JPS58198525A - Epoxy resin composition - Google Patents

Abstract

PURPOSE:An epoxy resin composition requiring no post curing and being excellent in moisture resistance and suitable for use for electronic parts, electronic instruments and devices, etc., obtained by mixing an epoxy resin with a curing agent for a phenolic resin, a specified cure accelerator and an inorganic filler. CONSTITUTION:100pts.wt. epoxy resin is mixed with about 10-150pts.wt. curing agent comprising a phenolic resin or a mixture of this resin with an acid anhydride (e.g., phthalic anhydride), about 0.05-8pts.wt. cure accelerator selected from the group consisting of a tert. amine (e.g., triethanolamine), a triazole (e.g., 5-methyltriazole) and an imidazole (e.g., 2-phenylimidazole), and about 20- 450pts.wt. inorganic filler (e.g., quartz glass). In the above mixing, at least two of the first three components are melt-blended first, and after cooling, the product is ground and used to obtain the purpose resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an embossment resin composition suitable for use in electronic parts and electronic devices, which does not require post-curing and has improved moisture resistance.

Since epoxy resin has excellent electrical properties, mechanical properties, etc., it is widely used for sealing and impregnating electronic components and devices such as semiconductor devices.

However, conventional Eboshi resin compositions have problems in industrial production, such as the need to post-cure at high temperatures for a long time after sealing or impregnating semiconductor devices, etc., and their moisture resistance is also insufficient. It has the disadvantage that the insulation properties deteriorate and leakage current increases as it is used.

As a result of intensive research into methods for solving the above problems and drawbacks, the inventors of the present invention found that at least 42 types of epoxy resin, curing agents, and curing accelerators are melted in whole or in part in advance. The inventors discovered that the object could be achieved by pre-processing the resin and completed the present invention.

That is, the present invention provides a curing agent selected from the group consisting of f+J epoxy resin, (2) a curing agent that is a phenol resin or a mixture thereof and an acid anhydride, and (3) tertiary amines, triaryls, and imidalyls. A composition containing as an essential component at least one hardening accelerator, as well as K (4) an inorganic filler, which comprises the above-mentioned (1).
, at least 2 m of the components (2) and (3) are obtained by melt-mixing all or a part of the amount used in advance, and then cooling and pulverizing. It depends.

The present invention provides a hardening agent which is +1) Evo + Shi resin, (2) phenol resin or a mixture of this and an acid anhydride, and (3)
Tertiary amines, triaryls and i! : At least two of the at least 411 types of curing accelerators selected from IJ reels are characterized in that all or part of the amount used is melt-mixed in advance, and then used in a pulverized state after cooling. shall be. By performing the above-mentioned melt hardening treatment, the epoxy resin composition of the present invention can omit the post-curing step required for this type of composition.
Furthermore, the components subjected to treatment I7 become more compatible, and the final product, the molded article, becomes denser and has improved moisture resistance. The process varies depending on the composition of the materials to be treated; however, the materials are melted and mixed at the melting temperature of the materials, usually around 60 to 130°C, cooled to solidify by standing to cool, water-cooled, etc., and then pulverized. It is preferable that the particle size of the pulverized product is smaller than that passing through a 1O mesh. If the mesh size is larger than 10, the mixing and dispersibility with other additives is poor.
], the balata + of the characteristics of the final product increases.

The amount to be treated during nuclear treatment differs depending on the material to be treated, but for component (1) K, the amount to be treated is 20 to 20% of the amount used.
100% by weight, component (2) K and then 50% of its usage amount
It is the ninth most preferable to obtain the desired effect of the present invention that the amount of the component (3) K is 100% by weight and 5 to 30% by weight. If component (3) is used in an amount exceeding 30% by weight of the amount used, side reactions may occur. Combinations of each component to be treated include (1) and (
2), tl) and (3), (2) and (3) and K (
11, (2) and (3) may be used.

The epoxy resin in the present invention is not particularly limited and any known resin can be used, such as phenol novolak type epoxy resin, freryl novolac type epoxy resin, bisphenol, A type epoxy resin, etc. resin,
Glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, chrycidyl amici type epoxy resin,
Epo+Si resin, linear aliphatic Ebony resin, alicyclic Ebony resin, which is produced by Epo+Si conversion of olefin υ bond.
1, such as heterocyclic epoxy resin, bald epoxy resin, etc.
Examples include those having two or more Ebo-gyu-shi groups in the molecule, and at least ll'l of these are used.

