JP2018024856A - (meth) allyl ether resin, epoxy resin, curable resin composition and cured product thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a (meth) allyl ether resin that is suitable as raw materials for an epoxy resin, and can be obtained inexpensively with a low content of halogen, and an epoxy resin prepared therewith.SOLUTION: The present invention provides a (meth) allyl ether resin represented by formula (1) (Ris an alkyl group; Ris H or an alkyl group; a is an integer of 1-3; n is a real number of 1-10, and an average value of n is a real number of 1-10.SELECTED DRAWING: None

Description

  The present invention relates to a (meth) allyl ether resin. Specifically, for insulating materials for electrical and electronic parts including high-reliability semiconductor encapsulating materials, for various composite materials including laminated boards (printed wiring boards) and CFRP (carbon fiber reinforced plastic), various adhesives The present invention relates to a (meth) allyl ether resin which is a raw material of an epoxy resin useful for coatings, various paints, structural members, and the like, an epoxy resin using the same, a curable resin composition containing them, and a cured product thereof.

  Epoxy resins have excellent electrical properties such as electrical insulation, high heat resistance, moisture resistance, and dimensional stability, and are used for semiconductor encapsulants, printed circuit boards, build-up boards, electronic components such as resist ink, and conductive materials such as conductive paste. Wide range of adhesives and other adhesives, liquid sealing materials such as underfill, liquid crystal sealing materials, flexible substrate coverlays, build-up adhesive films, composite matrixes, paints, photoresist materials, developer materials, etc. It is used. Among these, in the field of electronic materials such as semiconductors and printed wiring boards, demands for higher performance of sealing materials and substrate materials are increasing with technological innovation. In order to meet these requirements, a high-purity epoxy resin is desired. However, impurities such as halogen and metal are mixed in and remain in the production of the epoxy resin, and the performance is deteriorated.

  Epoxy resins are generally produced by the reaction of phenols, epichlorohydrin, and alkali metal oxides, but the epoxy resins produced by this method contain hydrolyzable chlorine compounds produced as a by-product from the reaction as impurities. It is. If this epoxy resin containing a large amount of hydrolyzable chlorine compounds is used as an underfill material, when exposed to harsh conditions such as high temperature and high humidity, hydrolyzable chlorine compounds are decomposed and chlorine ions are released, It is known that a phenomenon (migration) occurs in which the wiring metal (semiconductor junction) is corroded, which adversely affects the long-term reliability of the semiconductor package. Therefore, as a sealing material for semiconductor devices, a method of oxidizing a carbon-carbon double bond of a compound having a carbon-carbon double bond by using an oxidizing agent is examined instead of a method using epichlorohydrin. (Patent Document 1). One example is a method of obtaining an epoxy compound by introducing an allyl group into a phenol (synthesizes allyl ether) and then oxidizing the allyl group with hydrogen peroxide. In recent years, a method for producing an epoxy resin using an organic percarboxylic acid has also been reported (Patent Documents 2 and 3).

  Conventionally, (meth) 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 4). Furthermore, since it can be used as a raw material of an epoxy resin by an oxidation reaction as described above, development is progressing. For example, allyl ether resins having a phenol aralkyl structure have been studied (Patent Document 5).

JP 2011-225711 A JP 2012-52062 A JP 2006-151900 A JP 2005-170890 A International Publication No. 2014/123051

  On the other hand, as high-speed communication progresses, a curable resin excellent in dielectric characteristics is required. In IOT (Internet of Things) including inter-device communication, reduction of transmission loss is important, and dielectric characteristics are important characteristics. However, when it is intended to improve the dielectric properties of the epoxy resin, it is necessary to increase the distance between the cross-linking points or introduce an alkyl chain, so that the heat resistance and heat decomposition properties are deteriorated. Therefore, the conventional epoxy resin may not be able to withstand high speed communication. For such applications, highly functional resins such as benzoxazine and BT resin have begun to be studied, but since none of them has sufficient characteristics, a resin that can be used in a high frequency region is required.

  However, conventional allyl phenyl ether resins have a problem that the reactivity of epoxidation by an oxidation method is insufficient, and a (meth) allyl ether resin suitable as a raw material for epoxidation is demanded. Therefore, the present invention is suitable for an epoxy resin for electric and electronic materials and its raw material, and is a (meth) allyl ether resin obtained at low cost with low halogen, or an epoxy resin using the same, and a curable resin containing them. An object is to provide a composition.

