JP6282515B2 - Epoxy resin and production method thereof, epoxy resin composition and cured product thereof - Google Patents

Description

  The present invention relates to an epoxy resin, a resin composition containing the epoxy resin, and a cured product.

  A cured product of an epoxy resin composition composed of an epoxy resin and a curing agent is used in various applications including semiconductor packages and electronic components of semiconductor chips. For example, Patent Document 1 describes a method for producing an epoxy resin having a polyether group having a repeating unit composed of an alkyleneoxy group of less than 3. Patent Document 2 describes a method for producing an epoxy resin having a polyether group having a repeating unit composed of an alkyleneoxy group of less than 6.

Japanese Patent Publication No. 36-020393 JP 2003-246837 A

  In recent years, there has been a strong demand for miniaturization and thinning of semiconductor packages and semiconductor chips. Therefore, it is desired that the epoxy resin used as these materials has excellent adhesiveness while having low viscosity, and the cured product has excellent flexibility. Furthermore, from the viewpoint of heat resistance and electrical reliability, it is required that the cured product has excellent reactivity during curing and that the cured product has a high glass transition temperature. However, the conventional epoxy resin cannot sufficiently meet such a demand, and there is still room for development.

  For example, the cured product of the epoxy resin disclosed in Patent Document 1 cannot obtain sufficient flexibility. In addition, the epoxy resin cured product disclosed in Patent Document 2 cannot obtain sufficient flexibility, and further improvement in heat resistance is desired. Furthermore, this epoxy resin is inferior in reactivity since the content ratio of both terminal epoxy groups is small.

  The present invention has been made in view of the above circumstances, and provides, for example, an epoxy resin that is liquid and has excellent reactivity, and the cured product has excellent flexibility and heat resistance. The purpose is to do.

  As a result of intensive studies, the present inventors have found that the above problems can be solved by an epoxy resin having a specific structure, and have completed the present invention.

That is, the present invention is as follows.
[1]
The following general formula (1)
(In the formula, α, β and γ are each independently an integer of 0 to 3 and satisfy the relationship of 0 <(α + β + γ) ≦ 9. (Α + β + γ) R _{1 s} are each independently (A C1-C10 alkylene group is represented, X represents a C6-C45 trivalent aromatic group.)
Epoxy resin represented by
[2]
The epoxy resin according to [1], wherein R ₁ in the general formula (1) is an ethylene group, a trimethylene group, or a propylene group.
[3]
X in the general formula (1) is
(In the formula, R ₂ represents a hydrogen atom, a halogen atom, a methoxy group, a cyclohexyl group, or an alkyl group having 1 to 12 carbon atoms.)
The epoxy resin according to [1] or [2], which is one selected from the group consisting of:
[4]
An epoxy resin composition comprising the epoxy resin according to any one of [1] to [3] and a curing agent.
[5]
Furthermore, the epoxy resin composition of [4] containing another epoxy resin component.
[6]
Furthermore, the epoxy resin composition of [4] or [5] containing a hardening accelerator.
[7]
Furthermore, the epoxy resin composition in any one of [4]-[6] containing an inorganic filler.
[8]
Hardened | cured material formed by hardening | curing the epoxy resin composition in any one of [4]-[7].
[9]
[8] An electronic member comprising the cured product according to [8].

  According to the present invention, for example, it is possible to provide an epoxy resin which is liquid and has excellent reactivity, and whose cured product has excellent flexibility and heat resistance.

2 is a UPLC chart of a polyvalent hydroxy compound obtained in Synthesis Example 1. 2 is a mass spectrum of a polyvalent hydroxy compound obtained in Synthesis Example 1. FIG. It is UPLC area ratio according to the number of α + β + γ determined from the mass spectrum of the polyvalent hydroxy compound obtained in Synthesis Example 1. 2 is a UPLC chart of the epoxy resin obtained in Example 1. FIG. 2 is a mass spectrum of the epoxy resin obtained in Example 1. It is UPLC area ratio according to the number of (alpha) + (beta) + (gamma) calculated | required from the mass spectrum of the epoxy resin obtained in Example 1. FIG.

  Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail. This embodiment is an example for explaining the present invention, and is not intended to limit the present invention to the following contents. The present invention can be appropriately modified and implemented within the scope of the gist.

≪Epoxy resin≫
The epoxy resin of this embodiment is represented by the following general formula (1).
The following general formula (1)
(In the formula, α, β and γ are each independently an integer of 0 to 3 and satisfy the relationship of 0 <(α + β + γ) ≦ 9. (Α + β + γ) R _{1 s} are each independently (A C1-C10 alkylene group is represented, X represents a C6-C45 trivalent aromatic group.)

In formula (1), R _1, if an alkylene group having 1 to 10 carbon atoms is not particularly limited. R ₁ may be linear or branched. Furthermore, R ₁ may contain an unsaturated bond group. The number of carbon atoms of the alkylene group is preferably 1 to 6 from the viewpoint of the balance between flexibility and heat resistance, and more preferably 1 to 3 from the viewpoint of ease of manufacture. Preferable specific examples of R ₁ include, for example, an ethylene group, a trimethylene group, and a propylene group.

  In the formula (1), X is not particularly limited as long as X is a trivalent aromatic group having 6 to 45 carbon atoms. X is preferably a trivalent aromatic group having 6 to 33 carbon atoms from the viewpoint of viscosity.

In the formula (1), as a specific structure of a trivalent aromatic group having 6 to 45 carbon atoms represented by X,
(In the formula, R ₂ represents a hydrogen atom, a halogen atom, a methoxy group, a cyclohexyl group, or an alkyl group having 1 to 12 carbon atoms.)
One selected from the group consisting of

From the viewpoint of ease of production, X in formula (1) is preferably at least one selected from the group consisting of trivalent aromatic groups having the structure represented below.

