JPH0892231A - Spirobiindane diglycidyl ether and method for producing the same - Google Patents

Abstract

PURPOSE: To obtain spirobiindan diglycidyl ether having excellent heat resistance, excess moisture tolerance, adhesiveness and mechanical properties, causing a low melt viscosity and a low amount of hydrolyzable chlorine, and useful for in an electronic material field such as a sealing material for semiconductor integral circuits. CONSTITUTION: An epoxy compound obtained by the reaction of 6,6'- dihydroxy-3,3,3',3'-tetramethyl-1,1'-spirobiindan and epichlorohydrin is crystallized and isolated to afford 6,6'-dihydroxy-3,3,3',3'-tetramethyl-1,1'-spirobiindan diglycidyl ether expressed by the formula containing <=500ppm hydrolyzable chlorine and having a melting point of 100-130 deg.C. In the crystallization, 30-500 pts of methanol and 0.01-10 pts of surfactant such as polyvinyl alcohol are used to 100 pts of the epoxy compound, and preferably 10-50 pts of water to 100 pts of the methanol is used for dilution.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention is crystalline at 80 ° C.
6,6'-dihydroxy-3, with a melting point of ~ 140 ° C
The present invention relates to a diglycidyl ether of 3,3 ′, 3′-tetramethyl-1,1′-spirobiindane and a method for producing the same. The compound of the present invention has a low melt viscosity,
Since it gives a cured product having excellent heat resistance, moisture resistance, adhesiveness, mechanical properties, etc., it is used for applications such as casting, lamination, adhesion, molding, sealing, and composite materials. Further, since the content of hydrolyzable chlorine is small, it can be expected to be used in the field of electronic materials, particularly in the field of materials for sealing semiconductor integrated circuits (ICs).

[0002]

2. Description of the Related Art Generally, semiconductor elements mounted on a substrate such as a printed substrate, such as transistors, ICs and LSs.
I and the like are sealed with a sealing material in order to protect itself and a wire for conduction. Various materials such as ceramics and metals have been proposed as encapsulating materials to protect them, but currently, due to their physical properties, cost, workability during manufacturing, etc., epoxy resin is made into powder and pelletized. Formed products are well known, and many epoxy resin compositions comprising such pelletized epoxy resin and curing agent have been used. For example, as a typical epoxy resin for an IC encapsulant, an epoxy compound of phenol novolac or o-cresol novolac is most commonly used, and as a highly heat resistant epoxy resin, 4,4'-diaminodiphenylmethane is used. (MDA)
Epoxy resin obtained from On the other hand, typical curing agents are diethylenetriamine, isophoronediamine, m-xylylenediamine, m-phenylenediamine, 4,4′-diaminodiphenylsulfone and other aliphatic or aromatic amine compounds, phthalic anhydride, trimellitic anhydride. Examples thereof include acids, acid anhydrides such as pyromellitic dianhydride and maleic anhydride, phenolic resins such as phenol novolac, polyamides, modified polyamines and imidazoles.

These epoxy resins and hardeners have been used as resin compositions in various combinations according to their respective uses, and further by adding an inorganic filler. These epoxy resins are required to have the following properties: heat resistance during soldering, heat resistance to withstand heat generation of IC circuits, and cracks caused by vaporization of water contained in the resin in a heated state. Examples include low water absorption and mechanical properties. In addition, in the field of electronic materials, there is a strong demand for higher quality, that is, reduction of the total chlorine content, along with improvement of various physical properties. On the other hand, in addition to improving the performance required by the resin skeleton, it has been recently emphasized that the content of the filler component in the epoxy resin composition is improved to improve the water absorption rate and mechanical properties. That is, by basically improving the content of the inorganic filler that is not involved in the water absorption rate, the water absorption rate of the epoxy resin composition as a whole is reduced, and mechanical properties such as elastic modulus are improved. . Further, improving the filling rate of the filler component also contributes to a reduction in total cost. In order to increase the filling rate of the filler, in order to enable uniform kneading of the composition with a higher filling rate, and to prevent insufficient filling during mounting, deformation of the bonding wire, cutting, etc., melting of the resin component It is important to reduce the viscosity. In recent years, several epoxy resins aiming at low melt viscosity have been proposed for this purpose. For example, a biphenyl type epoxide represented by the formula (2) (Chemical formula 2) (JP-A-2-101761) and an epoxidized dihydroxynaphthalene represented by the formula (3) (Chemical formula 2) 61-73719)
Etc.

