JPH11256010A - Epoxy resin composition and manufacturing method - Google Patents

Abstract

(57) [Problem] To provide an epoxy resin composition having a low melting viscosity, a high softening point, and hardly causing blocking during storage, and a method for producing the same. A (A) crystalline epoxy resin having two epoxy groups in one molecule and (B) a polyfunctional and amorphous trisphenolmethane type epoxy resin having three or more epoxy groups in one molecule are provided. An epoxy resin composition as an essential component, wherein all or a part of the epoxy resin (A) is dispersed as microcrystals in the epoxy resin (B), and a method for producing the same. .

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxy resin composition useful for sealing electric and electronic materials such as adhesives, paints, insulating materials and laminates, and particularly for sealing electronic parts.

[0002]

2. Description of the Related Art In recent years, for molding semiconductors such as LSIs, ICs, and transistors, transfer molding of an economically useful epoxy resin composition has been performed. recently,
In particular, for the purpose of obtaining low moisture absorption of a package, a low-viscosity epoxy resin capable of filling a filler at a high density is desired. This resin requires a high softening point from the viewpoint of handleability. However, amorphous epoxy resins having a low melt viscosity generally have a low softening point and cause blocking during storage,
There was a problem that workability was reduced. In addition, there is a problem that the production efficiency is low and the economy is not economical because cooling is performed by using a cool box or the like during storage.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has as its object to provide an epoxy resin composition which has a low melting viscosity, a high softening point, and is hardly blocked during storage. An object of the present invention is to provide a product and a method of manufacturing the same.

[0004]

Means for Solving the Problems As a result of intensive studies, the present inventor has found that a system using a specific epoxy compound is suitable for the above object, and has reached the present invention. That is, the present invention is as follows. (1) Essentially (A) a crystalline epoxy resin having two epoxy groups in one molecule and (B) a polyfunctional and amorphous trisphenolmethane type epoxy resin having three or more epoxy groups in one molecule An epoxy resin composition as a component, wherein all or a part of the epoxy resin (A) is dispersed as microcrystals in the epoxy resin (B). (2) (A) The epoxy resin composition according to (1), wherein the crystalline epoxy resin having two epoxy groups in one molecule is represented by the following general formula (1).

[0005]

Embedded image (However, X is -N = N-, -CH = CH-, -OC.
O -, - CH = C ( CH 3) -, - CH = C (CN) -,
Represents a group or a single bond selected from —C≡C— and —CH = CH—CO—, and R _{1 to} R ₈ each independently represent a chain or cyclic alkyl group having 1 to 6 carbon atoms, a hydrogen atom or a halogen atom. Indicates an atom. (3) (A) a crystalline epoxy resin having two epoxy groups in one molecule and (B) a polyfunctional and amorphous trisphenolmethane type epoxy resin having three or more epoxy groups in one molecule. (1) The method for producing an epoxy resin composition according to (1) or (2), wherein the mixture is heated and mixed at a temperature not higher than the melting point of the former and not lower than the softening point of the latter. (4) (A) a crystalline epoxy resin having two epoxy groups in one molecule and (B) a polyfunctional and amorphous trisphenolmethane type epoxy resin having three or more epoxy groups in one molecule, It is characterized by mixing at a temperature not lower than the former melting point and at a temperature not lower than the softening point of the latter, then cooling the resulting mixture to a temperature lower than the melting point of the former to precipitate the crystals, and then kneading ( The method for producing the epoxy resin composition according to 1) or (2). (5) (A) a crystalline epoxy resin having two epoxy groups in one molecule and (B) a polyfunctional and amorphous trisphenolmethane type epoxy resin having three or more epoxy groups in one molecule, (1) or (2), wherein the mixture is mixed at a temperature not lower than the melting point of the former and at a temperature not lower than the softening point of the latter, and then the resulting mixture is kneaded while being cooled at a temperature not higher than the melting point of the former. A method for producing an epoxy resin composition.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is to disperse an epoxy resin having two epoxy groups in one molecule in a polyfunctional epoxy resin having three or more epoxy groups in one molecule to obtain a low melt viscosity and It is intended to provide a resin having a high softening point. At this time, a part or all of the bifunctional epoxy resin must be dispersed in the polyfunctional epoxy resin. The dispersion state is not particularly limited as long as the softening point of the composition is equal to or higher than the desired temperature and there is no unevenness in performance, but the dispersion state is preferably uniform. Also,
The domain size of the bifunctional epoxy resin is preferably 1
It is at most 00 μm, more preferably at most 50 μm. If the domain is larger than this, unevenness occurs in the performance, or the mixing property of the bifunctional epoxy resin and the polyfunctional epoxy resin is reduced at the time of molding and curing, resulting in poor molding. In particular, when a crystalline epoxy resin is used as the bifunctional epoxy resin and an amorphous epoxy resin is used as the polyfunctional epoxy resin, the effects of the present invention are more significantly exhibited. In this case, the domains of the bifunctional epoxy resin formed in the polyfunctional epoxy resin are composed of microcrystals of the bifunctional epoxy resin.