  In the formula (1), α, β, and γ are each independently an integer of 0 to 3, and satisfy the relationship of 0 <(α + β + γ) ≦ 9. When (α + β + γ) is 0, there is a tendency that sufficient flexibility cannot be obtained when a cured product is formed. Moreover, when (α + β + γ) exceeds 9, there is a tendency that sufficient heat resistance cannot be obtained when a cured product is formed. 3 <(α + β + γ) ≦ 9 is preferable from the viewpoint of the handleability of the epoxy resin and flexibility when it is made into a cured product, and from the viewpoint of the balance between flexibility and heat resistance when it is made into a cured product, 3 < (Α + β + γ) ≦ 7 is more preferable. In addition, as a method of controlling the value of α + β + γ in the above formula (1) within the above range, for example, a method in which the conditions in the epoxy resin production method described later, for example, the amount of raw material added, the reaction time, and the like are appropriately adjusted Can be mentioned.

The epoxy resin of this embodiment can be manufactured using, for example, a polyvalent hydroxy compound represented by the following general formula (2) as a raw material.
(In the formula, α, β and γ are each independently an integer of 0 to 3 and satisfy the relationship of 0 <(α + β + γ) ≦ 9. (Α + β + γ) R _{1 s} are each independently (A C1-C10 alkylene group is represented, X represents a C6-C45 trivalent aromatic group.)

  The polyhydric hydroxy compound used in the present embodiment can be produced, for example, by adding a solvent and an alkaline compound to a polyhydric phenol compound having three phenolic hydroxyl groups and then adding a halogenated alkylene alcohol. Hereinafter, the addition reaction will be described in detail.

  Although it does not specifically limit as a solvent, For example, Polar aprotic solvents, such as methanol, ethanol, 1-propanol; Polar aprotic solvents, such as acetone, acetonitrile, tetrahydrofuran, N, N- dimethylformamide, dimethyl sulfoxide; Hexane, Nonpolar solvents such as toluene, ethyl acetate, chloroform; water. These solvents may be used alone or in combination of two or more.

  Among the above solvents, polar protic solvents and polar aprotic solvents are preferred from the viewpoint of solubility, and polar aprotic solvents are more preferred from the viewpoint of reaction control.

  Although it does not specifically limit as an alkaline compound, For example, sodium hydroxide, potassium hydroxide, barium hydroxide, potassium carbonate etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. The state of the alkaline compound is not particularly limited, and may be, for example, solid, liquid, aqueous solution, alcohol solution or the like. The addition amount of the alkaline compound is preferably 1 to 10 equivalents, more preferably 1 to 5 equivalents, and further preferably 1.5 to 3 equivalents with respect to 1 equivalent of the phenolic hydroxyl group of the polyhydric phenol compound. is there. When the addition amount of the alkaline compound is 1 equivalent or more with respect to 1 equivalent of the phenolic hydroxyl group of the polyhydric phenol compound, the reaction proceeds sufficiently. When the addition amount of the alkaline compound is 10 equivalents or less with respect to 1 equivalent of the phenolic hydroxyl group of the polyhydric phenol compound, the reaction can be easily controlled.

  Examples of the halogenated alkylene alcohol include, but are not limited to, 2-chloroethanol, 2-bromoethanol, 2- (2-chloroethoxy) ethanol, 2- [2- (2-chloroethoxy) ethoxy] ethanol, and the like. Can be mentioned. These may be used individually by 1 type and may use 2 or more types together. The addition amount of the halogenated alkylene alcohol is preferably 1 to 5 equivalents and more preferably 1.5 to 3 equivalents with respect to 1 equivalent of the phenolic hydroxyl group of the polyhydric phenolic compound. When the addition amount of the halogenated alkylene alcohol is 1 equivalent or more with respect to 1 equivalent of the phenolic hydroxyl group of the polyhydric phenolic compound, the alkylene ether is sufficiently added, and oil-water separation is facilitated. When the addition amount of the halogenated alkylene alcohol is 5 equivalents or less with respect to 1 equivalent of the phenolic hydroxyl group of the polyhydric phenolic compound, it takes no time to remove the excess halogenated alkylene alcohol, and the cycle time can be shortened.

  The reaction temperature is preferably 30 to 150 ° C, more preferably 50 to 120 ° C. When the reaction temperature is 30 ° C. or higher, the reaction proceeds sufficiently. When the reaction temperature is 150 ° C. or lower, polymerization is suppressed and recovery becomes easy.

  As reaction time, Preferably it is 0.5 to 36 hours, More preferably, it is 1.5 to 24 hours, More preferably, it is 3 to 8 hours. When the reaction time is 0.5 hours or longer, the reaction proceeds sufficiently. When the reaction time is 36 hours or less, polymerization is suppressed and recovery is facilitated.

  After completion of the reaction, for example, the produced salt and the remaining alkaline compound are removed from the reaction solution by washing with water or the like. Next, for example, by heating the reaction solution under normal pressure or reduced pressure, the remaining solvent and an excessive amount of halogenated alkylene alcohol are removed from the reaction solution, and the polyvalent hydroxy compound is recovered.

  Moreover, the polyvalent hydroxy compound used in the present embodiment can be produced, for example, by adding a solvent and an alkaline compound to a polyhydric phenol compound having three phenolic hydroxyl groups, and then adding alkylene oxide under hermetically pressurized pressure. Hereinafter, the addition reaction will be described in detail.