[0004]

[Chemical 2] (In the above formula, G represents a glycidyl group)

However, these epoxides are
Although the melt viscosity is reduced, it is a bifunctional epoxy compound, so that it has the drawbacks that the crosslink density of the cured product is reduced, the heat resistance is reduced too much, and the price is expensive. . Further, as the same bifunctional epoxy compound, diglycidyl ether of 6,6'-dihydroxy-3,3,3 ', 3'-tetramethyl-1,1'-spirobiindane is known (Japanese Patent Laid-Open No. 63- 150270), which is obtained as an amorphous material having a softening point of about 50 ° C. Although this product has satisfactory properties such as low melt viscosity and heat resistance, it has a drawback that the target powdered epoxy resin composition is apt to cause blocking due to its low softening point, resulting in poor workability. are doing. Further, since the resin contains hydrolyzable chlorine as an impurity, it has a drawback that it corrodes the aluminum wiring on the semiconductor element.

[0006]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention An object of the present invention is to provide an epoxy compound having an excellent balance of properties such as moisture resistance, heat resistance, adhesiveness and mechanical strength, while suppressing the above-mentioned deterioration of physical properties as much as possible. It is to impart the required properties of low melt viscosity and low hydrolyzable chlorine content, and thereby to provide an epoxy compound useful in the use in the electronic material field.

[0007]

The present inventors have completed the present invention as a result of extensive studies to solve the above problems. That is, the present invention relates to a crystalline spirobiindane diglycidyl ether having a melting point of 80 ° C. to 140 ° C. represented by the formula (1) (Chemical Formula 3). The present invention also provides 6,6′-dihydroxy-3,
The above-mentioned crystallinity which is isolated by crystallization from an amorphous epoxidized product obtained by reacting 3,3 ′, 3′-tetramethyl-1,1′-spirobiindane with epichlorohydrin using an alcohol solvent The present invention relates to a method for producing spirobiindane diglycidyl ether.

[0008]

[Chemical 3]

The spirobiindane diglycidyl ether of the present invention has a specific melting point and exhibits an extremely low melt viscosity above the melting point.
It is a diglycidyl ether of 6′-dihydroxy-3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindane (hereinafter abbreviated as SPIDG). This SPI
DG is characterized by extremely low melt viscosity at the time of melting, little hydrolyzable chlorine, no blocking of the epoxy resin composition, and the like. Therefore, DG is melt-kneaded with a commonly known curing agent or filler component. In doing so, the curable composition is easily obtained, the corrosion resistance is excellent, and the workability is excellent.

The present invention is, for example, 6,6'-dihydroxy- obtained by a method such as heat treatment of 2,2'-bis (4-hydroxyphenyl) propane in the presence of a strong acid.
3,3,3 ', 3'-Tetramethyl-1,1'-spirobiindane is reacted with epichlorohydrin to obtain an amorphous epoxidized spirobiindane (hereinafter abbreviated as SPI epoxidized) as a raw material. The method of the present invention removes a by-product containing hydrolyzable chlorine by crystallizing this amorphous SPI epoxidized product from an alcoholic solvent to obtain a hydrolyzable chlorine content of 1000 ppm or less, and an electronic material. Considering its use in the field, it is preferably 500 ppm or less and has a melting point of 80 to 14
Crystalline SPIDG at 0 ° C, preferably 100-130 ° C
Is characterized in that The term "hydrolyzable chlorine" means that an epoxy resin is dissolved in acetone, an aqueous solution of sodium hydroxide is added, and chlorine ions desorbed when heated for 60 minutes under reflux are titrated and quantified with a silver nitrate solution. Refers to the chlorine atom in a compound expressed in ppm by weight.

