JPH01313519A - Epoxy resin composition, epoxy resin molding material and epoxy resin molding - Google Patents

Abstract

PURPOSE:To make it possible to obtain an epoxy resin composition which can give a cured product excellent in heat resistance and water resistance and has a low modulus and suitable as a sealing material for semiconductors by using a trisphenol compound as a curing agent. CONSTITUTION:An epoxy resin composition is formed by adding, usually, 20-120 pts.wt., desirably, 40-80 pts.wt. trisphenol compound having at least three phenolic hydroxyl groups in the molecule, represented by formula I (wherein R<1> and R<2> are each H, a 1-12C aliphatic hydrocarbon group which may have an unsaturated group, a monocyclic or fused ring aryl, or a 3-6C alicyclic hydrocarbon group which may have a halogen atom or an unsaturated bond), e.g., 1-[alpha- methyl-alpha-(4-hydroxyphenyl)ethyl]-4-[alpha,alpha-bis(4-hydroxypheny l)ethyl]benzene, as a curing agent to 100 pts.wt. epoxy resin (of an epoxy equivalent of 170-5000) especially of bisphenol A, AD or F type.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to an epoxy resin composition, an epoxy resin molding material obtained by semi-curing the composition, and an epoxy resin molding obtained by curing them.

More specifically, we will focus on epoxy resin compositions and epoxy resin molding materials that have excellent properties such as heat resistance and water resistance when cured, and have a low elastic modulus and are suitable for use as encapsulating materials for semiconductors, etc. This invention relates to an epoxy resin molded body.

<Conventional technology> Epoxy resin molding materials using various epoxy resins and novolac-type phenolic resins have excellent heat resistance, adhesion, and moisture resistance (
Due to its excellent water resistance, it is frequently used as a sealing material for semiconductors, etc.

However, in recent years, as the degree of integration of semiconductors has increased, the chip size has increased, causing problems such as cracks in the sealing material and breakage of bonding ears due to dimensional changes at high temperatures.

In order to solve these problems, polybutadiene, silicone rubber, etc. are added to the molding material to prevent cracks in the sealing material.
Attempts have been made to try to prevent bonding wire breakage from occurring.

However, resin molding materials to which such polybutadiene, silicone rubber, etc. are added have a low glass transition temperature and a decrease in heat resistance.

<Problems to be Solved by the Invention> An object of the present invention is to provide excellent heat resistance and moisture resistance, and when used as a encapsulating material for semiconductors, etc., the crank of the encapsulating material and the bonding wire can be maintained even when used at high temperatures. An object of the present invention is to provide an epoxy resin composition, an epoxy resin molding material, and an epoxy resin molded product obtained by curing them, which do not cause wire breakage or the like.

Means for Solving the Problems> The present inventors have conducted extensive studies in order to achieve the above object. As a result, when a specified trisphenol compound having three phenolic hydroxyl groups in the molecule is used as a curing agent for epoxy resin, thermal properties such as heat resistance can be improved without impairing the excellent properties of epoxy resin. We have discovered that this is possible, and have arrived at the present invention.

That is, the present invention is based on the following general formula [I1 formula [I] (in the above formula [I], R1 and R2 are each a hydrogen atom, an aliphatic compound having 1 to 12 carbon atoms and optionally having an unsaturated bond) Represents a hydrocarbon group, a monocyclic or fused ring aryl group that may have a substituent, a halogen atom, or an alicyclic hydrocarbon group that may have an unsaturated bond having 3 to 6 carbon atoms. represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 12 carbon atoms and which may have an unsaturated bond. In the above formula [I], R1 and R2 may be the same or different, and , R1 and R2 may be the same or different from each other.) An epoxy resin composition containing a trisphenol compound having three phenolic hydroxyl groups in the molecule as a curing agent. be.

Another aspect of the present invention is an epoxy resin molding material characterized in that the epoxy resin composition is semi-cured and brought into a B-stage state.

Another aspect of the present invention is an epoxy resin molded article, which is a cured product obtained by curing the epoxy resin composition or the B-stage epoxy resin molding material.

The present invention will be explained in detail below.

The epoxy resin used in the present invention may be any conventionally known epoxy resin and is not particularly limited, but is preferably a difunctional or higher functional epoxy resin, more preferably a trifunctional epoxy resin.
Preferably, it is a polyfunctional epoxy resin having more than a functional level.

Preferred examples of the epoxy resin used in the present invention are shown below, but the present invention is not limited thereto.