In the present invention, a phenol resin or a mixture of the resin and an acid anhydride is used as the curing agent. This significantly improves moisture resistance and heat resistance.

The phenolic resin curing agent used in the present invention includes:
A wide variety of known materials can be used, including, for example, phenol novolak TM resin, start-butylphenol novolac resin, nonylphenol novolac resin, polyvarabinylphenol resin, etc., and at least one of these is used.

The amount of the phenolic resin curing agent used is 10 to 150 coulometric parts per 100 parts by weight of the epoxy resin. 10
If the amount is less than 150 parts by weight or exceeds 150 parts by weight, heat resistance will decrease.

As an acid anhydride curing agent used in combination with the pressure of the present invention,
A wide variety of known 4 can be used, such as phthalic anhydride, tetradolphthalic anhydride, sahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, succinic anhydride, trimellitic anhydride, and pyromellitic anhydride. , 3. stomach,
4. Ebesi-nophenocytetracarposic acid anhydride, tetra-phthalic anhydride, redidic acid anhydride,
5- (2,5-diosotetrahydrofuryl)-3-
Methyl-3-Schiff0-1,2-; Carposiic acid anhydride, trimellitic acid dimer, 3,4-dimethyl-6
-(2-methyl-1-dbenyl) -3,4,5,6
-Titrahydro phthalic anhydride, 3,4-dimethyl-6
-(2-methyl-1-benyl) -1,2,3,6
-Titrahydro phthalic anhydride, etc.
At least 41 of these are used. The acid anhydride curing agent is used in place of a part of the phenolic resin curing agent. In that case, the amount used is preferably 5 to 60% by weight of the entire curing agent.

As the curing accelerator used in the present invention, a wide variety of known curing accelerators can be used, such as those selected from tertiary amici, triaryls, and diaryls, such as Beni J, dimethylamici, triethanolamine, dimethylaminomethyl Phenol, tris(dimethylaminomethyl)phenol, triethyltetramis, 3,9-bis(3-aminomethyl)-2,4,8,IO-tetraospirol (5,5), etc. tertiary ΣΣ class of, 1.2
．． 3-besylitriaryl, 5-methyltriaryl triaryl, 2-phenylyl, l:taryl, 2
-Ethyl-4-methylimitaryl, 2-methyltritalyl, 2-ethylimitaryl, 2,4-dimethyltrimethyl, 2-bodecyl-tri-4-lyl, 2-heztadecyl-tri-j2-lyl, 1- Vinyl-2-methyl-trizuryl, 2-phenyl-4,5-diso+dimethylimitaryl, 2-phenyl-4-methylimitaryl,
2-Isodubirutritalyl, 1-cyanomethyl-2
- Imidaryls such as methyl imitalyl can be mentioned, and at least one of these is used. The amount of curing accelerator used is 0.05 parts per 100 parts by weight of epoxy resin.
~8 parts by weight is suitable. When the amount is 0.05 parts by weight, the curing accelerating effect is not sufficient and uncured products are produced. If the amount exceeds 8 parts by weight, storage stability will deteriorate.

In addition, in the present invention, the moisture resistance is improved, the expansion coefficient is reduced,
As the inorganic filler used to improve thermal conductivity, a wide range of known materials can be used, such as quartz glass,
Examples include crystalline silica, glass fiber, talc, alumina, water-containing alumina, calcium silicate, calcium carbonate, barium sulfate, magnesia, zirconium silicate, clay, mica, and at least 1111 of these.
Use. These inorganic fillers are preferably used in powder form. The appropriate amount of the inorganic filler to be used is 20 to 450 parts by weight per 100 parts by weight of the epoxy resin. If the amount is less than 20 parts by weight, no reduction in the expansion coefficient can be expected. Ota,
If it exceeds 450 parts by weight, the melt viscosity will be extremely high and it will be difficult to use the resin.

Further, when the composition of the present invention is used for electronic parts or electronic equipment, a flame retardant is used. As the flame retardant in this case, a wide variety of known flame retardants can be used. Examples include piphenyl, red sushi, etc., and at least 4 of these
11 types are used. The flame retardant used is epoxy resin 100
A suitable amount is 3 to 150 parts by weight. If the amount is less than 3 parts by weight, no flame retardant effect can be expected.

