KR20050095783A - Epoxy resin, process for producing the same, epoxy resin composition containing the same, and cured object - Google Patents

Abstract

An epoxy resin having excellent curability and high crystallizability; an epoxy resin composition having excellent blocking resistance; and a cured epoxy resin excellent in heat resistance, moisture resistance, and adhesion. The epoxy resin is one obtained by reacting a 4,4'- dihydroxydiphenyl sulfide compound with epichlorohydrin, wherein the content of molecules in which the number of repetitions, n, is 0 is 90 wt. % or higher and the content of monoepoxy molecules is 2 wt.% or lower. For example, the epoxy resin is obtained by reacting 2,2'-dimethyl-5, 5'-di-tert-butyl-4,4'-dihydroxydiphenyl sulfide with excess epichlorohydrin in the presence of an alkali metal hydroxide.

Description

Epoxy resin, its manufacturing method, epoxy resin composition and hardened | cured material using the same {EPOXY RESIN, PROCESS FOR PRODUCING THE SAME, EPOXY RESIN COMPOSITION CONTAINING THE SAME, AND CURED OBJECT}

The present invention provides a sealing and powder coating for electrical / electronic parts typical of semiconductor devices that are excellent in handling properties such as low viscosity, curing reactivity, blocking resistance, and impart hardened materials excellent in low hygroscopicity and adhesion to metal materials. The present invention relates to a crystalline epoxy resin useful for a laminated material, a composite material, and the like, a production method thereof, an epoxy resin composition using the same, and a cured product thereof.

Background Art Conventionally, epoxy resins have been used for a wide range of industrial uses, and their required performance has been increasingly advanced in recent years. For example, there is a semiconductor sealing material in a typical field of a resin composition based on epoxy resin, but as the degree of integration of semiconductor devices improves in recent years, the package size becomes larger and thinner, and the mounting method is also surface mounted. The development of this material is progressing, and the development of the material which is excellent in the resistance to soldering heat is desired.

In order to overcome the above problems, a high degree of filling of the filler is strongly directed, and a low viscosity epoxy resin is desired. As the low-viscosity epoxy resin, although a wide range of epoxy resins such as a phenol phenol-A epoxy resin and a bisphenol-F epoxy resin are generally known, these epoxy resins are usually liquid at room temperature, and it is difficult to obtain a resin composition for transfer molding. Do. Thus, a crystalline epoxy resin having a melting point at room temperature has been proposed, and biphenyl epoxy resins (JP-A-4-7365) and diphenylmethane epoxy resins (JP-A-6-345850) It is proposed. These epoxy resins are excellent in low viscosity and have excellent properties such as high filling rate of the filler, whereas low viscosity tends to cause fusion of powder in the state of the epoxy resin composition, and has a problem in blocking resistance. . Moreover, even the obtained hardened | cured material was not enough in terms of low hygroscopicity and adhesiveness.

From the viewpoint of blocking resistance, low hygroscopicity and improved adhesion to metal materials, Japanese Patent Application Laid-open No. Hei 6-145300 discloses a tertiarybutyl group in a position adjacent to a glycidyl ether group. Although an epoxy resin having a diphenylsulfide structure has been proposed, eggplants were not sufficient in terms of curability, low viscosity, blocking resistance and heat resistance.

Accordingly, the present invention is to provide an epoxy resin, an epoxy resin composition, and a cured product which are excellent in curability, low viscosity and blocking resistance, and which provide a cured product excellent in low hygroscopicity and heat resistance.

The epoxy resin of the present invention is synthesized by reacting 4,4'-dihydroxydiphenylsulfide with epichlorohydrin. In the case of synthesizing an epoxy resin, in particular, when substituents such as tertiary butyl groups exist at positions adjacent to hydroxyl groups, the progress of the epoxidation reaction is inhibited due to the steric hindrance, and monoepoxy in which one terminal group is not epoxidized in the product. It was found that the remaining amount of the sieve increased. Furthermore, as a result of detailed examination, it discovered that the monoepoxy body greatly influenced the curability, blocking resistance, and the heat resistance and moisture resistance of hardened | cured material as an epoxy resin, and came to this invention.

The present invention is an epoxy resin obtained by reacting 4,4'-dihydroxydiphenylsulfides with epichlorohydrin, with 4,4'-diglycidyloxydiphenylsulfide as a main component and monoepoxy It is a crystalline epoxy resin whose content of a sieve is 2 wt% or less.

