JPH04217675A - Epoxy resin and its intermediate, production thereof and epoxy resin composition - Google Patents

Abstract

PURPOSE:To obtain an epoxy resin, having a low viscosity in solvents and excellent in all of heat and water resistance and toughness. CONSTITUTION:2,7-Dihydroxynaphthalene is reacted with formaldehyde to provide 1,1-bis(2,7-dihydroxy-1-naphthyl)methane in substantial 100% yield. The resultant compound is then reacted with epichlorohydrin to produce 1,1-bis(2,7- diglycidyloxy-1-naphthyl)methane, which is subsequently cured with a curing agent to afford an epoxy resin having performance satisfactory in all respects of heat and water resistance and toughness. The aforementioned epoxy resin is optimum for especially semiconductor sealing materials.

Description

Description: TECHNICAL FIELD The present invention relates to epoxy resins, intermediates thereof, methods for producing them, and epoxy compositions. In particular, the present invention relates to an epoxy resin that has a low melt viscosity and is excellent in heat resistance, water resistance, and toughness, particularly an epoxy resin that is excellent for use as a molding material for semiconductor encapsulation. [0002] Epoxy resins are generally cured using various curing agents to improve mechanical properties, water resistance,
It becomes a cured product with excellent chemical resistance and electrical properties, and is used in a wide range of fields, including adhesives, paints, laminates, molding materials, and casting materials. In particular, epoxy resins are widely used as semiconductor encapsulating resins due to their excellent properties and economic advantages. JP-A-61-69826 and JP-A-2
No. 189326 describes an epoxy resin obtained by reacting a novolak resin obtained by reacting 1,6-dihydroxynaphthalene with formaldehyde and further reacting epichlorohydrin. [0004] Problems to be Solved by the Invention However, 1,6-
The reaction product obtained by reacting dihydroxynaphthalene with formaldehyde is a mixture of dimers, trimers, tetramers, pentamers, etc., so the epoxy resin obtained by reacting it with epihalohydrin is Because it becomes a mixture of dimerized epoxy resin, trimerized epoxy resin, tetramerized epoxy resin, pentamerized epoxy resin, etc., it has low melt viscosity, ■heat resistance, ■water resistance, and No epoxy resin has been obtained that is satisfactory in any of the toughness characteristics (1) to (2). [Means for Solving the Problems] The inventors of the present invention made extensive studies in view of the above-mentioned circumstances and found that, unexpectedly, when formaldehyde is reacted with 2,7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene is produced. Although it has multiple reactive sites in its molecule, it never converts into novolacs and only produces dimerized products, which is a unique reactivity. The epoxy resin obtained by reacting the dimerized product with epihalohydrin is the first to discover that it can be obtained in 100% yield by reacting the dimerized product with epihalohydrin. The present inventors have completed the present invention by discovering that this resin also has the above-mentioned properties (1), (2), and (3), which are not found in epoxy resins obtained by reacting epihalohydrin. That is, the present invention provides 1,1-bis(2
, 7-dihydroxy-1-naphthyl) alkane, a method for producing 1,1-bis(2, A method for producing 7-diglycidyloxy-1-naphthyl)alkane, and an epoxy resin composition comprising an epoxy resin and a curing agent, wherein the epoxy resin is 1,1-bis(2,7-diglycidyloxy-1- The present invention provides an epoxy resin composition characterized in that it uses (naphthyl)alkane. In the present invention, 1,1-bis(2,7-dihydroxy-1-naphthyl)alkane can be produced by reacting 2,7-dihydroxynaphthalene with aldehydes. 1,1-bis(2,7-dihydroxy-1
