JPWO2017057140A1 - Substituted allyl ether resin, methallyl ether resin, epoxy resin, epoxy resin composition and cured product thereof - Google Patents

Abstract

（式中、Ｒ_１はそれぞれ独立してアルキル基を表し、Ｒ_２はそれぞれ独立して水素原子又はアルキル基を表し、ａはそれぞれ１〜３を表す。ｎは１〜１０の繰り返し数の平均値を表す。）An object of the present invention is to provide a substituted allyl ether resin represented by the following formula (1), which is suitable for electric and electronic materials and raw materials, and is obtained at low cost with low halogen, and an epoxy resin using the same. .

(In the formula, each R ₁ independently represents an alkyl group, each R ₂ independently represents a hydrogen atom or an alkyl group, a represents 1 to 3 and n represents an average of 1 to 10 repetitions. Represents the value.)

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 suitable for electrical and electronic material applications requiring heat resistance.

  Epoxy resin compositions are widely used in the fields of electrical and electronic parts, structural materials, adhesives, paints, etc. due to their workability and excellent electrical properties, heat resistance, adhesion, moisture resistance (water resistance), etc. It has been.

Conventionally, allyl ether compounds have been used as additives such as reactive diluents, crosslinking agents, and flame retardants, and raw materials for photocurable monomers (Patent Document 1). Furthermore, 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, etc., development is proceeding (Patent Document 2).
On the other hand, in recent years, in the field of electrical and electronic parts, gold wires used for wire bonding that connects IC chips to lead frames and printed circuit boards are rapidly changing from the viewpoint of cost reduction. It is out. Here, when an epoxy resin manufactured by a technique 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 is increased. There is a problem that the copper wire is corroded. For this reason, application of the epoxy resin to a semiconductor or the like is limited, and complicated purification has to be repeated for use in the application. In order to prevent such corrosion due to chlorine, it is effective to use an epoxy resin obtained by a technique not using 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 for producing a bifunctional epoxy resin by reacting hydrogen peroxide with a compound having a carbon-carbon double bond. Has been. In recent years, a method for producing an epoxy resin using an organic percarboxylic acid has also been reported (Patent Documents 4 and 5).

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

  The present inventors have developed an allyl ether resin that can be obtained at low cost with low halogen (Patent Document 6), but further improvement is required. SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a substituted allyl ether resin and a methallyl ether resin that are suitable for electric and electronic materials and raw materials, and are obtained at low cost with low halogen, 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, each R ₁ independently represents an alkyl group, each R ₂ independently represents a hydrogen atom or an alkyl group, a represents 1 to 3 and n represents an average of 1 to 10 repetitions. Represents the value.)
[2] A methallyl ether resin represented by the following formula (2).

(In the formula, each R ₂ independently represents a hydrogen atom or an alkyl group, a represents 1 to 3 respectively, and n represents an average value of 1 to 10 repetitions.)
[3] An epoxy resin using the substituted allyl ether resin according to [1] or the methallyl ether resin according to [2].
[4] An epoxy resin composition containing the epoxy resin according to [3] above and a curing agent and / or a curing catalyst.
[5] A cured product obtained by curing the epoxy resin composition according to [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. In addition, the substituted allyl ether resin or methallyl ether resin of the present invention can provide a precursor of a cured product having excellent low dielectric properties, flame retardancy, and toughness by polymerization, epoxidation, or Claisen transition.

First, a substituted allyl ether resin which is one embodiment 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, each R ₁ independently represents an alkyl group, each R ₂ independently represents a hydrogen atom or an alkyl group, a represents 1 to 3 and n represents an average of 1 to 10 repetitions. Represents the 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 the formula, each R ₂ independently represents a hydrogen atom or an alkyl group, a represents 1 to 3 respectively, and n represents an average value of 1 to 10 repetitions.)

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.

  Compared to resins such as general cresol novolac, these materials are excellent in flame retardancy, and a composition capable of exhibiting flame retardancy can be produced without adding halogen as a flame retardant. In addition, it is useful for the environmental load, and it can stop the movement of ions such as chlorine, which is contained somewhat due to its high hydrophobicity. In addition to high electrical reliability, a combination of low halogen and these structures is useful as an electrical and electronic material.

  Further, 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.

