JP2004331988A - Hardenable epoxy resin composition for semiconductor encapsulation - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a hardenable epoxy resin composition for semiconductor encapsulation containing a crystallized epoxy resin which is easy to mix with a hardener, or the like. <P>SOLUTION: This hardenable epoxy resin composition for semiconductor encapsulation essentially contains a crystallized epoxy resin derived from 4,4'-dihydroxy-3,3',5,5'-tetramethylbiphenyl and an epihalohydrin and has a value of not less than 1.03 for a ratio of the amount of endotherm between 50°C and 130°C measured using a DSC apparatus at the temperarure-raising rate of 10°C per minute and that between 80°C and 125°C, and a hardener for epoxy resins. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a crystallized tetramethylbiphenyl-type epoxy resin which can be easily blended with a curing agent, a method for producing the crystallized epoxy resin, and a semiconductor encapsulation using the crystallized epoxy resin, which has excellent physical properties. The present invention relates to a curable epoxy resin composition for use.

Epoxy resins are used in a wide range of fields such as adhesion, casting, sealing, lamination, molding, and painting because of their excellent cured physical properties and ease of handling.
Generally, an epoxy resin is mixed (blended) with various additives such as a curing agent, and then molded and cured as a curable epoxy resin composition. The components are uniformly mixed at the time of blending. If not, phenomena such as insufficient progress of the curing reaction and inhomogeneity of the cured product occur, and the performance cannot be sufficiently exhibited.

  The tetramethylbiphenyl type epoxy resin obtained by the reaction of 4,4′-dihydroxy-3,3 ′, 5,5′-tetramethylbiphenyl with epihalohydrin becomes a crystal having a melting point of 100 ° C. to 120 ° C. It is treated as a solid at room temperature, such as powder coatings and semiconductor encapsulants, and is widely used for heating, melting and flowing during molding and curing. However, since it is a crystal, it has a drawback that compatibility with a curing agent or the like is slow and poor mixing easily occurs. Therefore, if the temperature is raised to a temperature equal to or higher than the melting point at the time of compounding for uniform mixing, the reaction with the curing agent proceeds at that point, which tends to cause poor fluidity during molding. On the other hand, if the mixing time is lengthened, the productivity is lowered, which is disadvantageous industrially.

  The present invention relates to a crystallized tetramethylbiphenyl-type epoxy resin which can be easily blended with a curing agent and the like, a method for producing the crystallized epoxy resin, and a semiconductor encapsulation using the crystallized epoxy resin which is excellent in various physical properties. The present invention relates to a curable epoxy resin composition.

  The present inventors have conducted various studies in order to solve the above-mentioned problems, and as a result, the crystals of the tetramethylbiphenyl-type epoxy resin having a specific melting endothermic pattern are quickly compatible with a curing agent and the like, and are uniform. It was found that a curable epoxy resin composition was easily obtained, and that by taking specific crystallization conditions, it was possible to obtain a crystallized tetramethylbiphenyl type epoxy resin having a specific compatibility, which was fast. The present invention has been completed.

The present invention relates to a curable epoxy resin composition for semiconductor encapsulation containing the following crystallized epoxy resin of the invention as an essential component.
(1) A crystallized epoxy resin derived from 4,4′-dihydroxy-3,3 ′, 5,5′-tetramethylbiphenyl and epihalohydrin at a rate of 10 ° C./minute using a DSC device. A crystallized epoxy resin having a ratio of an endotherm between 50 ° C. to 130 ° C. and an endothermic amount between 80 ° C. to 125 ° C. measured by heating at 1.03 or more.

 (2) The ratio of the endothermic amount between 50 ° C. and 130 ° C. and the endothermic amount between 80 ° C. and 125 ° C. measured at a rate of 10 ° C./minute using the DSC apparatus is 1.05. As described above, the crystallized epoxy resin according to item (1), having a temperature of 1.50 or less and an endothermic peak temperature of 110 ° C. or less.