  Although it does not specifically limit as a solvent, For example, Polar aprotic solvents, such as methanol, ethanol, 1-propanol; Polar aprotic solvents, such as acetone, acetonitrile, tetrahydrofuran, N, N- dimethylformamide, dimethyl sulfoxide; Hexane, Nonpolar solvents such as toluene, ethyl acetate, chloroform; water.

  Among the above solvents, water is preferable from the viewpoint of suppressing side reactions.

Examples of the alkaline compound include, but are not limited to, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and cesium hydroxide; alkaline earth metal water such as magnesium hydroxide, calcium hydroxide, and barium hydroxide. Oxides; amines such as dimethylamine, trimethylamine and triethylamine; and quaternary ammonium salts such as tetramethylammonium hydroxide and benzyltrimethylammonium hydroxide. These may be used individually by 1 type and may use 2 or more types together. The state of the alkaline compound is not particularly limited, and may be, for example, solid, liquid, aqueous solution, alcohol solution or the like.
The addition amount of the alkaline compound is preferably 0.05 to 5.0 equivalents, more preferably 0.08 to 3.0 equivalents, and still more preferably with respect to 1 equivalent of the phenolic hydroxyl group of the polyhydric phenol compound. Is 0.1 to 1.0 equivalent.

  Although it does not specifically limit as alkylene oxide, For example, ethylene oxide, propylene oxide, etc. are mentioned. The addition amount of the alkylene oxide is preferably 1.0 to 5.0 equivalents, more preferably 1.5 to 3.0 equivalents, and still more preferably with respect to 1 equivalent of the phenolic hydroxyl group of the polyhydric phenol compound. Is 2.0 to 2.5 equivalents.

  The reaction temperature is preferably 60 to 150 ° C, more preferably 80 to 120 ° C. When the reaction temperature is 60 ° C. or higher, the reaction proceeds sufficiently. When the reaction temperature is 150 ° C. or lower, the reaction control becomes easy.

  The reaction pressure is preferably 0.5 MPa or less. When the reaction pressure is 0.5 MPa or less, the reaction control becomes easy, and an increase in internal pressure and an increase in internal temperature can be suppressed.

  After completion of the reaction, for example, the produced salt and the remaining alkaline compound are removed from the reaction solution by washing with water or the like. Next, for example, by heating the reaction solution under normal pressure or reduced pressure, the remaining solvent and excess amount of alkylene oxide are removed from the reaction solution, and the polyvalent hydroxy compound is recovered.

  The epoxy resin of this embodiment can be manufactured by, for example, reacting the polyvalent hydroxy compound represented by the general formula (2) with epihalohydrin. As a method for producing an epoxy resin of the present embodiment, for example, a compound obtained by adding alkylene oxide to a polyhydric phenol compound having three phenolic hydroxyl groups at a ratio of 1 to 9 times moles with respect to 3 moles of phenolic hydroxyl groups (hereinafter, And simply referred to as “oxyalkylene adduct”) and epihalohydrin with an alkaline compound. In the case of this method, it is preferable to use an alkaline compound and a phase transfer catalyst in combination from the viewpoint of promoting the reaction. Hereinafter, the method will be described in detail.

  Although it does not specifically limit as epihalohydrin, For example, epichlorohydrin, epibromohydrin, etc. are mentioned. The amount of epihalohydrin added is preferably 1 to 10 equivalents, more preferably 2 to 8 equivalents, per 1 equivalent of the alcoholic hydroxyl group of the oxyalkylene adduct.

  Although it does not specifically limit as an alkaline compound, For example, sodium hydroxide, potassium hydroxide, barium hydroxide, potassium carbonate etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. The state of the alkaline compound is not particularly limited, and may be, for example, solid, liquid, aqueous solution, alcohol solution or the like. The addition amount of the alkaline compound is preferably 1 to 10 equivalents, more preferably 1.5 to 7.5 equivalents, and further preferably 2 to 5 to 1 equivalent of the alcoholic hydroxyl group of the oxyalkylene adduct. Is equivalent.

  In the method for producing an epoxy resin of the present embodiment, it is preferable to use a phase transfer catalyst from the viewpoint of promoting the reaction. In particular, it is more preferable to use the alkaline compound and the phase transfer catalyst in combination.

  The phase transfer catalyst is not particularly limited. For example, tetramethylammonium chloride, tetramethylammonium bromide, tetrapropylammonium chloride, tetrapropylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, benzyl Quaternary ammonium salts such as trimethylammonium chloride, benzyltrimethylammonium bromide, benzyltriethylammonium chloride, benzyltriethylammonium bromide, phenyltrimethylammonium chloride; four such as tetramethylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide Grade ammonium hydroxides; Crown ethers such as 5-crown-5, 18-crown-6, dibenzo-18-crown-6, dicyclohexyl-18-crown-6, diaza-18-crown-6; [2.1.1] -cryptand , [2.2.1] -cryptand, [2.2.2] cryptand, [2.2.2] -decyl cryptand, [2.2.2] -benzocryptand, and the like. . These may be used individually by 1 type and may use 2 or more types together. The state of the phase transfer catalyst is not particularly limited, and may be, for example, solid, liquid, aqueous solution, alcohol solution or the like.

  The addition amount of the phase transfer catalyst is preferably 0.25 to 10 mol, more preferably 0.5 to 5 mol, per 1 mol of the alcoholic hydroxyl group of the oxyalkylene adduct.

  The reaction temperature is preferably 20 to 100 ° C, more preferably 30 to 80 ° C. When the reaction temperature is 20 ° C. or higher, the progress of the reaction is accelerated, so that the glycidyl group of epihalohydrin tends to be efficiently introduced into the oxyalkylene adduct. By setting the reaction temperature to 100 ° C. or lower, the polymerization reaction between epihalohydrins can be efficiently suppressed, so that the glycidyl group of epihalohydrin tends to be efficiently introduced into the oxyalkylene adduct.

