JP2016204647A - Polyfunctional epoxy resin and intermediate, epoxy resin composition, and cured product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an epoxy resin that has low viscosity, excellent moldability and workability, and low toxicity, and when cured, gives a cured product having excellent heat resistance.SOLUTION: The present invention provides a polyfunctional epoxy resin represented by general formula (1) (where A is a C3-C20, optionally-substituted, and monocyclic alicyclic hydrocarbon, Xs independently represent a glycidyl group or a glycidyloxy group, Rs independently represent a C1-C4 alkyl group, mand mare an integer of 0-2, nand nare 1 or 2).SELECTED DRAWING: None

Description

  The present invention relates to a novel polyfunctional epoxy resin and an intermediate thereof, an epoxy resin composition containing the resin, and a cured product obtained by curing the epoxy resin composition. In particular, the present invention relates to an epoxy resin composition having a low viscosity, excellent moldability and processability, low toxicity, and a cured product having excellent heat resistance when cured.

Epoxy resins are excellent in heat resistance, adhesiveness, water resistance, mechanical strength, and electrical properties, so they are used in various fields such as adhesives, paints, materials for civil engineering and construction, and insulation materials for electrical and electronic equipment. It is used. In particular, in the electric / electronic field, it is widely used in insulating materials, laminated materials, sealing materials and the like.
In recent years, especially for electrical and electronic equipment materials such as multilayer circuit boards, the miniaturization, weight reduction, and high functionality of equipment have progressed, and further multilayering, high density, thinning, weight reduction, reliability, and Improvements in molding processability and the like are required. In addition, improvement in heat resistance has been demanded for epoxy resins used in these applications. Therefore, in order to satisfy these requirements, an epoxy resin having a low viscosity when melted and excellent in heat resistance when cured is required.

Multifunctionalization is known as a technique for improving the heat resistance of an epoxy resin. This is because by increasing the number of epoxy groups in one resin molecule, the number of cross-linking points between the epoxy resin and the cured product increases, and a stronger network can be formed. As one of the polyfunctionalization methods, Patent Document 1 describes a method in which a benzene ring having a 2-allyloxy group and a 2-allyl group is repeatedly crosslinked to oxidize a double bond. As the compound, phenol novolac is mentioned. Specific examples of the crosslinking moiety is _{-CH 2 -C 6 H 4 -C 6} H 4 -CH 2 - _{group, -CH 2 -C 6 H 4 -CH} 2 - group, tetrahydrofuryl dicyclopentadienyl group, Alternatively, an unsubstituted tetrahydrodicyclopentadienyl group in which CH ₂ is bonded to both ends is mentioned. As another method, Patent Document 2 discloses a tetrafunctional epoxy resin obtained by glycidylation of a hydroxyl group of biscatechol having a fluorene group in the molecule. Patent Document 3 includes a tetrafunctional epoxy resin obtained by glycidylating a hydroxyl group of bisresorcinol having an adamantyl group in the molecule.

JP 2014-240376 A JP 2005-041925 A Japanese Patent No. 51222982

However, a phenol novolac type polyfunctional epoxy resin obtained by repeatedly crosslinking a benzene ring having a glycidyloxy group and a glycidyl group described in Patent Document 1 has high heat resistance, and has a high viscosity at the time of melting. There are problems in moldability and processability. Further, the bisphenol A and bisphenol F type tetrafunctional epoxy resins also cited in Patent Document 1 have a low viscosity because they do not have a repetitive structure, but have a low epoxy equivalent and have a problem in toxicity to workers.
In addition, a tetrafunctional epoxy resin made from biscatechol having fluorene in the molecule described in Patent Document 2 is excellent in heat resistance and has a high epoxy equivalent and low toxicity, but has a high viscosity at the time of melting. It is expected that. Moreover, the tetrafunctional epoxy resin obtained by glycidylating the hydroxyl group of bisresorcinol having an adamantyl group in the molecule described in Patent Document 3 is expected to have a high melting point. Therefore, these epoxy resins are considered to have problems in moldability and processability. Accordingly, an object of the present invention is to provide an epoxy resin that has a low viscosity, excellent moldability and processability, low toxicity, and becomes a cured product having excellent heat resistance when cured.

