KR20090075826A - Epoxy resin, phenol resin, their production methods, epoxy resin composition and cured product - Google Patents

Abstract

Disclosed is an epoxy resin having excellent fluidity and high filler filling property, which provides a cured product excellent in moisture resistance, heat resistance and flame retardance. This epoxy resin is suitable for sealing of electronic components and uses as circuit board materials. Also disclosed is a composition of such an epoxy resin. Specifically disclosed is an epoxy resin represented by the general formula (3) below, which is obtained by reacting epichlorohydrin with a phenol resin which is obtained by reacting 0.2-6.0 moles of indene or acenaphthylene with 1 mole of a bisphenol compound represented by the general formula (2) below. (In the formulae, X represents a single bond,-CH2-,-CH(CH3)-,-C(CH3)2-,-CO-,-O-,-S-or-SO2-; and R1-R4 independently represent a hydrogen atom or a substituent derived from indene or acenaphthylene.)

Description

Epoxy Resin, Phenolic Resin, Manufacturing Method thereof, Epoxy Resin Composition and Cured Product {EPOXY RESIN, PHENOL RESIN, THEIR PRODUCTION METHODS, EPOXY RESIN COMPOSITION AND CURED PRODUCT}

The present invention provides an epoxy resin which is excellent in low viscosity and gives a cured product excellent in moisture resistance, heat resistance, flame retardancy, etc., a phenol resin suitable as an intermediate thereof, a production method thereof, and an epoxy resin composition using the epoxy resin and the cured product thereof. The present invention relates to an insulating material in electric and electronic fields such as semiconductor sealing, printed wiring board, and the like.

As a semiconductor sealing material, although the resin composition which uses the epoxy resin as the main body is widely used, the transition from the conventional insertion method to the surface mounting method is advanced as a component mounting method to a printed board. In the surface mounting method, the whole package is heated to the soldering temperature, and the package crack caused by the rapid volume expansion of moisture absorbed has become a big problem. In addition, high integration of semiconductor devices, large device sizes, and miniaturization of wiring widths are rapidly progressing, and the problem of package cracks is becoming more serious. As a method of preventing a package crack, there exist methods, such as toughening of a resin structure, high strength by high filling of an inorganic filler, and low water absorption.

Among them, the high filler of the inorganic filler is strongly oriented, and for this purpose, an epoxy resin having excellent low hygroscopicity, high heat resistance and low viscosity is desired. As the low viscosity epoxy resin, bisphenol A type epoxy resins, bisphenol F type epoxy resins and the like are generally widely used. However, in these epoxy resins, it is difficult to make a low viscosity of the resin composition at room temperature and into a liquid composition for transfer molding. Do. In addition, such epoxy resins are not sufficient in terms of heat resistance, mechanical strength, and moisture resistance.

From the above background, biphenyl-based epoxy resins (JP-A-58-39677) and bisphenol-based epoxy resins (JP-A-6-345850) have been proposed as being excellent in low hygroscopicity and high heat resistance. It is not enough from the point of adhesiveness with a base material. Moreover, although the epoxy resin (Japanese Unexamined-Japanese-Patent No. 6-145300) which has a sulfide structure containing a sulfur atom from the viewpoint of adhesive improvement is proposed, heat resistance is not enough. Moreover, although the epoxy resin which has a conventionally known sulfone structure has high heat resistance, its water absorption is high and adhesiveness is not enough.

Patent Document 1: Japanese Patent Application Laid-Open No. 58-39677

Patent Document 2: Japanese Patent Application Laid-Open No. 6-345850

Patent Document 3: Japanese Patent Application Laid-Open No. 6-145300

Accordingly, an object of the present invention is to provide an epoxy resin suitably used for sealing an electronic component of a semiconductor device that gives a cured product excellent in fluidity, filler high filling property, moisture resistance, heat resistance, flame retardancy, and the like, and a composition thereof. .

That is, this invention relates to the epoxy resin represented by following General formula (3).