(3) An epoxy resin derived from 4,4′-dihydroxy-3,3 ′, 5,5′-tetramethylbiphenyl having an epoxy equivalent of 180 to 210 and epihalohydrin is cooled from a molten state at 105 ° C. or higher. A temperature of from 50 ° C. to 130 ° C. measured at a rate of 10 ° C./min using a DSC apparatus, characterized in that crystallization is carried out almost completely within 2 hours after the temperature becomes lower than 105 ° C. A method for producing a crystallized epoxy resin product, wherein the ratio of the endothermic amount between 80 ° C. and 125 ° C. is 1.03 or more.
(4) The ratio between the endothermic amount between 50 ° C. and 130 ° C. and the endothermic amount between 80 ° C. and 125 ° C. measured at a rate of 10 ° C./min using the DSC apparatus is 1.05. The method for producing a crystallized epoxy resin according to item (3), wherein the temperature is 1.50 or less and the endothermic peak temperature is 110 ° C. or less.

 (5) One of a method of adding a crystal nucleus and a method of applying a shearing force when cooling from a molten state of 105 ° C. or more and crystallizing almost completely within 2 hours after the temperature becomes lower than 105 ° C. The method for producing a crystallized epoxy resin product according to any one of the above items (3) and (4), wherein one or both methods are employed.

 (6) A crystallized epoxy resin derived from 4,4′-dihydroxy-3,3 ′, 5,5′-tetramethylbiphenyl and epihalohydrin at a rate of 10 ° C./minute using a DSC device. An epoxy resin crystallized product and a curing agent for epoxy resin having a ratio of an endotherm between 50 ° C. to 130 ° C. and an endotherm between 80 ° C. to 125 ° C. measured by raising the temperature of not less than 1.03 are essential. A curable epoxy resin composition formulated as a component.

 (7) The crystallized epoxy resin has an endotherm between 50 ° C. and 130 ° C. and an endotherm between 80 ° C. and 125 ° C., which are measured at a rate of 10 ° C. per minute by using a DSC device. The curable epoxy resin composition according to item (6), which is a crystallized epoxy resin having a ratio of 1.05 or more to 1.50 or less and an endothermic peak temperature of 110 ° C. or less.

  The crystallized epoxy resin of the present invention is easily blended with a curing agent or the like because of its quick compatibility. Further, according to the method for producing a crystallized epoxy resin of the present invention, the crystallized epoxy resin can be easily produced. Further, the curable epoxy resin composition of the present invention containing the crystallized epoxy resin has excellent curing properties and various cured properties because the curing reaction becomes uniform.

  The crystallized epoxy resin of the present invention is a crystallized epoxy resin derived from 4,4′-dihydroxy-3,3 ′, 5,5′-tetramethylbiphenyl and epihalohydrin, and has a melting endothermic pattern. The ratio between the endothermic amount between 50 ° C. and 130 ° C. and the endothermic amount between 80 ° C. and 125 ° C. measured by heating at a rate of 10 ° C. per minute using a DSC device is 1.03 or more. , Preferably 1.05 or more and 1.50 or less, more preferably 1.06 or more and 1.40 or less. The endothermic peak temperature is preferably 110 ° C. or lower, more preferably 109 ° C. or lower.

The endothermic amount is measured using a DSC apparatus (differential scanning calorimeter) by heating 5 to 20 mg of the crystal powder at a rate of 10 ° C. per minute, and the points at 50 ° C. and 130 ° C. of the obtained DSC curve are linearly measured. And can be calculated from the area of the portion surrounded by the straight line and the DSC curve. The amount of endotherm between 80 ° C. and 125 ° C. is determined similarly. The endothermic peak temperature is the peak temperature of the endothermic peak in the DSC curve.
If the ratio of the heat absorption between 50 ° C. and 130 ° C. and the heat absorption between 80 ° C. and 125 ° C. is too small, the compatibility with the curing agent or the like becomes slow, and the effect of the present invention is not sufficient. Crystals having an excessive endothermic ratio are not sufficiently crystallized, making it difficult to handle as a solid. Crystals having an excessively high endothermic peak temperature have a low compatibility with a curing agent or the like.

