JPWO2008041749A1 - Epoxy resin, phenol resin, production method thereof, epoxy resin composition and cured product - Google Patents

Abstract

An epoxy resin suitable for applications such as sealing of electronic parts and circuit board materials and a composition thereof are provided by providing a cured product excellent in fluidity, high filler filling, moisture resistance, heat resistance and flame retardancy. This epoxy resin is obtained by reacting a phenol resin obtained by reacting 0.2 to 6.0 moles of indene or acenaphthylene with epichlorohydrin with respect to 1 mole of a bisphenol compound represented by the following general formula (2). And is represented by the following general formula (3). (X represents a single bond, —CH 2 —, —CH (CH 3) —, —C (CH 3) 2 —, —CO—, —O—, —S—, —SO 2 —, wherein R 1 to R 4 are , H or a hydrogen atom or a substituent derived from indene or acenaphthylene.)

Description

  The present invention is an epoxy resin that provides a cured product that is excellent in low viscosity and also excellent in moisture resistance, heat resistance, flame retardancy, and the like, a phenol resin suitable as an intermediate thereof, a method for producing them, and the use of this epoxy resin The present invention relates to an epoxy resin composition and a cured product thereof, and is suitably used for insulating materials in the electric and electronic fields such as semiconductor sealing and printed wiring boards.

  Resin compositions based on epoxy resins have been widely used as semiconductor encapsulating materials, but the transition from the conventional insertion method to the surface mounting method has progressed as a method for mounting components on printed circuit boards. ing. In the surface mounting method, the entire package is heated to the solder temperature, and a package crack caused by a rapid volume expansion of moisture absorbed has become a serious problem. Furthermore, high integration of semiconductor elements, increase in element size, and miniaturization of wiring width are rapidly progressing, and the problem of package cracks is becoming more serious. As a method for preventing package cracks, there are methods such as toughening the resin structure, increasing strength by increasing the filling of inorganic filler, and reducing water absorption.

  In particular, high filling of inorganic fillers is strongly directed, and for this purpose, an epoxy resin that is excellent in low hygroscopicity, high heat resistance and low viscosity is desired. As low-viscosity epoxy resins, bisphenol A-type epoxy resins, bisphenol F-type epoxy resins and the like are generally widely used. Of these epoxy resins, low-viscosity resins are liquid at room temperature, and are resin compositions for transfer molding. It is difficult to make things. Furthermore, these epoxy resins are not sufficient in terms of heat resistance, mechanical strength, and moisture resistance.

  From the above background, biphenyl type epoxy resins (Japanese Patent Laid-Open No. 58-39677) and bisphenol type epoxy resins (Japanese Patent Laid-Open No. 6-345850) have been proposed as being excellent in low moisture absorption and high heat resistance. In terms of adhesion to the metal substrate, it is not sufficient. Further, from the viewpoint of improving adhesion, an epoxy resin having a sulfide structure containing a sulfur atom (Japanese Patent Laid-Open No. 6-145300) has been proposed, but the heat resistance is not sufficient. Moreover, although the epoxy resin which has a conventionally known sulfone structure has high heat resistance, its water absorption is high and its adhesiveness is not sufficient.

JP 58-39677 A JP-A-6-345850 JP-A-6-145300

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

（但し、Ｒ_１〜Ｒ_４は、独立に水素原子又は下記式（ａ）若しくは（ｂ）で表される置換基を示すが、少なくとも１つは上記置換基である。Ｘは、単結合、−ＣＨ_２−、−ＣＨ（ＣＨ_３）−、−Ｃ（ＣＨ_３）_２−、−ＣＯ−、−Ｏ−、−Ｓ−又は−ＳＯ_２−を示し、ｎは、０〜５０の数を示す。）

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), at least one of which is the above substituent. X is a single bond, —CH ₂ —, —CH (CH ₃ ) —, —C (CH ₃ ) ₂ —, —CO—, —O—, —S— or —SO ₂ — is shown, and n is a number from 0 to 50. Show.)

（但し、Ｒ_１〜Ｒ_４及びＸは、式（３）と同じ意味を有する。）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).)