Phenol novolac type epoxy resin; Orthocresol type epoxy resin; Epoxy resin derived from the polyhydric phenol described below by reaction with shrimp herohydrin or the like.

1-[α-methyl-α-(4-hydroxyphenyl)ethyl]-4-[α,α-bis(4-hydroxyphenyl)ethyl]benzene; (phenolic compound A) 1-[α-methyl-α -(2-methyl-4-hydroxy-5-tert-butylphenyl)ethyl]-4-[α, α-
Bis(2-methyl-4-hydroxy-5-tertiary butylphenyl)ethyl]benzene; (phenol compound B) 1-[α-methyl-α-(3,5-dimethyl-4-hydroxyphenyl)ethyl] - 4-[α, α-bis(3
,5-dimethyl-4-hydroxyphenyl)ethyl]benzene; (phenol compound C) 1-[α-methyl-α-(3-tert-butyl-4-hydroxyphenyl)ethyl]-4-[α.

α-bis(3-tertiary butyl-4-hydroxyphenyl)
(Phenol compound D) 1-[α-methyl-α-(3-methyl-4-hydroxy-5-tertiary butylphenyl)ethyl]-4-[α, α-
Bis(3-methyl-4-hydroxy-5-tertiary butylphenyl)ethylcobenzene; (phenol compound E) 1-[α-methyl-α-(2,5-dimethyl-4-hydroxyphenyl)ethyl] -4-[α, α-bis(2
,5-dimethyl-4-hydroxyphenyl)ethyl]benzene; (phenol compound F) 1-[α-methyl-α-(3,5-dibrom-4-hydroxyphenyl)ethyl”J -4-[α,α −Bis(
3,5-dibromo-4-hydroxyphenyl)ethyl]
Benzene; (phenolic compound G) 1.1.1-tris(hydroxyphenyl)methane; (
Phenol compound H) 1.1.3-tris(hydroxyphenyl)propane:
(Phenol compound I) 1.1,2.2-tetrakis(hydroxyphenyl)ethane; (Phenol compound J) 1.1.3-tris(
2-Methyl-4-hydroxy-5-tertiary butylphenyl)butane: (phenol compound K) Among them, phenol novolak type epoxy resin, orthocresol type epoxy resin, epoxy resin derived from phenol compound A, and derived from phenol compound G. epoxy resins derived from phenolic compound I and epoxy resins derived from phenolic compound J are preferred.

In addition to the above, in the present invention, 2.2-
Bis(4-hydroxyphenol)propane (commonly known as bisphenol A), bis(4-hydroxyphenyl)
Methane (commonly known as bisphenol F), 1,1-bis(4
-Hydroxyphenyl)ethane (commonly known as bisphenol)
AD) and other bisphenols, and epichlorohydrin,
Bisphenol A type epoxy resin obtained by reaction with heroboxide such as β-methylepichlorohydrin,
Bisphenol F type epoxy resin, Bisphenol AD
Bisphenol type epoxy resins such as type epoxy resins are also suitably used.

In the present invention, among such bisphenol type epoxy resins, 1. In particular, bisphenol A type epoxy resin, bisphenol AD type epoxy resin, bisphenol F type epoxy resin, etc. are preferably used.

The epoxy equivalent of such an epoxy resin used in the present invention is usually about 170 to 5,000.

The epoxy resin composition of the present invention has the following general formula [I] Formula [I] (In the above formula [I], R' and R2 each have a hydrogen atom and an unsaturated bond having 1 to 12 carbon atoms. an aliphatic hydrocarbon group which may have a substituent, a JIL ring or a fused ring aryl group which may have a substituent, an alicyclic hydrocarbon group which may have a halogen atom or an unsaturated bond having 3 to 6 carbon atoms; represents a group. Also, R3 represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 12 carbon atoms and which may have an unsaturated bond. In addition, in the above formula [I], R' and R2 may be the same or and R1 and R2 may be the same or different from each other.) A trisphenol compound having three phenolic hydroxyl groups in the molecule is contained as a curing agent. be.

Since the epoxy resin composition and epoxy resin molding material of the present invention contain the above-mentioned curing agents, the cured molded product has excellent properties in terms of heat resistance, moisture resistance, etc. becomes.