  As reaction time, Preferably it is 1 to 12 hours, More preferably, it is 1.5 to 8 hours, More preferably, it is 2 to 6 hours.

  After completion of the reaction, for example, the produced salt, the remaining alkaline compound, the phase transfer catalyst, and the like are removed from the reaction solution by washing with water or the like. Next, for example, by heating the reaction solution under normal pressure or reduced pressure, the remaining epihalohydrin is removed from the reaction solution, and the epoxy resin is recovered.

  When it is desired to further reduce the total chlorine content in the epoxy resin of this embodiment, the recovered epoxy resin is dissolved in a solvent such as toluene or methyl isobutyl ketone, and then an alkaline compound (either solid or liquid) is used. Or a solution, etc.) is added. Thereby, the ring-closure reaction of epihalohydrin proceeds, and the amount of hydrolyzable chlorine in the epoxy resin can be further reduced. In this case, the addition amount of the alkaline compound is preferably 0.5 to 5 equivalents, more preferably 1 to 3 equivalents with respect to 1 equivalent of hydrolyzable chlorine in the epoxy resin. Usually, the reaction temperature for the ring closure reaction of epihalohydrin is preferably 60 to 120 ° C., and the reaction time is preferably 0.5 to 3 hours.

  Since the epoxy resin of this embodiment is excellent in compatibility, it can be suitably used as an epoxy resin composition to which other components are added. Hereinafter, the epoxy resin composition will be described.

≪Epoxy resin composition≫
The epoxy resin composition of this embodiment can be obtained by combining with the above-mentioned epoxy resin and a hardening | curing agent, for example. That is, the epoxy resin composition of the present embodiment contains, for example, the above-described epoxy resin and a curing agent. The epoxy resin composition of this embodiment may further contain other epoxy resin components other than the above-described epoxy resin, a curing accelerator, and the like, as necessary.

  Examples of the curing agent include amine-based curing agents, amide-based curing agents, acid anhydride-based curing agents, and phenol-based curing agents, but are not limited thereto.

Specific examples of the curing agent are not particularly limited, but for example, synthesized from imidazoles, diaminodiphenylmethane, diaminodiphenylsulfone, diethylenetriamine, triethylenetetramine, isophoronediamine, polyalkylene glycol polyamine, linolenic acid dimer and ethylenediamine. Amide curing agents such as polyamide resins; Amide curing agents such as dicyandiamide; phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl anhydride Acid anhydride curing agents such as nadic acid, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride; phenol novolac resin, cresol novolac resin, phenol aralkyl resin, cresol aralate Kill resin, naphthol aralkyl resin, biphenyl modified phenol resin, biphenyl modified phenol aralkyl resin, dicyclopentadiene modified phenol resin, aminotriazine modified phenol resin, naphthol novolak resin, naphthol-phenol co-condensed novolak resin, naphthol-cresol co-condensed novolak resin And the like, and phenolic curing agents such as polyphenol compounds such as these and modified products thereof; BF ₃ -amine complexes, guanidine derivatives and the like. These curing agents may be used alone or in combination of two or more.

  Among the hardeners, amine-based hardeners are preferable when importance is attached to flexibility and reactivity. Moreover, when importance is attached to heat resistance, a phenolic curing agent is preferable.

  In the epoxy resin composition of this embodiment, it is preferable that content of a hardening | curing agent is 0.7-1.5 equivalent with respect to 1 equivalent of glycidyl groups of an epoxy resin. If content of a hardening | curing agent exists in this range, hardening reaction will advance efficiently and it exists in the tendency for much better hardened | cured physical property to express.

  As other components other than the curing agent, the epoxy resin composition of the present embodiment may be used in combination with other epoxy resin components other than the above-described epoxy resin. Although it does not specifically limit as another epoxy resin component, For example, although it corresponds to the structural formula of the said General formula (1), (alpha) of the said General formula (1), (beta), and (gamma) are integers of 0-3. And an epoxy resin that does not satisfy at least one of the following: satisfying the relationship of 0 <(α + β + γ) ≦ 9. Specific examples of the structure of the epoxy resin component that can be used in combination with other epoxy resin components are not particularly limited. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol M type Epoxy resin, bisphenol P type epoxy resin, tetrabromobisphenol A type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, tetrabromobiphenyl type epoxy resin, diphenyl ether type epoxy resin, benzophenone type epoxy resin, phenylbenzoate type epoxy Resin, diphenyl sulfide type epoxy resin, diphenyl sulfoxide type epoxy resin, diphenyl sulfone type epoxy resin, diphenyl disulfide type epoxy resin Naphthalene type epoxy resin, anthracene type epoxy resin, hydroquinone type epoxy resin, methyl hydroquinone type epoxy resin, dibutyl hydroquinone type epoxy resin, resorcin type epoxy resin, methyl resorcin type epoxy resin, catechol type epoxy resin, N, N-diglycidyl aniline Bifunctional epoxy resins such as epoxy resin; trifunctional epoxy such as N, N-diglycidylaminobenzene epoxy resin, o- (N, N-diglycidylamino) toluene epoxy resin, triazine epoxy resin Resins; Tetraglycidyldiaminodiphenylmethane type epoxy resin, tetrafunctional epoxy resins such as diaminobenzene type epoxy resin; phenol novolac type epoxy resin, cresol novolac type epoxy resin, triphenyl Polyfunctional epoxy resins such as tan type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene type epoxy resin, naphthol aralkyl type epoxy resin, brominated phenol novolac type epoxy resin; and alicyclic epoxy resins It is done. These may be used alone or in combination of two or more. Furthermore, epoxy resins modified with isocyanate or the like can be used in combination.