In order to solve the above-mentioned problems, the present inventors have found that a (meth) allyl ether resin having a specific structure is excellent in reactivity when obtaining an epoxy oxide compound, and have completed the present invention.
That is, the present invention is as follows.

（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、アルキル基を表し、ａはそれぞれ１〜３を表す。ｎは１〜１０の繰り返し数であり、ｎの平均値は１〜１０の実数を表す。）
［２］下記式（２）で表されるエポキシ樹脂。

（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、アルキル基を表し、ａはそれぞれ１〜３を表す。ｎは１〜１０の繰り返し数であり、ｎの平均値は１〜１０の実数を表す。）
［３］前項［１］に記載の（メタ）アリルエーテル樹脂を酸化したエポキシ樹脂。
［４］前項［１］に記載の（メタ）アリルエーテル樹脂を含有する硬化性樹脂組成物。
［５］前項［２］又は前項［３］に記載のエポキシ樹脂と、硬化剤及び／または硬化触媒を含有する硬化性樹脂組成物。
［６］前項［４］又は前項［５］に記載の硬化性樹脂組成物を硬化した硬化物。 [1] A (meth) 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, each a represents 1 to 3; n is a repeating number of 1 to 10; The average value of n represents a real number of 1 to 10.)
[2] An epoxy resin represented by the following formula (2).

(In the formula, each R ₁ independently represents an alkyl group, each R ₂ independently represents a hydrogen atom or an alkyl group, each a represents 1 to 3; n is a repeating number of 1 to 10; The average value of n represents a real number of 1 to 10.)
[3] An epoxy resin obtained by oxidizing the (meth) allyl ether resin according to [1].
[4] A curable resin composition containing the (meth) allyl ether resin according to [1] above.
[5] A curable resin composition comprising the epoxy resin according to [2] or [3], and a curing agent and / or a curing catalyst.
[6] A cured product obtained by curing the curable resin composition according to [4] or [5].

  The (meth) allyl ether resin of the present invention is suitable as a raw material for an epoxy resin because of its excellent epoxidation reactivity by an oxidation method. The (meth) allyl ether resin of the present invention can provide a precursor of a cured product having excellent low dielectric properties and toughness by polymerization, epoxidation, or Claisen transition. Moreover, the curable resin composition containing the (meth) allyl ether resin of the present invention can produce a cured product having excellent dielectric properties, heat resistance, and heat decomposition properties.

（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、アルキル基を表し、ａはそれぞれ１〜３を表す。ｎは１〜１０の繰り返し数であり、ｎの平均値は１〜１０の実数を表す。） The (meth) allyl ether resin of the present invention will be described.
The (meth) allyl ether resin (hereinafter referred to as “AEP”) 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, each a represents 1 to 3; n is a repeating number of 1 to 10; The average value of n represents a real number of 1 to 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. From the viewpoint of high electron density and reactivity of oxidative epoxidation, a methyl group and an ethyl group are preferable, and a methyl group is particularly preferable.

  Further, the total chlorine remaining in the AEP is preferably 500 ppm or less, more preferably 300 ppm or less, and particularly preferably 100 ppm or less in order to prevent migration and improve long-term reliability.

  The hydroxyl equivalent of the (meth) allyl ether resin of the present invention is 10,000 mgKOH / g or more, preferably 20000 mgKOH / g or more. When it exceeds 20000 mgKOH / g, it exceeds the hydroxyl equivalent which can be substantially measured, indicating that it is almost 100% allyl etherified. Furthermore, there is no allyl alcohol residue.

When the product containing AEP obtained by the production method described later is measured by high performance liquid chromatography (hereinafter also referred to as “HPLC”), the spectrum shows that the AEP having n = 1 in the above formula (1). An impurity peak may be observed between the peak and the peak of the AEP in which n = 2.
From the viewpoint of reactivity when epoxidizing AEP, the amount of this impurity peak is more preferably less than 1.5 area% in terms of the area ratio with respect to the entire product containing AEP. It is preferable that it is less than 1.0 area%. When this area ratio exceeds 2.0 area%, there is a possibility of greatly affecting the progress of the epoxidation reaction.

  The (meth) allyl ether resin of the present invention preferably has a softening point of 120 ° C. or lower. If the softening point of AEP exceeds 120 ° C, it will be very difficult to dissolve in a solvent, and it will be difficult to remove the salt contained in AEP by washing, etc., especially in fields where electrical reliability is required. Not preferred due to concerns.