The alcoholic solvent used in the production method of the present invention includes aliphatic alcohols such as methanol, ethanol and 2-propanol, glycols such as ethylene glycol, propylene glycol and diethylene glycol, ethylene glycol monomethyl ether and ethylene glycol. Examples thereof include cellosolves such as monoethyl ether and ethylene glycol monoisopropyl ether. Aliphatic alcohols are preferable, and methanol is more preferable. The amount of the alcohols used is sufficient if it is necessary to dissolve the SPI epoxidized product, and preferably the SPI epoxidized product 100 is used.
100 to 1000 parts, more preferably 30 parts
It is 0 to 500 parts.

In order to increase the yield of SPIDG,
At the time of crystallization, it is preferable to dilute the alcohol solvent with water. The amount of water used for dilution is 5 to 100 parts, preferably 10 to 50 parts, relative to 100 parts of alcohol used as a solvent. Furthermore, if a surfactant is used during the crystallization, it becomes more granular and more granular.
PIDG can be obtained. As the surfactant to be used, anionic surfactants such as alkyl sulfates and alkyl sulfonates, cationic amines such as higher amine halogenates and quaternary ammonium salts, polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, etc. And non-ionic activators, polyvinyl alcohol, polyacrylamide, and other polymeric activators. A polymer activator is preferable, and polyvinyl alcohol is more preferable. The amount of the surfactant used is 0.01 to 10 parts, and preferably 0.1 to 5 parts, relative to 100 parts of the SPI epoxidized product.

Pure crystalline SP thus obtained
IDG has an ICI melt viscosity of 0.25 at 150 ° C.
At the poise level, 15 of o-cresol type epoxy resin, which is currently the most general-purpose epoxy resin as an IC encapsulant, is used.
Compared with the ICI melt viscosity at 0 ° C. (6 to 7 poises), the viscosity is extremely low, and it is very advantageous for increasing the filling rate of the filler as an epoxy resin composition. For example, when phenol novolac is used as the curing agent for the encapsulating material as described above, the filler filling rate when the o-cresol novolac type epoxy resin is used is about 80% at the limit, whereas the present invention When the crystalline SPIDG is used as an epoxy component, it can be increased to 92%. Therefore, the water absorption derived from the resin component can be greatly reduced, and the filler can significantly increase the mechanical properties.

Further, as described above, a cured product generally obtained from a bifunctional epoxy compound has a low cross-linking density, so that the heat resistance is greatly reduced, whereas the crystalline SPIDG of the present invention is reduced. Has an alicyclic structure (spiro ring skeleton) in its molecular skeleton and is rigid, so that it has a feature that its heat resistance is higher than other bifunctional epoxy compounds. Furthermore, the crystalline SPIDG of the present invention is
Since it is isolated by solvent crystallization, the content of hydrolyzable chlorine can be significantly reduced. Therefore, when it is used as a resin raw material in the electronic material field, it does not swell due to heat during use and does not cause circuit breakage due to corrosion. Also,
The epoxy resin composition containing the crystalline SPIDG of the present invention does not cause blocking and is excellent in workability. From these, the crystalline SPID of the present invention
G is a promising next-generation semiconductor encapsulation material, and
Similarly, it is also superior as compared with a biphenyl type epoxidized product characterized by low melt viscosity.

[0015]

EXAMPLES The method of the present invention will now be described in detail with reference to Examples, but the present invention is not limited thereto. Experimental Example 1 In a reaction vessel equipped with a stirrer, a thermometer, and a reflux condenser,
6,6'-Dihydroxy-3,3,3 ', 3'-tetramethyl-1,1'-spirobiindane 50 g (0.162 mol), epichlorohydrin 150 g (1.62 mol) and tetramethylammonium chloride 0.18g
(0.00162 mol) was charged, the temperature was raised to 115 ° C. with stirring, and the reaction was carried out at the same temperature for 5 hours. Then, epichlorohydrin was distilled off from the reaction solution by vacuum distillation. Then, the residue was dissolved in 50 g of toluene, charged with 65 g of a 30% sodium hydroxide aqueous solution, and heated at 95 ° C. for 5 hours.
A time ring closure reaction was performed. After removing the aqueous layer by liquid separation,
The organic layer was washed repeatedly with water until free of residual chloride and sodium hydroxide. At this time, the internal temperature is 70-
It was kept at 75 ° C. The solvent was distilled off under reduced pressure from the organic layer to obtain 64 g of a brown resin. The softening point [by a ring and ball method softening point measuring device (JIS-K-2548)] was 65 ° C., and hydrolyzable chlorine was 1,400 ppm.