  The content of the other epoxy resin component is preferably 75% by mass or less, and more preferably 50% by mass or less, based on the total epoxy resin component in the epoxy resin composition of the present embodiment.

  Moreover, the epoxy resin composition of this embodiment may further contain a curing accelerator. Although it does not specifically limit as a specific example of a hardening accelerator, For example, imidazole type hardening accelerators, such as 2-methylimidazole, 2-ethylimidazole, and 2-ethyl-4-methylimidazole; 2- (dimethylaminomethyl) phenol Tertiary amine-based curing accelerators such as 1,5-diazabicyclo [4.3.0] non-5-ene, 1,8-diazabicyclo [5.4.0] undec-7-ene; A phosphorus curing accelerator; an organic acid metal salt; a Lewis acid; an amine complex salt, and the like. These can promote the curing reaction when used in combination with the above-described curing agent. An appropriate type of curing accelerator can be selected according to the type of curing agent described above.

  In the epoxy resin composition of the present embodiment, the content of the curing accelerator is not particularly limited as long as the effect of the present embodiment is obtained. It is preferable that content of a hardening accelerator is 0.1-5.0 mass parts normally with respect to 100 mass parts of total amounts of an epoxy resin. By setting the content of the curing accelerator in the above range, the curing reaction is sufficiently promoted and more excellent cured properties tend to be obtained.

  The epoxy resin composition of this embodiment may further contain an inorganic filler as necessary. Specific examples of the inorganic filler are not particularly limited, and examples thereof include fused silica, crystalline silica, alumina, talc, silicon nitride, and aluminum nitride.

  In the epoxy resin composition of the present embodiment, the content of the inorganic filler is not particularly limited as long as the effect of the present embodiment is obtained. In the epoxy resin composition of the present embodiment, the content of the inorganic filler is usually preferably 90% by mass or less. By making content of an inorganic filler into the said range, it exists in the tendency for the viscosity of an epoxy resin composition to be low enough, and to be excellent in handleability.

  The epoxy resin composition of this embodiment may further contain other compounding agents, such as a flame retardant, a silane coupling agent, a mold release agent, and a pigment, as needed. Any suitable one can be selected as long as the effects of the present embodiment can be obtained. Although it does not specifically limit as a flame retardant, For example, a halide, a phosphorus atom containing compound, a nitrogen atom containing compound, an inorganic type flame retardant compound, etc. are mentioned.

≪Hardened product≫
The cured product of the present embodiment is a cured product obtained by curing the above epoxy resin composition.
The cured product of this embodiment can be obtained by thermally curing the above epoxy resin composition by, for example, a conventionally known method. Specifically, for example, the cured product of the present embodiment can be obtained by the following method. First, the epoxy resin, the curing agent, and, if necessary, a curing accelerator, an inorganic filler, and / or a compounding agent, etc. are sufficiently used until they are uniform using an extruder, kneader, roll, or the like. Mix to obtain an epoxy resin composition. Thereafter, the epoxy resin composition is molded by casting or using a transfer molding machine, a compression molding machine, an injection molding machine, etc., and further heated at about 80 to 200 ° C. for about 2 to 10 hours to obtain a cured product. Can be obtained.

  Further, for example, the cured product of the present embodiment can be obtained by the following method. First, the above epoxy resin composition is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. to obtain a solution. The obtained solution is impregnated into a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc., and dried by heating to obtain a prepreg. Next, the obtained prepreg can be hot press molded to obtain a cured product.

≪Usage≫
The epoxy resin composition of the present embodiment and the cured product obtained from the epoxy resin composition can be used for various applications in which an epoxy resin is used as a material, but in particular, a sealing material, an adhesive, a printed board material, a paint, and a composite material. It is particularly useful for such applications. Among these, it is suitably used for semiconductor encapsulants such as underfill and molding, conductive adhesives such as anisotropic conductive film (ACF), printed wiring boards such as solder resist and coverlay film, and the like. The electronic member of the present embodiment includes the above cured product. Examples of the electronic member of the present embodiment include a semiconductor sealing material such as underfill and molding, a conductive adhesive such as ACF, and a printed wiring board such as a solder resist and a coverlay film. It is not limited.

  Next, although a synthesis example, an Example, and a comparative example demonstrate this invention further more concretely, this invention is not limited at all by these. In the following, “part” and “%” are based on mass unless otherwise specified.

The measuring method of each physical property was as follows.
(1) Number of (α + β + γ) The number of (α + β + γ) based on α, β and γ was confirmed using ultra high performance liquid chromatography (UPLC) and mass spectrometer (MS).
The UPLC measurement conditions were as follows.
-“ACQUITY UPLC H-Class” system manufactured by Nippon Waters Co., Ltd. Column: “Kinetex XB-C18 2.6 μm” manufactured by Phenomenex
Mobile phase: 10 mM ammonium acetate aqueous solution / acetonitrile (mixing ratio is 0 to 10 minutes in the case of polyvalent hydroxy compound, 10 mM ammonium acetate aqueous solution / acetonitrile = 75/25 to 50/50 (volume ratio), In the case of epoxy resin, 10 mM ammonium acetate aqueous solution / acetonitrile = 55/45 was changed in the range of 0 to 10 minutes. -50/50 (volume ratio), 10 mM ammonium acetate aqueous solution / acetonitrile = 55/45 was changed between 10 minutes and 20 minutes.
-Flow rate: 0.3 mL / min-Minute detector: 276 nm
-Preparation of measurement sample: 1 mg of acetonitrile was added to 2 mg of a polyvalent hydroxy compound or 5 mg of an epoxy resin to prepare a 0.2 mass% or 0.5 mass% -acetonitrile solution.
The measurement conditions for MS were as follows.
・ “Synapt G2” equipment manufactured by Nippon Waters Co., Ltd. ・ Ionization method: Electrospray ionization method (ESI)
Scan range: m / z = 50-2000
-Preparation of measurement sample: 1 mg of acetonitrile was added to 2 mg of a polyvalent hydroxy compound or 5 mg of an epoxy resin to prepare a 0.2 mass% or 0.5 mass% -acetonitrile solution.
The value of (α + β + γ) in the above formula (1) was obtained from the corresponding peak area ratio of UPLC identified by MS, as shown in FIGS.