-Naphthyl)alkane refers to a compound with the following structure. Formula (I) [0009] [In the formula, R is a hydrogen atom, a lower alkyl group, a phenyl group, a hydroxyphenyl group, a halogen
substituted phenyl group] and 1,1-bis(2,
In producing 7-diglycidyloxynaphthyl)alkane, the above 1,1-bis(2,7-dihydroxy-1-naphthyl)alkane may be reacted with epihalohydrin. 1,1-bis(2,7-diglycidyloxy-1-naphthyl)alkane refers to a compound having the following structure. Formula (II) [0013] [In the formula, R is a hydrogen atom, a lower alkyl group, a phenyl group, a hydroxyphenyl group, a halogen
is a substituted phenyl group] Hereinafter, 1,1-bis(2,7
-Production method of dihydroxy-1-naphthyl)alkane,
The method for producing 1,1-bis(2,7-diglycidyloxy-1-naphthyl)alkane will be explained in order. The dimerized product corresponding to the intermediate of the epoxy resin of the present invention, namely 1,1-bis(2,7-dihydroxy-
The 1-naphthyl)alkane can be produced by reacting 2,7-dihydroxynaphthalene and aldehydes in the presence of a catalyst if necessary. The aldehydes used in this case are not particularly limited, and examples thereof include formaldehyde, acetaldehyde, propylaldehyde, butyraldehyde, benzaldehyde, p-hydroxybenzaldehyde, and brombenzaldehyde. The catalyst to be used is not particularly limited, but examples of basic catalysts include alkali metal hydroxides or alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and calcium hydroxide. or alkali metal carbonates such as sodium carbonate and potassium carbonate. In addition, as acidic catalysts, sulfuric acid,
Mineral acids such as hydrochloric acid, nitric acid, hydrobromic acid, and perchloric acid, sulfonic acids such as para-toluenesulfonic acid and benzenesulfonic acid, and carboxylic acids such as oxalic acid, succinic acid, malonic acid, monochloroacetic acid, and dichloroacetic acid are used. be done. The amount of these catalysts used is usually 0.01 to 0.1 mol per 1 mol of hydroxynaphthalene. It is possible to use more than that, but the neutralization step requires a large amount of acid or alkali and extra time, so it may be determined appropriately. In conducting the reaction, 2,7-dihydroxynaphthalene may be used alone, but other phenols or naphthols may be used in combination as appropriate. For example, if 2,7-dihydroxynaphthalene is used alone and formaldehyde is used as the aldehyde, the corresponding dimer product 1,1-bis(2,7-diglycidyloxy-1) is used.
-naphthyl) methane is produced, for example, in an aqueous dispersion system in the presence of a basic catalyst or an acidic catalyst, 0.5 to 1.0 mol of formaldehyde, preferably 0.5 to 1.0 mol, per mol of 2,7-dihydroxynaphthalene. is 0.5~0
．． Add 55 mol and heat at 30-100°C, preferably 60-100°C.
The target compound can be obtained by stirring at a temperature of 80° C. for 0.5 to 3 hours, then neutralizing, filtering the product, washing with water, and drying. The present inventors have discovered that the target compound thus obtained is not a novolak compound which is a mixture of dimerized products, trimerized products, tetramerized products, pentamerized products, etc., but is composed of 1 with a component ratio of substantially 100%. ,1-bis(2,7-diglycidyloxy-1-
It was found that only naphthyl methane was present. At that time, neither unreacted hydroxynaphthalene nor condensate having three or more hydroxynaphthalene nuclei could be substantially observed. In addition, to explain the case where epoxy resin is produced by using β-naphthol in combination with 2,7-dihydroxynaphthalene and similarly selecting formaldehyde as the aldehyde, in an aqueous dispersion system, basic catalyst or In the presence of an acidic catalyst, 0.5-1.