（但し、Ｘは、式（３）と同じ意味を有する。）で表されるビスフェノール化合物１モルに対して、インデン又はアセナフチレンから選ばれる芳香族オレフィン０．２〜４モルを反応させることを特徴とする上記式（ａ）又は（ｂ）で表される置換基を有するフェノール樹脂の製造方法に関する。Further, the present invention provides the following general formula (2),

(However, X has the same meaning as in the formula (3).) 0.2 mol to 4 mol of an aromatic olefin selected from indene or acenaphthylene is reacted with 1 mol of the bisphenol compound represented by the formula (3). It relates to a method for producing a phenol resin having a substituent represented by the above formula (a) or (b).

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

  Furthermore, the present invention is an epoxy resin composition comprising an epoxy resin and a curing agent, wherein the epoxy resin composition is blended with the above epoxy resin as an epoxy resin component, and curing obtained by curing the epoxy resin composition. Related to things.

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 above formula (a) or (b), but at least one is a substituent represented by the formula (a) or (b). is there. From the viewpoint of low viscosity, R _{1 to} R ₄ are preferably a substituent represented by the general formula (a), and from the viewpoint of low hygroscopicity and flame retardancy, a substituent of the general formula (b) is preferable. In the general formula (3), R ₁ and R ₃ and R ₂ and R ₄ in parentheses may be interchanged.

R _{1 to} R ₄ may be composed of a hydrogen atom and a substituent represented by the formula (a), may be composed of a hydrogen atom and a substituent represented by the formula (b), It may consist of an atom and a substituent represented by formula (a) and formula (b), may consist of a substituent represented by formula (a) and formula (b), and in formula (a) You may consist only of the substituent represented only by the substituent represented by Formula (b).

X is selected from a single bond, —CH ₂ —, —CH (CH ₃ ) —, —C (CH ₃ ) ₂ —, —CO—, —O—, —S— or —SO ₂ —. A linking group is shown. From the viewpoint of low viscosity, a single bond, —CH ₂ —, —O— or —S— is preferably selected.

  n represents a number from 0 to 50, and a preferable value of n varies depending on the application to be applied. For example, for a semiconductor encapsulant application that requires a high filling rate of the filler, a material having a low viscosity is desirable, and the value of n is 0 to 5, preferably 0.1 to 2, and more preferably, Those in which n is 0 are contained in an amount of 50 wt% or more. 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, n is more preferably from 0.1 to 1. Moreover, a high molecular weight epoxy resin is used suitably for uses, such as a printed wiring board, The value of n in this case is 2-50, Preferably it is 2-40. In the case of a mixture having different values of n, the above range is preferable as the average value n. In this case, if the average value is 50 or less, a molecule where n is an integer of 50 or more may be included.

  The epoxy resin of the present invention is, for example, a phenol obtained by reacting a bisphenol compound represented by the general formula (2) with an aromatic olefin selected from indene or acenaphthylene (hereinafter sometimes referred to simply as an aromatic olefin). A resin can be obtained as an intermediate and can be produced by a method such as reacting this phenol resin with epichlorohydrin. Since indene and acenaphthylene are one kind of aromatic olefin, they can be substituted for the benzene ring of the bisphenol compound represented by the general formula (2) by Friedel-Crafts reaction. Then, the benzene ring is substituted as a substituent represented by the formula (a) or (b) (hereinafter sometimes simply referred to as a substituent). Note that up to two of these substituents can be substituted on one benzene ring due to steric hindrance. The substituent represented by formula (a) is a structure in which one hydrogen atom is removed from indene, and the substituent represented by formula (b) is a structure in which one hydrogen atom is removed from acenaphthylene, It can be said that each group is derived from indene or acenaphthylene.

The phenol resin of the present invention is represented by the above general formula (1). In the general formula _(1), R 1 to R ₄ and X corresponds to the _R 1 to R ₄ and X in the general formula (3). Accordingly, the same as the _R 1 to R ₄ and X of preferred _R 1 to R ₄ and X or the like is also the general formula (3).