When the product containing MEP obtained by the production method described later is measured by high performance liquid chromatography (hereinafter also referred to as “HPLC”), the chromatogram shows MEP in which n = 1 in the formula (2). There may be a case where an impurity peak is observed between the MEP peak and the MEP peak where n = 2.
From the viewpoint of reactivity when epoxidizing MEP, the peak of this impurity is more preferably less than 1.5 area% in terms of the area ratio relative to the entire product containing MEP. It is preferably less than 0 area%. When this area ratio exceeds 2.0 area%, there is a possibility of greatly affecting the progress of the epoxidation reaction.

  The methallyl ether resin of the present invention preferably has a softening point of 120 ° C. or lower. When the softening point of MEP exceeds 120 ° C., it is very difficult to dissolve in a solvent, so it becomes difficult to remove the salt contained in MEP by washing or the like. Not preferred due to concerns.

(Method for producing methallyl ether resin)
The methallyl ether resin of the present invention can be obtained by reacting a corresponding phenol resin and 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, and phenol and 4,4′-bis (methoxymethyl) -1,1. A reaction product with '-biphenyl is preferred.

(Methallyl halide)
The methallyl halide used for the production of MEP is preferably β-methallyl chloride from the viewpoint of reactivity with the phenol resin.
Here, β-methallyl chloride tends to be polymerized with each other to form a polymer (polymethallyl chloride). However, methallyl chloride used for the production of 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 large, it not only increases the total chlorine content of the resulting MEP, and also the epoxy resin of the present invention obtained using the MEP, but also MEP, and This contributes to an increase in the molecular weight of the resulting epoxy resin, and there is a risk of leaving a very small amount of gel in the product. Further, in order to reduce the amount of chlorine, it is necessary to add a considerable amount of a basic substance, which is industrially unfavorable, and there is a possibility that highly toxic methallyl alcohol is generated in the system.

  The content ratio of these polymethallyl chlorides can be easily confirmed by gas chromatography, and the specific content ratio of polymethallyl chloride is the area ratio when measured by gas chromatography. 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 is usually 1.0 to 2.0 mol, preferably 1.0 to 1.60 mol, based on 1 mol of the hydroxyl group of the phenol resin. More preferably, it is 1.0-1.50 mol.

  In addition, when manufacturing the substituted allyl ether resin of this invention, it replaces with the above-mentioned methallyl halide, and obtains the substituted allyl ether resin of this invention by taking the below-mentioned manufacturing method using substituted allyl halide. Can do.

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

  In the production of MEP, the amount of a base such as an alkali metal hydroxide used is usually 1.0 to 2.0 mol, preferably 1.0 to 1.60 mol, based on 1 mol of the hydroxyl group of the phenol resin. More preferably, it is 1.0-1.50 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 in the production of MEP contains an aprotic polar solvent, the solubility of the phenol resin in the solvent can be improved. Examples of such aprotic polar solvents include dimethyl sulfoxide, N-methylpyrrolidone, dimethylacetamide, dioxane, dimethoxyethane, diglyme, dimethylformamide and the like, and dimethyl sulfoxide is particularly preferable.
In the production of MEP, the amount of aprotic polar solvent such as dimethyl sulfoxide used is preferably 20 to 300% by mass, more preferably 25 to 250% by mass, particularly preferably based on the total mass of the phenol resin. Is 25-200 mass%. Since aprotic polar solvents such as dimethyl sulfoxide are not useful for purification such as washing with water, and have a high boiling point and are difficult to remove, it is preferable when the amount used exceeds 300% by mass with respect 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-mentioned water and aprotic polar solvent.
Moreover, the solvent used for manufacture of MEP may contain organic solvents (other organic solvents) other than the above-mentioned aprotic polar solvent and C1-C5 alcohol, 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, more preferably 0.5 to 50% by mass, based on the amount of the aprotic polar solvent used. If methylethylketone, methylisobutylketone, toluene, etc. are used in excess, Claisen transition will occur during the reaction, and the residual phenolic hydroxyl group will increase, resulting in a shortage of methallyl chloride in the system. This is not preferable because there is a possibility that a product may be formed or that all 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. In order to obtain MEP with higher purity, it is preferable to increase the reaction temperature in two or more stages. For example, the first stage is 35 to 50 ° C., and the second stage is 45 to 70 ° C. It 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 longer, the reaction proceeds sufficiently, and when it is 10 hours or shorter, the amount of by-products generated can be kept low.