Add 0 mol, preferably 0.5-0.55 mol, 30
At a temperature of ~100°C, preferably 60-80°C, 0.5
After stirring for ~3 hours and then neutralizing, the product is filtered, washed with water, and then dried to obtain the target compound. [0020] The inventors of the present invention also found that when a mixture of 2,7-dihydroxynaphthalene and β-naphthol was selected, a novolak compound, which is a mixture of dimerized products, trimerized products, tetramerized products, pentamerized products, etc. , the dimerization product is substantially 10
It was found that it was produced at a component ratio of 0%. However, in this case, not one type of dimer is produced, but 1,1-bis(2,7-dihydroxy-1-naphthyl)methane,
1-(2,7-dihydroxy-1-naphthyl)-1-(
It is a mixture of three types: 2-hydroxy-1-naphthyl)methane and 1,1-bis(2-hydroxy-1-naphthyl)methane. [0021] The above 1,1-bis(2,7-dihydroxy-1-naphthyl)methane and 1-(2,7-dihydroxy-1-naphthyl)-1-(2-hydroxy-1-
naphthyl)methane and 1,1-bis(2-hydroxy-
The structures of 1-naphthyl)methane are as shown in the following formulas in order. Formula (III) [Formula (III)] [Formula (IV)] [Formula (IV)] [Formula (V)] [Formula (V)] [Formula (V)] [Formula (V)] [Formula (V)] [Formula (V)] In this case, 2,7-dihydroxy Although the molar ratio of naphthalene and β-naphthol is not particularly limited, for example, if the amount of 2,7-dihydroxynaphthalene is large, the dimerized product represented by formula (III), i.e., 1,1-bis(2,7-dihydroxy- The production ratio of (1-naphthyl)methane is increased, and the heat resistance of the epoxy resin is further improved. On the other hand, the viscosity of the epoxy resin tends to increase. On the other hand, when the amount of β-naphthol increases, the production ratio of 1,1-bis(2,7-dihydroxynaphthyl)methane decreases, and in response, the formula (V)
The production ratio of the corresponding dimer, ie, 1,1-bis(2-hydroxy-1-naphthyl)methane, increases. In this case, although the heat resistance tends to decrease, the viscosity tends to further decrease. Therefore, the epoxy resin is difficult to crystallize during the heat resistance-viscosity balance and the epoxidation process described below.
Considering the ease of production, the molar ratio of 2,7-dihydroxynaphthalene/β-naphthol is 10/0 to
2/8 is preferred. Furthermore, when p-hydroxybenzaldehyde is selected as the aldehyde and reacted with 2,7-dihydroxynaphthalene, the dimer product is 1,1-bis(2,7-dihydroxy-1-naphthyl). -4-hydroxyphenylmethane, that is, a compound having a structure as shown in the following formula (VI) is obtained. As will be described later, the epoxy resin reacted with epihalohydrin becomes a pentafunctional epoxy, and the cured product thereof has extremely excellent heat resistance. Formula (VI) [Image Omitted] Further, β is added to 2,7-dihydroxynaphthalene
- When the reaction is carried out by using naphthol and selecting p-hydroxybenzaldehyde as the aldehyde, 2,
In addition to the above target compound when p-hydroxybenzaldehyde is used as the aldehyde using only 7-dihydroxynaphthalene, 1,1-bis(2-hydroxynaphthyl)-4-hydroxyphenylmethane, that is, the following formula (VII ) can also be obtained. Formula (VII) ##STR7## As described in detail above, by selecting and using the above hydroxynaphthalenes as starting materials,
The dimerized product can be obtained with a component ratio of substantially 100%. In short, when 2,7-dihydroxynaphthalene alone or a mixture of 2,7-dihydroxynaphthalene and β-naphthol is selected from among many hydroxynaphthalenes, the hydroxynaphthalene nucleus can be formed without being converted into a novolac. The present invention was completed by discovering that only a dimerized product of . In particular, although 2,7-dihydroxynaphthalene has multiple reactive sites in its molecule,
The present inventors are the first to discover that it exhibits a unique reactivity in that it never forms a novolak and only produces a dimerized product. 1,1-bis(2,7-dihydroxy-1-naphthyl)alkane can also be used as a curing agent for epoxy resins. The cured product using this is
It has extremely high heat resistance. Next, a method for producing 1,1-bis(2,7-diglycidyloxy-1-naphthyl)alkane will be explained. 1,1-bis(2,7-
Epoxidation of dihydroxy-1-naphthyl)alkane to produce 1,1-bis(2,7-diglycidyloxy-1-
In order to produce a naphthyl) alkane, monohydric or
