JP3414487B2 - Epoxy resin composition, cured product thereof, and semiconductor device - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention provides a β-naphthol aralkyl resin having a low melt viscosity by forming a mixture of a p-xylylene group and an o- and / or m-xylylene group as a linking group moiety. Epoxy resin composition used as a curing agent, which is excellent in heat resistance, moisture resistance, mechanical performance, oxidation resistance, and the like, and has excellent melt fluidity, a cured product thereof, and a semiconductor device encapsulated by the cured product It is about.

[0002]

2. Description of the Related Art Heretofore, phenol resins have been industrially used as matrix resins and various molding materials as an inexpensive material having an excellent performance balance. However, in recent years, the required performance has become more advanced with the development of each industrial field, and it is the current situation that it is difficult for the conventional phenol resin to meet the required performance. For example, in the field of IC encapsulants, conventionally, a method of encapsulating an element using an epoxy resin composition has been widely used.
Further, a phenol resin is used as a curing agent.

In recent years, the load on the encapsulant has increased due to the increase in the size of the device and the increase in the amount of heat generated due to the high integration of ICs, while technically the demand for the package is higher in order to increase the packaging density. It is required to be small and thin. In addition, recently, the mounting method has changed, and the conventional method of soldering from the back of the wiring board has changed to the method of dipping in a molten solder bath or IR reflow. It is becoming exposed to high temperatures. Therefore, a resin having excellent heat resistance is required. In addition, the moisture absorbed in the resin is suddenly evaporated at a high temperature,
There is a serious problem regarding the quality and reliability of the product itself, such as expansion, cracks in the package, and deformation of the bonding wire. As described above, the performance required for the encapsulant is at a high level, and particularly in the heat resistance and the moisture resistance, the required level is remarkably improved.

Therefore, the phenol novolac resin, which has been most widely used as a curing agent for epoxy resins for such applications, is strongly required to have a higher level in each performance, and the improvement of its moisture resistance is a major issue. Are under consideration. For example, in recent years, a phenol aralkyl resin represented by the general formula (5) (Chemical Formula 3) having a xylylene bridge instead of a methylene bridge of a novolak resin (Japanese Patent Application Laid-Open No. 59-105018, Japanese Patent Publication No. 62-2816).
5) and a naphthol aralkyl resin represented by the general formula (6) (Chemical Formula 3) (Japanese Patent Laid-Open No. 3-90075).

[0005]

[Chemical 3] (In the above formula, m represents an integer of 0 to 100 and n represents an integer of 0 to 15)

Since each of these has a p-xylylene group as a linking group, the density of hydroxyl groups is smaller than that of the novolac resin, and therefore the moisture absorption rate is greatly reduced. However, in the phenol aralkyl resin, the crosslink density is reduced as the hydroxyl group density is reduced, which causes a problem that the heat resistance such as glass transition temperature is reduced. On the other hand, regarding the naphthol aralkyl resin, the water absorption rate is further lower than that of the phenol aralkyl resin, and the lowering of the heat resistance is suppressed by the presence of the naphthalene skeleton, and a high level of physical properties has been achieved.

Further, for example, as the performance required for the matrix resin used as the sealing material, in addition to various performances such as heat resistance and mechanical properties, the softening point and low melt viscosity of the resin are required. There is. With respect to the softening point, it is required to be 100 ° C. or lower at which melt kneading is possible at the time of compounding. Regarding the melt viscosity, we aim to improve the filling rate of the filler from the viewpoints of cost and physical properties. By increasing the melt fluidity as a compound, insufficient filling during mounting, bonding by compound pressure during resin sealing From the viewpoint of preventing deformation of the wire, it is required that the melt viscosity is low, specifically 5 poise or less, more preferably 3 poise or less, ideally 2 poise or less in ICI melt viscosity at 150 ° C. . However, the above-mentioned naphthol aralkyl resin is excellent in heat resistance, moisture resistance, and other mechanical performance, but has a drawback that the melt viscosity is high. Therefore, as described above, during resin encapsulation, the bonding wire is deformed or cut by the load, or the product retention is reduced due to insufficient filling, and the filling rate of the filler cannot be increased. There are problems such as physical and cost disadvantages.

By the way, since the α-naphthol aralkyl resin gives a resin having a lower melt viscosity than the β-naphthol aralkyl resin, it is a general curing catalyst for epoxy resins, although it does not have the problems mentioned above. There is a fatal defect that triphenylphosphine (TPP) is oxidized by contact with α-naphthol aralkyl resin to become triphenylphosphine oxide (TPPO), and the catalytic ability is lost. This phenomenon was not observed in the β-naphthol aralkyl resin, and is presumed to be due to the difference in the bonding positions of the hydroxyl group and the linking group with respect to the naphthalene ring (Japanese Patent Application No. 6-1121). This means that when an α-naphthol aralkyl resin is used as a curing agent for an epoxy resin, the composition loses its curing ability over time, so that it is very difficult to store it, and practical use thereof is difficult. It shows that it is difficult. Therefore, when the α-naphthol resin is used as a curing agent for epoxy resin, a curing catalyst other than TPP is required, and the range of applications is substantially limited. Also, Japanese Patent Laid-Open No. 3-90075.
The naphthol aralkyl resins found in the above are not p-xylylene compounds in the general formula, but the examples are all p-xylylene compounds. In the specification, o- or m-xylylene group was introduced. There is no description about the physical properties of naphthol aralkyl resin.