(However, R ₁ to R ₄ independently represent a hydrogen atom or a substituent represented by the following formula (a) or (b), but at least one is the substituent. X is a single bond, -CH _2- , -CH (CH) _3- , -C (CH ₃ ) _2- , -CO-, -O-, -S- or -SO _2- , n represents a number from 0 to 50.)

Moreover, this invention relates to the phenol resin represented by following General formula (1).

(However, R ₁ to R ₄ And X have the same meaning as in formula (3).)

Moreover, this invention is following General formula (2),

(However, X has the same meaning as in formula (3).)

A phenol having a substituent represented by the formula (a) or (b), wherein 0.2 to 4 moles of an aromatic olefin selected from indene or acenaphthylene are reacted with 1 mole of a bisphenol compound represented by It is related with the manufacturing method of resin.

Moreover, this invention is a manufacturing method of the epoxy resin characterized by making epichlorohydrin react with the phenol resin represented by the said General formula (1), or the manufacturing method of the said phenol resin. Moreover, it is related with the epoxy resin obtained by the manufacturing method of this epoxy resin.

Moreover, this invention relates to the epoxy resin composition which mix | blended said epoxy resin as an epoxy resin component as an epoxy resin composition which consists of an epoxy resin and a hardening | curing agent, and the hardened | cured material obtained by hardening this.

First, the epoxy resin of this invention is demonstrated.

The epoxy resin of this invention is represented by the said General formula (3). Here, R ₁ to R ₄ represent a hydrogen atom or a substituent represented by the formula (a) or (b), but at least one is a substituent represented by the formula (a) or (b). From the viewpoint of low viscosity, R ₁ to R ₄ are preferably a substituent represented by general formula (a), and a substituent of general formula (b) is preferable from the viewpoint of low hygroscopicity and flame retardancy. In addition, in the said General formula (3), you may replace R <_1> , R <_3> and R <_2> and R <_4> in parentheses.

In addition, R ₁ to R ₄ may be composed of a hydrogen atom and a substituent represented by formula (a), may be composed of a hydrogen atom and a substituent represented by formula (b), and a hydrogen atom and formula (a) and formula It may consist of the substituent represented by (b), and may consist of the substituent represented by Formula (a) and Formula (b), and consists only of the substituent represented by Formula (a) or only the substituent represented by Formula (b) You may also

X represents a linking group selected from a single bond, -CH _2- , -CH (CH ₃ )-, -C (CH ₃ ) _2- , -CO-, -O-, -S- or -SO _2-. . In view of low viscosity, a single bond, -CH _2- , -O- or -S- is preferably selected.

n represents the number of 0-50, and the preferable value of n depends on the application to apply. For example, it is preferable that it is low viscosity as the use of the semiconductor sealing material which requires high filling rate of a filler, and the value of n is 0-5, Preferably it is 0.1-2, More preferably, it is 50 wt% that n is 0. It is included more than%. When the epoxy resin of this invention is a mixture from which the value of n differs, n means an average value (number average). In this case, More preferably, n is 0.1-1. Moreover, a high molecular weight epoxy resin is used suitably for uses, such as a printed wiring board, and the value of n in this case is 2-50, Preferably it is 2-40. When the value of n is a different mixture, the said range is good as average value n. In this case, when an average value becomes 50 or less, the molecule whose n becomes an integer of 50 or more may be included.

The epoxy resin of this invention is a phenol obtained by making the bisphenol compound represented by the said General formula (2) react with the aromatic olefin chosen from indene or acenaphthylene (henceforth simply an aromatic olefin), for example. A resin can be obtained as an intermediate, and can be manufactured by the method of making this phenol resin and epichlorohydrin react. Since indene and acenaphthylene are one of aromatic olefins, they can be replaced by a benzene ring of a bisphenol compound represented by the general formula (2) by a Friedel-Crafts reaction. And it is substituted by the benzene ring as a substituent (Hereinafter, it may only be called a substituent) represented by Formula (a) or (b). In addition, up to two of these substituents may be substituted in one benzene ring due to steric hindrance. The substituent represented by formula (a) is a structure in which one hydrogen atom is extracted from indene, and the substituent represented by formula (b) is a structure in which one hydrogen atom is extracted from acenaphthylene, each of which is formed from indene or acenaphthylene ( It can be said that the base station.