Moreover, this invention is an epoxy resin composition using the said crystalline epoxy resin as a part or all part of an epoxy resin component in the epoxy resin composition which consists of an epoxy resin and a hardening | curing agent. Furthermore, this invention is hardened | cured material formed by hardening | curing the said epoxy resin composition. Here, as 4,4'- dihydroxy diphenyl sulfide, 4,4'- dihydroxy diphenyl sulfide, 2,2'- dimethyl- 4,4'- dihydroxy diphenyl sulfide, 2,2 ', 5,5'-tetramethyl-4,4'-dihydroxydiphenylsulfide is exemplified, but preferably 2,2'-dimethyl-5,5'-dibutylbutyl-4,4'-dihydroxy Sidiphenylsulfide is exemplified. As 4,4'- diglycidyl oxydiphenyl sulfides, 2,2'-dimethyl-5,5'-dibutyl butyl-4,4'- diglycidyl oxydiphenyl sulfide is illustrated.

The epoxy resin of the present invention is obtained by reacting 4,4'-dihydroxydiphenylsulfides (hereinafter may be abbreviated as dihydroxy compound) and epichlorohydrin. The content of monoepoxy is 2wt. Less than or equal to Here, monoepoxy refers to a compound in which one terminal group is not epoxidized. For example, 1) Epichlorohydrin is not added to one phenolic hydroxyl group of a dihydroxy compound. Compound, 2) a chlorohydrin added by epichlorohydrin represented by formula (a) below, and 3) a diol body in which chlorine of chlorohydrin represented by formula (c) is hydrolyzed. 4) Furthermore, the main component is the chlorohydrin body represented by following formula (d) which added epichlorohydrin to the hydroxyl group of a chlorohydrin body, and was produced | generated further. In addition, the monoepoxy body of another structure is negligible even if it produces | generates, The monoepoxy body in this invention says the sum of said 1) -4). In addition, the following formula is for demonstrating the structure of an end group, Comprising: It is understood that it does not describe the epoxy resin of this invention.

In the epoxy resin of the present invention, the content of these monoepoxy bodies is 2 wt% or less, preferably 1.5 wt% or less, and more preferably 1.0 wt% or less. When these compounds remain, not only will the curability and the heat resistance be lowered, but the moisture resistance of the cured product will be lowered, and as a result, the reliability of the semiconductor sealing material is lowered. However, since the fall of physical property is not shown substantially, it is not necessarily required to be 0.1 wt% or less.

Although the epoxy resin of this invention is a crystalline solid of room temperature solid, when the residual amount of the monoepoxy body in the epoxy resin of this invention increases, it will raise melting | fusing point fall and will reduce the crystallinity of an epoxy resin. The good or bad crystallinity of the epoxy resin is judged by the endothermic amount, endothermic peak temperature, and the like accompanying the melting of the crystal. The preferred endothermic amount and the endothermic peak temperature are different depending on the structure of the target epoxy resin. In the case of 2'-dimethyl-5.5'-dibutylbutyl-4,4'-diglycidyloxydiphenylsulfide, the endothermic amount accompanying melting of the crystal is in the range of 68 to 80 J / g, furthermore preferably 70 to 80 J range of / g. The endothermic peak temperature is in the range of 118 to 124 degrees, more preferably in the range of 119 to 123 degrees. Moreover, the half value width of a preferable endothermic peak is 7.5 degrees or less, More preferably, it is 7.0 degrees or less. Below these ranges, the crystallinity as an epoxy resin becomes low, and blocking resistance falls as an epoxy resin composition. The endothermic amount referred to here is measured from room temperature to 180 degrees under a condition of temperature rising rate of 10 degrees / minute under a nitrogen stream using a sample weighed approximately 10 mg by a differential thermal analyzer. The amount of heat calculated by reducing the calorific value based on the progress of crystallization in the course of the temperature increase from the endothermic amount accompanying melting. The half width of the endothermic peak is represented by the peak width at the midpoint between the baseline of the endothermic curve and the endothermic peak in the endothermic peak based on the melting of the crystal.

Epoxy resins are generally synthesized by reacting a corresponding bisphenol compound with an excess of epichlorohydrin, wherein an epoxy compound produced in addition to the compound (monomer epoxy) in which both terminals of the bisphenol are epoxidized also reacts with the bisphenol body. By repeating this, the multimer epoxy compound (multimer epoxy) of bisphenol is by-product. In order to increase the crystallinity of the epoxy resin, the higher the content of the monomer epoxy is, the better, usually 88 wt% or more, preferably 90 wt% or more, and more preferably 92 wt% or more.