  After completion of the reaction, the solvent is distilled off under reduced pressure by heating to obtain the 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 a state where the water layer is heated, the water layer is washed until the pH becomes 5-8. By washing with water until the pH of the aqueous layer is 8 or less, it is possible to prevent the balance of the catalyst system from being lost and the progress of the reaction from being suppressed during the subsequent epoxidation reaction.

The methallyl etherification reaction of a phenol resin is usually performed while blowing an inert gas such as nitrogen into the system (in the air or in the liquid). By carrying out the reaction while blowing an inert gas into the system, the resulting product can be prevented from being colored.
The amount of inert gas blown per unit time varies depending on the volume of the kettle used for the reaction. For example, the amount of inert gas blown per unit time so that the volume of the kettle can be replaced in 0.5 to 20 hours. Is preferably adjusted.

Next, the epoxy resin of this invention is demonstrated.
The epoxy resin which is one embodiment of the present invention is represented by the following formula (3).

(In the formula, each R ₁ independently represents an alkyl group, each R ₂ independently represents a hydrogen atom or an alkyl group, a represents 1 to 3 and n represents an average of 1 to 10 repetitions. Represents the value.)

  Moreover, the epoxy resin which is another embodiment of this invention is represented by following formula (4).

(In the formula, each R ₂ independently represents a hydrogen atom or an alkyl group, a represents 1 to 3 respectively, and n represents an average value of 1 to 10 repetitions.)

  As a preferable resin characteristic of the epoxy resin of the present invention, an epoxy equivalent is 260 to 285 g / eq. And more preferably 260-280 g / eq. It is. Epoxy equivalent was 285 g / eq. Exceeding this indicates 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.
Methyl group-containing epoxy resins tend to have higher elastic modulus than ordinary epoxy resins, and tend to exhibit suitable characteristics for fiber reinforced plastic (FRP) and carbon fiber reinforced plastic (CFRP).

  As a softening point of the epoxy resin of this invention, 30-130 degreeC is preferable, More preferably, it is 40-120 degreeC. If the softening point is too low, blocking during storage becomes a problem, and there are many problems such as handling at low temperatures. On the other hand, if the softening point is too high, problems such as poor handling may occur during kneading with other resins.

Further, 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. The sulfate ion extracted by hot water extraction is also 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 as in the formula (3) or (4) tends to decrease. Particularly preferred is 0.02 Pa · s to 0.09 Pa · s.

The methallyl ether resin of the present invention can be oxidized to form the epoxy resin of the present invention. Examples of the oxidation method include 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 epoxidation method using peracid include the method described in Japanese Patent Application Laid-Open No. 2006-52187.
Various methods can be applied to the method of epoxidation with hydrogen peroxide solution. Specifically, Japanese Patent Application Laid-Open No. 59-108793, Japanese Patent Application Laid-Open No. 62-234550, Japanese Patent Application Laid-Open No. No. 5-291919, Japanese Patent Laid-Open No. 11-349579, Japanese Patent Publication No. 1-33341, Japanese Patent Publication No. 2001-17864, Japanese Patent Publication No. 3-57102, Japanese Patent Publication 2011-225654, Japan JP 2011-079794, JP 2011-084558, JP 2010-08383, JP 2010-095521, and the like. Various methods can be applied.

  Hereinafter, a particularly preferred method for obtaining an epoxy resin (hereinafter simply referred to as “the epoxy resin of the present invention”) which is one of the embodiments of the present invention represented by the formula (4) will be exemplified. The epoxy resin of the present invention is obtained by reacting a methallyl ether resin represented by the formula (2) and 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 a tungstate ion (WO ₄ ²⁻ ) in water. For example, tungstic acid, tungsten trioxide, phosphotungstic acid, ammonium tungstate, tungstic acid Examples include potassium dihydrate, sodium tungstate dihydrate, calcium tungstate, and barium tungstate. 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. The use amount of the tungstic acid compound is preferably 1 × 10 ^{−6 to} 0.2 mol per 1 mol of the compound represented by the formula (2) from the viewpoint of improving the production rate of the epoxy group, and is 0.0001 to 0 More preferred is 2 moles.