As a result of intensive investigations to solve the above problems, the present inventors have found that a specific polyfunctional epoxy resin having a monocyclic alicyclic hydrocarbon as a partial structure solves this problem, and the present invention Reached.
That is, the gist of the present invention is as follows.
[1] A polyfunctional epoxy resin represented by the following general formula (1).

(In the formula, A is an optionally substituted monocyclic alicyclic hydrocarbon having 3 to 20 carbon atoms, X is independently a glycidyl group or a glycidyloxy group, and R is independently an alkyl group having 1 to 4 carbon _atoms, m 1, _{m 2} represents an integer of 0 to _2, n 1, _{n 2} is 1 or 2.)
[2] The polyfunctional epoxy resin according to [1], wherein A in the general formula (1) is an optionally substituted monocyclic alicyclic hydrocarbon having 7 to 20 carbon atoms.
[3] The polyfunctional epoxy resin according to [1], wherein A in the general formula (1) is a monocyclic alicyclic hydrocarbon having 4 to 20 carbon atoms having an alkyl group as a substituent.
[4] The polyfunctional epoxy resin according to any one of [1] to [3], wherein X in the general formula (1) is a glycidyl group.
[5] The polyfunctional epoxy resin according to any one of [1] to [3], wherein X in the general formula (1) is a glycidyloxy group.
[6] An allyl compound represented by the following general formula (9).

(In the formula, A and m ₁ , m ₂ , n ₁ and n ₂ are the same as those in the general formula (1).)
[7] An epoxy resin composition comprising the polyfunctional epoxy resin according to any one of [1] to [5].
[8] A cured product obtained by curing the epoxy resin composition of [7].

ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the epoxy resin used as the hardened | cured material which is low viscosity, excellent in a moldability and workability, is low toxicity, and was excellent in heat resistance when it hardened.

Embodiments of the present invention will be described in detail below. However, the following description is an example of the embodiments of the present invention, and the present invention is not limited to the following descriptions unless it exceeds the gist. It is not something.
[1. Epoxy resin]
The polyfunctional epoxy resin of the present invention is represented by the following general formula (1).

(In the formula, A is an optionally substituted monocyclic alicyclic hydrocarbon having 3 to 20 carbon atoms, X is independently a glycidyl group or a glycidyloxy group, and R is independently an alkyl group having 1 to 4 carbon _atoms, m 1, _{m 2} represents an integer of 0 to _2, n 1, _{n 2} is 1 or 2.)
In general formula (1), A represents a monocyclic alicyclic hydrocarbon having 3 to 20 carbon atoms which may be substituted. In the present specification, the “optionally substituted monocyclic alicyclic hydrocarbon having 3 to 20 carbon atoms” means the total of the monocyclic alicyclic hydrocarbon constituting A and its substituents. It means that the carbon number is 3-20. The number of carbon atoms is preferably large for the purpose of reducing toxicity or water absorption, whereas it is preferably small for the purpose of improving processability by reducing the viscosity. Therefore, the carbon number of A is preferably 5 or more, and more preferably 7 or more. Moreover, 15 or less is preferable and 10 or less is more preferable.
When A is a monocyclic alicyclic hydrocarbon, the skeleton becomes rigid as compared with the case where A is a chain hydrocarbon, and thus the heat resistance when cured is increased. In addition, the crystallinity is lowered as compared with the case where A is a condensed ring hydrocarbon, and it is easy to melt at the temperature at the time of curing. Furthermore, since A has a lower viscosity than when A is a monocyclic aromatic hydrocarbon, processability and moldability are improved.

Monocyclic alicyclic hydrocarbons include saturated monocyclic structures such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cyclododecane, and cyclopentadecane; unsaturated groups such as cyclopentene and cyclohexene Although there is a monocyclic structure, a saturated monocyclic structure is preferable because synthesis is easy. Among these, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cyclododecane, and cyclopentadecane are preferable, and cyclohexane, cycloheptane, and cyclooctane are more preferable.