The phenol resin of this invention is represented by the said General formula (1). In the formula _{(1), R 1 ~ R} 4 and X correspond to the R ₁ ~ R ₄ and X in the formula (3). Thus, also preferred R ₁ ~ R _4, and X is the same as R ₁ ~ R ₄ and X in the formula (3).

In formula (2), X is a single bond, -CH _2- , -CH (CH ₃ )-, -C (CH ₃ ) _2- , -CO-, -O-, -S- or -SO _2- In view of low viscosity, a single bond, -CH _2- , -O- or -S- is suitably selected. In General formula (2), substitution position of a hydroxyl group is 4,4'-position, 3,4'-position, 3,3'-position, 2,4'-, 2 with respect to the linking group X. , 3'-up, 2,2'-up. These may be a compound consisting of a single isomer or a mixture of these isomers, but since the steric hindrance of the formula (a) or (b) is large, from the viewpoint of reactivity when the epoxy resin is used, 2,4'- It is preferable that a sieve or 2,2'- sieve is included. In this case, it is preferable that the total amount of 2,4'-body and 2,2'-body is 30 mol% or more, preferably 50 mol% or more of the whole. In addition, the same also applies to X in General Formulas (1) and (3).

The phenol resin of the present invention can be obtained by reacting an aromatic olefin selected from indene or acenaphthylene with 1 mole of an aromatic olefin with respect to 1 mole of a bisphenol compound to the bisphenol compound represented by the above general formula (2). have.

The manufacturing method of the phenol resin of this invention is what makes 0.2-4 mol of aromatic olefin react with the bisphenol compound represented by the said General formula (2) with respect to 1 mol of bisphenol compounds with aromatic olefin chosen from indene or acenaphthylene. By the benzene ring.

In the manufacturing method of the phenol resin of this invention, although the reaction amount of the aromatic olefin with respect to 1 mol of bisphenol compounds is the range of 0.2-4.0 mol, Preferably it is 0.5-4.0 mol, More preferably, it is the range of 1.0-3.0 mol. . When less than this, the improvement effect of moisture resistance and flame retardance at the time of using an epoxy resin will not fully be expressed. On the contrary, when more than this, a viscosity will become high and filler high filling property and moldability will fall.

In addition, since the usage-amount as a reaction raw material at the time of making a bisphenol compound and aromatic olefin react, it corresponds substantially with the target substitution mole number (mole number of the substituent with respect to 1 mol of bisphenol compounds), What is necessary is just to determine the usage-amount accordingly. In addition, although the reaction conditions in which either raw material remains unreacted may be employ | adopted, also in this case, the usage-amount of the aromatic olefin with respect to 1 mol of bisphenol compounds is good to be in the range of 0.2-6.0 mol. If either of the raw materials remains unreacted, it is preferable to separate them. Moreover, when a large amount of aromatic olefin is used, unreacted aromatic olefin may remain or the homo oligomer of an aromatic olefin may be produced, and it becomes a cause of reducing heat resistance and flame retardance as an epoxy resin. Therefore, even if the usage-amount of an aromatic olefin as a raw material with respect to 1 mol of bisphenol compounds is 6.0 mol.

As an aromatic olefin made to react with a bisphenol compound, it is indene, acenaphthylene, or a mixture thereof. It is preferable to have indene as a main component from a low viscosity viewpoint, and it is preferable to have acenaphthylene as a main component from a flame-retardant viewpoint.