Experimental Example 2 10 g of the resin obtained in Experimental Example 1 and 30 g of methanol were placed in a reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, and the temperature was raised to 60 ° C. with stirring to dissolve the resin. did. Then, it cooled to room temperature and crystallized at room temperature for 8 hours. The precipitated crystals were separated by filtration and washed with methanol to obtain the desired 6,6′-dihydroxy-3,3,3 ′, tetramethyl-1,1′-spirobiindane diglycidyl ether (SPIDG) 8 0.5 g was obtained. Melting point 114-130
° C, hydrolyzable chlorine was 400 ppm.

Experimental Example 3 10 g of the resin obtained in Experimental Example 1 and 30 g of methanol were placed in a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser and a dropping funnel, and the temperature was raised to 60 ° C. with stirring. And dissolved. Then, it cooled to room temperature and crystallized at room temperature for 8 hours. Thereafter, at room temperature, Gocelan 3266 (polyvinyl alcohol-based surfactant, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) 1
% Aqueous solution was dropped, and the mixture was stirred for 2 hours. The precipitated crystals were separated by filtration and washed with a 75% aqueous methanol solution to obtain 9.6 g of the desired product. Melting point is 111-129
° C, hydrolyzable chlorine was 450 ppm.

Experimental Example 4 Using SPIDG obtained in Experimental Example 2, a phenol resin [trade name BRG # 558, manufactured by Showa Polymer Co., Ltd.] as a curing agent, triphenylphosphine as a curing accelerator, and inorganic filling Spherical silica as an agent [Harimic S-C
O, manufactured by Tatsumori Co., Ltd. and amorphous fused silica [Hugh Rex RD-8, manufactured by Tatsumori Co., Ltd.] in a weight ratio of 1: 1 and a silane coupling agent [SZ] as other additives.
-6083, Toray Dow Corning Silicone Co., Ltd.
[Production], carnauba wax, carbon black, antimony oxide, etc. were compounded at a ratio shown in Table 1 (Table 1) (resin component / inorganic filler = 8/92), and roll kneaded at 100 ° C. for 3 minutes to obtain an epoxy resin. A composition was obtained. The physical properties of the cured product obtained by casting the epoxy resin composition were measured, and the results are shown in Table-1. In addition, the test piece for measuring the physical properties was obtained by transferring the epoxy resin composition by transfer molding (180
^{℃, 30kg / cm 2, 3min} .) Was obtained.

Experimental Example 5 An o-cresol novolac type epoxy resin (trade name EOCN102S, manufactured by Nippon Kayaku) was used as the epoxy resin in Experimental Example 4, and a phenol novolac resin (BRG # 558) was used as a curing agent. In the proportion shown in (resin component / inorganic filler = 8/92), roll kneading was carried out at 100 ° C. for 3 minutes, but since the melt flowability of the resin component was low, a uniform resin composition was obtained. I couldn't.

Experimental Example 6 Physical properties of a cured product obtained in the same manner as in Experimental Example 4 by mixing the inorganic filler in Experimental Example 5 in the ratio shown in Table 1 (resin component / inorganic filler = 20/80). Was measured and the results are shown in Table 1. Experimental Example 7 The inorganic filler in Experimental Example 4 was blended in a ratio shown in Table 1 (resin component / inorganic filler = 20/80), and physical properties of a cured product obtained in the same manner as in Experimental Example 4 were measured. The results are shown in Table-1.