A method commonly used for producing glycidyl ether from polyhydric phenol can be applied, and the method is not particularly limited. For example, 1.5 to 20 mol, preferably 3.0 to 10.0 mol of epihalohydrin is added to 1 mol of the hydroxyl group of the above-mentioned 1,1-bis(2,7-dihydroxy-1-naphthyl)alkane. and in the presence of a base 20-1
It can be easily produced by carrying out an epoxidation reaction at 20°C, preferably 50 to 80°C, for 2 to 7 hours. The base used in epoxidation is not particularly limited, and examples thereof include potassium hydroxide, sodium hydroxide, barium hydroxide, magnesium oxide, sodium carbonate, potassium carbonate, etc. Among them, water Potassium oxide and sodium hydroxide are preferred. [
[0040] As the epihalohydrin, epichlorohydrin, epibromohydrin, β-methylepichlorohydrin, etc. can be used, and epichlorohydrin is preferred from the viewpoint of industrial ease of availability. The molecular weight, epoxy equivalent, and Melt viscosity can be adjusted. Lowering the molar excess of epihalohydrin increases the molecular weight of the epoxy resin, and conversely increasing it lowers the molecular weight. As the molecular weight increases, the epoxy equivalent and melt viscosity also increase, and the heat resistance of the cured product tends to gradually decrease. However, in general, if the molar excess of epihalohydrin exceeds 10 times, the molecular weight, epoxy equivalent, and melt viscosity will not change much, so it is not desirable from an economic point of view to use an excess of epihalohydrin. . [0042] The epoxy resin composition of the present invention
, 1-bis(2,7-diglycidyloxy-1-naphthyl)alkane and a curing agent can be easily obtained. 1,1-bis(2,7-dihydroxy-1-naphthyl)methane, 1-(2,7-dihydroxy-1-naphthyl)-1-(2-hydroxy-1-naphthyl)methane, and 1,1-bis(2,7-dihydroxy-1-naphthyl)methane. -bis(2-hydroxy-1-naphthyl)methane may be used in combination. It goes without saying that other known and commonly used epoxy resins may be used in combination with the epoxy resin of the present invention, if necessary. The curing agent used in the present invention is not particularly limited, and any compound commonly used as a curing agent for epoxy resins can be used. Examples of curing agents include aliphatic polyamines such as triethylenetetramine; alicyclic polyamines such as bis(3-methyl-4-aminocyclohexyl)methane; aromatic polyamines such as diaminodiphenylmethane and diaminodiphenylsulfone; novolak. type phenolic resins; polybasic acid anhydrides such as methylhexahydrophthalic anhydride and benzophenonetetracarboxylic dianhydride; polyamide amine resins and modified products thereof; imidazole, dicyandiamide, boron trifluoride-amine complexes, guanidine derivatives, etc. Examples of latent curing agents include diaminodiphenylmethane, diaminodiphenylsulfone, novolac type phenol resin, dicyandiamide, and polybasic acid anhydride. These curing agents may be used alone or in combination of two or more. The amount of the curing agent to be used depends on the number of epoxy groups contained in one molecule of the epoxy resin, the number of active hydrogen groups such as amino groups, imino groups, phenolic hydroxyl groups, or acid anhydride groups in the curing agent. Generally, the amount is close to the equivalent amount. Furthermore, when using a curing agent, a curing accelerator can be used as appropriate. The curing accelerator that can be used in the present invention is not particularly limited, and any curing accelerator that is commonly used as a curing accelerator for epoxy resins can be used. Examples of the curing accelerator include tertiary amines such as dimethylbenzineamine, imidazole compounds such as 2-thimelimidazole, and organic phosphorus compounds such as triphenylphosphine. The epoxy resin composition of the present invention may further contain various known and commonly used additives such as fillers, colorants, flame retardants, mold release agents, silane coupling agents, etc., if necessary. I can do it. Typical fillers include silica powder, zircon silicate, alumina, calcium carbonate, quartz powder, zircon oxide, talc, clay, barium sulfate, asbestos powder, and milled glass as colorants. Typical examples include carbon black, typical flame retardants include antimony trioxide, and typical release agents include carnauba wax.