Although the aromatic olefin used for reaction may contain unsaturated bond containing components, such as styrene, (alpha) -methylstyrene, divinylbenzene, coumarone, benzothiophene, indole, and vinyl naphthalene, as another reactive component, All reaction components The content rate of indene and acenaphthylene in 50 wt% or more, Preferably it is 70 wt% or more. If less than this, the effect of improving heat resistance and flame resistance is small. Moreover, although the non-reactive compound, such as toluene, dimethylbenzene, trimethylbenzene, indane, naphthalene, methylnaphthalene, dimethylnaphthalene, acenaphthene, may be contained in aromatic olefin, the heat resistance, flame retardance, etc. when using as an epoxy resin From the viewpoint of improving the properties of these compounds, it is better to remove these non-reactive compounds out of the system. Preferably, it is removed until it is 5 wt% or less, more preferably 2 wt% or less. Generally as a removal method, methods, such as distillation under reduced pressure, are applied.

In the aromatic olefin used for reaction, when the other reactive component contains unsaturated bond containing components, such as styrene, (alpha) -methylstyrene, divinylbenzene, coumarone, benzothiophene, indole, and vinyl naphthalene, The group resulting from these will contain the compound substituted by the benzene ring. The phenol resin obtained by the manufacturing method of the phenol resin of this invention may contain the phenol resin which has such a substituent. Similarly, the epoxy resin obtained by the manufacturing method of the epoxy resin of this invention may contain the epoxy resin which has such a substituent.

As the reaction between the bisphenol compound and the aromatic olefin, a reaction method using a known Friedel Crafts catalyst such as an acid catalyst and the like can be adopted. By this reaction, the phenol resin in which the said substituent was substituted by the benzene ring of a bisphenol compound is obtained. Although this phenol resin is a mixture in which the number of substituents and a substitution position differ normally, it is good to have a substituent of 0.4-4 on average, Preferably it is 1-4. After completion | finish of reaction of a bisphenol compound and aromatic olefin, a catalyst or an unreacted component is removed as needed, and it uses for the next epoxidation reaction. However, neutralizing components such as components and acid catalysts that do not inhibit the epoxidation reaction do not have to be removed. Furthermore, even if they are removed in a purification process such as washing or distillation performed after the epoxidation reaction or contained in the epoxy resin, it is difficult to prevent them. If not, it does not need to be removed. The use of the reaction product after completion of the reaction between the bisphenol compound and the aromatic olefin in the epoxidation reaction is advantageous in that the purification step is reduced by one. Moreover, you may refine | purify or isolate with a phenol resin as a target.

The manufacturing method of the epoxy resin of this invention is the phenol resin represented by the said General formula (1), or the phenol resin obtained by the manufacturing method of the said phenol resin (henceforth, when it is not necessary to distinguish both), it is also simply called a phenol resin). It is obtained by reacting with epichlorohydrin.

In the reaction between the phenol resin and epichlorohydrin, an alkali metal hydroxide such as sodium hydroxide and potassium hydroxide in an amount of 0.80 to 1.20 times, preferably 0.85 to 1.05 times, is used relative to the hydroxyl group in the phenol resin. If less than this, the amount of remaining hydrolyzable chlorine increases, which is not preferable. As a metal hydroxide, it is used in the state of aqueous solution, alcohol solution, or solid.

At the time of reaction, an excess amount of epicrohydrin is used with respect to a phenol resin. Usually 1.5-15 times mole of epichlorohydrin is used with respect to 1 mol of hydroxyl groups in a phenol resin, Preferably it is the range of 2-8 times mole. If more than this, production efficiency will fall, and if less, the production | generation amount of the high molecular weight body of an epoxy resin will increase and a viscosity will become high.

Reaction is normally performed at the temperature of 120 degrees C or less. At the time of reaction, when temperature is high, the amount of what is called egg hydrolyzable chlorine will increase, and high purity will become difficult. Preferably it is 100 degrees C or less, More preferably, it is a temperature of 85 degrees C or less.

In the reaction, a quaternary ammonium salt or a polar solvent such as dimethyl sulfoxide or diglyme may be used. Examples of quaternary ammonium salts include tetramethylammonium chloride, tetrabutylammonium chloride, benzyltriethylammonium chloride, and the addition amount thereof is preferably in the range of 0.1 to 2.0 wt% based on the phenol resin. When less than this, the effect of addition of a quaternary ammonium salt is small, and when more than this, the quantity of formation of a hard hydrolyzable chlorine increases, and high purity becomes difficult. Moreover, as addition amount of a polar solvent, the range of 10-200 wt% is preferable with respect to a phenol resin. When less than this, the effect of addition is small, and when more than this, volumetric efficiency falls and it is not economically preferable.