[0009]

As described above, the problem to be solved by the present invention is to provide an epoxy resin composition satisfying the recent demands in the electric and electronic fields, and an epoxy resin cured product exhibiting excellent performance. Another object of the present invention is to provide a semiconductor device sealed with the cured product. Specifically, without lowering the excellent characteristics of β-naphthol aralkyl resin such as heat resistance and moisture resistance described above, by lowering the melt viscosity, a material more suitable for semiconductor encapsulant applications can be obtained. Is.

[0010]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that in a β-naphthol aralkyl resin, the linking group component in the resin is a p-form, an o- and / or a Alternatively, the melt viscosity can be lowered without lowering various physical properties by forming a mixture with the m-body in a fixed ratio, and the obtained low melt viscosity β-naphthol aralkyl resin is used as a semiconductor encapsulating material. The present invention has been completed by finding that it is useful as. That is, the present invention is an epoxy resin composition,
A) Epoxy resin as the main agent, an epoxy resin having two or more epoxy groups in one molecule, B) As a curing agent, 1) β
-Naphthol (N component), 2) p-xylylene compound represented by general formula (1) (formula 4) (X-1 component) 3) o- represented by general formula (2) (formula 4), and / Or the three components of the m-xylylene compound (X-2 component), N / [ (X
-1) + (X-2)] = 2 to 10, (X-1) / (X-
2) = 15 obtained by co-condensing in a molar ratio of 1 to 20,
Β-ICI melt viscosity at 0 ° C is 5 poise or less
The present invention relates to an epoxy resin composition containing a naphthol aralkyl resin.

[0011]

[Chemical 4] (In the above formula, R ₁ and R ₂ represent a halogen atom, a hydroxyl group or a lower alkoxy group having 1 to 4 carbon atoms)

In the present invention, the epoxy resin which has two or more epoxy groups in one molecule, which is the main component of the epoxy resin, is a) o-cresol novolac type epoxy resin,
b) an epoxy resin derived from a biphenol represented by the general formula (3) (Chemical formula 5), c) an epoxy resin derived from a spirobiindane bisphenol represented by a general formula (4) (Chemical formula 5) The present invention relates to the epoxy resin composition containing at least one kind.

[0013]

[Chemical 5] (In the above formula, R ₃ represents a hydrogen atom or a methyl group) Furthermore, the present invention provides the above epoxy resin composition,
50% to 92% by weight of inorganic and / or total weight
Alternatively, the present invention relates to an epoxy resin composition for semiconductor encapsulation containing an organic filler, a cured product of these epoxy resin compositions, and a semiconductor device encapsulated with the cured product of the epoxy resin composition for semiconductor encapsulation. is there.

The present invention provides a curing agent for epoxy resin,
Originally, by making the linking group component of β-naphthol aralkyl resin, which exhibits excellent performance in heat resistance, moisture resistance, mechanical performance, etc., a mixture of regioisomers of a certain specific composition, the melt viscosity was significantly reduced. That when used as a curing agent for epoxy resin, heat resistance, moisture resistance, and mechanical performance are not impaired as compared with those linked by p-xylylene group alone, It is based on the finding that an epoxy resin composition having excellent melt fluidity can be obtained.

In the epoxy resin composition of the present invention, β-oxy- and / or m-xylylene group is introduced into the p-xylylene group as a linking group in a certain specific range so as to have a low melt viscosity. Since it is characterized by using a naphthol aralkyl resin as a curing agent, it has excellent melt flowability in addition to various performances, so it has excellent moldability and can increase the filling rate of the filler. . Therefore, it is useful in applications such as casting, lamination, molding, adhesion, sealing, and composite materials, and is particularly preferable in use as a sealing material for semiconductor integrated circuits (ICs).

Next, a method for producing the low melt viscosity β-naphthol aralkyl resin used in the present invention will be described. Among the xylylene components to be condensed with β-naphthol, the compound serving as a p-xylylene source is an aralkyl compound having a structure represented by the general formula (1),
R ₁ is a chlorine atom, a bromine atom, a fluorine atom, a halogen atom such as an iodine atom, a hydroxyl group, and an alkoxy group having 1 to 4 carbon atoms. Specifically, α, α′-dichloro-p-xylene, α, α′-difluoro-p-xylene, α, α′-
Dibromo-p-xylene, α, α′-diiodo-p-xylene, α, α′-dimethoxy-p-xylene, α,
α'-diethoxy-p-xylene, α, α'-diisopropoxy-p-xylene, α, α'-di-n-propoxy-p-xylene, α, α'-di-n-butoxy-p-
Xylene, α, α′-di-sec-butoxy-p-xylene, α, α′-diisobutoxy-p-xylene, α,
α′-dihydroxy-p-xylene and the like can be mentioned, among which α, α′-dimethoxy-p-xylene and
It is α, α′-dichloro-p-xylene.