In the above formula [I1, R' and R2 are each a hydrogen atom, an aliphatic hydrocarbon group having 1 to 12 carbon atoms which may have an unsaturated bond, and a polycyclic or fused ring which may have a substituent. aryl group, halogen atom or carbon number 3 to 6
represents an alicyclic hydrocarbon group which may have an unsaturated bond.

The aliphatic hydrocarbon group represented by R1 and R2 is an aliphatic hydrocarbon group having 1 to 12 carbon atoms, preferably 1 to 4 carbon atoms, which may have an unsaturated bond, and specifically, a methyl group. , ethyl group, tert-butyl group, n-butyl group, etc.

The aryl group represented by R1 and R2 is a monocyclic or condensed ring aryl group which may have a substituent. In this case, preferred substituents include halogen, a hydrocarbon group having 1 to 4 carbon atoms, and the like. Further, specific examples of such an aryl group include a phenyl group, a naphthyl group, and the like.

Any halogen atom can be used as the halogen atom represented by R1 and R2, but brome and chloro are particularly preferably used.

The alicyclic hydrocarbon group represented by R1 and R2 is an alicyclic hydrocarbon group which may have an unsaturated bond having 3 to 6 carbon atoms, and specifically includes a cyclopentyl group, a cyclohexyl group, etc. is exemplified.

In addition, in the above formula [i, such R1 and R2
may be the same or different, and R1 and R2
may be the same or different from each other.

In the above formula [I], R3 is a hydrogen atom or has 1 carbon number
represents an aliphatic hydrocarbon group which may have 1 to 12 unsaturated bonds.

The aliphatic hydrocarbon group represented by R3 has 1 to 12 carbon atoms.
Preferably, it is an aliphatic hydrocarbon group which may have 1 to 4 unsaturated bonds, and specific examples include a methyl group, an ethyl group, a tertiary-butyl group, and an n-butyl group.

The trisphenol compound having three phenolic hydroxyl groups in the molecule contained as a curing agent in the present invention is not particularly limited as long as it has the above structure, but specifically, , the aforementioned phenolic compounds A, C%E and G. Furthermore, the following trisphenol compounds can be mentioned.

1-[α-methyl-α-(4-hydroxyphenyl)ethyl]-3-[α,α-bis(4-hydroxyphenyl)ethyl]benzene: (phenolic compound L) 1-[α-methyl-α -(2-methyl-5-tert-butyl-4-hydroxyphenyl)ethyl]-3-[α, α-
Bis(2-methyl-5-tert-butyl-4-hydroxyphenyl)ethyl]benzene; (phenolic compound M) 1-[α-methyl-α-(3,5-dibrom-4-hydroxyphenyl)ethyl] -3-[α, α-bis(3,
5-dibromo-4-hydroxyphenyl)ethyl]benzene; (phenol compound N) υ■ Among them, phenol compounds A and G are particularly preferably used.

In the present invention, such trisphenols may be obtained by any method; for example, any method synthesized by a known method such as a method of reacting an isopropenylacetophenone compound with a phenol is applicable. It is possible. An example of such a method for synthesizing trisphenols is disclosed in Japanese Unexamined Patent Publication No. 1986-8 by the present applicant.
It is detailed in the 4035 publication.

In the epoxy resin composition of the present invention, the trisphenol compound having three phenolic hydroxyl groups in the molecule contained as a curing agent is
0 parts by weight, usually 20 to 120 parts by weight, preferably 40 to 100 parts by weight, more preferably 40 to 8 parts by weight.
Contains 0 parts by weight.

When the content of such a curing agent in the epoxy resin composition is within the above range, more favorable results are obtained in terms of heat resistance, moisture (water) resistance, etc.

In the present invention, a novolac type phenol resin may be used in combination with the trisphenol compound within a range that does not impair the effects of the present invention.

This phenolic resin is obtained by condensing phenol or alkyl-substituted tk phenols such as orthocresol, baracresol, tertiary butyl cresol, and cumylphenol with formaldehyde in the presence of an acidic catalyst, Those having a softening point in the range of 60 to 130°C, preferably 70 to 110°C are suitably used.

In addition, when flame resistance is required for the obtained epoxy resin molded body, it is preferable to use a halogenated trisphenol compound among the above-mentioned trisphenol compounds as a curing agent for the epoxy resin. In this case, the amount of the curing agent is adjusted so that the content of the halogen element in the epoxy resin composition or epoxy resin molding material obtained upon curing is, for example, 10 to 25 wt% in the case of bromine, preferably 15 to 25 wt%. Just select the type
The content of such a halogen element may be appropriately determined depending on the type of halogen element.