(Organic carboxylic acid)
The manufacturing method of the epoxy resin of this invention is performed in presence of 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, but 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, anisic acid and the like.

  Among these, in order to improve the balance between hydrophobicity and hydrophilicity, those having a molecular weight of 46 to 150 are preferable, and those having a molecular weight of 46 to 120 are more preferable. And it is preferable that the carbon chain couple | bonded with the carbon atom of this carboxylic acid is a straight chain. Examples of the organic carboxylic acid having a linear carbon chain bonded to a carbon atom include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, malonic acid, succinic acid, and the like.

  The organic percarboxylic acid can be easily generated by reacting an organic carboxylic acid or organic carboxylic acid anhydride with hydrogen peroxide. Examples of organic carboxylic acids and anhydrides include formic acid, acetic acid, acetic anhydride, propionic acid, propionic anhydride, butyric acid, isobutyric acid, valeric acid, isovaleric acid, hydroangelic acid, pivalic acid, benzoic acid, and salicylic acid. 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 ease of removal after the reaction. The method of generating organic percarboxylic acid in the reaction system can be easily adjusted by simply mixing commonly used reagents, and the reaction proceeds while consuming the generated percarboxylic acid sequentially. 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 moles per mole of the methallyl ether resin represented by the formula (2) from the viewpoint of improving the production rate of the epoxy group, and 0.05 to 4 More preferred is 0.0 mole.

(Organic solvent)
The method for producing an epoxy resin of the present invention is carried out in the presence of a specific organic solvent. By performing in the presence of a specific organic solvent, the production rate of epoxy groups can be greatly improved. This is related to the compatibility with tungstic acid compounds, phosphoric acid compounds, organic carboxylic acids, etc., and when MEP is dissolved, the reaction is made smooth by preventing precipitation of hardly soluble components. Inferred to be advanced.

In the present invention, alcohols and nitriles cannot be used as the specific organic solvent from the viewpoint of solubility of the raw materials. In addition, when ketones or sulfoxides are used, side reactions proceed, so that acetone or dimethyl sulfoxide cannot be used. Accordingly, suitable organic solvents include diethyl ether, tetrahydrofuran, dioxane, dimethoxyethane, diglyme, triglyme, ethylene glycol diacetate, methyl acetate, ethyl acetate, N, N-dimethylformaldehyde (hereinafter “DMF”), N, N-dimethylacetamide (hereinafter referred to as “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 preferred.

(Phosphate compound)
The manufacturing method of the epoxy resin of this invention is performed in presence of a phosphoric acid compound. The phosphoric acid compound is not particularly limited as long as it is a compound that generates phosphate ions (PO ₄ ³⁻ ) in water. For example, phosphoric acid, alkali metal dihydrogen phosphate, alkaline earth metal dihydrogen phosphate Salt, hydrogen phosphate di-alkaline metal salt, hydrogen phosphate di-alkaline earth metal salt, alkali phosphate 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, those containing salts such as phosphoric acid, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, and potassium phosphate are preferable because they are easily available.

  The amount of the phosphoric acid compound used is preferably 0.01 to 1.0 mol, 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 epoxy groups. Is more preferable.

(hydrogen peroxide)
Although the hydrogen peroxide to be reacted with the methallyl ether resin represented by the formula (2) in the method for producing an epoxy resin of the present invention is not particularly limited, it is usually dissolved in water and added as a 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% by mass from the viewpoint of generation of epoxy groups. The amount of hydrogen peroxide water used is not particularly limited, but the amount of hydrogen peroxide is preferably 0.3 to 10 mol, more preferably 1 to 6 mol, relative to 1 mol of the allyl group of the methallyl ether resin. . The amount of hydrogen peroxide solution is 0.3 mol or more with respect to 1 mol of the methallyl group of the methallyl ether resin, so that the epoxidation can be advanced efficiently, and the epoxy to be produced is 10 mol or less. Hydrolysis of the group can be suppressed.