The o- and / or m-xylylene component to be co-condensed is an aralkyl compound having a structure represented by the general formula (2), and R ₂ is a chlorine atom, a bromine atom, a fluorine atom, an iodine atom or the like. Is a halogen atom, a hydroxyl group, or an alkoxy group having 1 to 4 carbon atoms. Specifically, α, α '
-Dichloro-o-xylene, α, α'-difluoro-o
-Xylene, α, α'-dibromo-o-xylene, α,
α'-diiodo-o-xylene, α, α'-dimethoxy-o-xylene, α, α'-diethoxy-o-xylene, α, α'-diisopropoxy-o-xylene, α,
α'-di-n-propoxy-o-xylene, α, α'-
Di-n-butoxy-o-xylene, α, α′-di-se
c-butoxy-o-xylene, α, α′-diisobutoxy-o-xylene, α, α′-dihydroxy-o-xylene, α, α′-dichloro-m-xylene, α, α′-
Difluoro-m-xylene, α, α′-dibromo-m-
Xylene, α, α′-diiodo-m-xylene, α,
α'-dimethoxy-m-xylene, α, α'-diethoxy-m-xylene, α, α'-diisopropoxy-m-
Xylene, α, α′-di-n-propoxy-m-xylene, α, α′-di-n-butoxy-m-xylene, α,
α'-di-sec-butoxy-m-xylene, α, α'-
Examples thereof include diisobutoxy-m-xylene, α, α′-dihydroxy-m-xylene, and among them, α, α
Examples include α'-dimethoxy-o-xylene, α, α'-dichloro-o-xylene, α, α'-dimethoxy-m-xylene, α, α'-dichloro-m-xylene.

The low melt viscosity β-used in the present invention
The specific method for producing naphthol aralkyl resin is
β-naphthol and p-xylylene compounds, o- and / or
Alternatively, an m-xylylene compound is reacted with an acid catalyst. Examples of the acid catalyst include inorganic acids such as hydrochloric acid, phosphoric acid, sulfuric acid or nitric acid, or Friedel-Crafts catalysts such as zinc chloride, stannic chloride, aluminum chloride and ferric chloride, p-toluene. Examples thereof include organic acids such as sulfonic acid and methanesulfonic acid, superfluoroacids such as trifluoromethanesulfonic acid, and Nafion H (trade name: manufactured by DuPont). These acids may be used alone or in combination. In addition, activated clay, solid acid catalysts of zeolites and heteropolyacids can also be used. When the xylylene compound used in the reaction is xylylene dichloride, hydrochloric acid produced by the reaction can be used as a catalyst.

Low melt viscosity β-used in the present invention
Naphthol aralkyl resin is β-
Naphthol (N component) and p-xylylene compound (X-
Resins having various molecular weights can be obtained depending on the ratio of one component) to the total amount of the o- and / or m-xylylene compound (X-2 component) (X component). That is, the molecular weight of the resin obtained increases as the N component approaches equimolar to the X component, and the molecular weight tends to decrease as the N component becomes excessive. However, the purpose of co-condensing the phenol component in the present invention is to reduce the melt viscosity of the resin, and from this viewpoint, increasing the molecular weight of the resin is against the purpose. Therefore, in the production of the β-naphthol aralkyl resin used in the present invention, it is necessary to use the N component in excess with respect to the X component. 10
Mol, preferably 2.5 to 8 mol, more preferably 3 to
The reaction is carried out in the range of 6 mol.

The reaction molar ratio between the p-xylylene compound and the o- and / or m-xylylene compound is within a range that does not impair the heat resistance of the obtained β-naphthol aralkyl resin. That is, o- and / or m-
The naphthol aralkyl resin containing a large amount of xylylene group as a linking group is inferior in heat resistance to a resin having a p-xylylene group as a linking group. P- in the present invention
The reaction molar ratio between the xylylene compound and the o- and / or m-xylylene compound is specifically X-1 / X-.
The range is 2 = 1 to 20, preferably 1.5 to 15, and more preferably 2 to 10.

The reaction temperature is 100 to 220 ° C, preferably 130 to 180 ° C, more preferably 140 to 170 ° C.
The reaction time depends on various conditions such as reaction temperature, catalyst, raw materials used, etc., but is usually 1 to 20 hours, and when reaction efficiency is taken into consideration, it is within 5 hours, more preferably within 3 hours. It is desirable to be adjusted as follows. After the reaction is completed, unreacted naphthol is vacuum distilled, steam distilled,
Distill off by any other method. The ICI melt viscosity at 150 ° C. of the resin obtained by the above method is 5 poises or less, preferably 0.1 to 3 poises.
Further, the softening point of the resin in the present invention needs to be 100 ° C. or lower at which melt kneading in compounding is substantially possible, as described above, and specifically, JIS-K-2548. The softening point by the ring and ball softening point measuring device is 35 to 100 ° C., preferably 50 to 90.
It is in the range of ° C.