After completion of the reaction, the excess epichlorohydrin and the solvent are distilled off, the residue is dissolved in a solvent such as toluene, methyl isobutyl ketone, filtered, washed with water to remove the inorganic salt or the remaining solvent, and then the solvent is removed. It can be set as an epoxy resin by distilling off.

Advantageously, the obtained epoxy resin is further added with alkali metal hydroxides such as sodium hydroxide or potassium hydroxide in an amount of 1 to 30 times to the remaining hydrolyzable chlorine, and the ring-closure reaction is performed again. The reaction temperature at this time is 100 degrees C or less normally, Preferably it is 90 degrees C or less.

It is preferable that the epoxy resin obtained by the manufacturing method of the epoxy resin of this invention is an epoxy resin represented by the said General formula (3), or an epoxy resin which uses this as a main component (50 wt% or more). However, in general formula (3), the substituent may have an average of 0.1 to 2.0, preferably 0.5 to 2.0, per benzene ring. Similarly, it is preferable that the phenol resin obtained by the manufacturing method of the phenol resin of this invention is a phenol resin represented by the said General formula (1), or the phenol resin which has this as a main component. However, in general formula (3), the substituent may have an average of 0.1 to 2.0, preferably 0.5 to 2.0, per benzene ring.

The epoxy resin composition of this invention is the epoxy resin represented by the said General formula (1), the epoxy resin which has this epoxy resin as a main component, or the epoxy resin obtained by the manufacturing method of the said epoxy resin (Hereafter, these are also collectively called the epoxy resin. And hardener are essential ingredients. As a hardening | curing agent mix | blended with the epoxy resin composition of this invention, 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, as polyhydric phenols, for example, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4'-biphenol, 2,2'-biphenol, hydroquinone, resorcinol, naphthalenediol Divalent phenols such as tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol novolak, o-cresol novolak, naphtholno Trihydric or higher phenols represented by volac, polyvinylphenol, and the like. Moreover, monovalent phenols, such as phenols and naphthols, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4'- biphenol, 2,2'- biphenol, hydroquinone, resorcinol, naphthalenediol And dihydric phenols such as formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, and p-xylene glycol, and the like. Moreover, you may use what hardened | cured the indene or acenaphthylene to these phenolic hardening | curing agents as a hardening | curing agent.

Examples of the acid anhydride include phthalic anhydride, tetrahydro phthalic anhydride, methyltetrahydro phthalic anhydride, hexahydro phthalic anhydride, methyl hexahydro phthalic anhydride, methyl anhydride, nadic acid anhydride, trimellitic anhydride and the like.

Moreover, as amines, 4,4'- diamino diphenylmethane, 4,4'- diamino diphenyl propane, 4,4'- diamino diphenyl sulfone, m-phenylenediamine, p-xylylenediamine And aromatic amines such as ethylenediamine, hexamethylenediamine, diethylenetriamine, and triethylenetetramine.

As the epoxy resin composition of this invention, 1 type, or 2 or more types of these hardening | curing agents can be mixed and used.

Moreover, in the epoxy resin composition of this invention, you may mix | blend another epoxy resin other than this epoxy resin as an epoxy resin component. As another epoxy resin in this case, the normal epoxy resin which has 2 or more epoxy groups in a molecule | numerator can be used. For example, bivalent phenols such as bisphenol A, bisphenol S, fluorene bisphenol, 4,4'-biphenol, 2,2'-biphenol, hydroquinone, resorcin, or tris- (4-hydroxy From trivalent or higher phenols such as phenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol novolak, o-cresol novolak or halogenated bisphenols such as tetrabromo bisphenol A Derived glycidyl ethers. These epoxy resins can be used 1 type or in mixture of 2 or more types. And in the case of the epoxy resin composition which uses this epoxy resin as an essential component, the compounding quantity of this epoxy resin is 5-100 weight% in the whole epoxy resin, Preferably it is good that it is the range of 60-100 weight%.