However, in such a case, in the present invention,
It goes without saying that an epoxy resin containing a halogen element may be used as the epoxy resin, and both may be used in combination.

In the present invention, examples of epoxy resins containing a halogen element used in such cases include tetrabromobisphenol A type epoxy resins, brominated phenol novolak type epoxy resins, and epoxy resins derived from the phenolic compound G. Ru.

The epoxy resin composition of the present invention contains a specific trisphenol compound as a curing agent. agent, mold release agent, coloring agent,
Flame retardants, coupling agents, flexibilizing agents, etc. can be added.

The curing accelerator used in the present invention includes imidazoles such as 2-methyl-4-methylimidazole, 2-phenylimidazole, and 2-ethyl-4-methylimidazoleazine; hydrazines such as dibasic acid hydrazine; Boron oxide-amine complex compound; Such a curing accelerator can be generally blended in an amount of 0.05 to 20 parts by weight, preferably 0.1 to 10 parts by weight, per 100 parts by weight of the epoxy resin.

Fillers include silica, alumina, talc, mica,
Examples include calcium bicarbonate, kaolin, diatomaceous earth, asbestos, graphite, boron, silicon carbide, carbon fiber, and glass fiber. The amount of filler used is usually 100% of the epoxy resin composition.
It can be used in a proportion of 50 to 900 parts by weight.

As a mold release agent, carnauba wax, montan wax,
Examples include ester wax, stearic acid, calcium stearate, zinc stearate, 12-hydroxystearic acid, calcium 12-hydroxystearate, and the like. Such a mold release agent can be used generally in a proportion of 0.1 to 10 parts by weight per 100 parts by weight of the epoxy resin.

Examples of the colorant include carbon black and the like. Such a coloring agent is used in epoxy resin composition 10.
It can be used in a ratio of usually 0.01 to 5 parts by weight relative to 0 parts by weight.

Examples of flame retardants include antimony oxide, etc.; halogenated polyhydric phenols such as tetrabromobisphenol A;
can be used.

Such flame retardants can generally be used in an amount of 12 to 25 parts by weight per 100 parts by weight of the epoxy resin composition.

As the coupling agent, a silane coupling agent such as γ-glycidoxytriprobyltrimethoxysilane can be used. Such a coupling agent is usually used in an amount of 0.1 to 1 per 100 parts by weight of the epoxy resin composition.
0 parts by weight, preferably 0.1 to 5 parts by weight can be used.

Furthermore, silicone resin, polybutadiene rubber, carboxyl group-terminated polybutadiene rubber, polybutadiene acrylonitrile rubber, etc. can be used as the flexibilizing agent. Such a flexibilizer is usually used in an amount of 1 to 30 parts by weight, preferably 5 parts by weight, per 100 parts by weight of the epoxy resin composition.
20 parts by weight can be used.

The epoxy resin composition of the present invention is prepared by kneading the various ingredients described above usually at a temperature of 80 to 120° C. using a twin-screw extruder or two rolls. The epoxy resin composition thus obtained is
For example, after kneading, it is cooled and pulverized to be used as various molding materials.

In addition, the method of semi-curing the epoxy resin composition thus obtained to obtain the epoxy resin molding material of the present invention, which is in a B-stage state, is different from the commonly used method of bringing an epoxy resin into a B-stage state. is also applicable.

The epoxy resin molding material thus obtained can be used as a prepreg by impregnating glass fiber or the like, or can be suitably used as a preform.

Furthermore, methods for curing the epoxy resin composition and epoxy resin molding material of the present invention to obtain the epoxy resin molded body of the present invention include methods using various molding machines, methods using pressure and heating, and other known methods. Both methods are applicable.
The epoxy resin molded product of the present invention thus obtained has excellent properties such as a high glass transition temperature, excellent heat resistance and moisture resistance, and a low elastic modulus, and is suitable for semiconductor encapsulation. It can be suitably used for molding materials such as stopper materials and laminates.

<Examples> Hereinafter, the present invention will be explained in more detail with reference to Examples. However, the present invention is not limited to this.

Example 1 According to the following recipe, each ingredient was rolled using two wooden rolls.
The mixture was kneaded for 5 minutes at a temperature of 0.degree. C., and then cooled and ground to obtain a molding material.