The epoxy resin used in the present invention can be used as long as it has two or more epoxy groups in one molecule. For example, 2,2
-Bis (4-hydroxyphenyl) propane (bisphenol A), bis (4-hydroxyphenyl) methane (bisphenol F), bis (4-hydroxyphenyl) sulfone, 6,6'-dihydroxy-3,3,3 ', 3 '
-Tetramethyl-1,1-spirobiindane, 1,3
3, -trimethyl-1- (4-hydroxyphenyl)-
Bisphenols such as indan-6-ol, novolak resins such as phenol novolac and o-cresol novolac, phenol aralkyl resins, resorcin aralkyl resins, phenylphenol aralkyl resins, naphthol aralkyl resins and other phenol aralkyl resins, phenol-dicyclopentadiene resins , Phenolic compounds such as dihydroxynaphthalene, biphenol, 2,2 ', 6,6'-tetramethylbiphenol, amines such as bis (4-aminophenyl) methane, aniline / formalin resin, aniline aralkyl resin, etc. It is an epoxy resin obtained by reacting a compound having two or more hydrogen atoms in one molecule with epihalohydrin.

Among these, biphenol and 2, are preferred.
Epoxy resin obtained from biphenols such as 2 ', 6,6'-tetramethylbiphenol or a mixture of both,
An epoxy resin obtained from 6,6′-dihydroxy-3,3,3 ′, 3′-tetramethyl-1,1-spirobiindane, an epoxy resin obtained from o-cresol novolac, and the like. In the present invention, these epoxy resins may be used alone or in combination of two or more. When these epoxy resins are mixed and used, it is necessary to mix them so that the characteristics of each epoxy resin are exhibited, and the amount is 10 parts by weight or more, preferably 20 parts by weight to 80 parts by weight per component. is there.

In the epoxy resin composition of the present invention,
Inorganic and / or organic fillers can be used if desired. In particular, when the epoxy resin composition of the present invention is used for semiconductor encapsulation, various fillers are mixed and used. As the filler used, silica, alumina, silicon nitride, silicon carbide, talc, calcium silicate,
Examples thereof include calcium carbonate, mica, clay, titanium white, glass fiber, carbon fiber, and further aramid fiber, boron fiber, paper and the like, which are used properly according to the purpose of use and required performance. For example, a semiconductor integrated circuit (I
When used as the encapsulant for C), crystalline silica and / or fused silica is often used from the viewpoint of mechanical strength, thermal expansion coefficient, thermal conductivity, etc. of the composition obtained, From the viewpoint of fluidity, the shape is more preferably spherical or a mixture of spherical and amorphous. The blending amount of the filler is
50 to 92% by weight based on the total weight of the epoxy resin composition
Is.

Further, in the epoxy resin composition of the present invention, it is possible to mix various additives for the purpose of improving mechanical strength, heat resistance and the like. For example, as described above, the epoxy resin composition of the present invention is applied to a semiconductor integrated circuit (I
When used as the encapsulant for C), a coupling material may be used for the purpose of improving the adhesiveness between the resin component and the filler component. As such a coupling material, silane-based, titanate-based, aluminate-based, and zircoaluminate-based coupling materials can be used. Among them, the silane coupling agent is preferable, and the silane coupling agent having a functional group that reacts with the epoxy resin is particularly preferable.

Examples of such silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, N- (2-aminomethyl) -3-aminopropylmethyldimethoxysilane, and N- (2-aminoethyl). )
-3-Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-anilinopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like. These coupling materials can be used alone or in combination, but when used, they are adsorbed on the surface of the filler in advance,
Alternatively, it is preferably immobilized by the reaction.

In the present invention, it is desirable to use a curing accelerator when curing the resin composition. Examples of the curing accelerator in such applications include imidazoles such as 2-methylimidazole, 2-methyl-4-ethylimidazole, and 2-heptadecylimidazole, amines such as triethanolamine, triethylenediamine, and N-methylmorpholine, tributyl. Organic phosphines such as phosphine, triphenylphosphine and tritolylphosphine, tetraphenylphosphonium tetraphenylborate, tetraphenylboron such as triethylammonium tetraphenylborate, 1,8-diaza-bicyclo (5,4,0) undecene- 7 and its derivatives. These curing accelerators may be used alone or in combination of two or more, and the amount used is in the range of 0.01 to 10 parts by weight based on the total weight of the epoxy resin and the curing agent.

Further, when the epoxy resin of the present invention is used, there is no problem in adding a silicone compound in order to reduce the internal stress of the obtained cured product. Furthermore, in the epoxy resin composition of the present invention, in addition to the above-mentioned components, if necessary, a releasing agent such as fatty acid, fatty acid salt, wax,
Brom compounds, flame retardants such as antimony and phosphorus, and colorants such as carbon black may be mixed, mixed and kneaded to obtain a molding material. In the present invention, the semiconductor element may be sealed by a known molding method such as ordinary transfer molding, but the method is not particularly limited. The semiconductor device obtained by the present invention exhibits excellent crack resistance when immersed in solder, and is stable in long-term use as a highly integrated IC, so that high reliability is obtained as a product.