Typical silane coupling agents include aminosilane and epoxysilane. The epoxy resin composition of the present invention thus obtained has extremely excellent properties in terms of heat resistance, moisture resistance, and toughness. Furthermore, since the epoxy resin of the present invention has an extremely low melt viscosity, a large amount of filler can be added. For example, when the epoxy resin of the present invention is used for semiconductor devices that require the stress of the cured product to be as low as possible, a larger amount of filler is used to bring the coefficient of linear expansion of the cured epoxy resin closer to that of the device itself. It is also very preferable in that the method can be applied. This also applies to electrical/electronic component sealing materials, electrical insulating materials such as insulating varnishes, laminates, and insulating powder coatings; structural materials such as laminates and prepregs for printed wiring boards, conductive adhesives, and honeycomb panels. It can be used for applications such as adhesives for use; fiber-reinforced plastics and their prepregs using various reinforcing fibers such as glass fibers, carbon fibers, and aramid fibers; and resist inks. In addition to trimers, tetramers, etc., the reaction product of 1,6-dihydroxynaphthalene and formaldehyde contains dimer 1,1-bis(1,6-dihydroxy-1
-Naphthyl)methane is present, but its proportion is less than 15% by weight of the total solid weight, and even if various purification methods are used, only its dimer can be isolated from its multiple nuclear bodies. This is extremely difficult. [0052] Therefore, the present inventors did not isolate only the dimer from a plurality of nuclear bodies, but instead created a method in which only the dimer could be obtained from the beginning with a component ratio of substantially 100%. They investigated synthesis methods. This completed the present invention. To repeat, the dihydroxynaphthalene novolak type epoxy resin described in JP-A No. 61-69826, as described in the examples in that publication,
Dimeric epoxy resins with 2.2 or 2.4 naphthalene nuclei and generally available in several different numbers of nuclei;
It can be seen that it is a mixture of condensates such as trimeric epoxy resin and tetrameric epoxy resin. Therefore, although the cured product has excellent heat resistance, it has a very high viscosity and is inferior in workability and moldability. In particular, its viscosity makes it impossible to use it as a semiconductor encapsulant using current molding methods. Furthermore, since a large amount of filler cannot be added at that viscosity, the most effective method for lowering the coefficient of linear expansion cannot be taken. Furthermore, the toughness has not reached a satisfactory level. Furthermore, the already known epoxy resin made from a dimerized product of β-naphthol via a methylene bond has insufficient heat resistance because it is difunctional, and is highly crystalline, making it difficult to epoxidize. Crystallization occurs during the process, making it extremely difficult to manufacture. On the other hand, 1,1-bis(2,7
-Diglycidyloxy-1-naphthyl)alkane has a naphthalene skeleton which is a heat-resistant skeleton and a hydrophobic skeleton, is tetrafunctional and has a high crosslinking density, and has a molecular structure with excellent symmetry. Because it satisfies all of these requirements, the cured product has extremely excellent heat resistance and water resistance. As for its heat resistance, its glass transition temperature is about 90° C. higher than that of a cured product of ortho-cresol novolac type epoxy resin (hereinafter referred to as ECN) having the same melt viscosity. Regarding water resistance, the water absorption rate is approximately 40% lower than that of ECN. [0057] Since it is different from the conventional novolak type, it also has excellent toughness. In addition, it has a low melt viscosity of about 3 ps at 150°C, and has good workability and moldability. [0058] Furthermore, since the amount of filler can be increased, this has an advantageous effect on lowering the coefficient of linear expansion, so that stress can be reduced when used as a semiconductor encapsulant. On the other hand, despite its highly symmetrical structure, it does not crystallize during the epoxidation process, and there are no manufacturing problems. Furthermore, 1,1-bis(2,7-bis) according to the present invention
diglycidyloxy-1-naphthyl)alkane and 1-
(2,7-diglycidyloxy-1-naphthyl)-1-
(2-glycidyloxy-1-naphthyl)alkane,
1,1-bis(2-glycidyloxy-1-naphthyl)
A cured product of an epoxy resin made of a mixture of three types of dimers of alkanes also has excellent heat resistance and moisture resistance. In addition, the melt viscosity is even lower, for example, when equimolar amounts of 2,7-dihydroxynaphthalene and β-naphthol are used,
Its dimerized product 1,1-bis(2,7-diglycidyloxy-1-naphthyl)methane and 1-(2,7-diglycidyloxy-1-naphthyl)-1-(2-glycidyloxy- 1-naphthyl)methane and 1,1-bis(2
-glycidyloxy-1-naphthyl)methane mixed epoxy resin has a melt viscosity of 1 ps or less at 150°C. In addition, the glass transition temperature of the cured product is as described in 1.