The epoxy resin of this invention is an epoxy resin obtained by making 4,4'- dihydroxy diphenyl sulfide react with epichlorohydrin, and is following formula (1)

In the compound represented by (wherein R ₁ to R ₄ independently represent hydrogen or an alkyl group having 1 to 6 carbon atoms, n represents a number of 0 to 10), the content of n = 0 is 90 wt% or more, Furthermore, the content rate of monoepoxy is 2 wt% or less.

This epoxy resin is following formula (2)

(Wherein R ₁ to R ₄ independently represent hydrogen or an alkyl group having 1 to 6 carbon atoms) and di (hydroxyphenyl) sulfide and epichlorohydrin are present in the presence of an alkali metal hydroxide. After reacting and obtaining a crude epoxy resin, it is obtained by making the obtained epoxy resin react with alkali metal oxide again.

R ₁ to R ₄ independently represent hydrogen or an alkyl group having 1 to 6 carbon atoms, and R ₁ or R ₂ is preferably a bulky group such as an isopropyl group or a t-butyl group. However, it is not preferable that both R ₁ and R ₂ are t-butyl groups. Moreover, it is more preferable that R <_3> and R <_4> is H or a methyl group.

Preferred bisphenol compounds are 2,2'-dimethyl-5,5'-dibutylbutyl-4,4'-dihydroxydiphenylsulfide. The epoxy resin of this invention can be synthesize | combined by making this and epichlorohydrin react using such a bisphenol compound. Although there is no limitation in particular as a manufacturing method of the epoxy resin of this invention, When the bisphenol compound to be used has a tertiary bulky tertiary butyl group in the adjacent position of a hydroxyl group, it is usually since the epoxidation reaction tends to be suppressed. It is difficult to obtain an epoxy resin excellent in crystallinity by applying the same synthetic conditions as the epoxy resin of. That is, an epoxy resin is generally synthesized by dissolving a bisphenol compound in excess epichlorohydrin and then reacting it in the presence of alkali metal hydroxides such as sodium hydroxide and potassium hydroxide (called primary reaction). When obtaining the epoxy resin which has a group like group, it is preferable to carry out the ring-closure reaction (referred to as secondary reaction) of the chlorohydrin body which remained by contacting with alkali metal hydroxide after that.

The epichlorohydrin used for the primary reaction needs to be used in excess of the amount of the phenolic hydroxyl group of the bisphenol compound, and is usually 2 mol or more with respect to 1 mol of the phenolic hydroxyl group, preferably 2.5 mol or more, more preferably. It is more than 5 moles. If it is less than this, the production amount of a multimeric epoxy will increase, and the formation property of an epoxy resin will fall. Moreover, although the usage-amount of alkali metal hydroxide is the range of 0.80-1.10 mol normally with respect to 1 mol of hydroxyl groups of a bisphenol compound, in this invention, it is preferable not to exceed 1.0 mol, and the range of 0.86-1.00 mol is preferable. More preferably, the range of 0.88-0.99 mol is good. If less than this, the amount of remaining chlorine increases and is not preferable. If more than this, the amount of gel produced increases. The reaction temperature is usually 20 to 120 degrees. The lower the reaction temperature is, the higher the epoxy resin having a lower chlorine content can be obtained. However, since the reaction time is longer, it is not industrially preferable. Therefore, preferable reaction temperature is 40-100 degree | times, More preferably, it is the range of 40-75 degree | times. The water produced during the reaction is preferably removed off-system, and can be removed off-system by azeotroping with epichlorohydrin under reduced pressure. It is preferable to keep the amount of epichlorohydrin in the system as constant as possible, and the released epichlorohydrin is returned to the system after separation from water. The reaction time is usually 1 to 10 hours.

In the first reaction, a solvent may be used. Examples of the solvent include aliphatic hydrocarbon solvents, aromatic solvents, alcohols, ethers, ketones, and the like. Among them, an aprotic solvent is suitably selected from the viewpoint of high purity of the epoxy resin, and for example, dimethylsulfoxide, diethylene glycol dimethyl ether, and the like can be exemplified. As addition amount of a solvent, the range of 10-300 wt% is preferable with respect to a bisphenol compound. If less than this, the effect of addition will be small. If more than this, volumetric efficiency will fall and it is economically unpreferable. In the reaction, a phase transfer catalyst such as a quaternary ammonium salt may be used. Examples of quaternary ammonium salts include tetramethylammonium chloride, tetrabutylammonium chloride, benzyltriethylammonium chloride, and the addition amount thereof is in the range of 0.1 to 2.0 wt% based on the bisphenol compound. desirable. If it is less than this, the effect of addition of quaternary ammonium salt is small, and if it is more than this, the amount of hard hydrolyzable chlorine will increase, and high purity will become difficult.