  The method for producing a crystallized epoxy resin product of the present invention is not particularly limited as long as a product having a ratio of endotherm of not less than a specified amount can be obtained. However, even when the same tetramethylbiphenyl-type epoxy resin is used, the crystal state changes under the crystallization conditions. Therefore, it is preferable to use the method for producing a crystallized epoxy resin of the present invention in which the crystallization conditions are specified.

  The tetramethylbiphenyl-type epoxy resin used in the method for producing a crystallized epoxy resin of the present invention is an epoxy resin derived from 4,4′-dihydroxy-3,3 ′, 5,5′-tetramethylbiphenyl and epihalohydrin. There are no particular restrictions on the production method and properties, but the epoxy equivalent needs to be from 180 to 210, preferably from 181 to 200. If the epoxy equivalent is too low, it is difficult to obtain a crystal having a ratio of endotherm of the specified or more even with the method for producing a crystallized epoxy resin of the present invention, and if the epoxy equivalent is too high, crystallization is completed within a specified time. It becomes difficult.

  In the method for producing a crystallized epoxy resin of the present invention, first, a tetramethylbiphenyl type epoxy resin is placed in a molten state at 105 ° C. or higher. Subsequently, the mixture is cooled and crystallized to a temperature equal to or lower than the melting point, but is almost completely crystallized within 2 hours, preferably within 1 hour and 30 minutes, more preferably within 1 hour after the resin temperature becomes lower than 105 ° C. . Substantially complete crystallization refers to a state in which it can be handled as a solid. The effect of the present invention becomes remarkable as the crystallization time is shorter, and the epoxy resin crystallized product of the present invention cannot be obtained if it is too long.

There are various methods for shortening the crystallization time, and there is no particular limitation.However, a method of adding a crystal nucleus prepared separately or a method of applying a shearing force to the resin by stirring or kneading can be performed easily in a short time. It is preferable because it can be crystallized.
The preferred crystallization temperature varies depending on other conditions, but is usually 10 to 90 ° C, preferably 20 to 80 ° C.

The curable epoxy resin composition of the present invention is a curable epoxy resin composition comprising the crystallized epoxy resin of the present invention and a curing agent for epoxy resin as essential components.
The curable epoxy resin composition of the present invention may contain an epoxy resin other than the crystallized epoxy resin of the present invention. The epoxy resin that can be used in combination is not particularly specified, and any epoxy resin other than the crystallized epoxy resin of the present invention can be used.

  Examples of such epoxy resins include bisphenol A, bisphenol F, bisphenol AD, tetrabutyl bisphenol A, hydroquinone, methylhydroquinone, dimethylhydroquinone, dibutylhydroquinone, resorcinol, methylresorcinol, biphenol, dihydroxynaphthalene, dihydroxydiphenylether, dihydroxystilbene. Phenol novolak resin, cresol novolak resin, bisphenol A novolak resin, dicyclopentadiene phenol resin, phenol aralkyl resin, naphthol novolak resin, terpene phenol resin, heavy oil modified phenol resin, brominated phenol novolak resin, etc. And various phenols and hydroxybenzaldehyde Various phenolic compounds such as polyhydric phenolic resins obtained by condensation reaction with various aldehydes such as crotonaldehyde and glyoxal, and epoxy resins produced from epihalohydrin and various kinds of diaminodiphenylmethane, aminophenol, xylenediamine, etc. And epoxy resins manufactured from epihalohydrin and various carboxylic acids such as methylhexahydrophthalic acid and dimer acid, and the like.