(2) Epoxy equivalent Based on JIS K7236, the epoxy equivalent was measured.

(3) Viscosity Viscosity was measured according to JIS K7117-2 (E-type viscometer).

(4) Gel time Gel time was measured based on JACT test method RS-5 and JIS K-6910-1995. Specifically, the epoxy resin compositions obtained in Examples and Comparative Examples described later were used as measurement samples, and the gel time was measured using a gelation tester. The measurement sample was heated on a hot plate at 170 ° C. with stirring, and the time until no yarn was pulled between the sample and the stirring bar was defined as gel time.

(5) Measurement of glass transition point (Tg) A test piece of 10 mm × 30 mm × 2 mm was produced from the cured epoxy resin obtained in Examples and Comparative Examples described later using a diamond cutter. The test piece was set in a solid viscoelasticity measuring apparatus (DMA; “Leovibron DDV-25FP” manufactured by Orientec Co., Ltd.), under the measurement conditions of a temperature range of 40 to 300 ° C. (temperature increase rate: 2 ° C./min) and a frequency of 10 Hz. It was measured. The temperature when tan δ reached the maximum value was defined as the glass transition point (Tg).

(6) Tensile elongation Based on JIS K7115, the tensile elongation of the cured epoxy resin obtained in Examples and Comparative Examples described below was measured.

(7) Viscoelastic modulus (DMA elastic modulus)
Based on JIS K7115, the viscoelastic modulus (DMA elastic modulus) of the cured epoxy resin obtained in Examples and Comparative Examples described later was measured.

(8) Fracture toughness (K _Ic ) test Based on JIS K6911, the fracture toughness of the cured epoxy resin obtained in Examples and Comparative Examples described later was measured.

[Synthesis Example 1]
In a flask equipped with a thermometer, a dropping funnel, a condenser tube and a stirrer, 50 g (163 mmol) of 4,4 ′, 4 ″ -ethylidinetrisphenol (Honshu Chemical Industry Co., Ltd .: trade name TrisP-HAP) and dimethyl 150 g of formamide was added and dissolved, and then 101.5 g (734 mmol) of potassium carbonate was added to the flask, and the solution in the flask was stirred at 120 ° C. A dropping funnel provided in the flask was charged with 2- Add 20.4 g (163 mmol) of bromoethanol, 30.5 g (245 mmol) of 2- (2-chloroethoxy) ethanol and 55.0 g (326 mmol) of 2- [2- (2-chloroethoxy) ethoxy] ethanol, and add a dropping funnel. The mixed solution was dropped into the flask over 1 hour. The reaction was carried out for 3 hours, the reaction temperature was 120 ° C., and the total reaction time was 4 hours, and the resulting reaction product was washed repeatedly with water to remove inorganic salts from the reaction product. Dimethylformamide, excess 2-bromoethanol, 2- (2-chloroethoxy) ethanol and 2- [2- (2-chloroethoxy) ethoxy] ethanol are removed from the product by distillation under reduced pressure. 88.6 g of hydroxy compound (PH-1) was obtained.

[Synthesis Example 2]
Except for changing the reaction temperature to 100 ° C. and the reaction time to 6 hours, the same procedure as in Synthesis Example 1 was carried out to obtain 66.1 g of a polyhydroxy compound (PH-2).

[Synthesis Example 3]
The addition amount of 2- (2-chloroethoxy) ethanol was changed to 40.6 g (326 mmol), and the addition amount of 2- [2- (2-chloroethoxy) ethoxy] ethanol was changed to 82.5 g (489 mmol). Was performed in the same manner as in Synthesis Example 1 to obtain 63.1 g of a polyvalent hydroxy compound (PH-3).

[Synthesis Example 4]
20.4 g (163 mmol) of 2-bromoethanol, 30.5 g (245 mmol) of 2- (2-chloroethoxy) ethanol and 55.0 g (326 mmol) of 2- [2- (2-chloroethoxy) ethoxy] ethanol -[2- (2-Chloroethoxy) ethoxy] ethanol was carried out in the same manner as in Synthesis Example 1 except that ethanol was changed to 165.2 g (980 mmol), to obtain 80.0 g of a polyvalent hydroxy compound (PH-4).

[Synthesis Example 5]
4,4'-4 "-Ethyridine trisphenol (Honshu Chemical Industry Co., Ltd .: Trade name TrisP-HAP) to 4,4 '-[1- {4- [1- (4-hydroxyphenyl) -1- Methyl ethyl] phenyl} ethylidene] bisphenol (manufactured by Wako Pure Chemical Industries, Ltd.) was used in the same manner as in Synthesis Example 1 to obtain 66.5 g of a polyvalent hydroxy compound (PH-5).