Furthermore, in the present invention, in addition to the above-mentioned components, additives commonly used in this type of composition, such as coloring agents such as Garbosilac and Beshigara, and mold release agents such as Carnouba and synthetic wax, are also used. , an adhesion improver such as Shirashikazuri υg agent, etc. may be added and used in combination.

The epoxy resin composition of the present invention can be applied to a wide range of applications without particular limitations, but it is suitable for sealing electronic parts and electronic equipment, and the molding method used in this case is Any conventionally known method for molding the composition can be applied, such as low-pressure transfer molding, injection molding, compression molding, and the like. Furthermore, the composition of the present invention can be used not only for sealing purposes but also for coating purposes, insulation purposes, etc. Furthermore, it can be impregnated by dissolving it in a suitable solvent such as methyl ethyl ketone, styrene, and methylcarbinol. You can read what you need.

As mentioned above, the epoxy resin composition of the present invention is produced by pre-melting the epoxy resin, curing agent, and curing accelerator (4.2), and by pre-melting the epoxy resin, curing agent, and curing accelerator. This method has the great advantage that it is unnecessary, so it is extremely advantageous in terms of industrial production. In addition, since the moisture resistance is improved compared to conventional products, the insulation properties are good and leakage current is reduced.

The epoxy resin composition of the present invention can be applied to a wide range of electronic components and devices without being limited in terms of percentage, but includes, for example, integrated circuits, large-scale integrated circuits, transistors, thyristors, diodes, Examples include resistors, insulators, sockets, cases, connectors, varistors, etc.

In addition to electronic applications, it can also be applied to various mechanical parts, various containers, etc.

Hereinafter, the present invention will be further explained in more detail with reference to Examples and Comparative Examples.

Example 1.2 and Comparative Example IF Epoxy resin compositions having the compositions shown in Table 1 were prepared. That is, the composition of the present invention (Example 1) was prepared using Flet-Cour Novolak type Evo+C resin (manufactured by Nippon Kayaku ■ [EOc
NJ) 60 parts by weight, brominated evo-cow dinovolac resin (
40 parts by weight of "Zurage" manufactured by Nippon Kayaku ■ and phenol novolac resin (r&P-120J manufactured by Gunei Chemical Industry ■)
60 parts by weight were placed in a super mixer and melted and mixed at 80 to 120°C, solidified by cooling with water, and then placed in an atomizer.
The powder was pulverized to 10 meshes or less.

The powder component obtained in Section h and all the other components shown in Table 1 were melted and mixed at 80 to 110°C at 0°C, cooled and solidified by water cooling, and then ground in an atomizer and heated. A test piece (disk shape with a diameter of 5 mm and a thickness of 3 mm) was obtained by molding by the loess method.

Furthermore, as another composition of the present invention (Example 2), 60 parts by weight of phenol novolak resin and 0.5 parts by weight of 2-phenylimimita cool were melted and blended in the same manner as above to obtain the desired powder component, 2- A test piece was obtained by processing and molding 15 parts by weight of Fe\nylimidalyl and all the other ingredients shown in Table 1 in the same manner as above.

As Comparative Example 1, a test piece having the same composition was obtained by melting and resin treatment as described above and molding in the same manner. In Comparative Example 1, post-curing was performed, but in Examples 1 and 2, post-curing was performed.

Next, the hardness and moisture resistance of each test piece obtained from Examples 1 and 2 and Comparative Example IK were examined. The curing conditions, hardness and moisture resistance test results are also shown in Table 1.

"KBM-4034-a'120" manufactured by Shin-Etsu Chemical Co., Ltd.
A loss seeker test was conducted under the conditions of ℃ and 2 atm, and the value after 200Ar was measured.

From Table 1, it can be seen that the composition of the present invention does not require post-curing and has excellent moisture resistance.

(that's all)

Claims (1)

[Scope of Claims] ■(1) Eboshi resin, (2) A curing agent which is a phenol resin or a mixture of this and an acid anhydride, (3) Tertiary alkalins, trialnols, and A composition comprising as essential components at least 411 types of curing accelerator selected from the group consisting of tritalyls, and (4) an inorganic filler, the composition comprising:
An epoxy resin composition characterized in that at least two of the components (2) and (3) are melt-mixed in advance, in whole or in part, and then cooled and pulverized. (2) The composition according to claim 1m, which further contains a flame retardant.