If necessary, an inorganic filler may be blended in the epoxy resin composition of the present invention. Examples of the inorganic fillers include spherical or fractured silica powders such as fused silica and crystalline silica, alumina powders and glass powders. In the case of application as a semiconductor sealing material, the amount of the inorganic filler is usually 75 wt% or more, but it is preferably 80 wt% or more in terms of low hygroscopicity and high soldering heat resistance.

Moreover, in the epoxy resin composition of this invention, you may mix | blend oligomers or high molecular compounds, such as polyester, a polyamide, a polyimide, a polyether, a polyurethane, a petroleum resin, an inden coumarone resin, a phenoxy resin, suitably, and a pigment, You may mix | blend additives, such as a flame retardant, a thixotropic agent, a coupling agent, and a fluidity improving agent. Examples of the pigment include organic or inorganic extender pigments and scaly pigments. Examples of the thixotropic agent include silicone, castor oil, aliphatic amide wax, polyethylene oxide wax, and organic bentonite. Moreover, as needed, as an epoxy resin composition of this invention, mold release agents, such as carnauba wax and OP wax, coupling agents, such as (gamma)-glycidoxy propyl trimethoxysilane, coloring agents, such as carbon black, antimony trioxide, etc. Flame retardants, low stress agents such as silicone oil, lubricants such as calcium stearate, and the like.

In addition, a well-known hardening accelerator can be used for the epoxy 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. Moreover, as addition amount of a hardening | curing agent, it is the range of 10-100 weight part with respect to 100 weight part of epoxy resins normally.

The hardened | cured material of this invention obtained by hardening | curing the resin composition of this invention can be shape | molded by the method of casting, compression molding, transfer molding, etc. of the said epoxy resin composition. The temperature at this time is the range of 120-220 degreeC normally.

1 is an infrared absorption spectrum of epoxy resin A. FIG.

2 is a ¹ H-NMR spectrum of Epoxy Resin A. FIG.

The present invention will be described in more detail with reference to the following examples.

<Example 1>

200 g (1.0 mol) of bisphenol F (Honshu Kagaku Co., 4,4 'sieve (31%), 2,4' sieve (49%), 2,2 'sieve (20%)) was added to a 1 L flask and 175 ° C. It heated up until. After melting, 0.1 g of p-toluenesulfonic acid was added while stirring, and 232 g (2.0 mol) of indene was dripped over about 3 hours at 175 degreeC. Moreover, reaction was continued for 3 hours under all reflux. Then, the low boiling point component was removed under reduced pressure and 413 g of indene addition phenol resins were obtained (phenol resin A). OH equivalent was 216 g / eq., And the softening point was 78 degreeC and melt viscosity in 150 degreeC was 0.06 Pa.s.

<Example 2>

200 g (1.0 mol) of bisphenol F was heated up to 175 degreeC in the 1 L flask. After melting, 0.15 g of p-toluenesulfonic acid was added while stirring, and 348 g (3.0 mol) of indene was dripped over about 3 hours at 175 degreeC. Then, the low boiling point component was removed under reduced pressure and 527 g of indene addition phenol resins were obtained (phenol resin B). OH equivalent was 274 g / eq., And the softening point was 86 degreeC and melt viscosity in 150 degreeC was 0.15 Pa.s.

<Example 3>

200 g (1.0 mol) of bisphenol F was put into a 1 L flask, and it heated up to 180 degreeC. After melting, 0.04 g of p-toluenesulfonic acid was added while stirring, and 304 g (2.0 mol) of acenaphthylene was dripped over about 3 hours at 180 degreeC. Then, it heated up at 200 degreeC under reduced pressure, removed the low boiling point component, and obtained 491 g of acenaphthylene addition phenol resins (phenol resin C). OH equivalent was 252 g / eq., And the softening point was 0.59 Pa.s at 99 degreeC and 150 degreeC.