In the general formula (2), X is a single bond, —CH ₂ —, —CH (CH ₃ ) —, —C (CH ₃ ) ₂ —, —CO—, —O—, —S— or —SO _2. - are illustrated, from the viewpoint of low viscosity, single bond, _-CH 2 -, - O-or -S- is preferably selected. In the general formula (2), the substitution position of the hydroxyl group is 4,4′-position, 3,4′-position, 3,3′-position, 2,4′-, 2,3 with respect to the linking group X. Some are in the '-position and the 2,2'-position. These may be a compound consisting of a single isomer or a mixture of these isomers. However, since the steric hindrance of the above formula (a) or (b) is large, an epoxy resin is used. From the viewpoint of reactivity at the time, those containing 2,4′-isomer or 2,2′-isomer are preferable. In this case, the total amount of the 2,4′-isomer and the 2,2′-isomer is preferably 30 mol% or more, and preferably 50 mol% or more. The same applies to X in the general formulas (1) and (3).

  In the phenol resin of the present invention, an aromatic olefin selected from indene or acenaphthylene is reacted with 1 to 4 mol of an aromatic olefin with respect to 1 mol of the bisphenol compound to the bisphenol compound represented by the general formula (2). Obtainable.

  In the method for producing a phenol resin of the present invention, an aromatic olefin selected from indene or acenaphthylene is added to the bisphenol compound represented by the general formula (2), and the aromatic olefin is added to 0.2 to 4 mol per 1 mol of the bisphenol compound. In this method, the benzene ring is substituted with the above substituent by reacting.

  In the method for producing a phenol resin of the present invention, the reaction amount of the aromatic olefin with respect to 1 mol of the bisphenol compound is in the range of 0.2 to 4.0 mol, preferably 0.5 to 4.0 mol, more preferably Is in the range of 1.0 to 3.0 moles. When less than this, the improvement effect of moisture resistance and a flame retardance at the time of setting it as an epoxy resin is not fully expressed. On the other hand, when the amount is larger than this, the viscosity becomes high and the high filling property and moldability of the filler are lowered.

  On the other hand, the amount used as a reaction raw material when reacting the bisphenol compound and the aromatic olefin substantially corresponds to the desired number of substituted moles (number of moles of substituents relative to 1 mole of bisphenol compound). You just have to decide. In addition, although reaction conditions in which any of the raw materials remain unreacted can be employed, the amount of the aromatic olefin used per 1 mol of the bisphenol compound may be in the range of 0.2 to 6.0 mol even in this case. Good. If any of the raw materials remain unreacted, it is desirable to separate them, but they can remain as long as they are in small amounts. In addition, if a large amount of aromatic olefin is used, unreacted aromatic olefin may remain or a homo-oligomer of aromatic olefin may be generated, which causes a decrease in heat resistance and flame retardancy as an epoxy resin. Become. Therefore, the amount of the aromatic olefin used as a raw material per 1 mol of the bisphenol compound is at most 6.0 mol.

  The aromatic olefin to be reacted with the bisphenol compound is indene, acenaphthylene, or a mixture thereof. From the viewpoint of low viscosity, those containing indene as the main component are preferred, and those containing acenaphthylene as the main component are preferred from the viewpoint of flame retardancy.

  The aromatic olefin used in the reaction may contain an unsaturated bond-containing component such as styrene, α-methylstyrene, divinylbenzene, coumarone, benzothiophene, indole, and vinylnaphthalene as other reactive components. In addition, the indene and acenaphthylene contents in all reaction components are 50 wt% or more, preferably 70 wt% or more. If it is less than this, the effect of improving heat resistance and flame retardancy is small. The aromatic olefin may contain non-reactive compounds such as toluene, dimethylbenzene, trimethylbenzene, indane, naphthalene, methylnaphthalene, dimethylnaphthalene, and acenaphthene. From the viewpoint of improving properties such as heat resistance and flame retardancy, these non-reactive compounds should be excluded from the system. Preferably, the total amount is 5 wt% or less, more preferably 2 wt% or less. As a removal method, generally, a method such as vacuum distillation is applied.

  When the aromatic olefin used for the reaction contains an unsaturated bond-containing component such as styrene, α-methylstyrene, divinylbenzene, coumarone, benzothiophene, indole, and vinylnaphthalene as other reactive components, the resulting phenol The resin contains a compound in which a group derived therefrom is substituted on the benzene ring. The phenol resin obtained by the method for producing a phenol resin of the present invention may include a phenol resin having such a substituent. Similarly, the epoxy resin obtained by the method for producing an epoxy resin of the present invention can include an epoxy resin having such a substituent.