After completion of the reaction, excess epichlorohydrin and solvent were removed, and then the residue was dissolved in a solvent such as toluene, methyl isobutyl ketone, filtered, washed with water to remove inorganic salts, and then the solvent was removed to obtain an epoxy resin. Can be.

In order to obtain the epoxy resin of the present invention, it is possible to perform only the first reaction, but it is advantageous to apply the manufacturing method of the present invention because there is a drawback that a high purification operation is required, and there is a drawback that the emulsion increases and the ratio decreases when washed with water. Do.

In the production method of the present invention, a secondary reaction is performed in which the prepared epoxy resin is reacted with an alkali metal hydroxide to generate a ring-closure reaction of the remaining chlorohydrin. In this secondary reaction, the epoxy resin obtained in the primary reaction can be dissolved in a solvent and brought into contact with an alkali metal hydroxide. As a solvent to be used, ketones, such as methyl isobutyl ketone, alcohols, such as n-butanol, and aromatic solvents, such as toluene, are selected. As a usage-amount of a solvent, it is the range of 200-1000 weight part normally with respect to 100 weight part of epoxy resins. The amount of alkali metal hydroxide used for the reaction is 1 to 30 times, preferably 1.2 to 10 times, the amount of hydrolyzable chlorine remaining in the epoxy resin. In addition, the reaction temperature is in the range of 40 to 120 degrees, and the reaction time is preferably in the range of 0.5 to 6 hours. After the secondary reaction, the epoxy resin of the present invention can be obtained by excluding the salt produced by filtration or washing with water, and further removing the solvent out of the system by distillation.

Since the obtained epoxy resin is easy to take a supercooled state, when it is taken out of a reactor and left at room temperature as it is, it exists as a viscous liquid over a long term. In order to obtain the crystalline epoxy resin of the present invention, it is preferable to perform an operation for promoting crystallization. As a method of crystallization, there exists a method of aiming at low viscosity using a solvent and promoting crystallization. As the solvent type in this case, alcohols such as methanol, ethanol and isopropyl alcohol, and hydrocarbon solvents such as pentane, hexane and heptane are suitably used. Alternatively, there is a method of crystallizing by adding a seed crystal prepared in advance to a liquid epoxy resin.

When the content of the multimer epoxy after synthesis is high, the monomer epoxy content in which n is 0 in General formula (1) can be raised by methods, such as molecular distillation and recrystallization. As a solvent in the case of recrystallization, alcohols such as methanol, ethanol and isopropyl alcohol, esters of ethyl acetate, hydrocarbon solvents such as pentane, hexane and heptane or a mixture thereof are suitably used.

As a hardening | curing agent used for the resin composition of this invention, all what is generally known as a hardening | curing agent of an epoxy resin can be used. Examples thereof include dicyandiamide, polyhydric phenols, acid anhydrides, aromatic and aliphatic amines, and the like.

Specifically, examples of the polyhydric phenols include a) bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4'-bisphenol, 2,2'-bisphenol, hydroquinone and resorcin. B) Tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol novolac, other than divalent phenols such as naphthylene diol -Trivalent or more phenols represented by cresol novolac, naphthol novolac, polyvinylphenol, etc .; c) monovalent phenols such as phenols and naphthols, bisphenol A, bisphenol F, Bivalent phenols such as bisphenol S, fluorene bisphenol, 4,4'-bisphenol, 2,2'-bisphenol, hydroquinone, resorcin, naphthylenediol, formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, Multivalent compound synthesized from condensing agents such as p-xylylene glycol And the like nolseong compound.

Examples of the acid anhydrides include phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl anhydride anhydride, nadic anhydride, and trimeric anhydride.

As amines, aromatics such as 4,4'-diaminediphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylsulfone, m-phenylenediamine, and p-xylylenediamine Fatty acid amines, such as amines, ethylenediamine, hexamethylenediamine, diethylenetriamine, and triethylenetetramine.

 1 type (s) or 2 or more types of these hardening | curing agents can be mixed and used for the resin composition of this invention.