  The production method of the epoxy resin of the present invention is not particularly limited, but the organic solvent such as toluene, xylene, mesitylene, dimethoxyethane, ethyl acetate, tetrahydrofuran, in which the methallyl ether resin can be dissolved, the methallyl ether resin, the tungstic acid compound, It is preferable to start the epoxidation reaction by adding a hydrogen peroxide solution after adding the phosphoric acid compound. However, the production method of the epoxy resin of the present invention is not limited to this addition order, and in the presence of a tungstic acid compound and a phosphoric acid compound, the carbon-carbon in the methallyl group of the methallyl ether resin. Conversion of a double bond to an epoxy group can be performed efficiently.

  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, and more preferably 25 to 100 ° C. By being 10 degreeC or more, reaction rate can be made suitable, and the hydrolysis reaction of the produced | generated epoxy group can be suppressed by being 120 degreeC or less.

  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., but in order to secure the time for the epoxidation to proceed sufficiently and to produce industrially efficiently, After the addition of a predetermined amount of hydrogen peroxide, 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. As a method for removing hydrogen peroxide, a method of performing a liquid separation operation and washing with water can be given. Add twice the weight of the resin methyl isobutyl ketone, perform a liquid separation operation with 1 times the weight of ion-exchanged water, and discard the aqueous layer. This procedure is performed until the hydrogen peroxide is completely removed. Whether hydrogen peroxide has been removed is confirmed by confirming that the potassium iodide starch paper test is negative.

  Next, after removing hydrogen peroxide, the organic phase is concentrated under reduced pressure. At this time, since the resin may cause polymerization if it is heated too much, the concentration operation is preferably performed at 90 to 180 ° C, more preferably at 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. Moreover, another epoxy resin can be contained as an arbitrary component.

  The epoxy resin composition of the present invention can be used in combination with the epoxy resin of the present invention and another epoxy resin. 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, phenol aralkyl type epoxy resins, and the like. 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, Glycidyl ethers derived from polycondensates with 4-bis (chloromethyl) benzene or 1,4-bis (methoxymethyl) benzene and their modified products, halogenated bisphenols such as tetrabromobisphenol A or alcohols , Cycloaliphatic epoxy resin, glycidylamine epoxy resin, glycidyl ester epoxy resin, silsesquioxane epoxy resin (chain structure, cyclic structure, ladder structure, or a mixed structure of at least two of these) Glycidyl group and / or epoxycyclohexane structure Examples thereof include, but are not limited to, solid or liquid epoxy resins.

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, and 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 Such as 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 these heterocyclic compounds and phthalic acid, isophthalic acid, terephthalic acid, Limellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, maleic acid, salts with polyvalent carboxylic acids such as succinic acid, amides such as dicyandiamide, 1,8-diaza-bicyclo (5.4.0) -7-undecene And diaza compounds such as tetraphenylborate of these diaza compounds, phenol novolacs, salts of the polyvalent carboxylic acids or phosphinic acids, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, Tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylpropylammonium hydroxide, trimethylbutylammonium hydroxide, trimethylcetylammonium hydroxide, trimethyl Ammonium salts such as octylmethylammonium hydroxide, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium acetate, trioctylmethylammonium acetate, triphenylphosphine, tri (tolyl) phosphine, tetraphenylphosphonium Phosphines and phosphonium compounds such as bromide and tetraphenylphosphonium tetraphenylborate, phenols such as 2,4,6-trisaminomethylphenol, amine adducts, metal carboxylates (2-ethylhexanoic acid, stearic acid, behenic acid) , Zinc salts such as myristyl acid, tin salts, zirconium salts) and zinc salts such as phosphate ester metals (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 at the time of curing and changes thereof. When a quaternary salt is used, the salt with halogen may leave halogen in the cured product.
If necessary, the curing catalyst is used in an amount of 0.01 to 5.0 parts by weight with respect to 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 of these include those described in International Publication No. 2006/090662.
Specific examples of the curing agent that can be used include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, and nitrogen-containing compounds such as polyamide resins synthesized from linolenic acid and ethylenediamine (amine, Amide compounds); phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methyl hexahydro Phthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, Cyclohe 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, dihydroxynaphtha Thalene and the like) 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 And modified products thereof, phenol resins such as halogenated bisphenols such as tetrabromobisphenol A, condensates of terpenes and phenols; imidazole, trifluoroborane-amine complexes, guanidine derivative compounds, etc. Also limited to Not. 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, particularly preferably 0.6 to 1.2 equivalents, relative to 1 equivalent of the epoxy group of the epoxy resin. Good hardened | cured material properties can be obtained because the usage-amount of a hardening | curing agent is said range.