  The proportion of the crystallized epoxy resin of the present invention used in the curable epoxy resin composition of the present invention is 10 to 100% by weight, preferably 20 to 100% by weight, based on all epoxy resin components. If the proportion of the high-performance epoxy resin composition of the present invention is small, the excellent properties of the tetramethylbiphenyl type epoxy resin will not be exhibited.

  In the curable epoxy resin composition of the present invention, a curing agent for epoxy resin is blended as an essential component, but there is no particular designation, and any curing agent for epoxy resin can be used. is there.

  Examples of the usable curing agent include bisphenol A, bisphenol F, bisphenol AD, tetrabutyl bisphenol A, hydroquinone, resorcin, methylresorcin, biphenol, tetramethylbiphenol, dihydroxynaphthalene, dihydroxydiphenyl ether, phenol novolak resin, and cresol novolak resin. , Bisphenol A novolak resin, dicyclopentadiene phenol resin, terpene phenol resin, naphthol novolak resin, heavy oil modified phenol resin, various polyhydric phenols such as brominated phenol novolak resin, and various phenols and hydroxybenzaldehyde, Polyvalent pheno obtained by condensation reaction with various aldehydes such as crotonaldehyde and glyoxal Phenolic resins such as phenolic resins, acid anhydrides such as methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, and methylnadic acid, diethylenetriamine, isophoronediamine, diaminodiphenylmethane, diaminodiphenylsulfone, dicyandiamide, and the like. Amines and the like.

  Examples of the curing agent of the type that initiates the polymerization of epoxy groups include phosphine compounds such as triphenylphosphine, phosphonium salts such as tetraphenylphosphonium tetraphenylborate, 2-methylimidazole, 2-phenylimidazole and 2-ethyl- Imidazoles such as 4-methylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-methylimidazole, 2,4-dicyano-6- [2-methylimidazolyl- (1)]-ethyl-S-triazine; -Cyanoethyl-2-undecylimidazolium trimellitate, 2-methylimidazolium isocyanurate, 2-ethyl-4-methylimidazolium tetraphenylborate, 2-ethyl-1,4-dimethylimidazolium tetraphenylborate Which imidazolium salt, amines such as 2,4,6-tris (dimethylaminomethyl) phenol and benzyldimethylamine, ammonium salts such as triethylammonium tetraphenylborate, 1,5-diazabicyclo (5,4,0)- Diazabicyclo compounds such as 7-undecene and 1,5-diazabicyclo (4,3,0) -5-nonene; tetraphenylborate, phenol salts, phenol novolak salts and 2-ethylhexanoate salts of these diazabicyclo compounds;

Furthermore, triflic acid (Triflic acid) salts, boron trifluoride ether complex compounds, metal fluoroboron complex salts, bis (perfluoroalkylsulfonyl) methane metal salts, aryldiazonium compounds, aromatic onium salts, and di-groups of IIIa to Va elements carbonyl chelates, thiopyrylium salts, MF ₆ ^- form of VIb elements anion (wherein M is selected from phosphorus, antimony and arsenic), arylsulfonium complex salts, aromatic iodonium complex salts, aromatic sulfonium complex salt, bis [4- (Diphenylsulfonio) phenyl] sulfide-bis-hexafluorometal salt (for example, phosphate, arsenate, antimonate and the like), arylsulfonium complex salt, and aromatic sulfonium or iodonium salt of halogen-containing complex ion may be used. it can. These curing agents for epoxy resins may be used alone or in combination of two or more.

When a compound having a group that reacts with an epoxy group is used, the proportion of the curing agent used in the curable epoxy resin composition of the present invention is based on 1 mol of epoxy group in all epoxy resin components. The amount of the group that reacts with the epoxy group in the curing agent component is preferably from 0.5 to 2.0 mol, more preferably from 0.7 to 1.5 mol.
When a curing agent of the type that initiates the polymerization of epoxy groups is used as the curing agent component, it is preferably 0.1 to 10 parts by weight, more preferably 0.3 to 10 parts by weight, based on 100 parts by weight of all epoxy resin components. 5 parts by weight.