[Multiple formulation] Orthocresol novolac type epoxy resin (epoxy equivalent: 188) 10 parts by weight 1-[α-methyl-α-(4-hydroxyphenyl)ethyl]-4-[α
, α-bis(4-hydroxyphenyl)ethyl]benzene 61 parts by weight 2-ethyl-4-methyl-imidazoleazine (hardening accelerator) 2 parts by weight amorphous silica
495 parts by weight Carbon black 1 part by weight Silane coupling agent (KBM-403, manufactured by Shin-Etsu Chemical ■) 2.5 parts by weight Carnauba wax 2 parts by weight This molding material was molded using a transfer molding machine at 70 kg/cm', It was molded for 5 minutes at 160° C. to produce a 4 mm thick sheet.

This sheet was then heated at 160°C for 8 hours and then at 200°C.
Bost cured for 2 hours to prepare a test piece based on JISK 6911. Regarding this test piece, its bending strength, bending elastic modulus, and glass transition temperature were measured using a differential scanning calorimeter (DSC) in accordance with JIS K6911.

The results are shown in Table 1.

Example 2 Instead of 100 parts by weight of orthocresol novolac type epoxy resin, 1-[α-methyl-α-(4-hydroxyphenyl)ethyl]-4-[α,α-bis(4-hydroxyphenyl)ethyl] Epoxy resin prepared by reaction of benzene and epichlorohydrin (epoxy equivalent weight 210) 10
Using 0 parts by weight, the content of 1-[α-methyl-α-(4-hydroxyphenyl)ethyl]-4-[α,α-bis(4-hydroxyphenyl)ethyl]benzene was increased from 61 parts by weight to 63 parts by weight. After molding and curing, test pieces were prepared in the same manner as in Example 1, except that the parts by weight were changed, and various things such as bending strength were measured in the same manner as in Example 1.

The results are shown in Table 1.

Example 3 Instead of 100 parts by weight of orthocresol novolac type epoxy resin, 1.1.3-tris(2-methyl-4-hydroxy-5
- epoxy resin prepared by the reaction of tertiary butylphenyl)butane with epichlorohydrin (epoxy equivalent weight 2
74) Using 100 parts by weight, the content of 1-[α-methyl-α-(4-hydroxyphenyl)ethyl]-4-[α,α-bis(4-hydroxyphenyl)ethylcobenzene was reduced to 61 parts by weight. After molding and curing, test piece materials were prepared in the same manner as in Example 1, except that 48 parts by weight was changed, and various physical properties such as bending strength were measured in the same manner as in Example 1.

The results are shown in Table 1.

Comparative Example 1 Instead of 61 parts by weight of 1-[α-methyl-α-(4-hydroxyphenyl)ethyl]-4-[α,α-bis(4-hydroxyphenyl)ethyl]benzene, a softening point of 97
After molding and curing, test pieces were prepared in the same manner as in Example 1, except that 45 parts by weight of novolac type phenol at 45° C. were used, and various physical properties such as bending strength were measured in the same manner as in Example 1.

The results are shown in Table 1.

Table 1 <Effects of the invention> The uninvented epoxy resin composition and epoxy resin molding material have high heat resistance (glass transition temperature) when cured;
A cured product with a low elastic modulus is obtained.

Furthermore, since the epoxy resin molded article of the present invention is obtained by curing the above-mentioned epoxy resin composition and epoxy resin molding material, it also has high heat resistance (glass transition temperature),
It has an excellent property of low elastic modulus.

Therefore, the epoxy resin composition of the present invention is very useful when used in fields that require high reliability at high temperatures, such as semiconductor encapsulation materials.

Claims (3)

[Claims] (1) The following general formula [I] Formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. an aliphatic hydrocarbon group which may have an unsaturated bond, a monocyclic or fused ring aryl group which may have a substituent, a halogen atom, or an unsaturated bond having 3 to 6 carbon atoms. represents a good alicyclic hydrocarbon group. R^3 represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 12 carbon atoms and which may have an unsaturated bond. In addition, in the above formula [I] , R^1 and R^2 may be the same or different, and R^1 and R^2 may be the same or different from each other, respectively. An epoxy resin composition comprising a trisphenol compound having a hydroxyl group as a curing agent. (2) An epoxy resin molding material characterized by semi-curing the epoxy resin composition according to claim 1 to bring it into a B-stage state. (3) An epoxy resin molded article, which is a cured product obtained by curing the epoxy resin composition according to claim 1 or the epoxy resin molding material according to claim 2.