The method for producing the epoxy resin composition of the present invention is not particularly limited as long as all or a part of the bifunctional epoxy resin is dispersed in the polyfunctional epoxy resin. And a method of mixing using a solvent. Among them, the former method is preferable from a practical point of view. Hereinafter, the former method will be described in detail. In order to obtain the epoxy resin composition of the present invention by melt mixing, the composition of the composition and the temperature during mixing are important. Regarding the composition, the bifunctional epoxy resin is 0.1% by weight or more of the whole,
Preferably at least 0.5% by weight, more preferably at least 1.0% by weight.
It is preferred that the content be at least 10% by weight. Below this,
The effect of reducing the viscosity of the entire resin is low, and there is a possibility that it may be difficult to make all or part of the bifunctional epoxy resin dispersed in the polyfunctional epoxy resin. The melt viscosity (ICI viscosity) at 150 ° C. of the resin composition of the present invention is 2.0 (P) or less, preferably 1.5 (P).
It is desirable that: It is desirable that the softening point is 40 ° C. or higher, preferably 50 ° C. or higher. When a crystalline epoxy resin is used as the bifunctional epoxy resin,
Since the precipitation of crystals can be utilized, domains can be formed more stably than in the case where the bifunctional epoxy resin is amorphous, and the softening point of the composition is maintained or improved and the melt viscosity is reduced. The effect is great.

As for the mixing temperature, there is firstly a method of heating and mixing at a temperature higher than the melting temperature of the polyfunctional epoxy resin and lower than the melting temperature of the bifunctional epoxy resin. According to this method, the mixing temperature is set at a value one more than the melting temperature of the bifunctional epoxy resin.
It is preferable that the temperature is lower by about 0 ° C. to 30 ° C. If the temperature is higher than this, the ratio of the bifunctional epoxy resin existing as a domain in the polyfunctional epoxy resin becomes low, which is not preferable. If the temperature is lower than this, a large amount of energy is required for kneading, which is industrially disadvantageous. Here, the melting temperature is a melting point in the case of a crystalline epoxy resin, and is a softening point in the case of an amorphous epoxy resin.

In particular, when a crystalline epoxy resin is used as the bifunctional epoxy resin, the following method utilizing the precipitation of crystals can be used. After adjusting the kneading temperature to a temperature higher than the melting point of the crystalline epoxy resin and preparing a resin composition having a uniform phase structure in which the amorphous epoxy resin and the crystalline epoxy resin are compatible, the amorphous epoxy resin is again formed. May be kneaded at a temperature equal to or higher than the softening point of the crystalline epoxy resin and at a temperature equal to or lower than the melting point of the crystalline epoxy resin to uniformly disperse the microcrystals of the crystalline epoxy resin in the amorphous epoxy resin. This temperature may be equal to or higher than the softening point of the amorphous epoxy resin, but in general, a part of the crystalline epoxy resin remains dissolved in the amorphous epoxy resin, Since the softening point of the resin may decrease, it is preferable to determine the temperature at which crystals are deposited and dispersed near the softening point depending on the situation. The timing of kneading may be kneading after cooling the melted composition to a temperature below the melting point of the crystalline epoxy resin, or kneading while cooling at a temperature below the melting point. For these production methods, a mixing mixer, a two-roller, an extruder or the like is used. Further, the dispersion state of the domains in the resin composition of the present invention can be visually observed, but preferably observation by an electron microscope is used. When the domain is composed of microcrystals, DSC measurement is a useful means in addition to observation using a polarizing microscope.