  For the reaction between the bisphenol compound and the aromatic olefin, a reaction method using a known Friedel-Crafts catalyst such as an acid catalyst can be employed. By this reaction, a phenol resin in which the above substituent is substituted on the benzene ring of the bisphenol compound is obtained. This phenol resin is usually a mixture having a different number of substituents and different substitution positions, but it has an average of 0.4 to 4, preferably 1 to 4 substituents. After completion of the reaction between the bisphenol compound and the aromatic olefin, the catalyst or unreacted components are removed if necessary, and the resultant is subjected to the next epoxidation reaction. However, components that do not inhibit the epoxidation reaction and components that can be neutralized such as an acid catalyst do not have to be removed, and when they are removed by a purification process such as washing and distillation performed after the epoxidation reaction, or epoxy resins Even if it is included in the case, it may not be removed. Use of the reaction product after completion of the reaction between the bisphenol compound and the aromatic olefin as it is for the epoxidation reaction is advantageous in that one purification step is reduced. In addition, it can also refine | purify or isolate a phenol resin as a target object.

  The production method of the epoxy resin of the present invention is the phenol resin represented by the general formula (1) or the phenol resin obtained by the production method of the phenol resin (hereinafter, when it is not necessary to distinguish both, the phenol resin is simply phenol. Resin) and epichlorohydrin.

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

  In the reaction, an excessive amount of epichlorohydrin is used with respect to the phenol resin. Usually, 1.5 to 15 times mole of epichlorohydrin is used with respect to 1 mole of hydroxyl group in the phenol resin, but preferably in the range of 2 to 8 times mole. If the amount is higher than this, the production efficiency is lowered.

  The reaction is usually performed at a temperature of 120 ° C. or lower. If the temperature is high during the reaction, the amount of so-called hardly hydrolyzable chlorine increases and it becomes difficult to achieve high purity. Preferably it is 100 degrees C or less, More preferably, it is the 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 the quaternary ammonium salt include tetramethylammonium chloride, tetirabutylammonium chloride, benzyltriethylammonium chloride, and the addition amount is preferably in the range of 0.1 to 2.0 wt% with respect to the phenol resin. . If the amount is less than this, the effect of adding a quaternary ammonium salt is small. Moreover, as an addition amount of a polar solvent, the range of 10-200 wt% is preferable with respect to a phenol resin. If the amount is less than this, the effect of addition is small.

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

  Advantageously, the obtained epoxy resin is further added with 1 to 30 times the amount of alkali metal hydroxide such as sodium hydroxide or potassium hydroxide with respect to the remaining hydrolyzable chlorine, and a re-ring closure reaction is carried out. Is called. The reaction temperature at this time is usually 100 ° C. or lower, preferably 90 ° C. or lower.

  The epoxy resin obtained by the method for producing an epoxy resin of the present invention is preferably an epoxy resin represented by the above general formula (3) or an epoxy resin containing this as a main component (50 wt% or more). However, as a whole, in the 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, the phenol resin obtained by the method for producing a phenol resin of the present invention is preferably a phenol resin represented by the above general formula (1) or a phenol resin mainly composed thereof. However, as a whole, in the 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 the present invention comprises an epoxy resin represented by the above general formula (1), an epoxy resin mainly composed of this epoxy resin, or an epoxy resin obtained by a method for producing the above epoxy resin (hereinafter referred to as these). Collectively, this epoxy resin is also called) and a curing agent as essential components. 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 include dicyandiamide, polyhydric phenols, acid anhydrides, aromatic and aliphatic amines.

  Specifically, examples of the polyhydric phenols include bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4′-biphenol, 2,2′-biphenol, hydroquinone, resorcin, and naphthalenediol. Divalent phenols, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol novolac, o-cresol novolak, naphthol novolak, polyvinylphenol, etc. There are representative trihydric or higher phenols. Furthermore, monohydric phenols such as phenols and naphthols, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4'-biphenol, 2,2'-biphenol, hydroquinone, resorcin, naphthalenediol, etc. And polyhydric phenolic compounds synthesized by a condensing agent such as formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, p-xylylene glycol, and the like. Moreover, you may use what made indene or acenaphthylene react with these phenolic hardening | curing agents for a hardening | curing agent.

