JP6688805B2 - Substituted allyl ether resin, methallyl ether resin, epoxy resin, epoxy resin composition and cured product thereof - Google Patents

Description

  The present invention relates to a substituted allyl ether resin, a methallyl ether resin, an epoxy resin, an epoxy resin composition, and a cured product thereof which are suitable for use in electric and electronic materials requiring heat resistance.

  Epoxy resin compositions are widely used in the fields of electric / electronic parts, structural materials, adhesives, paints, etc. due to their workability and cured products' excellent electrical properties, heat resistance, adhesiveness, moisture resistance (water resistance), etc. Has been.

Conventionally, allyl ether compounds have been used as reactive diluents, crosslinking agents, additives such as flame retardants, raw materials for photocurable monomers, and the like (Patent Document 1). Further, the allyl ether compound can be used as a raw material for an epoxy resin obtained by an oxidation reaction. Since the obtained epoxy resin can be used for various applications such as paints, structural materials, electric and electronic materials, development is underway (Patent Document 2).
On the other hand, in recent years, in the field of electric / electronic parts, the movement of converting a gold wire used for wire bonding connecting an IC chip to a lead frame or a printed circuit board into a copper wire at a rapid pace from the viewpoint of cost reduction. I'm out. Here, when an epoxy resin produced by a method using a chlorine-containing compound (epichlorohydrin) is used as a semiconductor sealing material using a copper wire, the total amount of chlorine remaining in the epoxy resin becomes high, There is a problem that the copper wire is corroded. Therefore, application of the epoxy resin to applications such as semiconductors is limited, and complicated purification must be repeated for use in the applications. In order to prevent such corrosion due to chlorine, it is effective to use an epoxy resin obtained by a method that does not use a chlorine-containing compound. As a technique for producing an epoxy resin without using a chlorine-containing compound, for example, Patent Document 3 reports a method of producing a bifunctional epoxy resin by reacting a compound having a carbon-carbon double bond with hydrogen peroxide. Has been done. Further, in recent years, a method for producing an epoxy resin using an organic percarboxylic acid has been reported (Patent Documents 4 and 5).

Japanese Patent Laid-Open No. 2005-170890 Japanese Patent Laid-Open No. 2012-067253 Japanese Patent Laid-Open No. 2011-225711 JP 2012-52062 A Japanese Patent Laid-Open No. 2006-151900 International Publication No. 2014/123051

  The present inventors have developed an allyl ether resin which is low in halogen and can be obtained at low cost (Patent Document 6), but further improvement is required. Therefore, an object of the present invention is to provide a substituted allyl ether resin and a methallyl ether resin which are suitable for an electric / electronic material and a raw material thereof and which are low in halogen and can be obtained at low cost, and an epoxy resin using them.

  The gist of the present invention for achieving the above object is as follows.

[1] A substituted allyl ether resin represented by the following formula (1).

(In the formula, R _1's each independently represent an alkyl group, R _2's each independently represent a hydrogen atom or an alkyl group, a represents 1 to 3, respectively, and n is the average of the number of repetitions of 1 to 10. It represents a value.)
[2] A methallyl ether resin represented by the following formula (2).

(In formula, R < ₂ > represents a hydrogen atom or an alkyl group each independently, a represents each 1-3, n represents the average value of the repeating number of 1-10.)
[3] An epoxy resin using the substituted allyl ether resin described in [1] above or the methallyl ether resin described in [2] above.
[4] An epoxy resin composition containing the epoxy resin according to the above [3] and a curing agent and / or a curing catalyst.
[5] A cured product obtained by curing the epoxy resin composition according to the above [4].

In the present invention, a low halogen substituted allyl ether resin or methallyl ether resin suitable for electric and electronic materials and raw materials thereof can be obtained. Further, the substituted allyl ether resin or methallyl ether resin of the present invention can provide a precursor of a cured product excellent in low dielectric properties, flame retardancy, and toughness by polymerization, epoxidation, or Claisen rearrangement of the resin.

First, a substituted allyl ether resin, which is one of the embodiments of the present invention, will be described.
The substituted allyl ether resin of the present invention is represented by the following formula (1).

(In the formula, R _1's each independently represent an alkyl group, R _2's each independently represent a hydrogen atom or an alkyl group, a represents 1 to 3, respectively, and n is the average of the number of repetitions of 1 to 10. It represents a value.)

Here, n is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 2 to 4.
Examples of the alkyl group in the formula include a methyl group, an ethyl group, a propyl group and an isopropyl group. From the viewpoint of high electron density and reactivity of oxidative epoxidation, a methyl group or an ethyl group is preferable, and a methyl group is particularly preferable.

Next, a methallyl ether resin (hereinafter referred to as “MEP”) which is another embodiment of the present invention will be described.
The MEP of the present invention is represented by the following formula (2).

(In formula, R < ₂ > represents a hydrogen atom or an alkyl group each independently, a represents each 1-3, n represents the average value of the repeating number of 1-10.)

Here, n is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 2 to 4.
Examples of the alkyl group in the formula include a methyl group, an ethyl group, a propyl group and an isopropyl group, and among them, a methyl group is preferable.

  These materials are excellent in flame retardancy as compared with general resins such as cresol novolac, and a composition capable of exhibiting flame retardancy can be produced without adding halogen as a flame retardant. In addition, it is useful for environmental load, and due to its high hydrophobicity, it is possible to stop the migration of a small amount of ions such as chlorine contained therein. In addition to having high electrical reliability, the combination of low halogen and these structures is useful as an electric / electronic material.

  The total chlorine remaining in the MEP is preferably 500 ppm or less, more preferably 300 ppm or less, and particularly preferably 100 ppm or less.

The MEP-containing product obtained by the production method described below is measured by high performance liquid chromatography (hereinafter also referred to as “HPLC”), and its chromatogram shows that MEP in which n = 1 in the above formula (2). There is a case where an impurity peak is confirmed between the peak of 1 and the peak of MEP where n = 2.
From the viewpoint of reactivity at the time of epoxidizing MEP, it is more preferable that the peak of this impurity is less than 1.5 area% with respect to the entire product containing MEP in terms of area ratio. It is preferably less than 0 area%. When this area ratio exceeds 2.0 area%, there is a possibility that the progress of the epoxidation reaction is greatly affected.