In addition, in Examples 1-3, the reaction rate of indene was about 100%.

<Example 4>

After dissolving in 300 L of phenol resin A synthesized in Example 1, 900 g of epichlorohydrin and 135 g of diglyme in a 3 L four-necked separation flask, 116 g of a 48% aqueous sodium hydroxide solution at 60 ° C. It dripped over time. The water produced in the meantime was removed out of the system by azeotroping with epichlorohydrin, and the distilled epichlorohydrin was returned to the system. After completion of the dropwise addition, the reaction was further continued for 1 hour. Thereafter, epichlorohydrin and diglyme were distilled off under reduced pressure, dissolved in 987 g of methyl isobutyl ketone, and then the salt produced by washing with water was removed. Then, 64 g of 12% sodium hydroxide aqueous solution was added, and it reacted at 80 degreeC for 2 hours. After the reaction, after washing with water, methyl isobutyl ketone as a solvent was distilled off under reduced pressure to obtain 346 g of a pale yellow epoxy resin (epoxy resin A). The epoxy equivalent of this epoxy resin A was 278 g / eq., The hydrolyzable chlorine was 420 ppm, The softening point was 58 degreeC, and melt viscosity in 150 degreeC was 0.045 Pa.s.

Herein, hydrolyzable chlorine was dissolved 0.5 g of a sample in 30 ml of dioxane, 10 ml of 1N-KOH was added thereto, and the mixture was boiled and refluxed for 30 minutes. a is a value measured by carrying out potentiometric titration with -AgNO ₃ aqueous solution. In addition, a softening point is a value obtained at the temperature increase rate of 5 degree-C / min by the ball & ring method, and the viscosity was measured using the cone plate type viscometer by Brookfield Corporation.

GPC measurement conditions include: apparatus; MODEL 151 (made by Waters Co., Ltd.), column; TSK-GEL 2000x3 and TSK-GEL4000x1 (all are the Tosoh Corporation make), a solvent; Tetrahydrofuran, flow rate; 1 ml / min, temperature; 38 ° C., detector; It carried out on condition of RI. Infrared absorption spectrum obtained by the KBr tablet molding, ¹ H-NMR spectrum, the apparatus; It measured in acetone-d6 using JNM-LA400 and Nippon Denshi Corporation.

Infrared absorption spectrum of epoxy resin A is shown in FIG. 1, and ¹ H-NMR spectrum is shown in FIG.

<Example 5>

In a 3-liter four-necked flask, 300 g of the phenol resin B synthesized in Example 2 was dissolved in 810 g of epichlorohydrin and 122 g of diglyme, and then Example 4 was carried out using a 96% aqueous 48% sodium hydroxide solution at 60 ° C. under reduced pressure. The reaction was carried out in the same manner as to obtain 335 g of a pale yellow epoxy resin (epoxy resin B). Epoxy equivalent was 336 g / eq., Hydrolyzable chlorine was 340 ppm, the softening point was 76 degreeC, and the melt viscosity in 150 degreeC was 0.136 Pa.s.

<Example 6>

After dissolving 300 g of the phenolic resin C synthesized in Example 3 in 810 g of epichlorohydrin and 122 g of diglyme in a 3 L four-necked separating flask, Example 4 was carried out using 99 g of 48% sodium hydroxide aqueous solution at 60 ° C. under reduced pressure. The reaction was carried out similarly to obtain 230 g of a pale yellow epoxy resin (epoxy resin C). Epoxy equivalent was 318 g / eq., Hydrolysable chlorine was 330 ppm, the softening point was 83 degreeC, and the melt viscosity in 150 degreeC was 0.226 Pa.s.