[Synthesis Example 6]
4,4 ', 4 "-Ethyridine trisphenol (Honshu Chemical Industry Co., Ltd .: trade name TrisP-HAP) to 4,4', 4" -methylidyne trisphenol (Honshu Chemical Industry Co., Ltd .: trade name TrisP) -PHBA), 20.4 g (163 mmol) of 2-bromoethanol, 30.5 g (245 mmol) of 2- (2-chloroethoxy) ethanol and 2- [2- (2-chloroethoxy) ethoxy] ethanol. The same procedure as in Synthesis Example 1 was carried out except that 0 g (326 mmol) was changed to only 127.8 g (1026 mmol) of 2- (2-chloroethoxy) ethanol, to obtain 60.4 g of a polyvalent hydroxy compound (PH-6). .

[Synthesis Example 7]
To a glass autoclave, 50 g (163 mmol) of 4,4 ′, 4 ″ -ethylidinetrisphenol (manufactured by Honshu Chemical Industry Co., Ltd .: trade name TrisP-HAP) and 50 g of water were added and stirred to obtain a dispersion. Further, 4.1 g (73 mmol) of potassium hydroxide was added, and then nitrogen substitution was performed in the autoclave, and 43.1 g (978 mmol) of ethylene oxide was dropped at 90 ° C. and 0.2 MPa or less for 6 hours. After completion of the dropwise addition, the reaction was further continued for 2 hours, and the reaction time was 8 hours in total, and then the resulting reaction product was repeatedly washed with water to remove inorganic salts from the reaction product. Then, excess ethylene oxide and low-molecular side reaction products are removed from the reaction product by distillation under reduced pressure. Compound was obtained (PH-7) 94.7g.

[Synthesis Example 8]
Except having changed into ethylene oxide from propylene oxide, it carried out similarly to the synthesis example 7, and obtained 101.9g of polyhydric hydroxy compounds (PH-8).

[Synthesis Example 9]
The same procedure as in Synthesis Example 1 was conducted except that 4,4 ′, 4 ″ -ethylidinetrisphenol (Honshu Chemical Industry Co., Ltd .: trade name TrisP-HAP) was changed to bisphenol A (Wako Pure Chemical Industries, Ltd.). As a result, 68.1 g of a polyvalent hydroxy compound (PH-9) was obtained.

[Synthesis Example 10]
Synthesis Example 7 except that the addition amount of potassium hydroxide was changed to 6.2 g (110 mmol), the addition amount of ethylene oxide was changed to 53.9 g (1223 mmol), and the dropping time of ethylene oxide was changed to 8 hours. In the same manner as above, 103.2 g of a polyvalent hydroxy compound (PH-10) was obtained.

[Example 1]
In a flask (reactor) equipped with a thermometer, dropping funnel, condenser and stirrer, polyhydroxy compound (PH-1), 218.8 g of epichlorohydrin (epichloro with respect to 1 mol of hydroxyl group of PH-1) Hydrin (5 mol) and a 50 mass% tetramethylammonium chloride aqueous solution (5 g) were mixed, and the resulting mixture was heated under reduced pressure and refluxed at 60 to 65 ° C. And 200 g of 50 mass% sodium hydroxide aqueous solution was dripped at the said reactor over 2 hours. During the addition, water was continuously removed as an azeotrope with epichlorohydrin and only the condensed epichlorohydrin layer was continuously returned to the reactor. After the addition, the mixture was further reacted for 2 hours, and then the mixture (reaction product) was cooled. The resulting reaction product was repeatedly washed with water to remove by-produced sodium chloride from the reaction product. Further, excess epichlorohydrin was removed from the reaction product by distillation under reduced pressure to obtain a crude resin. The obtained crude resin was dissolved in 100 g of methyl isobutyl ketone, and 0.18 g of a 50% by mass aqueous sodium hydroxide solution was added to the resulting solution and reacted at 80 ° C. for 2 hours. After completion of the reaction, washing of the reaction product with water was repeated to remove by-produced sodium chloride from the reaction product. Further, methyl isobutyl ketone was removed from the reaction product by distillation under reduced pressure to obtain 108.8 g of epoxy resin (EP-1).

[Example 2]
Except having changed polyhydric hydroxy compound (PH-1) into (PH-2), it carried out like Example 1 and obtained epoxy resin (EP-2) 78.2g.

[Example 3]
Except having changed polyhydric hydroxy compound (PH-1) into (PH-3), it carried out like Example 1 and obtained epoxy resin (EP-3) 79.3g.

[Example 4]
Except having changed polyhydric hydroxy compound (PH-1) into (PH-4), it carried out similarly to Example 1 and obtained epoxy resin (EP-4) 98.2g.

[Example 5]
Except having changed polyhydric hydroxy compound (PH-1) into (PH-5), it carried out like Example 1 and obtained epoxy resin (EP-5) 60.1g.

[Example 6]
Except having changed polyhydric hydroxy compound (PH-1) into (PH-6), it carried out like Example 1 and obtained epoxy resin (EP-6) 74.5g.

[Example 7]
Except having changed polyhydric hydroxy compound (PH-1) into (PH-7), it carried out like Example 1 and obtained 92.9 g of epoxy resins (EP-7).

[Example 8]
Except having changed polyhydric hydroxy compound (PH-1) into (PH-8), it carried out similarly to Example 1 and obtained 110.5g of epoxy resins (EP-8).

[Comparative Example 1]
Except having changed polyhydric hydroxy compound (PH-1) into (PH-9), it carried out similarly to Example 1 and obtained 91.3 g of epoxy resins (EP-9).

[Comparative Example 2]
Except having changed polyhydric hydroxy compound (PH-1) into (PH-10), it carried out like Example 1 and obtained 116.7g of epoxy resins (EP-10).