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

  Examples of amines include aromatic amines such as 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylpropane, 4,4′-diaminodiphenylsulfone, m-phenylenediamine, and p-xylylenediamine. There are aliphatic amines such as ethylenediamine, hexamethylenediamine, diethylenetriamine, and triethylenetetramine.

  In the epoxy resin composition of the present invention, one or more of these curing agents can be mixed and used.

  Moreover, you may mix | blend another kind of epoxy resin other than this epoxy resin as an epoxy resin component in the epoxy resin composition of this invention. As another kind of epoxy resin in this case, a normal epoxy resin having two or more epoxy groups in the molecule can be used. Examples include divalent phenols such as bisphenol A, bisphenol S, fluorene bisphenol, 4,4′-biphenol, 2,2′-biphenol, hydroquinone, resorcin, or tris- (4-hydroxyphenyl) methane. , Glucidyl derived from trivalent or higher phenols such as 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol novolak, o-cresol novolak or halogenated bisphenols such as tetrabromobisphenol A There are etherified products. These epoxy resins can be used alone or in combination of two or more. 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 wt% in the whole epoxy resin, Preferably it is good to be the range of 60-100 wt%.

  If necessary, an inorganic filler can be blended in the epoxy resin composition of the present invention. Examples of the inorganic filler include spherical or crushed fused silica, crystalline silica or other silica powder, alumina powder, glass powder, and the like. When applied to a semiconductor encapsulant, the amount of inorganic filler used is usually 75 wt% or more, but is preferably 80 wt% or more from the viewpoint of low moisture absorption and high solder heat resistance.

  Furthermore, in the epoxy resin composition of the present invention, an oligomer or a polymer compound such as polyester, polyamide, polyimide, polyether, polyurethane, petroleum resin, indene coumarone resin, phenoxy resin may be appropriately blended, You may mix | blend additives, such as a pigment, a refractory agent, a thixotropic agent, a coupling agent, and a fluid improvement agent. Examples of the pigment include organic or inorganic extender pigments and scaly pigments. Examples of the thixotropic agent include silicon-based, castor oil-based, aliphatic amide wax, polyethylene oxide wax, and organic bentonite. Furthermore, if necessary, the epoxy resin composition of the present invention includes a release agent such as carnauba wax and OP wax, a coupling agent such as γ-glycidoxypropyltrimethoxysilane, a colorant such as carbon black, Flame retardants such as antimony trioxide, low stress agents such as silicone oil, lubricants such as calcium stearate, and the like can be used.

  Furthermore, a known hardening accelerator can be used for the epoxy resin composition of this invention as needed. Examples include amines, imidazoles, organic phosphines, Lewis acids and the like. The addition amount is usually in the range of 0.2 to 5 parts by weight with respect to 100 parts by weight of the epoxy resin. Moreover, as addition amount of a hardening | curing agent, it is the range of 10-100 weight part normally with respect to 100 weight part of epoxy resins.

  The cured product of the present invention obtained by curing the resin composition of the present invention can be molded by a method such as casting, compression molding, transfer molding or the like. The temperature at this time is usually in the range of 120 to 220 ° C.

Infrared absorption spectrum of epoxy resin A ¹ H-NMR spectrum of epoxy resin A

  Hereinafter, the present invention will be described more specifically with reference to examples.

Example 1
Bisphenol F (4,4 ′ form (31%), 2,4 ′ form (49%), 2,2 ′ form (20%)) 200 g (1.0 mol) charged to a 1 L flask 175 The temperature was raised to ° C. After melting, 0.1 g of p-toluenesulfonic acid was charged with stirring, and 232 g (2.0 mol) of indene was added dropwise at about 175 ° C. over about 3 hours. Further, the reaction was continued for 3 hours under total reflux. Thereafter, low-boiling components were removed under reduced pressure to obtain 413 g of indene-added phenol resin (phenol resin A). The OH equivalent is 216 g / eq. The softening point was 78 ° C., and the melt viscosity at 150 ° C. was 0.06 Pa · s.