Although the temperature decreases by about 50°C compared to the cured product of 1-bis(2,7-diglycidyloxy-1-naphthyl)methane, the value is higher by more than 50°C compared to the cured product of ECN having the same melt viscosity. In addition, the water absorption rate is about 40% lower. Furthermore, as mentioned above, since the melt viscosity is very low, a large amount of filler can be added, and the coefficient of linear expansion can be made smaller. Also, by adjusting the molar ratio, crystallization does not occur during the epoxidation process. [Example] Next, the present invention will be specifically explained with reference to Synthesis Examples, Examples, and Comparative Examples. Synthesis Example 1 (Synthesis of tetrahydric phenols and their epoxidized products) In a 2-liter flask equipped with a thermometer, cooling tube, dropping funnel, and stirrer,
160 g (1 mol) of 2,7-dihydroxynaphthalene was dispersed in 1600 g of water, and 4.1 g (0.05 mol) of 49% by weight sodium hydroxide was added at 40°C. After that, 8
While raising the temperature to 0° C., 40.2 g of a 41% by weight formaldehyde aqueous solution (containing 0.55 mol of formaldehyde) was continuously added from the dropping funnel over 0.5 hours. After dropping and keeping warm at 80°C for 1 hour, 36% by weight hydrochloric acid 5.
1 g was added to neutralize. Thereafter, the reaction product was filtered off, washed with warm water, and dried to obtain 160 g of product. This substance was crystalline at room temperature and had a melting point of 253°C. According to GPC, the purity was 99%. This substance was dissolved in carbon-13-N using deuterated dimethyl sulfoxide as a solvent.
An MR image was measured. The chart is shown in Figure 1. From these results, the product of the above reaction is 1
, 1-bis(2,7-dihydroxy-1-naphthyl)methane. This 1,1-bis(
83g (2,7-dihydroxy-1-naphthyl)methane (
0.25 mol) was dissolved in 463 g (5 mol) of epichlorohydrin, and while stirring, 220 g of a 20% by weight aqueous sodium hydroxide solution was added dropwise at 80° C. over 5 hours, and the mixture was further kept at the same temperature for 1 hour. Then, after discarding the aqueous layer, 210 g of methyl isobutyl ketone was added to the reaction product obtained by distilling and recovering excess epichlorohydrin, and the mixture was uniformly dissolved. Then, 70 g of water was added and washed with water to separate oil and water. Water was removed from the oil layer by azeotropic distillation, filtered, and methyl isobutyl ketone was distilled off to obtain 128 g of epoxy resin (A) that was solid at room temperature. The softening point of this resin is 96℃, and the melt viscosity at 150℃ is 3
It was ps. Moreover, the epoxy equivalent was 159. This resin was dissolved in deuterium-substituted chloroform, and carbon-13
- NMR diagram was measured. The chart is shown in Figure 2. From these results, the product of the above reaction is 1
, 1-bis(2,7-diglycidyloxy-1-naphthyl)methane. Synthesis Example 2 (Synthesis Example Regarding 2, 3, Tetrahydric Phenols Mixture and Its Epoxidized Product) Instead of 2,7-dihydroxynaphthalene alone, 2,
80 g (0.5 mol) of 7-dihydroxynaphthalene and β
The same operation as in Synthesis Example 1 was carried out except that 72 g of -naphthol was used to obtain 137 g of a reaction product. The reaction product was a mixture of three compounds. According to gel permeation chromatography (hereinafter referred to as GPC), the production ratio is 1,1-bis(2,7-dihydroxy-
32% by weight of 1-naphthyl)methane, 1-(2,7-dihydroxy-1-naphthyl)-1-(2-hydroxy-1