In the curable epoxy resin composition of the present invention, if necessary, an inorganic filler, a reinforcing fiber, a curing accelerator, a coupling agent, a plasticizer, a pigment, a solvent, a flame retardant, and the like can be appropriately compounded. .
Examples of the type of the inorganic filler include fused silica, crystalline silica, glass powder, alumina, and calcium carbonate. Its shape is crushed or spherical. Various inorganic fillers are used alone or in combination of two or more. The amount used is 30 to 95% by weight of the whole composition, preferably 50 to 95% by weight, more preferably 70 to 93% by weight.

The curing accelerator is a compound that promotes a reaction between an epoxy group in the epoxy resin and an active group in the curing agent.
Examples of the curing accelerator include phosphine compounds such as tributylphosphine, triphenylphosphine, tris (dimethoxyphenyl) phosphine, tris (hydroxypropyl) phosphine, and tris (cyanoethyl) phosphine, tetraphenylphosphonium tetraphenylborate, and methyltributylphosphonium. Tetraphenylborate, phosphonium salts such as methyltricyanoethylphosphonium tetraphenylborate, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-methylimidazole, 2,4-dicyano-6- [2-methylimidazolyl- (1)]-ethyl-S-triazine, 2,4-dicyano-6- [2-un Imidazoles such as silimidazolyl- (1)]-ethyl-S-triazine, 1-cyanoethyl-2-undecylimidazolium trimellitate, 2-methylimidazolium isocyanurate, 2-ethyl-4-methylimidazolium tetra Imidazolium salts such as phenylborate, 2-ethyl-1,4-dimethylimidazolium tetraphenylborate, 2,4,6-tris (dimethylaminomethyl) phenol, benzyldimethylamine, tetramethylbutylguanidine, N-methylpiperazine , 2-dimethylamino-1-pyrroline and other amines, triethylammonium tetraphenylborate and other ammonium salts, 1,5-diazabicyclo (5,4,0) -7-undecene, 1,5-diazabicyclo (4,3 , 0) -5 Nene, 1,4-diazabicyclo (2,2,2) - diazabicyclo compounds such as octane, tetraphenylborate thereof diazabicyclo compounds, phenol salts, phenol novolak salts and 2-ethyl hexanoate and the like.

Among these compounds that serve as curing accelerators, tertiary amines, phosphine compounds, imidazole compounds, diazabicyclo compounds, and salts thereof are preferable.
These curing accelerators are used alone or as a mixture of two or more kinds, and the amount used is 0.1 to 7% by weight based on all epoxy resin components.

  Examples of the flame retardant include halogen-based flame retardants such as brominated epoxy resins, antimony compounds such as antimony trioxide, phosphorus-based flame retardants such as phosphate esters and phosphines, nitrogen-based flame retardants such as melamine derivatives, and hydroxylated flame retardants. Examples include inorganic flame retardants such as aluminum and magnesium hydroxide.

  The crystallized epoxy resin of the present invention is easily blended with the curing agent and the like because of its rapid compatibility, and the method for producing a crystallized epoxy resin of the present invention can easily produce the crystallized epoxy resin. Further, the curable epoxy resin composition of the present invention is excellent in curability and various cured physical properties because the curing reaction occurs uniformly.

  Examples of the production of the tetramethylbiphenyl-type epoxy resin, the crystallized epoxy resin of the present invention, the method for producing the crystallized epoxy resin, and examples and comparative examples of the curable epoxy resin composition will be described in further detail.