  The use of cyanate ester compounds as other components is preferred. 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 alone. Examples of the cyanate ester compounds include 2,2-bis (4-cyanatephenyl) propane, bis (3,5-dimethyl-4-cyanatephenyl) methane, 2,2-bis (4-cyanatephenyl) ethane, and These derivatives, aromatic cyanate ester compounds, etc. are mentioned. Further, for example, as described in the above-mentioned curing agent, synthesis can be performed by reaction of various phenol resins with hydrocyanic acid or salts thereof. In the present invention, those having a structure having no methylene structure at the benzyl position in the molecule, such as 2,2-bis (4-cyanatephenyl) propane and derivatives thereof (partially polymerized products, etc.) are particularly preferred. You may use independently and may use 2 or more types together.

  The epoxy resin composition of the present invention may contain a phosphorus-containing compound as a flame retardant component. The phosphorus-containing compound may be a reactive type or an additive type. Specific examples of phosphorus-containing compounds include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylylenyl phosphate, 1,3-phenylenebis ( Phosphoric acid esters such as dixylylenyl phosphate), 1,4-phenylenebis (dixylylenyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate); 9,10-dihydro-9-oxa Phosphanes such as -10-phosphaphenanthrene-10-oxide, 10 (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide; epoxy resin and active hydrogen of the phosphanes A phosphorus-containing product obtained by reacting with Poxy compounds, red phosphorus and the like can be mentioned, and phosphoric esters, phosphanes or phosphorus-containing epoxy compounds are preferable, and 1,3-phenylenebis (dixylylenyl phosphate), 1,4-phenylenebis (dixylylene). Nyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate) or phosphorus-containing epoxy compounds are particularly preferred. The phosphorus-containing compound content 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, it may adversely affect the hygroscopicity and dielectric properties of the cured product.

  Furthermore, a binder resin can also be mix | blended with the epoxy resin composition of this invention as needed. Examples of the binder resin include butyral resins, acetal resins, acrylic resins, epoxy-nylon resins, NBR-phenol resins, epoxy-NBR resins, polyamide resins, polyimide resins, and silicone resins. However, it is not limited to these. The blending amount 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 in total of the epoxy resin and the curing agent, 0.05 to 20 parts by weight is used as necessary.

  If necessary, an inorganic filler can be added to the epoxy resin composition of the present invention. Examples of inorganic fillers include crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, titania, talc, and the like. However, the present invention is not limited to these. These fillers may be used alone or in combination of two or more. In the epoxy resin composition of the present invention, the content of these inorganic fillers is generally 0 to 95% by weight, although it depends on the use. It is preferable to use properly depending on the shape of the package in the range of 50 to 95% by weight, particularly preferably 65 to 95% by weight. Furthermore, the epoxy resin composition of the present invention includes an antioxidant, a light stabilizer, a silane coupling agent, a release agent such as stearic acid, palmitic acid, zinc stearate and 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 material having an epoxy group or a coupling agent having a thiol.

  The epoxy resin composition of this invention is obtained by mixing each component uniformly. 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 a curing accelerator, a phosphorus-containing compound, a binder resin, an inorganic filler, a compounding agent, and the like, if necessary, uniformly using an extruder, kneader, roll, planetary mixer, etc. Mix thoroughly until the epoxy resin composition is obtained. If the resulting epoxy resin composition is liquid, the substrate is impregnated with a potting or casting, or poured into a mold and cast. Or cured by heating. When the obtained epoxy resin composition is solid, it is molded using a cast after casting or a transfer molding machine, 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 at a stretch, but it is preferable to increase the temperature stepwise to advance the curing reaction. Specifically, initial curing is performed between 80 and 150 ° C., and post-curing is performed between 100 and 200 ° C. As the curing stage, the temperature is preferably divided into 2 to 8 stages, more preferably 2 to 4 stages.