The component (A) used in the present invention is a bifunctional epoxy resin, and is not particularly limited as long as it is dispersed in the polyfunctional epoxy resin and reduces the melt viscosity without lowering the softening point. It is preferable to use a crystalline epoxy resin having two epoxy groups in one molecule and having a mesogen skeleton or a bisphenol skeleton and having a low molecular weight. Specific examples of such a crystalline epoxy resin include those having a mesogen skeleton represented by the general formula (1). Specifically, 2,2'-dihydroxy-3,3 ', 5,5'-tetramethylstilbene, 4,4'-dihydroxy-3,3', 5,5'-tetramethylstilbene,
4,4'-dihydroxy-3,3'-di-t-butyl-5,5'-dimethylstilbene, 4,4'-dihydroxy-3,3'-di-t-butyl-6,6'-dimethyl Stilbene, 2,2'-dihydroxy
-3,3'-di-t-butyl-6,6'-dimethylstilbene, 2,
4'-dihydroxy-3,3'-di-t-butyl-6,6'-dimethylstilbene, 3-t-butyl-4,4'-dihydroxy-3,5,5 '
-Trimethylstilbene, 3-t-butyl-2,4'-dihydroxy-3 ', 5', 6-trimethylstilbene, 3-t-butyl-
Glycidyl ethers such as 4,4'-dihydroxy-3 ', 5', 6-trimethylstilbene and biphenol 2,2 ', 4,4'-tetramethylbiphenol are exemplified. These epoxy resins may be a mixture of two or more.
Further, these melting points are 80 to 15 from the viewpoint of handleability.
Preferably it is 0 ° C. In addition, 2,5-di-t-
It is also a useful technique to use glycidyl ethers of hydroquinones such as butyl hydroquinone diglycidyl ether and glycidyl ether of terephthalic acid.

The epoxy resin (B) used in the present invention is not particularly limited as long as it is a polyfunctional trisphenolmethane type epoxy resin having three or more epoxy groups in one molecule, but is preferably a solid at room temperature. And softening point is 1
It is not more than 00 ° C. To illustrate these,
A glycidyl ether compound derived from a reaction product of a phenol such as phenol, o-cresol, and catechol, or a naphthol such as hydroxynaphthalene and dihydroxynaphthalene and an aromatic carbonyl compound such as hydroxybenzaldehyde, a trisphenolmethane compound. . More specifically, it is derived from trivalent or higher phenols such as trishydroxyphenylmethane, 1,1,1-trishydroxyphenylethane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane. And glycidyl ether compounds.

The epoxy resin composition of the present invention contains known epoxy resin curing agents, curing accelerators, fillers such as silica, alumina, titanium white, alumina hydroxide, talc, clay, glass fiber, natural wax, and synthetic wax. A releasing agent such as higher fatty acids and metal salts thereof, or a paraffin or a coloring agent such as carbon black, and a surface treating agent such as a silane coupling agent may be added. The epoxy resin composition of the present invention is used for sealing electrical and electronic materials such as adhesives, paints, insulating materials and laminates, especially electronic components.

[0013]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to these examples. The softening point is measured by JI
The measurement was performed by the ring and ball method according to SK7234. Synthesis Example 1 195.5 g (0.16 mol) of 2,6-xylenol (hereinafter abbreviated as 26XY) and 65.7 g (0.4 mo) of 2-t-butyl-5-methylphenol were placed in a flask.
l), 174.4% aqueous chloroacetaldehyde solution 174.4
g (1.0 mol). H. Siebe, Liebi
gs, Ann. Chem. , 730, 31 (1969)
Stilbene bisphenol (yellow crystals 2)
08g). Next, this stilbene bisphenol was subjected to epoxidation according to the method of Japanese Patent Publication No. Hei 7-91360 to obtain an intended product. Its melting point is 110-130
C., epoxy equivalent was 208 g / eq, and hydrolyzable chlorine was 170 ppm. The melt viscosity was 0.1 poise at 150 ° C. This epoxy resin is referred to as an epoxy resin.

Example 1 An epoxy resin and an amorphous epoxy resin, a trisphenol methane novolak type epoxy resin (trade name: TMH574, manufactured by Sumitomo Chemical Co., Ltd .; hereinafter, referred to as an epoxy resin), as a crystalline epoxy resin, are shown in Table 1. And melt-mixed at 150 ° C. in a beaker to obtain a uniform resin composition. Subsequently, this mixture was stirred on a hot plate heated to 80 ° C. to obtain an opaque resin composition. As a result of DSC measurement (10 ° C./min) of this composition, an endothermic peak was observed, and it was confirmed that the epoxy resin in the epoxy resin was present as a crystalline phase.
Further, when the crystallization ratio of the epoxy resin was calculated, it was found that 63% of the added amount was present as a crystal phase.
The ICI viscosity (＠ 150 ° C.) and softening point of this resin composition were measured and are shown in Table 1. As a result, it was found that the viscosity of the composition can be reduced without lowering the softening point.