(Example of producing tetramethylbiphenyl type epoxy resin)
In a 5 L three-necked flask equipped with a thermometer, a stirrer, and a condenser, 363 g of 4,4′-dihydroxy-3,3 ′, 5,5′-tetramethylbiphenyl, 1665 g of epichlorohydrin, and 2-propanol After charging 600 g and dissolving by raising the temperature to 50 ° C., 273 g of a 48.5% by weight aqueous sodium hydroxide solution was added dropwise over 1 hour. During this period, the temperature was gradually raised so that the temperature in the system reached 70 ° C. at the end of the dropping. Thereafter, the reaction was carried out at 70 ° C. for 30 minutes. After the completion of the reaction, the product was washed with water to remove by-product salts and excess sodium hydroxide. Then, excess epichlorohydrin and 2-propanol were distilled off from the product under reduced pressure to obtain a crude epoxy resin.

  This crude epoxy resin was dissolved in 750 g of methyl isobutyl ketone, 6 g of a 48.5% by weight aqueous sodium hydroxide solution was added, and the mixture was reacted at a temperature of 70 ° C. for 1 hour. After the completion of the reaction, sodium phosphate monobasic was added to neutralize excess sodium hydroxide, and washed with water to remove by-product salts. Then, methyl isobutyl ketone was completely removed under reduced pressure while heating to obtain the desired epoxy resin. The state of the epoxy resin at this point is a molten state at a resin temperature of about 150 ° C.

Example 1
50 g of the molten tetramethylbiphenyl-type epoxy resin produced in the above-mentioned production example was placed in a glass container, and gradually cooled to obtain a crystal powder of the tetramethylbiphenyl-type epoxy resin separately prepared when the resin temperature reached 70 ° C. 3 g was added and mixed quickly. When the resin was allowed to cool as it was, it crystallized almost completely after 25 minutes from the time when the resin temperature reached 105 ° C., and became ready to be handled as a solid.

Table 1 shows the epoxy equivalent of the crystallized epoxy resin, the endothermic amount between 50 ° C. and 130 ° C., the endothermic amount between 80 ° C. and 125 ° C., their ratio, and the endothermic peak temperature.
The DSC data was measured using an MDSC 2920 type device manufactured by TA Instruments, at a sample amount of about 10 mg and a heating rate of 10 ° C. per minute. The calculation of the endothermic amount was performed by automatic calculation by a computer. (See the DSC charts in FIGS. 1 and 2)

Example 2
50 g of the molten tetramethylbiphenyl-type epoxy resin produced in the above production example was placed in a glass container, and gradually cooled. When the resin temperature reached 70 ° C., the mixture was vigorously stirred with a glass rod for 5 minutes. Some crystals began to precipitate during the stirring. When the resin was allowed to cool as it was, it crystallized almost completely after 15 minutes from the time when the resin temperature reached 105 ° C., and became ready to be handled as a solid.
Table 1 shows the epoxy equivalent of the crystallized epoxy resin, the endothermic amount between 50 ° C. and 130 ° C., the endothermic amount between 80 ° C. and 125 ° C., their ratio, and the endothermic peak temperature.

Comparative Example 1
50 g of the molten tetramethylbiphenyl type epoxy resin produced in the above production example was placed in a glass container, allowed to stand, and allowed to cool. Crystal precipitation was very slow, and after the resin temperature reached 105 ° C., it crystallized almost completely three hours later, and was ready to be handled as a solid.
Table 1 shows the epoxy equivalent of the crystallized epoxy resin, the endothermic amount between 50 ° C. and 130 ° C., the endothermic amount between 80 ° C. and 125 ° C., their ratio, and the endothermic peak temperature. (See the DSC charts in FIGS. 3 and 4)

Comparative Example 2
50 g of the molten tetramethylbiphenyl-type epoxy resin produced in the above production example was placed in a glass container and dissolved in 50 g of methyl isobutyl ketone at about 100 ° C. It was cooled slowly and kept at about 20 ° C. for about 5 hours. After the precipitated needle-like crystals were separated by filtration, they were vacuum-dried at 50 ° C. for about 5 hours to remove methyl isobutyl ketone, thereby obtaining a crystallized epoxy resin.
Table 1 shows the epoxy equivalent of the crystallized epoxy resin, the endothermic amount between 50 ° C. and 130 ° C., the endothermic amount between 80 ° C. and 125 ° C., their ratio, and the endothermic peak temperature.