  The methallyl ether resin of the present invention preferably has a softening point of 120 ° C or lower. If the softening point of MEP exceeds 120 ° C., it will be very difficult to dissolve it in a solvent, and it will be difficult to remove the salt contained in MEP by washing or the like. Not preferable due to concern.

(Method for producing methallyl ether resin)
The methallyl ether resin of the present invention is obtained by reacting a corresponding phenol resin and a methallyl halide in a solvent in the presence of a base.

(Phenolic resin)
Examples of the phenol resin used in the production of MEP include a reaction product of phenol and 4,4′-bis (chloromethyl) -1,1′-biphenyl, phenol and 4,4′-bis (methoxymethyl) -1,1. A reaction product with'-biphenyl is preferable.

(Metalyl halide)
As the methallyl halide used for the production of MEP, β-methallyl chloride is preferable from the viewpoint of reactivity with the phenol resin.
Here, β-methallyl chloride tends to be a polymer (polymethallyl chloride) in which methallyl chlorides are polymerized with each other, but methallyl chloride used for producing a compound having a methallyl ether moiety is polymethallyl chloride. It is preferable to use one having a low chloride content.
When the content ratio of polymethallyl chloride in the methallyl chloride used is high, it not only becomes a factor for increasing the total chlorine content of the obtained MEP, and further the epoxy resin of the present invention obtained by using the MEP, MEP, and This contributes to an increase in the molecular weight of the obtained epoxy resin, and there is a possibility that a slight amount of gel will remain when the product is commercialized. Further, in order to reduce the chlorine content, it is necessary to add a considerable amount of a basic substance, which is not industrially preferable, and there is a possibility that highly toxic methallyl alcohol is produced in the system.

  The content ratio of these polymethallyl chlorides can be easily confirmed by gas chromatography or the like, and the specific content ratio of polymethallyl chloride is, when measured by gas chromatography, the area ratio thereof, methallyl chloride. It is preferably 1 area% or less, more preferably 0.5 area% or less, and particularly preferably 0.2 area% or less with respect to the chloride monomer.

  In the production of MEP, the amount of methallyl halide such as methallyl chloride used is usually 1.0 to 2.0 mol, preferably 1.0 to 1.60 mol, per 1 mol of the hydroxyl group of the phenol resin. It is more preferably 1.0 to 1.50 mol.

  In the case of producing the substituted allyl ether resin of the present invention, the substituted allyl ether resin of the present invention is obtained by using the substituted allyl halide instead of the above methallyl halide and employing the production method described below. You can

[base]
As a base used for the production of MEP, alkali metal hydroxide is preferable, and specific examples thereof include sodium hydroxide, potassium hydroxide and the like. Such an alkali metal hydroxide may be used in a solid state or may be used in an aqueous solution state thereof, but in particular, it is formed into a flake shape from the viewpoint of solubility in a solvent and handling. It is preferably used in the solid state.

  In the production of MEP, the amount of the base such as alkali metal hydroxide used is usually 1.0 to 2.0 mol, preferably 1.0 to 1.60 mol, per 1 mol of the hydroxyl group of the phenol resin. It is more preferably 1.0 to 1.50 mol.

[solvent]
The solvent used for the production of MEP preferably contains an aprotic polar solvent, and more preferably contains water and an aprotic polar solvent. When the solvent used for the production of MEP contains the aprotic polar solvent, the solubility of the phenol resin in the solvent can be improved. Examples of such aprotic polar solvent include dimethylsulfoxide, N-methylpyrrolidone, dimethylacetamide, dioxane, dimethoxyethane, diglyme, dimethylformamide, and the like, and dimethylsulfoxide is particularly preferable.
In the production of MEP, the amount of the aprotic polar solvent such as dimethyl sulfoxide used is preferably 20 to 300% by mass, more preferably 25 to 250% by mass, and particularly preferably, the total amount of the phenol resin. Is 25 to 200 mass%. An aprotic polar solvent such as dimethylsulfoxide is not useful for purification such as washing with water, and has a high boiling point and is difficult to remove. Therefore, it is preferable when the amount used exceeds 300% by mass relative to the total mass of the phenol resin. Absent.

The solvent used for the production of MEP may contain an alcohol having 1 to 5 carbon atoms in addition to the above water and the aprotic polar solvent.
Further, the solvent used for the production of MEP may include an organic solvent (other organic solvent) other than the aprotic polar solvent and the alcohol having 1 to 5 carbon atoms such as methyl ethyl ketone, methyl isobutyl ketone, and toluene. The amount of the other organic solvent used is preferably 100% by mass or less, and more preferably 0.5 to 50% by mass, based on the amount of the aprotic polar solvent used. If methyl ethyl ketone, methyl isobutyl ketone, toluene, etc. are used in excess, Claisen rearrangement occurs during the reaction, and the residual phenolic hydroxyl group increases, and the amount of methallyl chloride in the system becomes insufficient. This is not preferable because there is a risk of problems such as the generation of substances and that all of the phenolic hydroxyl groups are not methallyl etherified.

[Reaction conditions, etc.]
In the production of MEP, the reaction temperature of the methallyl etherification reaction of the phenol resin is usually 30 to 90 ° C, preferably 35 to 80 ° C. Further, in order to obtain MEP with higher purity, it is preferable to raise the reaction temperature in two or more steps, for example, the first step is 35 to 50 ° C and the second step is 45 to 70 ° C. Is particularly preferred.
The reaction time of the methallyl etherification reaction of the phenol resin is usually 0.5 to 10 hours, preferably 1 to 8 hours, particularly preferably 1 to 5 hours. When the reaction time is 0.5 hours or more, the reaction proceeds sufficiently, and when the reaction time is 10 hours or less, the amount of by-products can be suppressed low.