[0029]

The present invention will be described in more detail with reference to Examples. However, the present invention is not limited to these examples. Experimental Example 1 576 g (4 mol) of β-naphthol was charged into a glass reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, and the internal temperature was raised to 150 ° C. to melt it. While stirring
166.3 g of α, α′-dichloro-p-xylene (0.
95 mol) and α, α′-dichloro-m-xylene 8.7.
A mixture with 5 g (0.05 mol) was melt-dropped over about 1 hour, and hydrogen chloride produced by the reaction was trapped outside the system by a nitrogen stream. 3 while keeping the internal temperature at 150-160 ℃
After continued stirring for a period of time, the naphthol was removed by vacuum distillation and the reddish brown transparent resin was discharged while hot. Yield 324
The g and the hydroxyl equivalent (g / eq) were 220. The melt viscosity of this resin at 150 ° C. measured by an ICI melt viscometer was 4.8 poise.

Experimental Example 2 β-naphthol 57 was placed in a glass reaction vessel equipped with a stirrer, a thermometer, a Dean Stark water separator and a reflux condenser.
6 g (4 mol), trifluoromethanesulfonic acid 0.4 g
Was charged and the internal temperature was raised to 150 ° C. to melt it. While stirring, α, α'-dimethoxy-p-xylene 14
9.4 g (0.9 mol) and α, α'-dimethoxy-m-
Xylene 16.6 g (0.1 mol) was added dropwise over about 1 hour, and the methanol produced by the reaction was trapped outside the system by a Dean-Stark water separator. Internal temperature 150
After stirring for 3 hours while maintaining at ~ 160 ° C,
After cooling to 00 ° C. and neutralizing the reaction catalyst with a 0.5% aqueous barium hydroxide solution, unreacted naphthol was removed by vacuum distillation, and the reddish brown transparent resin was discharged during heating. The yield was 318 g, and the hydroxyl group equivalent (g / eq) was 221.
The melt viscosity of this resin at 150 ° C. measured by an ICI melt viscometer was 3.1 poise.

Experimental Example 3 β-naphthol 57 was placed in a glass reaction vessel equipped with a stirrer, a thermometer, a Dean Stark water separator and a reflux condenser.
6 g (4 mol), trifluoromethanesulfonic acid 0.4 g
Was charged and the internal temperature was raised to 150 ° C. to melt it. While stirring, α, α′-dimethoxy-p-xylene 13
2.8 g (0.8 mol) and 33.2 g (0.2 mol) of α, α'-dichloro-m-xylene were added dropwise over about 1 hour, and the methanol produced by the reaction was a Dean Stark water separator. , And hydrochloric acid was trapped outside the system with a nitrogen stream. After continuing stirring for 3 hours while maintaining the internal temperature at 150 to 160 ° C., the system was cooled to 100 ° C.,
After neutralizing the reaction catalyst with a 0.5% aqueous barium hydroxide solution, unreacted naphthol was removed by vacuum distillation, and the reddish brown transparent resin was discharged during heating. The yield was 330 g, and the hydroxyl group equivalent (g / eq) was 216. ICI of this resin
The melt viscosity at 150 ° C. measured by the melt viscometer is 2.6.
It was a poise.

Experimental Example 4 β-naphthol 57 was placed in a glass reaction vessel equipped with a stirrer, a thermometer, a Dean Stark water separator and a reflux condenser.
6 g (4 mol), trifluoromethanesulfonic acid 0.4 g
Was charged and the internal temperature was raised to 150 ° C. to melt it. With stirring, α, α'-dihydroxy-p-xylene 6
9.0 g (0.5 mol) and α, α'-dimethoxy-m-
83.0 g (0.5 mol) of xylene was added dropwise over about 1 hour, and water and methanol produced by the reaction were trapped outside the system by a Dean-Stark water separator. After continuing stirring for 3 hours while maintaining the internal temperature at 150 to 160 ° C,
The system was cooled to 100 ° C., the reaction catalyst was neutralized with a 0.5% aqueous barium hydroxide solution, unreacted naphthol was removed by vacuum distillation, and the reddish brown transparent resin was discharged during heating. Yield 326g, hydroxyl equivalent (g / eq) 219
Met. 150 ICI melt viscosity of this resin
The melt viscosity at ° C was 2.3 poise.

Experimental Example 5 A glass reaction vessel equipped with a stirrer, a thermometer and a reflux condenser was charged with 720 g (5 mol) of β-naphthol and the internal temperature was raised to 150 ° C. to melt it. . While stirring
166.3 g of α, α′-dichloro-p-xylene (0.
95 mol) and α, α′-dichloro-o-xylene 8.
A mixture with 75 g (0.05 mol) was melt-dried over about 1 hour, and hydrogen chloride produced by the reaction was trapped outside the system by a nitrogen stream. After continuing stirring for 3 hours while maintaining the internal temperature at 150 to 160 ° C., naphthol was removed by vacuum distillation, and the reddish brown transparent resin was discharged during heating. The yield is 320
The g and the hydroxyl equivalent (g / eq) were 213. The melt viscosity of this resin at 150 ° C. measured by an ICI melt viscometer was 4.2 poise.