Moreover, in the resin composition of this invention, you may use together the normal epoxy resin which has two or more epoxy groups in a molecule other than the epoxy resin of this invention. For example, a) bivalent phenols such as bisphenol A, bisphenol S, fluorene bisphenol, 4,4'-bisphenol, 2,2'-bisphenol, hydroquinone, resorcin, or b) tris- (4-hydride Trihydric or higher phenols such as oxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol novolak, o-cresol novolak, or c) tetrabromobisphenol A And glycidyl ether compounds derived from phenols such as halogenated bisphenols. Although these epoxy resins can be used 1 type or in mixture of 2 or more types, The compounding quantity of the epoxy resin which concerns on this invention is 5-100 weight% in the whole epoxy resin, Preferably it is 30-100 weight%, More preferably, 50 It is in the range of ˜100 wt%.

Furthermore, in the composition of this invention, you may mix suitably oligoma or high molecular compounds, such as polyester, a polyamide, a polyimide, a polyether, a polyurethane, a petroleum resin, a coumarone indene resin, a phenoxy resin. In addition, additives, such as an inorganic filler, a pigment, a thixotropic agent, a cuffing agent, and a fluidity improving agent, can be mix | blended with the resin composition of this invention.

As the inorganic filler, for example, spherical or crushed silica powder such as fused silica and crystalline silica, alumina powder, glass powder, or mica, talc, calcium carbonate, alumina, hydrated alumina Etc., and pigments include organic or inorganic extender pigments and scale pigments. Examples of the thixotropic agent include silicone type, castor oil type, aliphatic amide wax, polyethylene oxide wax, organic bentonite type and the like.

Moreover, a well-known hardening accelerator can be used for the resin composition of this invention as needed. For example, there are amines, imidazoles, organic phosphines, Lewis acids and the like. As addition amount, it is the range of 0.2-5 weight part with respect to 100 weight part of epoxy resins normally. Furthermore, if necessary, the resin composition of the present invention includes mold release agents such as carnauba wax and OP wax, cuffing agents such as γ-glycidoxypropyltrimethoxysilane, colorants such as carbon black, antimony trioxide and the like. Low stress agents such as flame retardants, silicone oils, lubricants such as calcium stearate, and the like can be used.

The epoxy resin of this invention is used suitably for semiconductor sealing. In this case, the high purity of the epoxy resin used for this invention is used suitably, It is preferable that hydrolysable chlorine amount is 1,000 ppm or less. In the case of this application, by increasing the compounding quantity of an inorganic filler, it is possible to aim at the absorption rate, the reduction of thermal expansion rate, the improvement of the thermal time intensity | strength, and the solder heat resistance can be improved significantly. Although the compounding quantity of the inorganic filler used for the epoxy resin composition used for this use is 75 weight% or more normally, it is preferable that it is 80 weight% or more from a viewpoint of low hygroscopicity and high solder heat resistance.

The epoxy resin composition of this invention can be obtained by heating said epoxy resin composition, and this is excellent in low hygroscopicity, high solder heat resistance, etc. As a method for obtaining a hardened | cured material, transfer molding, compression molding, a casting mold, etc. can be used suitably, As a temperature in that case, it is the range of 140-230 degree normally.

Hereinafter, the present invention will be described in more detail with reference to Examples. In addition, the measurement of the hydrolyzable chlorine in the following Example followed the following method. That is, 0.5 g of the resin sample is weighed into a 100 ml capped flask, and 30 ml of dioxane is added to dissolve it. 5 ml of 1N-KOH is added to this and refluxed. After cooling to room temperature, 10 ml of the reflux condenser was washed with MeOH and the total amount was transferred to a 200 ml beaker. Furthermore, the flask is washed with 100 ml of 80% acetone water and transferred to a beaker. Then 2 ml of conc. HNO ₃ is added, the potentiometric titration is performed with 1 / 500N-AgNO ₃ aqueous solution, and a blank test is also performed.

In addition, purity analysis of the epoxy resin was performed by GPC measurement. Measurement conditions include: apparatus; HLC-82A (manufactured by Tosoh Corporation), column; TSK-GEL2000 × 3 units and TSK-GEL4000 × 1 unit (all products from Tosoh Corporation), solvent; THF, flow rate; 1 ml / min, Temperature; 38 degrees, a detector; R1. In this purity analysis, content of monomer epoxy, a multimer epoxy, and the four types of monoepoxy bodies of said 1) -4) is measured.

The symbol used in an Example is as follows.