  After completion of the reaction, the solvent is distilled off under reduced pressure with heating to obtain a product. The recovered product is dissolved in a ketone compound having 4 to 7 carbon atoms (for example, methyl isobutyl ketone, methyl ethyl ketone, cyclopentanone, cyclohexanone, etc.), and 40 ° C to 90 ° C, more preferably 50 to 80 ° C. In the state of being heated to 1, the water layer is washed with water until the pH becomes 5 to 8. By washing with water until the pH of the aqueous layer becomes 8 or less, it is possible to prevent the balance of the catalyst system from being disturbed and the progress of the reaction from being suppressed in the subsequent epoxidation reaction.

The methallyl etherification reaction of the phenol resin is usually carried out while blowing an inert gas such as nitrogen into the system (in air or in liquid). By carrying out the reaction while blowing an inert gas into the system, it is possible to prevent the obtained product from being colored.
The amount of the inert gas blown in per unit time also depends on the volume of the kettle used for the reaction. For example, the amount of the inert gas blown in per unit time can be replaced in 0.5 to 20 hours. Is preferably adjusted.

Next, the epoxy resin of the present invention will be described.
The epoxy resin, which is one of the embodiments of the present invention, is represented by the following formula (3).

(In the formula, R _1's each independently represent an alkyl group, R _2's each independently represent a hydrogen atom or an alkyl group, a represents 1 to 3, respectively, and n is the average of the number of repetitions of 1 to 10. It represents a value.)

  An epoxy resin which is another embodiment of the present invention is represented by the following formula (4).

(In formula, R < ₂ > represents a hydrogen atom or an alkyl group each independently, a represents each 1-3, n represents the average value of the repeating number of 1-10.)

  The epoxy resin of the present invention preferably has an epoxy equivalent of 260 to 285 g / eq. And more preferably 260 to 280 g / eq. Is. Epoxy equivalent is 285 g / eq. When it exceeds, it means that the amount of epoxy groups per unit structure decreases, which means that the number of epoxy groups decreases. Therefore, it is not preferable in terms of heat resistance.

Examples of the alkyl group in the formula include a methyl group, an ethyl group, a propyl group and an isopropyl group. A methyl group or an ethyl group is preferable, and a methyl group is particularly preferable.
The methyl group-containing epoxy resin tends to have a higher elastic modulus than ordinary epoxy resins, and tends to exhibit suitable properties for fiber reinforced plastics (FRP) and carbon fiber reinforced plastics (CFRP).

  The softening point of the epoxy resin of the present invention is preferably 30 to 130 ° C, more preferably 40 to 120 ° C. If the softening point is too low, blocking during storage becomes a problem, and there are many problems such as handling at low temperature. On the other hand, if the softening point is too high, problems such as poor handling may occur during kneading with other resins.

The total chlorine remaining in the epoxy resin obtained by the reaction is preferably 1000 ppm or less, more preferably 600 ppm or less, and particularly preferably 300 ppm or less. Also, the sulfate ion extracted by hot water extraction is preferably 1000 ppm or less, and particularly preferably 600 ppm or less.
The pressure cooker test (PCT) extracted chlorine extracted from the cured product of the present invention is preferably 5 ppm or less, more preferably 2.5 ppm or less, and particularly preferably 1.5 ppm or less.

  The melt viscosity range of the epoxy resin of the present invention is preferably 0.01 Pa · s to 0.10 Pa · s. When the melt viscosity is low, the molecular weight tends to be small, and the content of the skeleton such as the formula (3) or (4) tends to be small. Particularly preferably, it is 0.02 Pa · s to 0.09 Pa · s.

The epoxy resin of the present invention can be obtained by oxidizing the methallyl ether resin of the present invention. Examples of the oxidation method include, but are not limited to, a method of oxidizing with a peracid such as peracetic acid, a method of oxidizing with a hydrogen peroxide solution, a method of oxidizing with air (oxygen), and a method of oxidizing with a carboxylic acid peroxide. Absent.
Specific examples of the method of epoxidation with peracid include the method described in Japanese Patent Laid-Open No. 2006-52187.
Various methods can be applied to the method of epoxidation with hydrogen peroxide solution, and specifically, specifically, JP-A-59-108793, JP-A-62-234550, and JP-A-Hei. JP-A-5-213919, JP-A-11-349579, JP-B1-33471, JP-A-2001-17864, JP-B-3-57102, and JP-A-57102. 2011-225654, Japanese Unexamined Patent Publication No. 2011-079794, Japanese Unexamined Patent Publication No. 2011-084558, Japanese Unexamined Patent Publication No. 2010-083836, Japanese Unexamined Patent Publication No. 2010-095521, and the like. Various techniques can be applied.

  Hereinafter, a particularly preferable method for obtaining the epoxy resin represented by the formula (4), which is one of the embodiments of the present invention (hereinafter, simply referred to as “epoxy resin of the present invention”), will be illustrated. The epoxy resin of the present invention is obtained by reacting a methallyl ether resin represented by the above formula (2) with hydrogen peroxide in the presence of a tungstic acid compound, an organic carboxylic acid, and a phosphoric acid compound. .

(Tungstic acid compound)
The method for producing an epoxy resin of the present invention is performed in the presence of a tungstic acid compound. In the present invention, the tungstic acid compound is not particularly limited as long as it is a compound that generates tungstate ion (WO ₄ ²⁻ ) in water, and examples thereof include tungstic acid, tungsten trioxide, phosphotungstic acid, ammonium tungstate, tungstic acid. Examples thereof include potassium dihydrate, sodium tungstate dihydrate, calcium tungstate, barium tungstate, and the like. Among these, tungstic acid, tungsten trioxide, phosphotungstic acid, sodium tungstate dihydrate, and potassium tungstate dihydrate are preferable from the viewpoint of improving the production rate of epoxy groups. These tungstic acid compounds may be used alone or in combination of two or more kinds. The amount of the tungstic acid compound used is preferably 1 × 10 ^{−6 to} 0.2 mol, and 0.0001 to 0 mol per mol of the compound represented by the formula (2) from the viewpoint of improving the production rate of the epoxy group. 0.2 mol is more preferable.

(Organic carboxylic acid)
The method for producing an epoxy resin of the present invention is performed in the presence of an organic carboxylic acid. In the present invention, the organic carboxylic acid is not particularly limited as long as it functions as a peroxide.