Experimental Example 6 β-naphthol 86 was placed in a glass reaction vessel equipped with a stirrer, a thermometer, a Dean Stark water separator and a reflux condenser.
4 g (6 mol), trifluoromethanesulfonic acid 0.4 g
Was charged and the internal temperature was raised to 150 ° C. to melt it. While stirring, α, α'-dimethoxy-p-xylene 14
9.4 g (0.9 mol) and α, α'-dimethoxy-o-
Xylene 16.6 g (0.1 mol) was added dropwise over about 1 hour, and the methanol produced by the reaction was trapped outside the system by a Dean-Stark water separator. Internal temperature 150
After stirring for 3 hours while maintaining at ~ 160 ° C,
After cooling to 00 ° C. and neutralizing the reaction catalyst with a 0.5% aqueous barium hydroxide solution, unreacted naphthol was removed by vacuum distillation, and the reddish brown transparent resin was discharged during heating. The yield was 318 g and the hydroxyl equivalent (g / eq) was 209.
The melt viscosity of this resin at 150 ° C. measured by an ICI melt viscometer was 2.8 poise.

Experimental Example 7 β-naphthol 57 was placed in a glass reaction vessel equipped with a stirrer, a thermometer, a Dean Stark water separator and a reflux condenser.
6 g (4 mol), trifluoromethanesulfonic acid 0.4 g
Was charged and the internal temperature was raised to 150 ° C. to melt it. With stirring, α, α'-dihydroxy-p-xylene 10
3.5 g (0.75 mol) and α, α′-dimethoxy-o
-Xylene 41.5 g (0.25 mol) was added dropwise over about 1 hour, and water and methanol produced by the reaction were trapped outside the system by a Dean-Stark water separator.
After stirring for 3 hours while keeping the internal temperature at 150 to 160 ° C, the system was cooled to 100 ° C, the reaction catalyst was neutralized with 0.5% barium hydroxide aqueous solution, and the unreacted naphthol was vacuumed. It was removed by distillation and the reddish brown transparent resin was discharged while hot. The yield is 323 g and the hydroxyl equivalent (g / eq) is 21.
It was 9. This resin has an ICI melt viscometer of 15
The melt viscosity at 0 ° C. was 2.0 poise.

Experimental Example 8 β-naphthol 57 was placed in a glass reaction vessel equipped with a stirrer, a thermometer, a Dean Stark water separator and a reflux condenser.
6 g (4 mol), trifluoromethanesulfonic acid 0.4 g
Was charged and the internal temperature was raised to 150 ° C. to melt it. With stirring, α, α′-dimethoxy-p-xylene 12
4.5 g (0.75 mol) and α, α'-dimethoxy-m
-24.9 g (0.15 mol) of xylene and 16.6 g (0.1 mol) of α, α'-dimethoxy-o-xylene were added dropwise over about 1 hour, and the methanol produced by the reaction was Dean Stark water. It was trapped outside the system by a separator. After stirring for 3 hours while maintaining the internal temperature at 150 to 160 ° C, the system was cooled to 100 ° C and the reaction catalyst was adjusted to 0.5
After neutralization with a 1% aqueous solution of barium hydroxide, unreacted naphthol was removed by vacuum distillation, and the reddish brown transparent resin was discharged during heating. The yield was 323 g, and the hydroxyl group equivalent (g / eq) was 218. According to the ICI melt viscometer of this resin,
The melt viscosity at 150 ° C. was 2.1 poise.

Experimental Example 9 576 g (4 mol) of β-naphthol was placed in a glass reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, and the internal temperature was raised to 150 ° C. to melt it. While stirring
166 g (1 mol) of α, α′-dimethoxy-p-xylene was added over about 1 hour, and hydrochloric acid produced by the reaction was trapped outside the system by a nitrogen stream. Internal temperature is 150-16
After stirring for 3 hours while maintaining the temperature at 0 ° C., unreacted naphthol was removed by vacuum distillation, and the reddish brown transparent resin was discharged while hot. The yield was 315 g, and the hydroxyl equivalent (g / eq) was 218. According to the ICI melt viscometer of this resin,
The melt viscosity at 150 ° C. was 11.0 poise.