<Examples 7-11 and Comparative Examples 1-2>

As the epoxy resin component, epoxy resins A to C synthesized in Examples 4 to 6, bisphenol F type epoxy resins (epoxy resin D; manufactured by Totokasei, YDF-170, epoxy equivalent 169), biphenyl type epoxy resins (epoxy resins) E; Japan epoxy resin agent, YX-4000H, epoxy equivalent weight 195, melting | fusing point 105 degreeC, phenol novolak (hardening agent A; OH equivalent 107, softening point 82 degreeC) as a hardening | curing agent, phenol aralkyl resin (hardening agent B; Mitsui Chemicals make, Using an XL-225-LL, an OH equivalent of 175, and a softening point of 74 ° C, silica (average particle diameter: 22 µm) as a filler and triphenylphosphine as a curing accelerator were kneaded in the formulations shown in Table 1 to obtain an epoxy resin composition. . It shape | molded at 175 degreeC using this epoxy resin composition, postcure was carried out at 175 degreeC for 12 hours, and after obtaining a hardened | cured material test piece, it used for measuring various physical properties. In addition, the compounding quantity shown in Table 1 is a weight part.

The glass transition point (Tg) was calculated | required on the conditions of the temperature increase rate of 10 degree-C / min by the thermometer measuring apparatus. A water absorption is when the disk of diameter 50mm and thickness 3mm is shape | molded using this epoxy resin composition, and after postcure, it was made to absorb moisture for 100 hours on 85 degreeC and the conditions of 85% of a relative humidity. The adhesive strength is evaluated by obtaining a tensile shear strength after molding a 25 mm x 12.5 mm x 0.5 mm molded product at 175 ° C with a compression molding machine between two 42 alloy plates at 175 ° C for 12 hours. It was. The flame retardance was molded into a 1 / 16-inch thick test piece and evaluated according to the UL94V-O standard. The combustion time is the total combustion time in the test of n = 5. Table 2 shows the results of the evaluation.

When the epoxy resin of the present invention and the epoxy resin obtained by the production method of the present invention are applied to an epoxy resin composition, they have excellent moldability and filler high filling properties and impart a cured product excellent in moisture resistance, heat resistance and flame resistance, It is possible to use suitably for uses, such as sealing of electrical and electronic components, a circuit board material. In particular, it is excellent in flame retardancy, which unnecessarily or reduces the use of flame retardants with environmental loads.

Claims (8)

It is represented by following General formula (1), The phenol resin characterized by the above-mentioned.

Here, R ₁ to R ₄ independently represent a hydrogen atom or a substituent represented by the following formula (a) or (b), but at least one is the substituent. X is a single bond, -CH _2- , -CH (CH ₃ )-, -C (CH ₃ ) _2- , -CO-, -O-, -S- or -SO _2- .

General formula (2)

(Wherein X represents a single bond, -CH _2- , -CH (CH ₃ )-, -C (CH ₃ ) _2- , -CO-, -O-, -S- or -SO _2- ). 0.2-4 mol of aromatic olefins selected from indene or acenaphthylene are reacted with 1 mol of bisphenol compounds represented by the following formula (a) or (b)

It has a substituent represented by the manufacturing method of the phenol resin characterized by the above-mentioned. The epoxy resin represented by following General formula (3).

(Wherein R ₁ to R ₄ independently represent a hydrogen atom or a substituent represented by the following formula (a) or (b), but at least one is the substituent, X is a single bond, -CH _2- , -CH (CH ₃ ) —, —C (CH ₃ ) ₂ —, —CO—, —O—, —S— or —SO ₂ —, and n represents a number from 0 to 50.)

A method for producing the epoxy resin according to claim 3, wherein the phenol resin according to claim 1 is reacted with epichlorohydrin. A method for producing an epoxy resin, wherein the phenol resin obtained by the method for producing a phenol resin according to claim 2 is reacted with epichlorohydrin. It is obtained by the manufacturing method of the epoxy resin of Claim 5, The epoxy resin characterized by the above-mentioned. An epoxy resin composition comprising an epoxy resin and a curing agent, wherein the epoxy resin according to claim 3 is blended as an epoxy resin component. The hardened | cured material obtained by hardening | curing the epoxy resin composition of Claim 7.

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