  The carboxylic acid constituting the organic carboxylic acid is not particularly limited, formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, hydroangelic acid, pivalic acid, caproic acid, oxalic acid, malonic acid , Succinic acid, tartaric acid, citric acid, maleic acid, malic acid, benzoic acid, salicylic acid, toluic acid, chlorobenzoic acid, nitrobenzoic acid, phthalic acid and anisic acid.

  Among these, those having a molecular weight of 46 to 150 are preferable, and those having a molecular weight of 46 to 120 are more preferable in order to achieve a good balance between hydrophobicity and hydrophilicity. The carbon chain bonded to the carbon atom of the carboxylic acid is preferably linear. Examples of the organic carboxylic acid having a straight carbon chain bonded to a carbon atom include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, malonic acid and succinic acid.

  The organic percarboxylic acid can be easily generated by reacting an organic carboxylic acid or an organic carboxylic acid anhydride with hydrogen peroxide. Formic acid, acetic acid, acetic anhydride, propionic acid, propionic acid anhydride, butyric acid, isobutyric acid, valeric acid, isovaleric acid, hydroangelic acid, pivalic acid, benzoic acid, salicylic acid and the like as organic carboxylic acids and their anhydrides, Among these, formic acid, acetic acid, acetic anhydride, and propionic acid are particularly preferable from the viewpoint of improving the production rate of epoxy groups and easiness of removal after the reaction. The method of generating organic percarboxylic acid in the reaction system can be easily adjusted simply by mixing commonly used reagents.Since the reaction proceeds while sequentially consuming the generated percarboxylic acid, the specified concentration It is also excellent in that it is not necessary to store the percarboxylic acid.

  The amount of the organic carboxylic acid used is preferably 0.01 to 5.0 mol, and more preferably 0.05 to 4 mol, per mol of the methallyl ether resin represented by the formula (2), from the viewpoint of improving the production rate of the epoxy group. 0.0 mol is more preferred.

(Organic solvent)
The method for producing an epoxy resin of the present invention is performed in the presence of a specific organic solvent. By carrying out in the presence of a specific organic solvent, the production rate of epoxy groups can be significantly improved. This is related to the compatibility with tungstic acid compounds, phosphoric acid compounds, organic carboxylic acids, etc., and when MEP is dissolved, by preventing the precipitation of hardly soluble components, the reaction proceeds smoothly. It is presumed that it can be advanced.

In the present invention, alcohols or nitriles cannot be used as the specific organic solvent from the viewpoint of solubility of the raw materials. In addition, acetone and dimethyl sulfoxide cannot be used because side reactions proceed when ketones or sulfoxides are used. Accordingly, suitable organic solvents include diethyl ether, tetrahydrofuran, dioxane, dimethoxyethane, diglyme, triglyme, ethylene glycol diacetate, methyl acetate, ethyl acetate, N, N- dimethyl formaldehyde (hereinafter, "DMF"), Examples include N, N-dimethylacetamide (hereinafter, “DMA”), N-methylmorpholine, N-methylpyrrolidone, ε-caprolactam, toluene, xylene, mesitylene and the like.
The step of reacting a compound having a bifunctional or higher functional methallyl ether moiety with hydrogen peroxide is performed in a two-phase system of an organic phase and an aqueous phase.

  The amount of the specific organic solvent used is preferably 10 to 1000 parts by mass, and 10 to 500 parts by mass, per 100 parts by mass of the methallyl ether resin represented by the formula (2), from the viewpoint of improving the production rate of the epoxy group. More preferable.

(Phosphate compound)
The method for producing an epoxy resin of the present invention is performed in the presence of a phosphoric acid compound. The phosphoric acid compound is not particularly limited as long as it is a compound that generates a phosphate ion (PO ₄ ³⁻ ) in water, and examples thereof include phosphoric acid, alkali metal dihydrogen phosphate, and alkaline earth metal dihydrogen phosphate. Salt, di-alkali metal hydrogen phosphate, di-alkaline earth metal hydrogen phosphate, alkali metal phosphate, alkaline earth metal phosphate, polyphosphoric acid, alkali metal polyphosphate, alkaline earth metal polyphosphate , Tripolyphosphate, alkali metal tripolyphosphate, alkaline earth metal tripolyphosphate, and the like. Among these, salts containing salts of phosphoric acid, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, potassium phosphate, etc. are preferable because they are easily available.

  The amount of the phosphoric acid compound used is preferably 0.01 to 1.0 mol, and more preferably 0.05 to 0.5 mol, per mol of the compound represented by the formula (2) from the viewpoint of improving the production rate of the epoxy group. Is more preferable.

(hydrogen peroxide)
The hydrogen peroxide reacted with the methallyl ether resin represented by the above formula (2) in the method for producing an epoxy resin of the present invention is not particularly limited, but it is usually dissolved in water and added as hydrogen peroxide solution. The concentration of hydrogen peroxide in the hydrogen peroxide water is not particularly limited, but the hydrogen peroxide concentration is preferably 10 to 90 mass% from the viewpoint of generation of epoxy groups. The amount of hydrogen peroxide used is not particularly limited, but the amount of hydrogen peroxide is preferably 0.3 to 10 mol, and more preferably 1 to 6 mol, based on 1 mol of the methallyl group of the methallyl ether resin. . When the amount of hydrogen peroxide water is 0.3 mol or more per 1 mol of the methallyl group of the methallyl ether resin, epoxidation can be efficiently progressed, and when the amount is 10 mol or less, the epoxy produced Hydrolysis of the group can be suppressed.

  The method for producing the epoxy resin of the present invention is not particularly limited, but the methallyl ether resin is soluble in toluene, xylene, mesitylene, dimethoxyethane, ethyl acetate, an organic solvent such as tetrahydrofuran, the methallyl ether resin, a tungstic acid compound, It is preferable to add the phosphoric acid compound and then add aqueous hydrogen peroxide to start the epoxidation reaction. However, the production method of the epoxy resin of the present invention is not limited to this addition order, and in the presence of the tungstic acid compound and the phosphoric acid compound, carbon-carbon in the methallyl group of the methallyl ether resin. The double bond can be efficiently converted into an epoxy group.