Examples 3 and 4 and Comparative Examples 3 and 4
As shown in Table 2, crystallized epoxy resin produced in Examples 1 and 2 or Comparative Examples 1 and 2 as epoxy resin component, phenol aralkyl resin as curing agent component, fused silica powder as inorganic filler, cured Triphenylphosphine was used as an accelerator, and carnauba wax was used as a release agent.
Next, each component was pulverized and mixed, and then kneaded at 70 ° C. for 5 minutes using a mixing roll. Each of the obtained mixtures was taken out into a sheet and pulverized to obtain each curable epoxy resin composition.

The gel time of each curable epoxy resin composition was measured at 180 ° C. Each of these curable epoxy resin compositions was molded by a low-pressure transfer molding machine at a mold temperature of 180 ° C. and a molding time of 90 seconds, and each test piece was obtained and post-cured for 5 hours. The glass transition temperature and the bending strength at 23 ° C. of each test piece were measured and are shown in Table 2.
The curable epoxy resin compositions produced in Examples 3 and 4 were excellent in curability, heat resistance and mechanical strength as compared with the curable epoxy resin compositions produced in Comparative Examples 3 and 4.

The figure which shows the measurement example of the heat absorption amount between 50 degreeC-130 degreeC of the epoxy resin crystallized substance of Example 1. The figure which shows the example of a measurement of the endothermic amount between 80 degreeC and 125 degreeC of the crystallized epoxy resin of Example 1. The figure which shows the measurement example of the endothermic amount between 50 degreeC and 130 degreeC of the crystallized epoxy resin of the comparative example 1. The figure which shows the measurement example of the endothermic amount between 80 degreeC and 125 degreeC of the crystallized epoxy resin of the comparative example 1.

Claims (6)

  A crystallized epoxy resin derived from 4,4′-dihydroxy-3,3 ′, 5,5′-tetramethylbiphenyl and epihalohydrin, which is heated at a rate of 10 ° C./minute using a DSC device. An epoxy resin crystallized product having a ratio of an endotherm between 50 ° C. to 130 ° C. and an endothermic amount between 80 ° C. to 125 ° C. of 1.03 or more and a curing agent for epoxy resin as essential components A curable epoxy resin composition for semiconductor encapsulation comprising:   An epoxy resin crystallized product derived from 4,4′-dihydroxy-3,3 ′, 5,5′-tetramethylbiphenyl and epihalohydrin is cooled from a molten state of 105 ° C. or higher to a temperature lower than 105 ° C. 2. The curable epoxy resin composition for semiconductor encapsulation according to claim 1, which is a crystallized epoxy resin obtained by crystallizing almost completely within two hours from the start.   A method of adding crystal nuclei at a temperature lower than 105 ° C. and a shearing force at a temperature lower than 105 ° C. when the crystallized epoxy resin crystallizes almost completely within 2 hours after the temperature becomes lower than 105 ° C. 3. The curable epoxy resin composition for semiconductor encapsulation according to claim 2, wherein the curable epoxy resin composition is obtained by crystallization by one or both of the following methods. The curable epoxy resin composition for semiconductor encapsulation according to any one of claims 1 to 3, wherein the epoxy resin curing agent is a phenol resin. The semiconductor curable epoxy resin composition according to any one of claims 1 to 4, wherein the curable epoxy resin composition further comprises a curing accelerator and an inorganic filler. Curable epoxy resin composition. A cured product for semiconductor encapsulation obtained by curing the curable epoxy resin composition for semiconductor encapsulation according to claim 1.

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