DHS: 2,2'-dimethyl-5,5'-di-tert-butyl-4,4'-dihydroxydiphenylsulfide

DGS: 2,2'-dimethyl-5,5'-di-tert-butyl-4,4'-diglycidyloxydiphenylsulfide

DEGME: diethylene glycol dimethyl ether

Example 1

240 g of DHS was dissolved in 240 g of DEGME and 1480 g of epichlorohydrin, and 108.4 g of a 48% aqueous sodium hydroxide aqueous solution was added dropwise at 45 degrees over 4hr while refluxing under reduced pressure. The water produced during this time was removed out of the system by azeotroping with epichlorohydrin, and the outflowed epichlorohydrin was condensed and returned to the system. After completion of the dropwise addition, the reaction was continued for 1 hr again. Thereafter, the salt produced by filtration was removed, washed with water, and then DEGME and epichlorohydrin were removed to obtain 302 g of a colorless, transparent, and prepared liquid epoxy resin. Epoxy equivalent was 248 and hydrolysable chlorine was 2100 ppm. The DGS (monomer epoxy) purity in resin was 91.0 wt%, and the content of the dimer epoxy containing two bisphenol compound units was 5.7 wt%. Moreover, content of the said monoepoxy body was 3.3 wt%.

100 g of the obtained crude epoxy resin was dissolved in 800 g of methyl isobutyl ketone (MIBK), 14.2 g of a 10% -NaOH aqueous solution was added at 80 degrees, and reacted for 2 hours. After the reaction, 97 g of a mono yellow liquid epoxy resin was obtained by filtration and washing with water to remove MIBK. The epoxy equivalent of the obtained epoxy resin was 241, the hydrolyzable chlorine was 260 ppm, the purity of DGS in resin was 94.5 wt%, and content of dimer epoxy was 4.2 wt%. Moreover, the content rate of monoepoxy body was 1.3 wt%.

1 g of fine powder crystals of DGS prepared separately were added while heating the obtained epoxy resin at 120 degree | times, stirring. After finely dispersing the fine powder crystals, the resultant was taken out to a batt, left at 30 degrees to crystallize the resin, and a solid epoxy resin (crystal) was obtained (epoxy resin A). The peak temperature of melting | fusing point in the DSC measurement of the obtained crystal | crystallization was 121.3 degree, the endothermic amount was 74.3 J / g, and the half value width of the endothermic peak was 5.9 degree.

Example 2

100 g of the epoxy resin obtained in Example 1 was recrystallized from methanol to obtain 88 g of a white crystalline epoxy resin (epoxy resin B). The epoxy equivalent was 236, the hydrolyzable chlorine was 90 ppm, the purity of DGS in the resin was 98.2 wt%, and the content of dimer epoxy was 1.5 wt%. Moreover, the content rate of monoepoxy body was 0.3 wt%. The peak temperature of melting | fusing point in the DSC measurement of the obtained crystal | crystallization was 122.2 degree | times, the endothermic amount was 77.2 J / g, and the half value width of the endothermic peak was 5.6 degree | times.

Example 3

240 g of DHS, 240 g of DEGDME, 900 g of epichlorohydrin, and 107.0 g of a 48% aqueous sodium hydroxide solution were reacted in the same manner as in Example 1 to obtain 298 g of a liquid epoxy resin. Epoxy equivalent was 253 and hydrolyzable chlorine was 4600 ppm. The DGS purity in the resin was 88.5 wt% and the content of dimer epoxy was 8.4 wt%. Moreover, the content rate of monoepoxy body was 3.1 wt%.

100 g of the obtained crude epoxy resin was dissolved in 800 g of MIBK, and an aqueous 10% -NaOH solution and 10.3 g were added at 80 degrees to react for 2 hours. After the reaction, filtration and washing with water to remove MIBK yielded 94 g of a mono yellow liquid epoxy resin. The epoxy equivalent of the obtained epoxy resin was 242, the hydrolyzable chlorine was 240 ppm, the purity of DGS in resin was 92.6 wt%, and the content of the dimer of the bisphenol compound was 6.2 wt%. Moreover, content of the monoepoxy body was 1.4 wt%.

1 g of fine powder crystals of DGS prepared separately were added while heating the obtained epoxy resin at 120 degree | times, stirring. After finely dispersing the fine powder crystals, the resultant was taken out to the batt, left at 30 degrees to crystallize the resin, and a solid epoxy resin was obtained (epoxy resin C). The peak temperature of melting | fusing point in DSC measurement of the obtained crystal | crystallization was 120.8 degree, the endothermic amount was 71.9 J / g, and the half value width of the endothermic peak was 6.2 degree.