  In the method for producing an epoxy resin of the present invention, the reaction temperature during epoxidation is not particularly limited, but is preferably 10 to 120 ° C, more preferably 25 to 100 ° C. When the temperature is 10 ° C or higher, the reaction rate can be optimized, and when the temperature is 120 ° C or lower, the hydrolysis reaction of the generated epoxy group can be suppressed.

  In the method for producing an epoxy resin of the present invention, the reaction time depends on the reaction temperature, the amount of the catalyst, etc., to secure a time for the epoxidation to proceed sufficiently, and for industrially efficient production, After adding a predetermined amount of hydrogen peroxide water, 1 to 48 hours are preferable, 3 to 36 hours are more preferable, and 4 to 24 hours are particularly preferable.

  After completion of the reaction, excess hydrogen peroxide is removed. Examples of the method for removing hydrogen peroxide include a method of performing a liquid separation operation and washing with water. Methyl isobutyl ketone in an amount of 2 times the weight of the resin is added, and liquid separation operation is performed with 1 times the weight of ion-exchanged water to discard the aqueous layer. This procedure is repeated until the hydrogen peroxide is completely removed. Whether or not hydrogen peroxide has been removed is confirmed by confirming that the potassium iodide starch paper test is negative.

  Next, after removing the hydrogen peroxide, the organic phase is concentrated under reduced pressure. At this time, if the resin is heated excessively, the resin may be polymerized. Therefore, the concentration operation is preferably performed at 90 to 180 ° C, more preferably 110 to 150 ° C.

<Epoxy resin composition>
The epoxy resin composition of the present invention contains a curing catalyst (curing accelerator) and / or a curing agent in addition to the epoxy resin of the present invention. Further, other epoxy resin can be contained as an optional component.

  The epoxy resin composition of the present invention can use the epoxy resin of the present invention in combination with other epoxy resins. Other epoxy resins that can be used in combination with the epoxy resin of the present invention include novolac type epoxy resins, bisphenol type epoxy resins, biphenyl type epoxy resins, triphenylmethane type epoxy resins, and phenol aralkyl type epoxy resins. Specifically, bisphenol A, bisphenol S, thiodiphenol, fluorene bisphenol, terpene diphenol, 4,4'-biphenol, 2,2'-biphenol, 3,3 ', 5,5'-tetramethyl- [ 1,1'-biphenyl] -4,4'-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol (Phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol or dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetate Phenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4'-bis (chloromethyl) -1,1'-biphenyl, 4,4'-bis (methoxymethyl) -1,1'-biphenyl, 1, Polycondensates with 4-bis (chloromethyl) benzene, 1,4-bis (methoxymethyl) benzene and the like and modified products thereof, glycidyl ethers derived from halogenated bisphenols such as tetrabromobisphenol A or alcohols Compound, alicyclic epoxy resin, glycidyl amine epoxy resin, glycidyl ester epoxy resin, silsesquioxane epoxy resin (chain, cyclic, ladder, or mixed siloxane structure of at least two of them) Glycidyl group and / or epoxy cyclohexane structure However, the present invention is not limited to these.

Specific examples of the curing catalyst that can be used in the present invention include amine compounds such as triethylamine, tripropylamine and tributylamine, pyridine, dimethylaminopyridine, 1,8-diazabicyclo [5.4.0] undec-7-ene, imidazole. , Triazole, tetrazole, 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2 -Methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2,4-diamino-6 (2'-methylimidazole (1 ')) Ethyl-s Triazine, 2,4-diamino-6 (2′-undecylimidazole (1 ′)) ethyl-s-triazine, 2,4-diamino-6 (2′-ethyl, 4-methylimidazole (1 ′)) ethyl -S-triazine, 2,4-diamino-6 (2'-methylimidazole (1 ')) ethyl-s-triazine isocyanuric acid adduct, 2-methylimidazole isocyanuric acid 2: 3 adduct, 2-phenyl Imidazole isocyanuric acid adduct, 2-phenyl-3,5-dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole, etc. Various heterocyclic compounds, and those heterocyclic compounds and phthalic acid, isophthalic acid, terephthalic acid, Salts with polyvalent carboxylic acids such as trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, maleic acid, oxalic acid, amides such as dicyandiamide, 1,8-diaza-bicyclo (5.4.0) -7-undecene Diaza compounds such as tetraphenylborate of those diaza compounds, phenol divolaks with these diaza compounds, salts of the above polycarboxylic acids or phosphinic acids, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, Tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylpropylammonium hydroxide, trimethylbutylammonium hydroxide, trimethylcetylammonium hydroxide, tri Ammonium salts such as octylmethylammonium hydroxide, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium acetate, trioctylmethylammonium acetate, triphenylphosphine, tri (toluyl) phosphine, tetraphenylphosphonium Phosphines such as bromide and tetraphenylphosphonium tetraphenylborate, phosphonium compounds, phenols such as 2,4,6-trisaminomethylphenol, amine adducts, carboxylic acid metal salts (2-ethylhexanoic acid, stearic acid, behenic acid) , Zinc salt of mistyric acid, tin salt, zirconium salt) and zinc salt of phosphoric acid ester metal (octyl phosphate, stearyl phosphate) , Alkoxy metal salt (tributyl aluminum, tetrapropyl zirconium, etc.), acetylacetonates (acetylacetone zirconium chelate, acetylacetone titanium chelate) metal compounds such as, and the like. In the present invention, phosphonium salts, ammonium salts, and metal compounds are particularly preferable in terms of coloring during curing and changes thereof. When a quaternary salt is used, the salt with halogen may leave halogen in the cured product.
The curing catalyst may be used in an amount of 0.01 to 5.0 parts by weight based on 100 parts by weight of the epoxy resin.