  Further, the epoxy resin composition of the present invention is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. to obtain an epoxy resin composition varnish, which is composed of glass fiber, A cured product of the epoxy resin composition of the present invention is obtained by hot press-molding a prepreg obtained by impregnating a base material such as bon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc. and drying by heating. Can do. The solvent in this case 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.

  Moreover, the epoxy resin composition of this invention can also be used as a film type sealing composition. When obtaining such a film-type resin composition, the epoxy resin composition varnish is applied onto a release film, the solvent is removed under heating, and a B-stage is obtained to obtain a sheet-like adhesive. This sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like, and a batch film sealing of an optical semiconductor.

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

  Examples of the adhesive include civil engineering, architectural, automotive, general office, and medical adhesives, and electronic material adhesives. Among these, adhesives for electronic materials include interlayer adhesives for multilayer substrates such as build-up substrates, die bonding agents, semiconductor adhesives such as underfills, BGA reinforcing underfills, anisotropic conductive films ( ACF) and an adhesive for mounting such as anisotropic conductive paste (ACP).

  As sealing materials and substrates, potting sealing for capacitors, transistors, diodes, light emitting diodes, ICs, LSIs, etc., dipping, transfer mold sealing, ICs, LSIs for COB, COF, TAB, etc. Examples include underfill for flip chip, sealing (including reinforcing underfill) and package substrate when mounting IC packages such as QFP, BGA, and CSP. Moreover, it is suitable also for the board | substrate use as which a functionality, such as a network board | substrate and a module board, is calculated | required.

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

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited to these Examples. The various analysis methods used in the examples are described below.
Epoxy equivalent: Conforms to JIS K 7236 (ISO 3001)
ICI melt viscosity: JIS K 7117-2 (ISO 3219) compliant Softening point: JIS K 7234 compliant Total chlorine:
Automatic sample combustion-ion chromatograph AQF-2100H type manufactured by Mitsubishi Chemical Corp. Ion content was measured after combustion decomposition with an argon gas flow rate of 200 ml / min and an oxygen gas flow rate of 400 ml / min.
HPLC:
Column (Inertsil ODS-2)
The coupled eluent was tetrahydrofuran and a 1 mM aqueous solution of monosodium dihydrogen phosphate. 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 manufactured by TA-instruments, Q400EM
Measurement temperature range: 40 ° C to 280 ° C
Temperature increase rate: 2 ° C / min

Example 1
A flask equipped with a stirrer, a reflux condenser, and a stirrer is purged with nitrogen, 25 parts by weight of water, 500 parts by weight of dimethyl sulfoxide, and phenol resin (phenol-biphenylene type hydroxyl group equivalent 200 g / eq. Softening point 65 ° C.) 500 Mass parts were added, and the mixture was heated to 45 ° C. and dissolved. Subsequently, the mixture was cooled to 38 to 40 ° C., and 130.0 parts by mass of flaky caustic soda (purity 99%, manufactured by Tosoh Corp.) was added over a period of 60 minutes (1.3 molar equivalents relative to 1 molar equivalent of the hydroxyl group of the phenol resin). Thereafter, 294.3 parts by mass of methallyl chloride (purity 99%, manufactured by Tokyo Chemical Industry Co., Ltd.) (1.3 molar equivalents relative to 1 molar equivalent of the hydroxyl group of the phenol resin) was added dropwise over 60 minutes, and the temperature was 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 by heating on a rotary evaporator at 125 ° C. or lower under reduced pressure. And 740 mass parts of methyl isobutyl ketone was added, and water washing was repeated, and it confirmed that the water layer became neutral. Thereafter, the solvent was distilled off from the oil layer using a rotary evaporator under nitrogen bubbling under reduced pressure to obtain 600 parts by mass of MEP of formula (2) where n = 2.0.