Experimental Example 10 β-naphthol 57 was placed in a glass reaction vessel equipped with a stirrer, a thermometer, a Dean Stark water separator and a reflux condenser.
6 g (4 mol), trifluoromethanesulfonic acid 0.4 g
Was charged and the internal temperature was raised to 150 ° C. to melt it. With stirring, α, α′-dimethoxy-m-xylene 166
g (1 mol) was added dropwise over about 1 hour, and water and methanol produced by the reaction were trapped outside the system by a Dean-Stark water separator. After stirring for 3 hours while keeping the internal temperature at 150 to 160 ° C, the system was cooled to 100 ° C, the reaction catalyst was neutralized with 0.5% barium hydroxide aqueous solution, and the unreacted naphthol was vacuumed. It was removed by distillation and the reddish brown transparent resin was discharged while hot. The yield was 321 g, and the hydroxyl group equivalent (g / eq) was 217. IC of this resin
The melt viscosity at 150 ° C. measured by a melt viscosity meter is 1.
It was 6 poise.

Experimental Example 11 In a glass reaction vessel equipped with a stirrer, a thermometer, a Dean Stark water separator, a dropping funnel and a reflux condenser, 6,
6′-Dihydroxy-3,3,3 ′, 3′-tetramethyl-1,1-spirobiindane 308 g (1 mol) and epichlorohydrin 925 g (10 mol) were charged, and the temperature was raised to 115 ° C. with stirring. Next, 220 g (2.2 mol) of 40% aqueous sodium hydroxide solution was added dropwise over about 2 hours while adjusting the temperature in the system to be kept at 100 ° C or higher. The Dean-Stark water separator trapped azeotropic water outside the system and returned epichlorohydrin into the system. After the completion of dropwise addition of the aqueous sodium hydroxide solution, the reflux was continued for 2 hours after the distillation of water was substantially stopped, and aging was carried out. Next, the reaction solution was cooled to room temperature, the salt produced as a by-product was filtered, and excess epichlorohydrin was distilled under reduced pressure to obtain 412 g of a crude epoxy resin. This crude epoxy resin was dissolved in 1 L of toluene, 200 g of a 5% aqueous sodium hydroxide solution was added at 60 ° C., and the mixture was stirred for 1 hour. Then, the mixture was allowed to stand still, the aqueous layer was discharged, and washing with water was repeated until the aqueous layer became neutral. After confirming that the water layer was completely neutralized, the organic layer was distilled under reduced pressure and 6,6'-dihydroxy-3,3,3 ', 3'-tetramethyl-1,1-spirobiindane was purified. 387 g of resin was obtained. The epoxy equivalent of this product was 220 g / eq.

Experimental Examples 12 to 35 The resin of the present invention obtained in Experimental Examples 1 to 5 and 8, 9, and 10 was used as an o-cresol novolac type epoxy resin (trade name; EOCN102S, epoxy equivalent 193 g /
eq, manufactured by Nippon Kayaku), tetramethylbiphenol type epoxy resin (trade name; YX-4000, epoxy equivalent 18)
4 g / eq, made of oiled shell epoxy), 6,6′-dihydroxy-3,3 produced in Experimental Example 11
3 ', 3'-Tetramethyl-1,1-spirobiindane epoxy resin was used as a curing agent, triphenylphosphine was used as a curing accelerator, and spherical silica (Harimic S-CO, Micron Co., Ltd.) was used as an inorganic filler. Made) and amorphous fused silica (Hugh Rex RD-8,
1: 1 weight ratio mixture of Tatsumori Co., Ltd., and other additives such as silane coupling agent (SZ-6083, Toray Dow Corning Silicone Co., Ltd.), carnauba wax, carbon black, antimony oxide, etc. Blended in the proportions shown in Table-1 (Table 1, Table 2, Table 3, Table 4, Table 5), 1
Roll kneading was carried out at 00 ° C. for 3 minutes to obtain an epoxy resin composition.

The physical properties of a cured product obtained by casting the epoxy resin composition were measured. The results are shown in Table-1. Triphenylphosphine was used in an amount of 1% by weight based on the total amount of the epoxy resin and the curing agent. A test piece for measuring physical properties is prepared by mounting the test element (10 mm × 10 mm square) on the element mounting portion of the lead frame for a flat package type semiconductor device using the above epoxy resin composition,
It is a test semiconductor device obtained by transfer molding. The test semiconductor device was molded at 180 ° C. for 30 minutes.
After molding under conditions of Kg / cm ² and 3 minutes, post-curing was performed at 145 ° C. for 3 hours and then at 185 ° C. for 2 hours. Using this test semiconductor device, a solder bath immersion test (crack generation test, 240 ° C.) was performed. The results are shown in Table-1.