As the curing agent used in the epoxy resin composition of the present invention, for example, known curing agents such as amine compounds, acid anhydride compounds, amide compounds, phenol compounds and carboxylic acid compounds can be used. Specific examples thereof include those described in WO 2006/090662.
Specific examples of the curing agent that can be used include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, nitrogen-containing compounds such as polyamide resins synthesized from a dimer of linolenic acid and ethylenediamine (amine, Amide compound); phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic acid anhydride, nadic acid anhydride, hexahydrophthalic anhydride, methylhexahydro Phthalic anhydride, butanetetracarboxylic acid anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, Cyclo Acid anhydrides such as sun-1,3,4-tricarboxylic acid-3,4-anhydride; carboxylic acid resins obtained by addition reaction of various alcohols, carbinol-modified silicones and the above-mentioned acid anhydrides; bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpene diphenol, 4,4'-biphenol, 2,2'-biphenol, 3,3 ', 5,5'-tetramethyl- [1,1'-biphenyl] -4,4'-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane or phenols (phenol, alkyl-substituted phenol) , Naphthol, alkyl substituted naphthol, dihydroxybenzene, dihydroxyna Talene) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4′-bis (chloromethyl) -1,1. Polycondensation with'-biphenyl, 4,4'-bis (methoxymethyl) -1,1'-biphenyl, 1,4'-bis (chloromethyl) benzene or 1,4'-bis (methoxymethyl) benzene Compounds and their modified products, halogenated bisphenols such as tetrabromobisphenol A, phenol resins such as condensation products of terpenes and phenols; imidazole, trifluoroborane-amine complex, compounds of guanidine derivatives, and the like. Limited to Not of. These may be used alone or in combination of two or more.

  In the epoxy resin composition of the present invention, the amount of the curing agent used is preferably 0.5 to 1.5 equivalents, and particularly preferably 0.6 to 1.2 equivalents, relative to 1 equivalent of the epoxy groups of the epoxy resin. When the amount of the curing agent used is in the above range, good cured physical properties can be obtained.

  In addition, it is preferable to use a cyanate ester compound as another component. The cyanate ester compound can be made into a heat-resistant cured product having a higher crosslinking density by a reaction with an epoxy resin in addition to a curing reaction by itself. Examples of the cyanate ester compound include 2,2-bis (4-cyanatephenyl) propane, bis (3,5-dimethyl-4-cyanatephenyl) methane, 2,2-bis (4-cyanatephenyl) ethane and These derivatives, an aromatic cyanate ester compound, etc. are mentioned. In addition, for example, it can be synthesized by reacting various phenolic resins with hydrocyanic acid or salts thereof as described in the above-mentioned curing agent. In the present invention, those having a structure having no benzylic methylene structure in the molecule such as 2,2-bis (4-cyanatephenyl) propane and its derivatives (partially polymerized products) are particularly preferable. They may be used alone or in combination of two or more.

The epoxy resin composition of the present invention may contain a phosphorus-containing compound as a flame retardancy-imparting component. The phosphorus-containing compound may be a reaction type or an addition type. Specific examples of the phosphorus-containing compound include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6- dixylenyl phosphate, 1,3-phenylene bis ( dixylenyl phosphate), 1, Phosphoric acid esters such as 4-phenylene bis ( dixylenyl phosphate) and 4,4'-biphenyl ( dixylenyl phosphate); 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10 (2, 5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide and other phosphanes; phosphorus-containing epoxide compounds obtained by reacting an epoxy resin with active hydrogen of the phosphanes , Phosphoric acid esters, phosphanes or phosphorus-containing epoxy compounds are preferred, and 1,3-phenylene bis ( dixylenyl phosphate), 1,4-phenylene bis ( dixylenyl phosphate), 4,4 Particularly preferred are'- biphenyl ( dixylenyl phosphate) or phosphorus-containing epoxy compounds. The content of the phosphorus-containing compound is preferably phosphorus-containing compound / total epoxy resin = 0.1 to 0.6 (weight ratio). If it is less than 0.1, the flame retardancy is insufficient, and if it exceeds 0.6, the hygroscopicity and dielectric properties of the cured product may be adversely affected.

  Further, the epoxy resin composition of the present invention may contain a binder resin if necessary. Examples of the binder resin include butyral resin, acetal resin, acrylic resin, epoxy-nylon resin, NBR-phenol resin, epoxy-NBR resin, polyamide resin, polyimide resin, and silicone resin. However, the present invention is not limited to these. The content of the binder resin is preferably in a range that does not impair the flame retardancy and heat resistance of the cured product, and is usually 0.05 to 50 parts by weight, preferably 100 parts by weight of the total of the epoxy resin and the curing agent. 0.05 to 20 parts by weight is used if necessary.

An inorganic filler can be added to the epoxy resin composition of the present invention, if necessary. As the inorganic filler, crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, forsterite , steatite, spinel, titania, talc and the like powders or these However, the present invention is not limited to these. These fillers may be used alone or in combination of two or more. The content of these inorganic fillers in the epoxy resin composition of the present invention is generally 0 to 95% by weight, although it depends on the application, and is preferably an amount of 0 to 95% by weight. It is preferable to use properly in the range of 50 to 95% by weight, particularly preferably 65 to 95% by weight, depending on the shape of the package. Further, in the epoxy resin composition of the present invention, antioxidants, light stabilizers, silane coupling agents, stearic acid, palmitic acid, zinc stearate, release agents such as calcium stearate, various compounding agents such as pigments, Various thermosetting resins can be added. Particularly for the coupling agent, it is preferable to add a coupling agent having an epoxy group or a coupling agent having a thiol.

  The epoxy resin composition of the present invention is obtained by uniformly mixing the components. The epoxy resin composition of the present invention can be easily made into a cured product by a method similar to a conventionally known method. For example, an epoxy resin component, a curing agent component, and if necessary, a curing accelerator, a phosphorus-containing compound, a binder resin, an inorganic filler, a compounding agent, etc. are uniformly used by using an extruder, a kneader, a roll, a planetary mixer, etc., if necessary. Until sufficiently mixed to obtain an epoxy resin composition, and when the obtained epoxy resin composition is in a liquid state, the composition is impregnated into the base material by potting or casting, or poured into a mold and cast. It is hardened by heating. Further, when the obtained epoxy resin composition is solid, it is cast after melting and molded by using a transfer molding machine or the like, and further cured by heating. The curing temperature and time are 80 to 200 ° C. and 2 to 10 hours. As a curing method, it is possible to cure at a high temperature all at once, but it is preferable to raise the temperature stepwise to proceed the curing reaction. Specifically, the initial curing is performed at 80 to 150 ° C., and the post curing is performed at 100 ° C. to 200 ° C. The curing step is preferably carried out by raising the temperature in 2 to 8 steps, more preferably 2 to 4 steps.