-naphthyl)methane, 33% by weight, and 1,1-bis(2-hydroxy-1-naphthyl)methane, 34%. 105 g of the mixture of these three types of dimers was dissolved in 463 g (5 moles) of epichlorohydrin, and epoxidized in the same manner as in Synthesis Example 1. As a result, 152 g of solid epoxy resin (B) was obtained. The softening point of this mixed epoxy resin is 80℃, and the melt viscosity at 150℃ is 0.8
It was ps. Moreover, the epoxy equivalent was 180. Synthesis Example 3 1,6-dihydroxynaphthalene 160g (1 mol),
Formalin (35%) 57g, oxalic acid 1.8g, water 1
8g was heated to 100-120°C and reacted for 8 hours. Water was added to the reaction mixture and heated, the water was separated by decantation, and the product was then dried at 80° C. under reduced pressure to obtain a novolac resin. The 1,1-bis(1,6-dihydroxy-1-naphthyl)methane content in the solid weight of this novolac resin was 5% by weight. Next, 100 g of this novolak resin was dissolved in 555 g (6 moles) of epichlorohydrin, and 26% by weight of a 26% by weight aqueous sodium hydroxide solution was heated at 80° C. with stirring.
0 g was added dropwise over 5 hours, and the mixture was further kept at the same temperature for 1 hour. After that, after discarding the aqueous layer, 330 g of methyl isobutyl ketone was added to the reaction product obtained by distilling and recovering excess epichlorohydrin, and the mixture was dissolved uniformly. Then, 80 g of water was added and washed with water to separate oil and water. and
Water was removed from the oil layer by azeotropic distillation, filtered, and methyl isobutyl ketone was distilled off to obtain 155 g of novolac type epoxy resin (C) that was solid at room temperature. The softening point of this resin was 97°C, and the melt viscosity at 150°C was 45 ps. Moreover, the epoxy equivalent was 159. Synthesis Example 4 The same procedure as in Synthesis Example 1 was performed except that 144 g (1 mol) of β-naphthol was used instead of 2,7-dihydroxynaphthalene, and 1,1-bis(2-dihydroxy-
148 g of 1-naphthyl)methane were obtained. 78 g of this was dissolved in 463 g (5 moles) of epichlorohydrin, and heated at 80° C. with stirring in a 20% by weight aqueous sodium hydroxide solution.
20 g was added dropwise over 5 hours, and the mixture was further kept at the same temperature for 1 hour. During this process, crystals began to precipitate. Therefore, during the liquid separation process, the crystals were mixed into the aqueous layer, making the liquid separation process impossible. Therefore, after filtering both the water and oil layers and washing the filtration residue with water, the epoxy resin (D
) 120g was obtained. Softening point: 174℃, epoxy equivalent: 1
It was 45. The melt viscosity at 150°C could not be measured. Examples 1 to 2 and Comparative Examples 1 to 3 Synthesis Examples 3 and 4, which are the epoxy resins of the present invention and for comparison obtained in Synthesis Examples 1 and 2, and orthocresol novolak epoxy resin (softening point 67 ° C., Phenol novolac (softening point 80°C) was used as a hardening agent at 150°C (melt viscosity 3.2 ps, epoxy equivalent 212),
Triphenylphosphine was used as a curing accelerator, and after compounding the composition as shown in the table below so that one hydroxyl group of the curing agent was present for one epoxy group, the mixture was heated at 150°C for 2 hours and then at 180°C for 3 hours. After curing under the following conditions, test pieces were prepared and measurements were made on the test items listed in Table 1. The results are shown in Table 1 as Examples 1-2 and Comparative Examples 1-3, respectively. The test method was to measure the glass transition temperature (a measure of heat resistance) using a dynamic viscoelasticity measuring machine (hereinafter referred to as DMA).