Example 4

In the same manner as in Example 1, 120 g of DHS, 240 g of DEGME, 340 g of epichlorohydrin, and 52.0 g of a 48% sodium hydroxide aqueous solution were used to obtain 149 g of a liquid crude epoxy resin. Epoxy equivalent was 255 and hydrolyzable chlorine was 5300 ppm. The purity of DGS in the resin was 87.6 wt% and the content of dimer epoxy was 8.6 wt%. Content of the monoepoxy body was 3.8 wt%.

100 g of the obtained crude epoxy resin was dissolved in 800 g of MIBK, and 9.0 g of a 10% -NaOH aqueous solution was added at 80 degrees to react for 2 hours. After the reaction, 95 g of a mono yellow liquid epoxy resin was obtained by filtration and washing with water to remove MIBK. The epoxy equivalent of the obtained epoxy resin was 243, hydrolysable chlorine was 180 ppm, the purity of DGS in resin was 91.8 wt%, and the content of dimer epoxy was 6.7 wt%. Moreover, the content rate of monoepoxy body was 1.1 wt%.

1 g of fine powder crystals of DGS prepared separately were added while heating the obtained epoxy resin at 120 degree | times, stirring. After finely dispersing the fine powder crystals, the resultant was removed from the batter, left at 30 degrees to crystallize the resin, and a solid epoxy resin was obtained (epoxy resin D). The peak temperature of melting | fusing point in the DSC measurement of the obtained crystal | crystallization was 121.3 degree, the endothermic amount was 71.2 J / g, and the half value width of the endothermic peak was 6.1 degree.

Comparative Example 1

The prepared epoxy resin obtained in Example 1 was left to stand at room temperature for 3 days to precipitate crystals to obtain a solid epoxy resin (epoxy resin E). The peak temperature of the melting point in the DSC measurement of the obtained crystal was 119.1 degrees, the endothermic amount was 53.2 J / g, and the half width of the endothermic peak was 7.4 degrees.

Comparative Example 2

The prepared epoxy resin obtained in Example 3 was allowed to stand at room temperature for 3 days to precipitate crystals to obtain a solid epoxy resin (epoxy resin F). The peak temperature of the melting point in the DSC measurement of the obtained crystal was 118.6 degrees, the endothermic amount was 61.6 J / g, and the half width of the endothermic peak was 7.2 degrees.

Comparative Example 3

120 g of DHS was dissolved in 430 g of epichlorohydrin and 220 g of dimethyl sulfoxide, and 56.0 g of an aqueous 48% sodium hydroxide solution was added dropwise at 50 ° C over 4hr while refluxing under reduced pressure. The water produced during this time was removed out of the system by azeotroping with epichlorohydrin, and the spilled epichlorohydrin was returned to the system. After completion of the dropwise addition, the reaction was continued for 1 hr again. Then, the salt produced | generated by filtration was removed, Furthermore, after wash | cleaning with water, epichlorohydrin was removed and 148 g of liquid preparation epoxy resins were obtained, being colorless and transparent. Epoxy equivalent was 244 and hydrolysable chlorine was 450 ppm. The DGS purity in the resin was 89.6 wt% and the content of dimer epoxy was 7.6 wt%. Moreover, the content rate of monoepoxy body was 2.8 wt%.

1 g of fine powder crystals of DGS prepared separately were added while heating the obtained epoxy resin at 120 degree | times, stirring. After finely dispersing the fine powder crystals, the resultant was taken out to the batter, left at 30 degrees to crystallize the resin, and a solid epoxy resin was obtained (epoxy resin G). The peak temperature of the melting point in the DSC measurement of the obtained crystal was 118.7 degrees, the endothermic amount was 67.5 J / g, and the half value width of the endothermic peak was 7.3 degrees.

Examples 5-8, Comparative Examples 4-6

Phenol novolak resin (softening point 71 degrees, OH equivalence 107), crushed silica (average particle diameter 16 micrometers) as a hardening | curing agent using the epoxy resins A-G obtained by Examples 1-4 and Comparative Examples 1-3 as an epoxy resin composition ) Or spherical silica (average particle diameter: 22 µm), triphenylphosphine as a curing accelerator, γ-glycidoxypropyltrimethoxysilane as a silane coupling agent, and other additives shown in Table 1 (parts by weight) After mix | blending with, it knead | mixed by heat and obtained the epoxy resin composition.