  Further, the epoxy resin composition of the present invention is dissolved in a solvent such as toluene, xylene, acetone, methylethylketone, methylisobutylketone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone to obtain an epoxy resin composition varnish, which is made of glass fiber To obtain a cured product of the epoxy resin composition of the present invention by hot press-molding a prepreg obtained by impregnating a base material such as Bonn fiber, polyester fiber, polyamide fiber, alumina fiber, and paper, and heating and drying. You can In this case, the solvent is usually 10 to 70% by weight, preferably 15 to 70% by weight in the mixture of the epoxy resin composition of the present invention and the solvent.

  The epoxy resin composition of the present invention can also be used as a film-type encapsulating composition. When obtaining such a film-type resin composition, a sheet-like adhesive is obtained by applying the above-mentioned epoxy resin composition varnish on a release film, removing the solvent under heating, and performing B stage. This sheet-like adhesive can be used as an interlayer insulating layer in a multi-layer substrate or the like, and as a collective film sealing of optical semiconductors.

  Specific applications of these compositions include adhesives, paints, coating agents, molding materials (including sheets, films, FRPs, etc.), insulation materials (printed circuit boards, wire coatings, etc., as well as sealing materials, Examples include encapsulating materials, cyanate resin compositions for substrates), additives such as acrylic acid ester resins as resist curing agents, and other resins. In the present invention, use as an insulating material for electronic materials (a sealing material including a printed circuit board, an electric wire coating and the like, a sealing material, a cyanate resin composition for a substrate) is particularly preferable.

  Examples of the adhesive include adhesives for civil engineering, construction, automobiles, general office work and medical use, as well as adhesives for electronic materials. Among them, adhesives for electronic materials include interlayer adhesives for multi-layer substrates such as build-up substrates, die bonding agents, adhesives for semiconductors such as underfills, BGA reinforcing underfills, anisotropic conductive films ( ACF), an anisotropic conductive paste (ACP), and other mounting adhesives.

  As the encapsulating material and the substrate, potting for capacitors, transistors, diodes, light emitting diodes, ICs, LSIs, etc., dipping, transfer mold encapsulation, potting encapsulations for ICs, LSIs such as COB, COF, TAB, etc., Examples include underfill for flip chips, encapsulation (including reinforcing underfill) when mounting IC packages such as QFP, BGA, CSP, and package substrates. Further, it is also suitable for use as a circuit board or a module board in which functionality is required.

The epoxy resin composition of the present invention is particularly preferably used for semiconductor devices.
The semiconductor device is the IC package group mentioned above. The semiconductor device can be obtained by encapsulating a silicon chip installed on a package substrate or a support such as a die with the epoxy resin composition of the present invention. The molding temperature and the molding method are as described above.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. The various analytical methods used in the examples are described below.
Epoxy equivalent: conforms to JIS K 7236 (ISO 3001)
ICI melt viscosity: according to JIS K 7117-2 (ISO 3219) Softening point: according to JIS K 7234 Total chlorine:
Automatic sample combustion-ion chromatograph AQF-2100H type manufactured by Mitsubishi Chemical Co., Ltd. Argon gas flow rate is 200 ml / min, oxygen gas flow rate is 400 ml / min, and the ion content is measured after combustion decomposition.
HPLC:
Column (Inertsil ODS-2)
The coupled eluent was tetrahydrofuran and a 1 mM monosodium dihydrogen phosphate aqueous solution. The flow rate was 1.0 ml / min.
Column temperature is 40 ° C
NMR:
JNM-ECS400 manufactured by JEOL Ltd. Heavy solvent is deuterated chloroform glass transition point (Tg):
TMA thermomechanical measuring device TA-instruments, Q400EM
Measurement temperature range: 40 ° C to 280 ° C
Temperature rising rate: 2 ° C / min

Example 1
To a flask equipped with a stirrer, a reflux condenser, and a stirrer, 25 parts by mass of water, 500 parts by mass of dimethyl sulfoxide, phenol resin (phenol-biphenylene type hydroxyl group equivalent 200 g / eq. Softening point 65 ° C.) 500 while nitrogen purging was performed. A mass part was added, and it heated up at 45 degreeC and melted. Then, the mixture was cooled to 38 to 40 ° C., and 130.0 parts by mass of flaky caustic soda (purity: 99%, manufactured by Tosoh) (1.3 mol equivalent to 1 mol equivalent of hydroxyl group of phenol resin) was added over 60 minutes. Thereafter, 294.3 parts by mass of methallyl chloride (purity 99%, manufactured by Tokyo Kasei Kogyo Co., Ltd.) (1.3 molar equivalents to 1 molar equivalent of hydroxyl group of phenol resin) was added dropwise over 60 minutes, and the temperature was kept at 38 to 40 ° C. For 5 hours and at 60 to 65 ° C. for 1 hour.
After completion of the reaction, water, dimethyl sulfoxide and the like were distilled off under reduced pressure while heating at 125 ° C. or lower with a rotary evaporator. Then, 740 parts by mass of methyl isobutyl ketone was added, and washing with water was repeated to confirm that the aqueous layer became neutral. Then, the solvent was distilled off from the oil layer using a rotary evaporator under reduced pressure while bubbling nitrogen to obtain 600 parts by mass of MEP of the formula (2) with n = 2.0.