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

(Phenolic resin)
Preferable examples of the phenol resin used for the production of AEP include a reaction product of phenol and dicyclopentadiene.

As the allyl halide used for the production of AEP, allyl chloride and β-methallyl chloride are preferable from the viewpoint of reactivity with the phenol resin.
Here, for example, β-methallyl chloride tends to polymerize methallyl chloride to become a polymer (polymethallyl chloride), but methallyl chloride used for the production of a compound having a methallyl ether moiety is It is preferable to use one having a low content of methallyl chloride.
If the content ratio of poly (meth) allyl chloride in the (meth) allyl chloride to be used is large, not only will the AEP to be obtained, and further, the AEP increase the total chlorine content of the epoxy resin of the present invention, the AEP In addition, it contributes to an increase in the molecular weight of the resulting epoxy resin, and there is a risk that a trace amount of gel material may be left upon commercialization. In addition, in order to reduce the amount of chlorine, it is necessary to add a considerable amount of a basic substance, which is not preferable industrially, and there is a possibility that highly toxic methallyl alcohol is produced in the system.

  The content ratio of these poly (meth) allyl chlorides can be easily confirmed by gas chromatography or the like, and the specific poly (meth) allyl chloride content ratio is the area ratio when measured by gas chromatography. Thus, 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 (meth) allyl chloride monomer.

  In the production of AEP, the amount of (meth) allyl halide such as (meth) allyl chloride used is usually 1.0 to 2.0 mol, preferably 1.0 to 1 mol per mol of the hydroxyl group of the phenol resin. .60 mol, more preferably 1.0 to 1.50 mol.

  The base used for the production of AEP 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 AEP, the use amount of a base such as an alkali metal hydroxide is usually 1.0 to 2.0 mol, preferably 1.0 to 1.60 mol, relative to 1 mol of the hydroxyl group of the phenol resin. More preferably, it is 1.0-1.50 mol.

The solvent used for the production of AEP preferably contains an aprotic polar solvent, and more preferably contains water and an aprotic polar solvent. When the solvent used for the production of AEP 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 AEP, 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%. Aprotic polar solvents such as dimethyl sulfoxide are not useful for purification such as washing, and have a high boiling point and are difficult to remove. Therefore, 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 AEP may contain an alcohol having 1 to 5 carbon atoms in addition to the water and the aprotic polar solvent described above.
Moreover, the solvent used for manufacture of AEP 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 risk that a product may be formed or that all phenolic hydroxyl groups are not (meth) allyl etherified.

In the production of AEP, the reaction temperature of the (meth) allyl etherification reaction of the phenol resin is usually 30 to 90 ° C, preferably 35 to 80 ° C. In order to obtain AEP 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 (meth) allyl 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. Washing is performed until the aqueous layer has a pH of 5 to 8 in a state of being warmed. By washing with water until the pH of the aqueous layer is less than 8, 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.

（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、アルキル基を表し、ａはそれぞれ１〜３を表す。ｎは１〜１０の繰り返し数であり、ｎの平均値は１〜１０の実数を表す） Next, the epoxy resin of this invention is demonstrated.
The epoxy resin of the present invention is represented by the following formula (2).

(In the formula, each R ₁ independently represents an alkyl group, each R ₂ independently represents a hydrogen atom or an alkyl group, each a represents 1 to 3; n is a repeating number of 1 to 10; The average value of n represents a real number of 1 to 10)

  As a preferable resin characteristic of the epoxy resin of the present invention, an epoxy equivalent is 230 to 260 g / eq. And more preferably 240-255 g / eq. It is. Epoxy equivalent is 260 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 and an ethyl group are preferable, and a methyl group is particularly preferable.
Methyl group-containing epoxy resins tend to have a higher elastic modulus than ordinary epoxy resins, and tend to exhibit suitable characteristics for FRP and 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.
Since the cured product of the resin composition using these epoxy resins has a total chlorine content of 50% or less than the conventional one, the electrical characteristics and metal corrosivity under high temperature and high humidity can be greatly improved.

  The melt viscosity range of the epoxy resin of the present invention is preferably 0.01 to 0.20 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 (1) tends to decrease. Particularly preferred is 0.02 Pa · s to 0.19 Pa · s.