[0021]

[Table 1]

The present invention has been described above by way of experimental examples. From these results, the SPIDG of the present invention has a high melt fluidity, so that a larger amount of filler can be used to obtain a composition with a phenol resin and an inorganic filler. It can be seen that the agent can be introduced. That is, as is clear from the results of Experimental Example 4, in the case of the epoxy resin composition using SPIDG and phenol novolac of the present invention, the filler component was 92%.
Despite being contained, roll kneading was possible and the spiral flow was also 75 cm. Moreover, since the deformation number of the bonding wire when the test semiconductor device was actually molded was 0/20, it can be seen that it can be used as a sealant. On the other hand, in Experimental Example 5, an o-cresol novolac type epoxy resin (EOCN), which is a general epoxy resin, was used, and an attempt was made to obtain a composition by using a large amount of filler as in Experimental Example 4. When kneading, there was almost no fluidity, and it was impossible to obtain a uniform kneaded product. From this, it is understood that the SPIDG of the present invention can contain a larger amount of filler when obtaining the cured product.

The o-cresol novolac type epoxy resin has a filling rate of 8 when phenol novolac is used as a curing agent.
From 0%, it is clear from the result of Experimental Example 6 that the same spiral flow as that of Experimental Example 4 is exhibited. However, it was found that the physical properties of the cured product obtained at this time were inferior to those of Experimental Example 4 in terms of flexural modulus and water absorption. It can be considered that this difference is largely influenced by the content of the filler in addition to the essential difference of the resin. This is also clear from the results of Experimental Example 7. Experimental Example 7 is Experimental Example 4
In the same combination of SPIDG and novolac of the present invention as described above, the amount of the filler was set to 80%, which is the same as in Experimental Example 6. From this result, it can be seen that even if the resin components are the same, if the amount of the filler is small, the fluidity as a whole as shown by the spiral flow is excellent, but the cured physical properties thereof are deteriorated. From this, it can be said that the physical properties of the cured product obtained from the epoxy resin composition depend on the properties of the resin and the filler filling rate, and one of the points to improve the physical properties of the cured product is to increase the filling rate of the filler. Can be listed in. In this respect, it can be said that the SPIDG of the present invention is very excellent. Further, in Experimental Examples 6 and 7, since the filler filling amount and the curing agent are the same, it is possible to compare the SPIDG of the present invention with a typical epoxy resin, an o-cresol novolac type epoxy resin. Although the SPIDG of the present invention is slightly inferior in heat resistance, its level is in the range judged to be sufficient as a sealing agent, while it is found that it is excellent in water absorption. Taking the above into consideration comprehensively, the SPIDG of the present invention has low water absorption as a characteristic of the resin and also has a very low melt viscosity, so that the filler is used as an epoxy resin composition more than a conventional one. Since it can be contained in a large amount, it can be judged that the physical properties of the obtained cured product are very low in water absorption and the mechanical properties are excellent. Therefore, it can be said to be particularly useful in the field of sealants.

[0024]

The present invention provides 6,6'-dihydroxy-3,
From the amorphous epoxidized product obtained from 3,3 ′, 3′-tetramethyl-1,1′-spirobiindane and epichlorohydrin, a crystalline 6,6 '-Dihydroxy-3,
It is intended to provide a method for obtaining 3,3 ′, 3′-tetramethyl-1,1′-spirobiindane diglycidyl ether. The diglycidyl ether compound of the present invention is not only excellent in melt fluidity, but can reduce the content of hydrolyzable chlorine, so that when used in the field of electronic materials, swelling due to heat and a circuit due to corrosion Does not cause disconnection. The epoxy resin composition containing the diglycidyl ether compound of the present invention does not cause blocking and is excellent in workability.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akihiro Yamaguchi 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd.

Claims (5)

[Claims] 1. The melting point represented by formula (1) (formula 1) is 80.
Crystalline spirobiindane diglycidyl ether that is between 140 ° C and 140 ° C. [Chemical 1] 2. 6,6′-Dihydroxy-3,3,
A crystalline epoxidized product obtained by reacting 3 ', 3'-tetramethyl-1,1'-spirobiindane with epichlorohydrin, is crystallized using an alcohol solvent, and is isolated. Item 1. A method for producing spirobiindane diglycidyl ether according to Item 1. 3. The method for producing spirobiindane diglycidyl ether according to claim 2, wherein the alcohol solvent is methanol. 4. The method for producing spirobiindane diglycidyl ether according to claim 3, wherein the crystallization is performed by diluting with water. 5. The method for producing spirobiindane diglycidyl ether according to claim 3, wherein a surfactant is used in the crystallization.