Example 2
A flask equipped with a stirrer, a reflux condenser, and a stirrer was charged with 1000 parts by mass of an ethyl acetate solution containing the MEP obtained in Example 1 (concentration of MEP: 50% by mass) while performing a nitrogen purge. Furthermore, 0.04 mol part of potassium tungstate as a tungstic acid compound, 0.06 mol part of potassium phosphate as a phosphoric acid compound per 1 mol part of MEP, and 60 parts of acetic acid as an organic carboxylic acid per 100 mass parts of MEP. 0.0 parts by mass was added, and the temperature of this mixed solution was raised to 50 ° C. After the temperature was raised, a 35% aqueous hydrogen peroxide solution was added with stirring for 20 minutes in such an amount that hydrogen peroxide was 2 molar equivalents with respect to 1 molar equivalent of methallyl groups in MEP. After the addition was completed, the mixture was stirred as it was at 50 ° C. for 24 hours.
Then, a liquid separation washing treatment was carried out to separate the aqueous phase to obtain a solution containing the epoxy resin (EP1) of the present invention. The epoxy equivalent of the obtained epoxy resin (EP1) was 288 g / eq. The ICI melt viscosity at a softening point of 59 ° C. and 150 ° C. was 0.07 Pa · s, and the total chlorine content was 15 ppm or less.

Example 3, Comparative Example 1
The epoxy resin of the present invention (EP1) obtained in Example 2 and the comparative epoxy resin (EP2; phenol-biphenylene aralkyl type epoxy resin NC-3000 manufactured by Nippon Kayaku Co., Ltd.) are used, and the epoxy resin and the curing agent are used. (Phenol resin (H-1 manufactured by Meiwa Kasei Co., Ltd.) or phenol-biphenylene aralkyl type phenol resin (GPH-65 manufactured by Nippon Kayaku Co., Ltd.) was added in an equivalent amount, and a curing catalyst (curing accelerator, triphenyl) was added. Phosphine (TPP, manufactured by Tokyo Kasei Kogyo Co., Ltd.) and, if necessary, a filler (Kykuros MSR2212 manufactured by Tatsumori Co., Ltd., the filler amount% in the table is a ratio with respect to the entire epoxy resin composition), and a wax as a release agent (Carnauba wax No. 1 manufactured by Ceralica NODA Co., Ltd.) and a coupling agent (KBM-303 manufactured by Shin-Etsu Chemical Co., Ltd.) were added and mixed The epoxy resin composition of the present invention was obtained by uniformly mixing and kneading using a resin, the epoxy resin composition was crushed with a mixer and further tableted with a tablet machine. Also, the epoxy resin composition for comparison was transfer-molded (175 ° C. × 60 seconds), and after demolding, cured at 160 ° C. × 2 hours + 180 ° C. × 6 hours to obtain a test piece for evaluation.
The physical properties of the cured product were measured as follows. In addition, depending on the evaluation items of the physical properties of the cured product, the types of curing agents used are as shown in Tables 1 and 2 below. The amount of the curing accelerator used is the epoxy resin weight in the sample used for the evaluation of heat resistance and shrinkage. 1%, and 2% based on the weight of the epoxy resin in the sample used for flame retardancy evaluation.

<Bending test>
-Based on JIS K 6911 Tested at room temperature and 120 ° C.
<Dielectric constant test / Dielectric loss tangent test>
-A test was performed by a cavity resonator perturbation method using a 1 GHz cavity resonator manufactured by Kanto Electronics Co., Ltd. However, the sample size was 1.7 mm wide x 100 mm long, and the thickness was 1.7 mm. <Flame retardancy test>
-Judgment of flame retardance: It carried out based on UL94. However, the test was conducted with a sample size of 12.5 mm width × 120 mm length and a thickness of 0.8 mm.
-Combustion time: Total afterflame time after flame contact with a set of 5 samples 10 times <PCT extracted chlorine content measurement>
The epoxy resin cured product was pulverized with a cyclomill, and 1.5 g of the powder remaining at 100 mesh of the sieve and 200 mesh was PCT-extracted (121 ° C. × 24 h) with 20 ml of ultrapure water, and the extract was filtered through a 0.45 μm filter. The result of the ion chromatography analysis was converted into the resin unit amount.

  From Tables 1 and 2, the cured product using the methallyl ether resin of the present invention and the epoxy resin thereof has excellent low dielectric properties, flame retardancy, and toughness as compared with the cured product using the comparative epoxy resin. You can confirm that it is a thing.

Although the present invention has been described in detail with reference to particular embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
The present application is based on Japanese Patent Application (2015-190654) filed on September 29, 2015, which is incorporated by reference in its entirety. Also, all references cited herein are incorporated in their entirety.

The substituted allyl ether resin, methallyl ether resin, epoxy resin, epoxy resin composition and cured product thereof of the present invention can be used in the fields of electric / electronic parts, structural materials, adhesives, paints and the like.

Claims (8)

A substituted allyl ether resin represented by the following formula (1).

(In the formula, R _1's each independently represent an alkyl group, R _2's each independently represent a hydrogen atom or an alkyl group, a represents 1 to 3, respectively, and n is the average of the number of repetitions of 1 to 10. It represents a value.) A methallyl ether resin represented by the following formula (2).

(In formula, R < ₂ > represents a hydrogen atom or an alkyl group each independently, a represents each 1-3, n represents the average value of the repeating number of 1-10.) An epoxy resin represented by the following formula (3) or the following formula (4) .

(In the formula (3), R _1's each independently represent an alkyl group, R _2's each independently represent a hydrogen atom or an alkyl group, a represents 1 to 3, respectively, and n is 1 to 10 repeats. Represents the average number.)

(In formula (4), R < ₂ > represents a hydrogen atom or an alkyl group each independently, a represents each 1-3, n represents the average value of the repeating number of 1-10.)   An epoxy resin composition containing the epoxy resin according to claim 3 and a curing agent and / or a curing catalyst.   A cured product obtained by curing the epoxy resin composition according to claim 4.   A method for producing an epoxy resin, wherein the substituted allyl ether resin according to claim 1 or the methallyl ether resin according to claim 2 is oxidized to obtain an epoxy resin.   A method for producing an epoxy resin composition, comprising mixing the epoxy resin obtained by the method for producing an epoxy resin according to claim 6 with a curing agent and / or a curing catalyst to obtain an epoxy resin composition.   A method for producing a cured product, comprising curing the epoxy resin composition obtained by the method for producing an epoxy resin composition according to claim 7 to obtain a cured product.