The epoxy resin of the present invention can be obtained by oxidizing the (meth) allyl ether resin represented by the formula (1). 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 such as peracetic acid 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 preferable method for obtaining the epoxy resin of the present invention will be exemplified. The epoxy resin of the present invention reacts the (meth) allyl ether resin represented by the formula (1) and hydrogen peroxide in the presence of a tungstic acid compound, an organic carboxylic acid, and a phosphoric acid compound. Is obtained.

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 amount of the tungstic acid compound used is preferably 1 × 10 ^{−6 to} 0.2 mol per mol of the (meth) allyl ether resin represented by the formula (1) from the viewpoint of improving the production rate of the epoxy group. 0.0001 to 0.2 mol is more preferable.

  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 organic carboxylic acids having 25 to 120 carbon atoms in the quaternary ammonium cation and having a linear carbon chain bonded to a carbon atom include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, and malonic acid. And succinic acid.

  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 (1) from the viewpoint of improving the production rate of the epoxy group. 4.0 moles is more preferred.

  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 AEP 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 per 100 parts by mass of the (meth) allyl ether resin represented by the formula (1) from the viewpoint of improving the production rate of the epoxy group. 500 parts by mass is more preferable.

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 mole per mole of the (meth) allyl ether resin represented by the formula (1) from the viewpoint of improving the production rate of the epoxy group. 05-0.5 mol is more preferable.

  The hydrogen peroxide to be reacted with the (meth) allyl ether resin represented by the formula (1) in the method for producing an epoxy resin of the present invention is not particularly limited, but is usually dissolved in water and added as hydrogen peroxide water. . 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 used is not particularly limited, but the amount of hydrogen peroxide is preferably from 0.3 to 10 mol, preferably from 1 to 6 mol, based on 1 mol of the allyl group of the (meth) allyl ether resin. Is more preferable. Since the amount of the hydrogen peroxide solution is 0.3 mol or more with respect to 1 mol of the methallyl group of the (meth) allyl ether resin, epoxidation can be advanced efficiently, and is 10 mol or less. Hydrolysis of the generated epoxy group can be suppressed.

  The production method of the epoxy resin of the present invention is not particularly limited, but the (meth) allyl ether is added to an organic solvent such as toluene, xylene, mesitylene, dimethoxyethane, ethyl acetate, tetrahydrofuran, etc. in which the (meth) allyl ether resin can be dissolved. It is preferable to start the epoxidation reaction by adding a hydrogen peroxide solution after adding the resin, tungstic acid compound, and 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, (meth) allyl of (meth) allyl ether resin The carbon-carbon double bond in the group 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, 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 amount of resin methyl isobutyl ketone, perform liquid separation with 1 times the amount 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.

<Curable resin composition>
The curable resin composition of the present invention contains a curing catalyst (curing accelerator) and / or a curing agent in addition to the (meth) allyl ether resin of the present invention or the epoxy resin of the present invention. Moreover, another epoxy resin can be contained as an arbitrary component.

  When the curable resin composition of the present invention contains the epoxy resin of the present invention, another epoxy resin can be used in combination. 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, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetate Enone, 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, and 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 curable resin composition of the present invention include amine compounds such as triethylamine, tripropylamine, and tributylamine, pyridine, dimethylaminopyridine, and 1,8-diazabicyclo [5.4.0] undeca. -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′-methyl Imidazole ( 1 ′)) ethyl-s-triazine, 2,4-diamino-6 (2′-undecylimidazole (1 ′)) ethyl-s-triazine, 2,4-diamino-6 (2′-ethyl, 4- 2 of methylimidazole (1 ′)) ethyl-s-triazine, 2,4-diamino-6 (2′-methylimidazole (1 ′)) ethyl-s-triazine isocyanuric acid adduct, 2-methylimidazole isocyanuric acid : 3-adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3,5-dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3, Various heterocyclic compounds such as 5-dicyanoethoxymethylimidazole, and these heterocyclic compounds and phthalic acid, isophthalic acid Salts with polyvalent carboxylic acids such as terephthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, maleic acid and succinic acid, amides such as dicyandiamide, 1,8-diaza-bicyclo (5.4.0) undecene Diaza compounds such as -7 and salts thereof such as tetraphenylborate and phenol novolac, salts with the above polyvalent carboxylic acids or phosphinic acids, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetra Butylammonium hydroxide, trimethylethylammonium hydroxide, trimethylpropylammonium hydroxide, trimethylbutylammonium hydroxide, trimethylcetylammonium hydroxide, trioctylmethyl Ammonium salts such as tylammonium hydroxide, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium acetate, trioctylmethylammonium acetate, triphenylphosphine, tri (tolyl) phosphine, tetraphenylphosphonium bromide Phosphines and phosphonium compounds such as tetraphenylphosphonium tetraphenylborate, phenols such as 2,4,6-trisaminomethylphenol, amine adducts, carboxylic acid metal salts (2-ethylhexanoic acid, stearic acid, behenic acid, Zinc salts such as myristyl acid, tin salts, zirconium salts) and phosphate metal (zinc salts such as octyl phosphate and stearyl phosphate), alcohol Shi 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.
The curing catalyst is used in an amount of 0.01 to 5.0 parts by mass based on 100 parts by mass of the epoxy resin.