[Comparative Example 3]
An epoxy resin was prepared in the same manner as in Example 1 except that the polyvalent hydroxy compound (PH-1) was changed to 4,4 ′, 4 ″ -ethylidinetrisphenol (Honshu Chemical Industry Co., Ltd .: trade name TrisP-HAP). 91.8 g of resin (EP-11) was obtained.

  (Α + β + γ) number of polyvalent hydroxy compounds (PH-1 to 10) obtained in Synthesis Examples 1 to 10, epoxy resins (EP-1 to 8) obtained in Examples 1 to 8 and Comparative Examples 1 to The epoxy equivalent and viscosity of the epoxy resin (EP-9-11) obtained in 3 were measured. The results are shown in Table 1.

[Examples 9 to 16]
As shown in Table 2, to the epoxy resins (EP-1 to 8) obtained in Examples 1 to 8, diaminodiphenylmethane was added at a ratio of 0.5 equivalent (1 equivalent of amino group) to 1 equivalent of epoxy group. An epoxy resin composition was obtained. The obtained epoxy resin composition was cured at 180 ° C. for 2 hours to obtain a cured epoxy resin. The epoxy resin cured product was measured for glass transition point (Tg), tensile elongation, DMA elastic modulus, and fracture toughness (K _Ic ). And the gel time was measured about the epoxy resin composition before hardening.

[Comparative Examples 4 to 7]
As the epoxy resin, the epoxy resins (EP-9 to 11) obtained in Comparative Examples 1 to 3 and the bisphenol F type epoxy resin (manufactured by Mitsubishi Chemical Corporation: trade name YL983U (epoxy equivalent 170 g / eq.)) Are used. Except for the points described above, the epoxy resin composition and the cured epoxy resin were obtained in the same manner as in Examples 9 to 16, and their physical properties were evaluated.

  Table 2 shows the evaluation results of Examples 9 to 16 and Comparative Examples 4 to 7. In Table 2, “−” in tensile elongation, DMA elastic modulus and fracture toughness of Comparative Example 4 was soft and the measurement sample was soft, and no maximum point appeared when graphed, and these could not be quantified. It shows that. In addition, “−” in Tg, tensile elongation, DMA elastic modulus, and fracture toughness of Comparative Example 6 has a high melt viscosity and high reactivity of the epoxy resin (EP-11). Indicates that it could not be produced.

[Examples 17 to 24]
Table 3 shows bisphenol F type epoxy resins (manufactured by Mitsubishi Chemical Corporation: trade name YL983U (epoxy equivalent 170 g / eq.)) In the epoxy resins (EP-1 to 8) obtained in Examples 1 to 8. A mixture of epoxy resins was prepared by mixing at a blending ratio of

As shown in Table 3, diaminodiphenylmethane was added to the obtained mixture of epoxy resins at a ratio of 0.5 equivalent (1 equivalent of amino group) to 1 equivalent of epoxy group to obtain an epoxy resin composition. The obtained epoxy resin composition was cured at 180 ° C. for 2 hours to obtain a cured epoxy resin. The epoxy resin cured product was measured for glass transition point (Tg), tensile elongation, DMA elastic modulus, and fracture toughness (K _Ic ). And the gel time was measured about the epoxy resin composition before hardening.

[Comparative Examples 8 to 10]
In the same manner as in Examples 17 to 24 except that the epoxy resins (EP-9 to 11) obtained in Comparative Examples 1 to 3 were used in place of the epoxy resins (EP-1 to 8), the epoxy resin was used. A resin composition and a cured epoxy resin were obtained, and their physical properties were evaluated.

  Table 3 shows the evaluation results of Examples 17 to 24 and Comparative Examples 7 to 10.

  From the results of Tables 2 and 3, the epoxy resins (EP-1 to 8) obtained in Examples 1 to 8 have excellent reactivity while being liquid, and the epoxy resins obtained in Examples 9 to 24 It was confirmed that the cured resin product is at least excellent in flexibility and further has high heat resistance.

  The epoxy resin of the present invention can be used for sealing materials, adhesives, printed circuit board materials, paints, composite materials, semiconductor sealing materials such as underfill and molding, conductive adhesives such as ACF, solder resists, coverlay films, etc. It can utilize suitably for a printed wiring board etc.

Claims (9)

The following general formula (1)
(In the formula, α, β and γ are each independently an integer of 0 to 3 and satisfy the relationship of 0 <(α + β + γ) ≦ 9. (Α + β + γ) R _{1 s} are each independently represents an alkylene group having 1 to carbon atoms 3, X represents a trivalent aromatic group from 6 to 33 carbon atoms.)
Epoxy resin represented by The epoxy resin according to claim 1, wherein R ₁ in the general formula (1) is an ethylene group, a trimethylene group, or a propylene group. X in the general formula (1) is
(In the formula, R ₂ represents a hydrogen atom, a halogen atom, a methoxy group, a cyclohexyl group, or an alkyl group having 1 to 12 carbon atoms.)
The epoxy resin according to claim 1 or 2, which is one selected from the group consisting of: The epoxy resin composition containing the epoxy resin of any one of Claims 1-3, and a hardening | curing agent. Furthermore, the epoxy resin composition of Claim 4 containing another epoxy resin component. Furthermore, the epoxy resin composition of Claim 4 or 5 containing a hardening accelerator. Furthermore, the epoxy resin composition of any one of Claims 4-6 containing an inorganic filler. Hardened | cured material formed by hardening | curing the epoxy resin composition of any one of Claims 4-7. An electronic member comprising the cured product according to claim 8.