It shape | molded at 175 degree | times using this epoxy resin composition, 12 hours postcure (cure) at 175, and after obtaining a hardened | cured material test piece, various physical properties were measured. The glass transition point was calculated | required on the conditions of the temperature increase rate of 10 degree / min by the thermometer. Flexural strength and flexural modulus were measured at two levels, room temperature (25 degrees) and high temperature (260 degrees). The adhesive strength was compression molded at 175 degrees between two substrates at a thickness of 0.5 mm, and evaluated at shear strength after performing 175 degrees and 12 hr postcure. In addition, the water absorption is when the disk of diameter 50mm and thickness 3mm is shape | molded using this epoxy resin composition, and it is made to adsorb | suck 24hr and 100hr on 85 degreeC and 85% R.H. Conditions after postcure. The element defect rate is shown in Table 2 under conditions of 85 degrees and 85% RH using a package obtained by transferring a test chip having aluminum wiring to the copper frame at 175 degrees for 2 minutes and then 175 degrees and 12hr postcure. After absorbing for a predetermined time and immersing again in the solder bath at 260 degrees for 10 sec, the PCT test was conducted under conditions of 121 degrees and 2 atmospheres, and the evaluation was made by the ratio of the package in which the disconnection of the aluminum wiring with respect to the package used for the test occurred. The blocking property was made into the weight ratio of the aggregated composition which left the unpulverized epoxy resin composition at 25 degree | times for 24 hours. Integrity stability was made into 25 degree | times of the pulverized epoxy resin composition, and the preservation rate with respect to the initial value (staying for 0 days) of the spiral flow after leaving for 7 days.

The results are summarized in Table 2.

Since the epoxy resin of this invention is excellent in sclerosis | hardenability and has high crystallinity, it is excellent also in the blocking resistance at the time of the storage at the time of using an epoxy resin composition. Furthermore, since hardened | cured material has high heat resistance, moisture resistance, and high adhesiveness, when applied to the resin composition for semiconductor sealing, the reliability of the package obtained by sealing a semiconductor element improves significantly.

Claims (8)

The following formula (1) obtained by reacting 4-4'-dihydroxy-diphenylsulfide and epichlorohydrin However, R <_1> -R <_4> is hydrogen resin or the epoxy resin which consists of a compound represented by C1-C6 alkyl group, n represents the number of 0-10, The content rate of n = 0 body is 90wt. The epoxy resin of the crystalline phase, characterized in that the content of monoepoxy body is 2 wt% or less while being more than%. Epoxy resin obtained by reacting 2,2'-dimethyl-5,5'-dibutylbutyl-4,4'-dihydroxydiphenylsulfide and epichlorohydrin, and 2,2'-dimethyl-5,5 A crystalline epoxy resin, wherein the content of '-dibutylbutyl-4,4'-diglycidyloxydiphenylsulfide is at least 90 wt% and the content of monoepoxy is at most 2 wt%. The crystalline epoxy resin according to claim 1 or 2, wherein the endothermic amount by sequential thermal analysis of the crystalline epoxy resin is in the range of 68 to 80 J / g, and the half value width of the endothermic peak is 7.0 degrees or less. In preparing the crystalline epoxy resin according to claim 1, the following formula (2) (However, R ₁ to R ₄ independently represent hydrogen or an alkyl group having 1 to 6 carbon atoms.) Di (hydroxyphenyl) sulfides and epichlorohydrin are reacted in the presence of an alkali metal hydroxide to prepare an epoxy. A method for producing a crystalline epoxy resin, wherein the crude epoxy resin obtained is reacted with an alkali metal hydroxide after obtaining the resin. In preparing the crystalline epoxy resin according to claim 2, 2,2'-dimethyl-5-5'-dibutylbutyl-4,4'-dihydroxydiphenylsulfide and epichlorohydrin are alkali metals. After reacting in presence of a hydroxide and obtaining a preparation epoxy resin, the obtained preparation epoxy resin is made to react with alkali metal hydroxide again, The manufacturing method of the crystalline epoxy resin characterized by the above-mentioned. The method according to claim 5, wherein 0.85-0.99 mol of alkali metal hydroxide is reacted with 1 mol of hydroxyl groups in 2,2'-dimethyl-5,5'-dibutylbutyl-4,4'-dihydroxydiphenylsulfide. After obtaining a crude epoxy resin, 1.0-15.0 times mole alkali metal oxide is made to react with 1 mol of hydrolysable chlorine in a crude epoxy resin, The manufacturing method characterized by the above-mentioned. Epoxy resin composition which consists of an epoxy resin and a hardening | curing agent WHEREIN: The epoxy resin composition of Claim 1 or 2 is used as a part or all part of an epoxy resin component. Hardened | cured material formed by hardening | curing the epoxy resin composition of Claim 7.