As the curing agent used in the curable resin composition of the present invention, for example, a known curing agent such as an amine compound, an acid anhydride compound, an amide compound, a phenol compound, or a carboxylic acid compound may be used. Specific examples thereof 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, phenols (phenol, alkyl-substituted phenol) , Naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphth ) 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. Limited to is not. These may be used alone or in combination of two or more.

  In the curable 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 per 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 resin include 2,2-bis (4-cyanatephenyl) propane, bis (3,5-dimethyl-4-cyanatephenyl) methane, 2,2-bis (4-cyanatephenyl) ethane, 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 curable 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 Contains phosphorus 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 content of the phosphorus-containing compound is preferably phosphorus-containing compound / total epoxy resin = 0.1 to 0.6 (mass 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, binder resin can also be mix | blended with the curable 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 mass, preferably 100 parts by mass with respect to the total of the epoxy resin and the curing agent. 0.05-20 mass parts is used as needed.

An inorganic filler can be added to the curable resin composition of the present invention as necessary.
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. The content of these inorganic fillers is generally in the curable resin composition of the present invention, although depending on the use, an amount generally occupying 0 to 95% by mass is used. Is preferably in the range of 50 to 95 mass%, particularly preferably 65 to 95 mass%, depending on the shape of the package. Furthermore, the curable resin composition of the present invention includes various additives such as antioxidants, light stabilizers, silane coupling agents, mold release agents such as stearic acid, palmitic acid, zinc stearate, calcium stearate, and 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 curable resin composition of this invention is obtained by mixing each component uniformly. The curable 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 curable resin composition is obtained. If the resulting curable resin composition is in liquid form, the composition is impregnated into the substrate or poured into a mold by potting or casting. It is cast and cured by heating. When the obtained curable 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 curable 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 a curable resin composition varnish, glass fiber, A cured product of the curable resin composition of the present invention is obtained by hot press molding a prepreg obtained by impregnating a substrate such as carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, and the like, followed by heating and drying. It can be. The solvent in this case is usually 10 to 70% by mass, preferably 15 to 70% by mass in the mixture of the curable resin composition of the present invention and the solvent.

  Moreover, the curable resin composition of this invention can also be used as a film type sealing composition. When obtaining such a film-type resin composition, the curable resin composition of the present invention is coated on the release film with the varnish, the solvent is removed under heating, and a B-stage adhesive is formed. Get. 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 with which functionality, such as a network board | substrate and a module board, is calculated | required.

The curable 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 curable resin composition of the present invention. The molding temperature and molding method are as described above.

  Since the carbon fiber reinforced composite material produced using the curable resin composition of the present invention is lightweight and has excellent resistance to external impacts, the fuselage, main wing, tail wing, and moving wing Aircraft parts such as fairings, cowls, doors, seats and interior materials; spacecraft parts such as motor cases and main wings; satellite members such as structures and antennas; automotive parts such as skins, chassis, aerodynamic members and seats; It can be suitably used for many structural materials such as railway vehicle members such as structures and seats; ship members such as hulls and seats.

The present invention includes the curable resin composition containing the (meth) allyl ether resin of the present invention and various resins and / or curing accelerators, and the cured product thereof is also included in the present invention.
Specific examples of resins that can be combined include hydrosilylation materials as described in JP2003-073552A and curing accelerators thereof, thiol compounds as described in JP2011-052148A and / or their Examples thereof include a curing accelerator and a commercially available bismaleimide compound.