The bending strength, bending elastic modulus, tensile strength, and tensile elongation rate (measures of toughness) are measured according to JIS K
-6911. In addition, melt viscosity and water absorption rate after 9 hours of boiling (a measure of water resistance) were also measured. The resin of Synthesis Example 5 had a melting point of 174° C., and therefore a cured product could not be obtained under these conditions, so the measured values were not recorded in Table 1. All compositions comprising the epoxy resin and curing agent of the present invention were suitable as semiconductor encapsulation materials. As can be seen from the results in Table 1, the cured product of the epoxy resin of the present invention has a low melt viscosity, and has excellent properties in terms of heat resistance, water resistance, and toughness. It is clear that it is also superior. Effects of the Invention The epoxy resin of the present invention has a low melt viscosity and is excellent in all properties including heat resistance, water resistance, and toughness. Therefore, the cured product of this epoxy resin has extremely excellent heat resistance and moisture resistance. Furthermore, it overcomes the drawbacks of hardness and brittleness, which are generally experienced by cured products of high heat-resistant epoxy resins, and has excellent toughness. In addition, since the melt viscosity of the resin itself is low, workability and moldability are also good, and since a large amount of filler can be added, the coefficient of linear expansion can be reduced. Therefore, when the epoxy resin composition of the present invention is used in the various uses mentioned above, high performance and reliability as well as good workability and moldability can be obtained. In particular, reliability in terms of solder heat resistance and thermal shock resistance is extremely improved when used for encapsulating highly integrated large chip semiconductors mounted on surface mount packages.

[Brief explanation of the drawing]

FIG. 1 is a carbon-13 nuclear magnetic resonance spectrum diagram of 1,1-bis(2,7-dihydroxy-1-naphthyl)methane.

FIG. 2 is a carbon-13-nuclear magnetic resonance spectrum diagram of 1,1-bis(2,7-diglycidyloxy-1-naphthyl)methane.

Claims (8)

[Claims] 1. 1,1-bis(2,7-diglycidyloxy-1-naphthyl)alkane. 2. 1,1-bis(2,7-diglycidyloxy-1-naphthyl) characterized by reacting 1,1-bis(2,7-dihydroxy-1-naphthyl)alkane with epihalohydrin. ) Method for producing alkanes. 3. 1,1-bis(2,7-dihydroxy-1-naphthyl)alkane. 4. A method for producing 1,1-bis(2,7-dihydroxy-1-naphthyl)alkane, which comprises reacting 2,7-dihydroxynaphthalene with an aldehyde. 5. An epoxy resin composition comprising an epoxy resin and a curing agent, wherein the epoxy resin comprises 1
, 1-bis(2,7-diglycidyloxy-1-naphthyl)alkane. 6. An epoxy resin composition comprising an epoxy resin and a curing agent, wherein the epoxy resin is 1,1
-bis(2,7-diglycidyloxy-1-naphthyl)
Alkane and 1-(2,7-diglycidyloxy-1-
An epoxy resin composition characterized by using a mixture of (naphthyl)-1-(2-glycidyloxy-1-naphthyl)alkane and 1,1-bis(2-glycidyloxy-1-naphthyl)alkane. 7. An epoxy resin composition comprising an epoxy resin and a curing agent, wherein the epoxy resin is 1,1
-bis(2,7-dihydroxy-1-naphthyl)alkane and 1-(2,7-dihydroxy-1-naphthyl)-
1-(2-hydroxy-1-naphthyl)alkane and 1
, 1-bis(2-hydroxy-1-naphthyl)alkane, and an epoxy resin obtained by reacting epihalohydrin. 8. 1,1-bis(2,7-dihydroxy-1-naphthyl)alkane and 1-(2,7-dihydroxy-1-naphthyl)-1-(2-hydroxy-1-naphthyl)alkane and 1,1-bis(2-hydroxy-
8. The composition according to claim 7, wherein the mixture with 1-naphthyl) alkane is a mixture of 2,7-dihydroxynaphthalene and β-naphthol reacted with an aldehyde.