Example 2 An epoxy resin and a trisphenol methane novolak type epoxy resin (hereinafter referred to as an epoxy resin) starting from a mixture of salicylaldehyde and phenol as an amorphous epoxy resin were mixed at a ratio shown in Table 1. The mixture was melted and mixed at 150 ° C. in a beaker to obtain a uniform resin composition. Subsequently, the mixture was stirred on a hot plate heated to 50 ° C. to obtain an opaque resin composition. The ICI viscosity (＠ 150 ° C.) and softening point of this resin composition were measured and are shown in Table 1. As a result, by using this method, the viscosity of the resin composition was reduced, and at the same time, the softening point was significantly increased.

Example 3 An epoxy resin synthesized from dihydroxytetramethylbiphenyl (hereinafter referred to as "epoxy resin") as a crystalline epoxy resin and an epoxy resin were mixed in the proportions shown in Table 1, and melted and mixed at 150 ° C. in a beaker. A resin composition was obtained. Subsequently, the mixture was stirred on a hot plate heated to 70 ° C. to obtain an opaque resin composition. The ICI viscosity (＠ 150 ° C.) and softening point of this resin composition were measured and are shown in Table 1. As a result, it was found that the viscosity of the composition could be reduced.

Comparative Example 1 The ICI viscosity (＠ 150 ° C.) and softening point of an epoxy resin were measured, and the results are shown in Table 1.

Comparative Example 2 The ICI viscosity (＠ 150 ° C.) and softening point of the epoxy resin were measured and are shown in Table 1.

Comparative Example 3 An epoxy resin and an epoxy resin were mixed at a ratio shown in Table 1, and melted and mixed at 150 ° C. in a beaker to obtain a uniform resin composition. Subsequently, the mixture was quenched to obtain a transparent resin composition in which the amorphous epoxy resin and the crystalline epoxy resin were visually compatible. The ICI viscosity of this resin composition (# 1
(50 ° C.) and the softening point were measured and are shown in Table 1. As a result, it was found that the softening point was greatly reduced.

[0020]

[Table 1]

[0021]

The epoxy resin composition of the present invention satisfies a high softening point while having a low melt viscosity. It can be significantly improved.

Claims (5)

[Claims] 1. A (A) crystalline epoxy resin having two epoxy groups in one molecule and (B) a polyfunctional and amorphous trisphenolmethane type epoxy resin having three or more epoxy groups in one molecule. An epoxy resin composition comprising (A) an epoxy resin composition, wherein all or a part of the epoxy resin (A) is dispersed as microcrystals in the epoxy resin (B). 2. The epoxy resin composition according to claim 1, wherein the crystalline epoxy resin (A) having two epoxy groups in one molecule is represented by the following general formula (1). Embedded image (However, X is -N = N-, -CH = CH-, -OC.
O -, - CH = C ( CH 3) -, - CH = C (CN) -,
Represents a group or a single bond selected from —C≡C— and —CH = CH—CO—, and R _{1 to} R ₈ each independently represent a chain or cyclic alkyl group having 1 to 6 carbon atoms, a hydrogen atom or a halogen atom. Indicates an atom. ) 3. A (A) crystalline epoxy resin having two epoxy groups in one molecule and (B) a polyfunctional amorphous trisphenolmethane type epoxy resin having three or more epoxy groups in one molecule. 3. The method for producing an epoxy resin composition according to claim 1, wherein the mixture is heated and mixed at a temperature lower than the melting point of the former and higher than the softening point of the latter. 4. A (A) crystalline epoxy resin having two epoxy groups in one molecule, and (B) a polyfunctional, amorphous trisphenolmethane-type epoxy resin having three or more epoxy groups in one molecule. Are mixed at a temperature equal to or higher than the melting point of the former, and at a temperature equal to or higher than the softening point of the latter, and then the resulting mixture is cooled to a temperature equal to or lower than the melting point of the former to precipitate the crystals, and then kneaded. Claim 1 or 2
A method for producing the epoxy resin composition as described above. 5. A (A) crystalline epoxy resin having two epoxy groups in one molecule and (B) a polyfunctional amorphous trisphenolmethane type epoxy resin having three or more epoxy groups in one molecule. Is mixed at a temperature equal to or higher than the melting point of the former and at a temperature equal to or higher than the softening point of the latter, and then the resulting mixture is kneaded while being cooled at a temperature equal to or lower than the melting point of the former. A method for producing an epoxy resin composition.