Specific examples of the curing accelerator include radical polymerization initiators.
The radical polymerization initiator is not particularly limited. For example, a commonly used radical polymerization initiator can be used in addition to tert-amyl peroxypivalate and AIBN. For example, tert-butyl peroxyacetate, tert -Butylperoxyisobutyrate, tert-butylperoxypivalate, tert-butylperoxyoctoate, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxyneodecanoate, dicumyl peroxide Tert-amyl peroxyneodecanoate, tert-amyl peroxyoctoate, tert-amylperoxy-2-ethylhexanoate, tert-amylperoxyneodecanoate, tert-butylperoxybenzoate Benzoyl peroxide, lauroyl peroxide, isobutyryl peroxide, succinic peroxide, di-tert-butyl peroxide, isobutyl peroxide, 2,2'-azobis-2,4-dimethylvaleronitrile, 2,2'- Azobis- (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis-2-methylbutyronitrile and the like can be mentioned.
Only 1 type may be used for a radical polymerization initiator and it may use 2 or more types together.

  The usage-amount of a radical polymerization initiator is about 0.1-10 mass% normally with respect to 100 mass% of monomer compositions to be used, Preferably it is 0.3-7 mass%.

  The curable resin composition of the present invention may be combined with the inorganic filler, phosphorus-based flame retardant, various binder resins, organic solvents and the like described above.

  The curable resin composition of this invention is obtained by mixing each component uniformly. For example, meta) allyl ether resins use various resins and / or curing accelerators and, if necessary, phosphorus-containing compounds, binder resins, inorganic fillers, compounding agents, etc., if necessary using an extruder, kneader, roll, planetary mixer, etc. Mix thoroughly until uniform to obtain a curable resin composition. If the resulting curable resin composition is liquid, the substrate is impregnated by potting or casting, or a mold is formed. It is poured into a mold, casted, and cured by heating. When the obtained curable 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, for example, 100 to 250. As a curing method, curing can be performed at a high temperature at a stretch, but since there is also volatilization of a low molecular weight, it is preferable to increase the temperature stepwise to advance the curing reaction. Specifically, initial curing is performed between 100 ° C. and 200 ° C., and post curing is performed between 200 ° C. and 250 ° C. As the curing stage, the temperature is preferably divided into 2 to 8 stages, more preferably 2 to 4 stages.

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: Conforms to JIS K 7117-2 (ISO 3219) Softening point: Conforms to JIS K 7234 Total chlorine:
Automatic sample combustion-ion chromatograph AQF-2100H type manufactured by Mitsubishi Chemical Co., Ltd. After combustion decomposition with an argon gas flow rate of 200 ml / min and an oxygen gas flow rate of 400 ml / min, ion content is measured HPLC:
Column (Inertsil ODS-2)
The coupled eluent was tetrahydrofuran and 5 mM phosphoric acid aqueous solution. The flow rate was 1.0 ml / min.
Column temperature is 40 ° C

Example 1
In a flask equipped with a stirrer, a reflux condenser, and a stirrer, 720 parts by mass of dimethyl sulfoxide, 535 parts by mass of phenol resin (phenol-dicyclopentadiene type hydroxyl group equivalent 178 g / eq. Softening point 106 ° C.), methallyl chloride (purity) 99% (manufactured by Tokyo Chemical Industry Co., Ltd.) 299 parts by mass (1.1 molar equivalents relative to 1 molar equivalent of the hydroxyl group of the phenol resin) was added, and the mixture was heated to 27 ° C. and dissolved. Next, 134 parts by mass of a 46.3% by mass aqueous sodium hydroxide solution was slowly added so that the internal temperature did not exceed 35 ° C., and then 70.0 parts by mass of flaky caustic soda (purity 99%, manufactured by Tosoh) (hydroxyl group 1 of phenol resin) 1.1 molar equivalents to molar equivalents) was added over 60 minutes. The reaction was carried out at 30-35 ° C for 4 hours, at 40-45 ° C for 1 hour, and at 55-60 ° C for 1 hour. Reaction tracking at this time was performed using HPLC, and it was confirmed that the disappearance of the raw material phenol resin and the peak between n = 1 and n = 2 peaks did not increase.
After completion of the reaction, water, dimethyl sulfoxide and the like were distilled off by heating on a rotary evaporator at 120 ° C. or lower under reduced pressure. And 30 mass parts of acetic acid was added and neutralized, 700 mass parts of methyl isobutyl ketone was added, and water washing was repeated, and it confirmed that the water layer became neutral. Then, 690 parts by mass of the methallyl ether resin (hereinafter referred to as “MEP1”) of the present invention in which n = 2.0 is obtained by distilling off the solvents from the oil layer using a rotary evaporator while bubbling nitrogen under reduced pressure. It was.

