, blended products were created by changing the ratio of the curing agent diaminodiphenylmethane and bis(4-71-3-methylcyclohexyl)methane.

Table 2 shows the results of measuring the performance and pot life of the cured product.
Shown below.

Table 2 (Comparative Examples 1 and 2) Table 3 shows the results when the curing agent used in Example 2 was used alone.

Table 3 Since the cyanodiphenylmethane of Comparative Example 1 is solid, it is difficult to disperse it with the main ingredient when used alone, and a uniform molded product could not be obtained. Comparative Example 2 has a short pot life and a problem with workability.

(Examples 5 to 6) 150 parts by weight of aluminum powder having an average particle size of 35 μm was uniformly mixed with 100 parts by weight of AER-331, and the main ingredient A2
It was created. The performance of the cured product was measured by changing the blending ratio of the curing agent B1 prepared in Example 1. The results are shown in Table 4.

(Comparative Examples 3 to 4) Table 5 shows the results when the ratio of the curing agent Bl was further changed in Example 3.

Table (Execution N7 to 9) In Example 1, the performance of the cured product was investigated by changing the ratio of the aluminum powder used. The results are shown in Table-6.

(Comparative Examples 5 and 6) Table 7 shows the results when the ratio of A2 powder was further changed in Example 4.

When the weight of the AN powder was increased by 1000 parts by weight, the viscosity of the composition increased significantly, making casting difficult, and when the amount was too small, the thermal conductivity was significantly lowered.

Example 10 Epoxy citrus AER3311 used in Example 1
,00 parts by weight, AER33150 parts by weight and triglycylylagonophenol compound (Sumitomo Chemical ■
A base material A3 was prepared in exactly the same manner as in Example 1, except that 50 parts by weight of ELM-100 (manufactured by ELM-100) was used.

301 parts by weight of the base agent A3 and 39 parts by weight of the curing agent Bl are thoroughly mixed, poured into a predetermined mold, and heated at 60°C for 15 hours and at 200°C for 3 hours to produce a molded product. I got it.

Indicates the results of physical property evaluation of molded products.

Table 8 (Effects of the Invention) As explained above, the epoxy resin composition of the present invention contains a specific amount of metal powder together with a specific mixed curing agent, so it maintains high electrical insulation while maintaining low temperature resistance. This has the effect of providing short-term reactivity and high heat dissipation.

(1 other person)

Claims (1)

[Claims] [1] (1) 100 parts by weight of a liquid epoxy resin; (2)
10-75% by weight of diaminodiphenylmethane and 90-90% of bis(4-amino-3-methylcyclohexyl)methane or bis(4-aminocyclohexyl)methane
An epoxy resin composition comprising: 15 to 45 parts by weight of a mixed curing agent containing 25% by weight; and (3) 50 to 800 parts by weight of at least one metal powder selected from aluminum powder, iron powder, and copper powder. [2] The liquid epoxy resin is at least one type of epoxy resin selected from bisphenol A epoxy resin, bisphenol F epoxy resin, tetraglycidylcyclohexyldiamine, and triglycidylaminophenols. 1) The composition described.