The substituent that the monocyclic alicyclic hydrocarbon may have can be appropriately selected depending on the application. In epoxy resins, it is known that the greater the epoxy equivalent, the lower the toxicity. Therefore, it is preferable that A has a substituent for the purpose of reducing toxicity. Toxicity includes skin sensitization, eye irritation and mutagenicity. Specific examples of the substituent include saturated linear alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-hexyl group; an isopropyl group, an iso-butyl group, a sec-butyl group, Saturated branched alkyl group such as tert-butyl group; alkenyl group such as vinyl group, 1-propenyl group, allyl group, 1-methylethenyl group, 1-butenyl group, 2-butenyl group, 2-methyl-1-propenyl group Alkynyl groups such as ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group and 2-butynyl group; saturated cyclic alkyl groups such as cyclopropyl group, cyclopentyl group and cyclohexyl group; cyclopentenyl group and cyclohexenyl An unsaturated cyclic alkyl group such as a phenyl group; an aryl group such as a phenyl group, a 4-methylphenyl group and a naphthyl group; a hydroxyl group; Group, substituted or unsubstituted amino group such as methylamino group and dimethylamino group; thiol group; alkoxy group such as methoxy group and ethoxy group; thioether group such as methylthio group and ethylthio group; chloro group and bromo group A halogen group is mentioned. For the purpose of improving the heat resistance of the cured product, an alkyl group, an aryl group, a hydroxyl group, an unsubstituted amino group, and a thiol group are preferable. For the purpose of reducing the viscosity, an alkyl group, an alkoxy group, and a thioether group are preferable. Therefore, from the viewpoint of achieving both high heat resistance and low viscosity, an alkyl group is preferable, an alkyl group having 1 to 4 carbon atoms is more preferable, and a methyl group is more preferable. In addition, a saturated linear alkyl group and a saturated branched alkyl group are preferable because of easy synthesis, and a saturated linear alkyl group is more preferable from the viewpoint of obtaining raw materials, and a methyl group is more preferable.

  Specific examples of A include an unsubstituted saturated monocyclic group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononane group, a cyclodecane group, a cyclododecane group, and a cyclopentadecane group. 2,2,4-trimethylcyclopentyl group, 2,4,4-trimethylcyclopentyl group, 2-hexylcyclopentyl group, 2-heptylcyclopentyl group, 2-cyclopentylcyclopentyl group, 2-chlorocyclopentyl group, 2-acetylpentyl group; 3-methylcyclohexyl group, 4-methylcyclohexyl group, 5-methylcyclohexyl group, 2,6-dimethylcyclohexyl group, 2,5-dimethylcyclohexyl group, 3,5-dimethylcyclohexyl group, 3,3-dimethylcyclohexyl 4,4-dimethylcyclohexyl group, 3,3,5-trimethylcyclohexyl group, 4-ethylcyclohexyl group, 4-propylcyclohexyl group, 4-sec-butylcyclohexyl group, 4-tert-butylcyclohexyl group, 2-cyclohexyl Substituted saturated monocyclic groups such as cyclohexyl group, 2-cyclohexenylcyclohexyl group, menthyl group, 2-methoxycyclohexyl group, 2-chlorocyclohexyl group; unsubstituted unsaturated groups such as 2-cyclopentenyl group and 2-cyclohexenyl group Monocyclic groups; substituted unsaturated monocyclic groups such as 3-methyl-2-cyclopentenyl group, 3-pentyl-2-cyclopentenyl group, 3-methyl-2-cyclohexenyl group, and isophoronyl group.