Example 2
658 parts by mass of MEP obtained in Example 1 and 720 parts by mass of toluene were charged into a flask equipped with an agitator, a reflux condenser, and an agitator while purging nitrogen, and potassium tungstate as a tungstate compound. 36 parts by mass, 36 parts by mass of tripotassium phosphate as a phosphoric acid compound, and 432 parts by mass of acetic acid as an organic carboxylic acid per 1100 parts by mass of MEP were added, and this mixture was heated to 50 ° C. After the temperature rise, with stirring, a 35% aqueous hydrogen peroxide solution was added over 20 minutes in an amount that resulted in 2.1 molar equivalents of hydrogen peroxide per 1 molar equivalent of methallyl groups in MEP. After completion of the addition, the mixture was stirred at 50 ° C. for 24 hours.
Subsequently, 360 parts by mass of methyl isobutyl ketone was added to perform a liquid separation washing treatment, 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 255 g / eq. The ICI melt viscosity at a softening point of 76 ° C. and 150 ° C. was 0.19 Pa · s, and the total chlorine content was 10 ppm or less.

Example 3, Comparative Example 1
Using the epoxy resin (EP1) of the present invention obtained in Example 1 and a comparative epoxy resin (EP2: phenol-dicyclopentadiene type epoxy resin XD-1000 manufactured by Nippon Kayaku Co., Ltd.), curing with the epoxy resin Agent (phenol resin (Miwa Kasei Co., Ltd. H-1) is blended in equal equivalents, curing catalyst (curing accelerator, triphenylphosphine (TPP, Tokyo Chemical Industry Co., Ltd.)) is added, mixing roll The curable resin composition was mixed and kneaded uniformly to obtain a curable resin composition, which was pulverized with a mixer and then tableted with a tablet machine. The obtained curable resin composition was transfer-molded (175 ° C. × 60 seconds), and after demolding, 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. Moreover, the kind of hardening | curing agent to be used was as shown in following Table 1 with the evaluation item of the physical property of hardened | cured material.
<Bending elasticity test>
・ Tested at room temperature according to JIS K 6911.
<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 width × 100 mm length, and the thickness was 1.7 mm.

(Table 1)

  From Table 1, the cured product using the epoxy resin obtained by oxidizing the (meth) allyl ether resin of the present invention is a cured product excellent in low dielectric properties and toughness compared to a cured product using a comparative epoxy resin. It can be confirmed that there is.

Example 4
The methallyl ether compound described in Example 2 was subjected to two-stage step cure of 180 ° C. × 2 hours and 230 ° C. × 4 hours to obtain a black solid cured product of the present invention. The obtained cured product was pulverized, and the thermal decomposition characteristics of the cured product were measured.

In addition, the physical property of hardened | cured material was measured in the following ways.
<Pyrolysis characteristics>
・ TG / DTA6200 (manufactured by SII)
Temperature range: 30-550 ° C
Temperature increase rate: 10 ° C / min
Gas flow: Air 200ml / min
Sample shape: powder (particle size 50-150 μm)
Td 5-30: The temperature (° C.) at the time of 5-30 mass% reduction was measured.

(Table 2)

From Table 2, it can confirm that the hardened | cured material of the curable resin composition containing the (meth) allyl ether resin of this invention is a hardened | cured material which is excellent in a thermal decomposition characteristic.

Claims (6)

(Meth) 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, each a represents 1 to 3; n is a repeating number of 1 to 10; The average value of n represents a real number of 1 to 10.) An epoxy resin represented by the following formula (2).

(In the formula, each R ₁ independently represents an alkyl group, each R ₂ independently represents a hydrogen atom or an alkyl group, each a represents 1 to 3; n is a repeating number of 1 to 10; The average value of n represents a real number of 1 to 10.)   An epoxy resin obtained by oxidizing the (meth) allyl ether resin according to claim 1.   A curable resin composition comprising the (meth) allyl ether resin according to claim 1.   A curable resin composition comprising the epoxy resin according to claim 2 or 3 and a curing agent and / or a curing catalyst. A cured product obtained by curing the curable resin composition according to claim 4.