Example 2
To a flask equipped with a stirrer, a reflux condenser, and a stirrer, while purging with nitrogen, 1000 parts by mass of an ethyl acetate solution containing MEP obtained in Example 1 (concentration of MEP: 50% by mass) was added, Further, 0.04 mol part of potassium tungstate as a tungstate compound, 0.06 mol part of potassium phosphate as a phosphoric acid compound, and 60 acetic acid as an organic carboxylic acid per 100 mass parts of MEP per 1 mol part of MEP. 0.0 parts by mass was added, and the temperature of the mixture was increased to 50 ° C. After the temperature rise, with stirring, a 35% aqueous hydrogen peroxide solution was added over 20 minutes in an amount that would give 2 molar equivalents of hydrogen peroxide to 1 molar equivalent of methallyl groups in MEP. After completion of the addition, the mixture was stirred at 50 ° C. for 24 hours.
Subsequently, a liquid separation washing treatment was performed, and the aqueous phase was separated 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
Using the epoxy resin (EP1) of the present invention obtained in Example 2 and a comparative epoxy resin (EP2: phenol-biphenylene aralkyl epoxy resin, Nippon Kayaku Co., Ltd. NC-3000), an epoxy resin and a curing agent (Phenolic resin (Mayka Kasei Co., Ltd. H-1) or phenol-biphenylene aralkyl type phenolic resin (Nippon Kayaku Co., Ltd. GPH-65) is blended in equal equivalents, and a curing catalyst (curing accelerator, triphenyl). Phosphine (TPP, manufactured by Tokyo Chemical Industry Co., Ltd.) and, if necessary, filler (manufactured by Tatsumori Co., Ltd. Kikurosu MSR2212, the filler amount% in the table is a ratio to the entire epoxy resin composition), wax as a release agent (Carelava wax No. 1 manufactured by Celerica NODA Co., Ltd.), coupling agent (KBM-303 manufactured by Shin-Etsu Chemical Co., Ltd.), and Mixingro The epoxy resin composition of the present invention was obtained by uniformly mixing and kneading using a tablet, and this epoxy resin composition was pulverized with a mixer and further tableted with a tablet machine. Then, the epoxy resin composition for comparison was transfer molded (175 ° C. × 60 seconds), and after demolding, it was cured under the conditions of 160 ° C. × 2 hours + 180 ° C. × 6 hours to obtain a test piece for evaluation.
In addition, the physical property of hardened | cured material was measured in the following ways. Also, 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, and the amount of curing accelerator used is the weight of the epoxy resin in the samples used for the evaluation of heat resistance and shrinkage. 1% relative to the weight of the epoxy resin in the sample used for evaluation of flame retardancy.

<Bending test>
-According to JIS K 6911 The test was performed at room temperature and 120 ° C.
<Dielectric constant test and dielectric loss tangent test>
-Using a 1 GHz cavity resonator manufactured by Kanto Electronics Co., Ltd., a test was performed by the cavity resonator perturbation method. However, the sample size was 1.7 mm wide × 100 mm long, and the thickness was 1.7 mm. <Flame Retardancy Test>
-Determination of flame retardancy: performed in accordance with UL94. However, the test was conducted with a sample size of 12.5 mm wide × 120 mm long and a thickness of 0.8 mm.
・ Burning time: Total after-flame time after flame contact 10 times to a set of 5 samples <Measurement of PCT extracted chlorine content>
The epoxy resin cured product was pulverized with a cyclomill, and 1.5 g of the powder which passed through 100 mesh of the sieve and remained at 200 mesh was subjected to PCT extraction (121 ° C. × 24 h) with 20 ml of ultrapure water, and the extract was filtered through a 0.45 μm filter. The result of ion chromatography analysis was converted into a 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 compared to the cured product using the comparative epoxy resin. Can be confirmed.

Although the invention has been described in detail with reference to specific 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.
In addition, this application is based on the Japan patent application (2015-190654) for which it applied on September 29, 2015, The whole is used by reference. Also, all references cited herein are incorporated as a whole.

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 (5)

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

(In the formula, each R ₁ independently represents an alkyl group, each R ₂ independently represents a hydrogen atom or an alkyl group, a represents 1 to 3 and n represents an average of 1 to 10 repetitions. Represents the value.) A methallyl ether resin represented by the following formula (2).

(In the formula, each R ₂ independently represents a hydrogen atom or an alkyl group, a represents 1 to 3 respectively, and n represents an average value of 1 to 10 repetitions.)   An epoxy resin using the substituted allyl ether resin according to claim 1 or the methallyl ether resin according to claim 2.   An epoxy resin composition comprising the epoxy resin according to claim 3 and a curing agent and / or a curing catalyst. Hardened | cured material which hardened | cured the epoxy resin composition of Claim 4.