  Among them, 2,2,4-trimethylcyclopentyl group, 2,4,4-trimethylcyclopentyl group, 2-hexylcyclopentyl group, 2-heptylcyclopentyl group, 2-cyclopentylcyclopentyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group 5-methylcyclohexyl group, 2,6-dimethylcyclohexyl group, 2,5-dimethylcyclohexyl group, 3,5-dimethylcyclohexyl group, 3,3-dimethylcyclohexyl group, 4,4-dimethylcyclohexyl group, 3,3 , 5-trimethylcyclohexyl group, 4-ethylcyclohexyl group, 4-propylcyclohexyl group, 4-sec-butylcyclohexyl group, 4-tert-butylcyclohexyl group, 2-cyclohexylcyclohexyl group, 2-cyclohexenyl group Alkyl group-substituted saturated monocyclic groups such as a cyclohexyl group and a menthyl group are preferred, and 2,2,4-trimethylcyclopentyl group, 2,4,4-trimethylcyclopentyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, 5-methylcyclohexyl group, 2,6-dimethylcyclohexyl group, 2,5-dimethylcyclohexyl group, 3,5-dimethylcyclohexyl group, 3,3-dimethylcyclohexyl group, 4,4-dimethylcyclohexyl group, 3,3, A methyl group-substituted saturated monocyclic group such as a 5-trimethylcyclohexyl group is more preferable.

In the general formula (1), X represents a glycidyl group or a glycidyloxy group. Regardless of which is selected, the heat resistance of the cured product does not vary greatly, but can be appropriately selected depending on the application. The glycidyl group is preferable because it not only has a lower viscosity than the glycidyloxy group, but also has a low oxygen functional group, so that the water absorption of the cured product can be kept low. On the other hand, a glycidyloxy group is preferable because it can be synthesized in a short process compared to a glycidyl group and has a large amount of oxygen functional groups, and thus has high adhesion to a metal or the like.

In general formula (1), the bonding position of the glycidyloxy group and X on the benzene ring is not particularly limited. From the viewpoint of easy synthesis, the glycidyloxy group is bonded to the para position of the carbon atom bonded to A. X is preferably bonded to the carbon atom adjacent to the carbon atom to which the glycidyloxy group is bonded. Moreover, in order to raise the reactivity at the time of hardening, it is preferable that a glycidyloxy group and X are the meta position of the carbon atom couple | bonded with A, or a para position.
In general formula (1), n ₁ and n ₂ each independently represent 1 or 2. In order to improve heat resistance, polyfunctionality is preferable. However, if there are too many epoxy groups, epoxy groups remain in the cured product, and heat resistance may be lowered. Therefore, n ₁ and n ₂ are 1 is preferable. Further, n ₁ and n ₂ are preferably 1 in order to reduce viscosity and toxicity. N ₁ and n ₂ may be the same or different, but n ₁ and n ₂ are preferably the same from the viewpoint of easy synthesis.

In General Formula (1), R represents a C1-C4 alkyl group each independently, It is preferable that it is C1-C2 from the ease of raw material acquisition, and a methyl group is more preferable.
In the general formula (1), m ₁ and m ₂ represent integers of 0 to 2, preferably 0 or 1, and most preferably 0 for ease of synthesis.
The theoretical epoxy equivalent of the polyfunctional epoxy resin of the present invention is preferably as large as possible from the viewpoint of reducing toxicity, and is preferably as small as possible for the purpose of improving heat resistance. Specifically, it is preferably 115 or more, more preferably 120 or more, and particularly preferably 130 or more. On the other hand, it is preferably 170 or less, more preferably 150 or less, and particularly preferably 140 or less. Here, the theoretical epoxy equivalent represents a value (unit is g / equivalent) obtained by dividing the molar mass of the molecule in the general formula (1) by the number of epoxy groups in the general formula (1).
Specific examples of general formula (1) are shown below.

  Among these, the following compounds are preferable.

  In particular, the following compounds are preferable.

[2. Manufacturing method]
The manufacturing method of the polyfunctional epoxy resin of this invention is not specifically limited, According to the substrate to be used and a desired physical property, it can manufacture suitably. Hereinafter, typical production methods will be described.
<2.1. Manufacturing method I>
The polyfunctional epoxy resin represented by the general formula (1) can be produced by a method of oxidizing the double bond contained in the allyl compound represented by the following general formula (2).