Example 2
In a 1 L flask, 200 g (1.0 mol) of bisphenol F was heated to 175 ° C. After melting, 0.15 g of p-toluenesulfonic acid was charged with stirring, and 348 g (3.0 mol) of indene was added dropwise at about 175 ° C. over about 3 hours. Thereafter, low-boiling components were removed under reduced pressure to obtain 527 g of indene-added phenol resin (phenol resin B). The OH equivalent is 274 g / eq. The softening point was 86 ° C., and the melt viscosity at 150 ° C. was 0.15 Pa · s.

Example 3
In a 1 L flask, 200 g (1.0 mol) of bisphenol F was charged and the temperature was raised to 180 ° C. After melting, 0.04 g of p-toluenesulfonic acid was charged with stirring, and 304 g (2.0 mol) of acenaphthylene was added dropwise at 180 ° C. over about 3 hours. Then, it heated up at 200 degreeC under pressure reduction, the low boiling point component was removed, and 491 g of acenaphthylene addition phenol resin was obtained (phenol resin C). The OH equivalent is 252 g / eq. The softening point was 99 ° C., and the melt viscosity at 150 ° C. was 0.59 Pa · s.
In Examples 1 to 3, the reaction rate of indene was about 100%.

Example 4
After dissolving in 300 g of phenol resin A synthesized in Example 1, 900 g of epichlorohydrin and 135 g of diglyme in a 3 L 4-neck separable flask, 116 g of 48% aqueous sodium hydroxide solution was added dropwise at 60 ° C. over 4 hours under reduced pressure. . During this time, the generated water was removed from the system by azeotropy with epichlorohydrin, and the distilled epichlorohydrin was returned to the system. After completion of dropping, the reaction was continued for another hour. Thereafter, epichlorohydrin and diglyme were distilled off under reduced pressure and dissolved in 987 g of methyl isobutyl ketone, and then the salt produced by washing with water was removed. Thereafter, 64 g of a 12% aqueous sodium hydroxide solution was added and reacted at 80 ° C. 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 light yellow epoxy resin (epoxy resin A). The epoxy equivalent of this epoxy resin A is 278 g / eq. The hydrolyzable chlorine was 420 ppm, the softening point was 58 ° C., and the melt viscosity at 150 ° C. was 0.045 Pa · s.

Here, hydrolyzable chlorine is obtained by dissolving 0.5 g of a sample in 30 ml of dioxane, adding 10 ml of 1N KOH, boiling and refluxing for 30 minutes, cooling to room temperature, and further adding 100 ml of 80% acetone water. Is a value measured by performing potentiometric titration with 0.002N-AgNO ₃ aqueous solution. The softening point is a value obtained by a ball & ring method at a heating rate of 5 ° C./min, and the viscosity was measured using a corn plate viscometer manufactured by Brookfield.

GPC measurement conditions were as follows: apparatus; MODEL 151 (manufactured by Waters Co., Ltd.), column; TSK-GEL2000 × 3 and TSK-GEL4000 × 1 (both manufactured by Tosoh Corp.), solvent; tetrahydrofuran, flow rate: 1 ml / min, temperature; 38 ° C., detector; RI. The infrared absorption spectrum was determined by the KBr tablet molding method, and the ¹ H-NMR spectrum was measured in acetone-d6 using an apparatus; JNM-LA400, manufactured by JEOL Ltd.
The infrared absorption spectrum of the epoxy resin A is shown in FIG. 1, and the ¹ H-NMR spectrum is shown in FIG.

Example 5
In a 3 L 4-neck separable 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 96 g of 48% sodium hydroxide aqueous solution was used at 60 ° C. under reduced pressure. The reaction was conducted in the same manner as above to obtain 335 g of a light yellow epoxy resin (epoxy resin B). Epoxy equivalent was 336 g / eq. The hydrolyzable chlorine was 340 ppm, the softening point was 76 ° C., and the melt viscosity at 150 ° C. was 0.136 Pa · s.

Example 6
In a 3 L four-necked separable flask, 300 g of phenol resin C synthesized in Example 3 was dissolved in 810 g of epichlorohydrin and 122 g of diglyme, and then 99 g of 48% sodium hydroxide aqueous solution was used at 60 ° C. under reduced pressure. Then, 230 g of a light yellow epoxy resin was obtained (epoxy resin C). Epoxy equivalent was 318 g / eq. The hydrolyzable chlorine was 330 ppm, the softening point was 83 ° C., and the melt viscosity at 150 ° C. was 0.226 Pa · s.