[0042]

[Table 1]

[0043]

[Table 2]

[0044]

[Table 3]

[0045]

[Table 4]

[0046]

[Table 5]

The present invention has been described with reference to the experimental examples. When the resins obtained in Experimental Examples 1 to 4 and the resin obtained in Experimental Example 9 are compared, the reaction molar ratio between β-naphthol and the xylylene compound is the same. Despite being
In the case of Experimental Examples 1 to 4 in which the p-xylylene compound and the m-xylylene compound were co-condensed, the melt viscosity of the obtained resin was significantly reduced, as compared with Experimental Example 9 in which the p-xylylene compound was reacted alone. It is understood that there is. This difference in melt viscosity appears as a difference in fluidity of the epoxy resin composition (o-cresol novolac type epoxy), and the results of Experimental Example 12 to
It affects the spiral flow of 15 (epoxy resin composition using resin of Experimental Examples 1 to 4) and experimental example 16 (epoxy resin composition using resin of Experimental Example 9) and the number of deformation of bonding wires. That is, since the resin of Experimental Example 9, which is a curing agent, has a high melt viscosity, the composition of Experimental Example 16 has a low spiral flow exhibiting fluidity, and as a result, the load applied to the bonding wire during sealing is high, It has been transformed. In addition, Experimental Example 10
The resin obtained by using the m-xylylene compound alone does not cause such a problem because the resin has a very low melt viscosity, but as shown in Experimental Example 17, the heat resistance (Tg)
Has the drawback of low.

This tendency is the same when an o-xylylene compound is co-condensed, when an o- and m-xylylene compound is co-condensed, and when another epoxy resin is used. Is the melt viscosity in Experimental Examples 5 to 7 (co-condensation resin of o-xylylene compound) and Experimental Example 8 (co-condensation resin of o-xylylene and m-xylylene compound), Experimental Examples 18 to 29 (Experimental Examples 12 to 17). In various epoxy resins), Experimental Examples 30 to 32 (when the o-xylylene compound co-condensed resin of Experimental Example 5 was used as a curing agent) and Experimental Example 33 (o of Experimental Example 8). -And m-xylylene compound co-condensation resin is used as a curing agent), Experimental Examples 34 to 35
(When the epoxy resin is a mixture).
That is, this means that resins having almost the same physical properties have different defective rates of the final product due to the difference in their melt viscosities, and various physical properties, particularly heat resistance and moisture resistance This shows how it is important to reduce the melt viscosity of the resin that serves as a curing agent without reducing the properties.

The present invention solves this problem, and the epoxy resin composition obtained by the present invention has a high level of physical properties required in the industrial field such as heat resistance, moisture resistance, and mechanical properties. Is shown. Also, because of its low melt flowability, when it is used as a sealant for semiconductor integrated circuits, it prevents cracks from being generated even under severe conditions, as shown in the solder bath test (crack generation test). It greatly contributes to the improvement of the reliability of typical products.

[0050]

The epoxy resin composition obtained by the present invention gives a cured product which is excellent in melt fluidity, heat resistance, moisture resistance, mechanical strength and the like. The obtained epoxy resin composition is useful in a wide range of fields such as casting, laminating, molding, bonding, sealing, and composite materials. To give a concrete example, the semiconductor device has a great effect in use as a sealing material of a semiconductor integrated circuit (IC), and the obtained semiconductor device has high reliability as a product.

─────────────────────────────────────────────────── ─── Continuation of front page (56) References JP-A-6-9753 (JP, A) JP-A-5-206331 (JP, A) JP-A-5-105742 (JP, A) JP-A-5- 214076 (JP, A) JP-A-3-90075 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08G 59/00-59/72 H01L 23/29 H01L 23/31

Claims (6)

(57) [Claims] 1. In an epoxy resin composition, A) an epoxy resin having two or more epoxy groups in one molecule as an epoxy resin main agent, B) a curing agent, 1) β-naphthol (N component), 2). P-xylylene compound (X-1 component) represented by the general formula (1) (Formula 1) 3) General formula (2)
O- and / or m-xylylene compound represented by (Chemical formula 1) (X-2 component) (In the above formula, R1 and R2 represent a halogen atom, a hydroxyl group or a lower alkoxy group having 1 to 4 carbon atoms),
/ [ (X-1) + (X-2)] = 2 to 10, (X-1)
An epoxy resin composition containing a β-naphthol aralkyl resin having an ICI melt viscosity of 0.1 to 5 poises at 150 ° C., which is obtained by co-condensing at a molar ratio of / (X-2) = 1 to 20. 2. The curing agent is N / [ (X-1) + (X-
2)] = 3 to 6, IC obtained at 150 ° C. by co-condensation at a molar ratio of (X-1) / (X-2) = 2 to 10
The epoxy resin composition according to claim 1, which is a β-naphthol aralkyl resin having a melt viscosity of 0.1 to 3 poises. 3. An epoxy resin having two or more epoxy groups in one molecule, which is the main component of the epoxy resin, is a) an o-cresol novolac type epoxy resin, b) a general formula (3)
An epoxy resin derived from a biphenol represented by (Chemical formula 2), c) an epoxy resin derived from a spirobiindane bisphenol represented by the formula (4) (Chemical formula 2), The epoxy resin composition according to claim 1 or 2, which contains at least one of (in the above formula, R3 represents a hydrogen atom or a methyl group). 4. The method of claim 1 and an epoxy resin composition according to 3, epoxy semiconductor encapsulating which contains inorganic and / or organic fillers, in the range of 50 wt% to 92 wt% relative to the total weight Resin composition. 5. A cured product of the epoxy resin composition according to any one of claims 1-4. 6. A semiconductor device encapsulated with the cured product of the epoxy resin composition according to claim 5.