In general formula (2), A, R, m ₁ , m ₂ , n ₁ , and n ₂ are the same as in general formula (1), and each Y independently represents a 2-allyl group or 2-allyloxy group. Show.
The oxidation method is not particularly limited as long as the polyfunctional epoxy resin of the present invention can be obtained, and can be performed by a known method. For example, specifically, a method using a nitrile and a hydrogen peroxide solution in the presence of a base (hereinafter referred to as oxidation method i), a method using a quaternary ammonium salt and a hydrogen peroxide solution in the presence of tungstic acids (hereinafter referred to as an oxidation method ii). ), A method using an organic peracid such as peracetic acid or m-chlorobenzoic acid (hereinafter referred to as oxidation method iii) and the like, and a method can be appropriately selected according to the properties of the epoxy resin. Among them, the oxidation method i and the oxidation method ii can use inexpensive hydrogen peroxide as an oxidizing agent, and are preferable from the environmental viewpoint because the by-product is water. Furthermore, since the oxidation method ii can be carried out in a two-layer system in which the aqueous layer and the organic layer are separated, the ring opening reaction of the epoxy group can be suppressed. Further, it is not necessary to use excessive hydrogen peroxide as compared with the oxidation method i. Therefore, the oxidation method ii is more preferable.

<2.2. Manufacturing Method II>
Among the general formula (1), the following general formula (4) in which X is a glycidyl group can be produced by a method of oxidizing a double bond contained in the epoxy resin represented by the following general formula (3).

In General Formula (3) and General Formula (4), A, R, m ₁ , m ₂ , n ₁ , and n ₂ are the same as in General Formula (1).
The oxidation is the same as in production method I.

<2.3. Manufacturing Method III>
Of the general formula (1), the general formula (6) in which X is a glycidyloxy group can also be produced by glycidylating a phenol compound represented by the following general formula (5) using an epihalohydrin.

A, R, m ₁ , m _2, n ₁ , and n ₂ in the general formula (5) and the general formula (6) are the same as those in the general formula (1).
The method for glycidylation is not particularly limited, but any one of the conventionally known one-stage method or two-stage method may be used. The one-step method can be carried out by reacting epihalohydrin in the presence of a base. The two-stage process can be carried out by adding an epihalohydrin in the presence of an acid catalyst, followed by hydrohalation using a base. Epihalohydrin includes epichlorohydrin and epibromohydrin, but epichlorohydrin is preferably used from the viewpoint of availability and low cost.

When the polyfunctional epoxy resin of the present invention is produced by any of the above production methods I to III, the polyfunctional epoxy resin of the present invention may contain unreacted raw materials and various reaction byproducts. For example, in glycidylation, oligomers are formed and the viscosity of the resin tends to increase. Therefore, for the purpose of lowering the viscosity, production method I which does not go through glycidylation is preferable.
Furthermore, when X is a glycidyloxy group, in Production Method III, a side reaction in which adjacent hydroxyl groups form a cyclic structure via an epihalohydrin tends to occur. Since this prevents the polyfunctionalization, the production method I is preferable also from the viewpoint of heat resistance. On the other hand, when X is a glycidyl group, since the amount of double bonds to be oxidized is smaller in production method II than in production method I, the amount of oxidizing agent to be used can be reduced. Therefore, production method II is preferable from the viewpoint of safety. Moreover, since the reaction time required for oxidation can be shortened, side reactions such as an epoxy ring opening reaction can be suppressed. Therefore, production method II is preferable from the viewpoint of yield.

<2.4. Oxidation method i>
The oxidation method i will be described. Oxidation method i is a method performed with a nitrile and an aqueous hydrogen peroxide solution in the presence of a base.
Examples of the base used in the reaction include alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal salts, alkaline earth metal salts, and the like. Among these, alkali metal salts are preferable.

  Specific examples of the alkali metal salt include phosphorous such as disodium phosphate, dipotassium phosphate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium diphosphate, sodium tripolyphosphate, sodium hexametaphosphate, and sodium polyphosphate. Acid alkali metal salts, potassium carbonate, potassium hydrogen carbonate, sodium carbonate, sodium hydrogen carbonate, lithium carbonate, cesium carbonate and other alkali metal carbonates, organic acid alkali metal salts such as sodium acetate, potassium acetate, potassium sulfate, sodium sulfate, etc. And alkali metal silicates such as potassium silicate and sodium silicate. Among these, alkali metal carbonates are preferable from the viewpoint of reactivity, and potassium carbonate and sodium carbonate are particularly preferable. These may be used individually by 1 type and may use 2 or more types together by arbitrary combinations.