Examples 7-11 and Comparative Examples 1-2
As epoxy resin components, epoxy resins A to C synthesized in Examples 4 to 6, bisphenol F type epoxy resin (epoxy resin D; manufactured by Tohto Kasei, YDF-170, epoxy equivalent 169), biphenyl type epoxy resin (epoxy resin E) Made by Japan Epoxy Resin, YX-4000H, epoxy equivalent 195, melting point 105 ° C., phenol novolak (curing agent A; OH equivalent 107, softening point 82 ° C.) as a curing agent, phenol aralkyl resin (curing agent B; manufactured by Mitsui Chemicals) , XL-225-LL, OH equivalent 175, softening point 74 ° C.), silica (average particle size, 22 μm) as a filler, and triphenylphosphine as a curing accelerator are kneaded with the composition shown in Table 1 to form an epoxy resin composition I got a thing. This epoxy resin composition was molded at 175 ° C. and post-cured at 175 ° C. for 12 hours to obtain a cured product test piece, which was then subjected to various physical property measurements. In addition, the compounding quantity shown in Table 1 is a weight part.

  The glass transition point (Tg) was determined by a thermomechanical measuring device under a temperature rising rate of 10 ° C./min. The water absorption rate is obtained when a disk having a diameter of 50 mm and a thickness of 3 mm is formed using the epoxy resin composition, and after post-curing, the moisture is absorbed for 100 hours under the conditions of 85 ° C. and relative humidity of 85%. The adhesive strength was 25 mm × 12.5 mm × 0.5 mm between two 42 alloy plates, molded at 175 ° C. with a compression molding machine, post-cured at 175 ° C. for 12 hours, and then tensile shear strength Was evaluated. The flame retardancy was evaluated by the UL94V-0 standard by molding a test piece having a thickness of 1/16 inch. The burning time is the total burning time in a test with n = 5. Table 2 shows the evaluation results.

Industrial applicability

  When applied to an epoxy resin composition, the epoxy resin obtained by the epoxy resin of the present invention and the production method of the present invention has excellent moldability, high filler filling property, moisture resistance, heat resistance and flame retardancy. It provides an excellent cured product and can be suitably used for applications such as sealing electric and electronic parts, circuit board materials, and the like. In particular, the use of a flame retardant having excellent flame retardancy and environmental impact is made unnecessary or reduced.

Claims (8)

A phenol resin represented by the following general formula (1).

Here, R _{1 to} R ₄ independently represent a hydrogen atom or a substituent represented by the following formula (a) or (b), at least one of which is the above substituent. X represents a single bond, —CH ₂ —, —CH (CH ₃ ) —, —C (CH ₃ ) ₂ —, —CO—, —O—, —S— or —SO ₂ —;

The following general formula (2),

Here, X represents a single bond, —CH ₂ —, —CH (CH ₃ ) —, —C (CH ₃ ) ₂ —, —CO—, —O—, —S— or —SO ₂ —;
The following formula (a) or (b), wherein 0.2 to 4 mol of an aromatic olefin selected from indene or acenaphthylene is reacted with 1 mol of a bisphenol compound represented by the formula:

The manufacturing method of the phenol resin which has a substituent represented by these. An epoxy resin represented by the following general formula (3).

Here, R _{1 to} R ₄ independently represent a hydrogen atom or a substituent represented by the following formula (a) or (b), at least one of which is the above substituent, and X is a single bond, —CH ₂ —, —CH (CH ₃ ) —, —C (CH ₃ ) ₂ —, —CO—, —O—, —S— or —SO ₂ — is shown, and n is a number from 0 to 50. Show;

  4. The method for producing an 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, comprising reacting a phenol resin obtained by the method for producing a phenol resin according to claim 2 with epichlorohydrin.   An epoxy resin obtained by the method for producing an epoxy resin according to claim 5.   An epoxy resin composition comprising an epoxy resin and a curing agent, wherein the epoxy resin composition according to claim 3 is blended as an epoxy resin component.   A cured product obtained by curing the epoxy resin composition according to claim 7.

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