  The amount of the base used is not particularly limited, but is preferably 0.05 equivalents or more, more preferably 0.1 equivalents or more, and still more preferably, with respect to 1 equivalent of the carbon-carbon double bond in the allyl compound used as a raw material. It is 0.2 equivalents or more, preferably 5 equivalents or less, more preferably 2 equivalents or less, and even more preferably 1 equivalent or less. When the amount used is less than 0.05 equivalent, the reaction does not proceed sufficiently, and when the amount used is more than 5 equivalents, hydrogen peroxide is decomposed and the reactivity tends to decrease.

  The nitrile may be either an aliphatic nitrile or an aromatic nitrile. Examples of the aliphatic nitriles include acetonitrile, propionitrile, n-butyronitrile, isobutyronitrile, malononitrile, adiponitrile, monochloroacetonitrile, dichloroacetonitrile, trichloroacetonitrile, and the like. Examples of aromatic nitriles include benzonitrile, tolunitrile, chlorobenzonitrile, and fluorobenzonitrile. Acetonitrile, propionitrile, and benzonitrile are preferable from the viewpoint that reactivity is high and by-products derived from nitrile can be easily removed, and acetonitrile is particularly preferable. Moreover, these may be used individually by 1 type and may use 2 or more types together by arbitrary combinations.

  The amount of nitrile used is not particularly limited and varies depending on the type of allyl compound or base used as a raw material, reaction conditions, etc., but preferably 1 equivalent per 1 equivalent of carbon-carbon double bond in the allyl compound used as a raw material. More preferably, it is 1.5 equivalents or more, preferably 10 equivalents or less, more preferably 5 equivalents or less. When the amount used is less than 1 equivalent, the reaction does not proceed sufficiently, and when the amount used is more than 10 equivalents, the reactivity tends to decrease. In addition, when introducing hydrogen peroxide water additionally, it is preferable to add 1 equivalent-2 equivalent nitrile with respect to hydrogen peroxide additionally.

  The concentration of hydrogen peroxide introduced into the reaction solution is not particularly limited, but is preferably 10% or more, more preferably 20%, and preferably 60% or less, more preferably 50% or less. If the concentration is lower than 10%, the reaction rate and batch efficiency are reduced. If the concentration is higher than 60%, it becomes difficult to control the internal temperature during the reaction or abnormal hydrogen peroxide decomposition occurs. It tends to be easier and the risk increases.

  The amount of hydrogen peroxide used is not particularly limited and varies depending on the type of allyl compound or base used as a raw material, reaction conditions, etc., but peroxidation is performed on one equivalent of the carbon-carbon double bond in the allyl compound used as a raw material. In terms of hydrogen, it is preferably 1 equivalent or more, more preferably 2 equivalents or more, and preferably 20 equivalents or less, more preferably 10 equivalents or less. When the amount used is less than 1 equivalent, the reaction does not proceed sufficiently, and when the amount used is more than 20 equivalents, in addition to controlling the reaction and ensuring safety, it tends to be difficult to recover the generated epoxy resin. .

Hydrogen peroxide is quickly consumed in the epoxidation reaction, so even if the required amount of hydrogen peroxide is added all at once, the concentration of hydrogen peroxide in the system does not increase too much. It is preferable to add in portions or continuously.
A solvent can also be used for the reaction. Although the solvent to be used is not particularly limited, for example, alcohols such as methanol, ethanol, propanol and isopropanol; ketones such as acetone and methyl ethyl ketone; amides such as N, N-dimethylformamide and N, N-dimethylacetamide; Examples include 1,2-dimethoxyethane and diethylene glycol dimethyl ether. These may be used individually by 1 type and may use 2 or more types together by arbitrary combinations. Among these, alcohols, particularly methanol, is preferable in terms of miscibility with water and availability at low cost.

The amount of the solvent used is not particularly limited, but if it is small, the raw materials are not mixed in the system and the reactivity tends to decrease. On the other hand, if the amount is large, the concentration of the reaction substrate in the system tends to decrease, and the reaction rate tends to decrease. Therefore, it is preferably 1 to 100 parts by weight, more preferably 2 to 50 parts by weight, with respect to 1 part by weight of the allyl compound used as a raw material.
Although reaction temperature is not specifically limited, Preferably it is 0 degreeC or more, More preferably, it is 20 degreeC or more, Preferably it is 100 degrees C or less, More preferably, it is 80 degrees C or less, More preferably, it is 50 degrees C or less. When it exceeds 100 ° C., decomposition of hydrogen peroxide and hydrolysis of the generated epoxy resin tend to be promoted. If it is less than 0 ° C., a sufficient reaction rate cannot be obtained, and the reaction tends not to proceed completely.

The reaction time varies depending on the reaction scale and the like, but is usually 1 hour or more, preferably 2 hours or more, and can be selected from the range of usually 72 hours or less, preferably 24 hours or less.
As described above, in the oxidation method i, an allyl compound as a raw material is oxidized with a nitrile and an aqueous hydrogen peroxide solution in the presence of a base to produce an epoxy resin. The order of addition of these compounds is not particularly limited, but in a normal reaction, first the raw material allyl compound, base, and nitrile are mixed in a reaction solvent, and hydrogen peroxide is added dropwise while paying attention to the temperature of the mixture, followed by stirring. To do. Thereafter, if necessary, nitrile and hydrogen peroxide may be introduced. After the reaction, the remaining hydrogen peroxide is quenched with a reducing agent such as an aqueous sodium thiosulfate solution, and an ordinary operation such as washing with water or concentration is performed to obtain an epoxy resin. If necessary, purification by crystallization or column chromatography may be carried out.

<2.5. Oxidation method ii>
The oxidation method ii will be described. The oxidation method ii is a method of oxidizing with an onium salt and an aqueous hydrogen peroxide solution in the presence of tungstic acids.
Examples of tungstic acids include tungsten compounds and salts thereof. The tungsten compound is not particularly limited as long as it contains tungsten and has an action as a catalyst for the epoxidation reaction.

Specific examples of the tungstic acids include tungstic acid; tungstates such as sodium tungstate, potassium tungstate, calcium tungstate, and ammonium tungstate; hydrates of the tungstates; 12-tungstophosphoric acid Phosphotungstic acids such as 18-tungstophosphoric acid; silicotungstic acids such as 12-tungstosilicic acid; 12-tungstoboric acid or metal tungstens, and tungstic acid, tungstate and phosphotungstic acid are preferred and available. In terms of ease, tungstic acid, sodium tungstate, calcium tungstate, and 12-tungstophosphoric acid are more preferable.

  The amount of tungstic acid used is not particularly limited, but is preferably 0.001 equivalent or more, more preferably 0.005 equivalent, in terms of catalytic metal atom, per equivalent of carbon-carbon double bond of the allyl compound used as a raw material. More preferably, it is 0.01 equivalent or more, preferably 5 equivalent or less, more preferably 3 equivalent or less, more preferably 1 equivalent or less. When the amount used is less than 0.001 equivalent, the reaction does not proceed sufficiently, and when the amount used is more than 5 equivalents, removal of tungstic acids tends to be difficult.

  As the onium salt used in the reaction, the active catalyst is preferably one that becomes fat-soluble during the epoxidation reaction and is usually dissolved in a solvent used as necessary. Therefore, it is preferable to use an onium salt having higher fat solubility. One measure of the fat solubility of the onium salt is the number of carbons of the onium salt, and (carbon number / number of onium salts in one molecule) is usually 20 or more, more preferably 25 or more. . More preferably, a cationic onium salt having 20 or more carbon atoms in its structure is more preferable. Examples thereof include ammonium salts such as methyltrioctylammonium salt, tetrahexylammonium salt, dilauryldimethylammonium salt and benzyltributylammonium salt, pyridinium salts such as cesylpyridinium salt, and phosphonium salts such as tetrahexylphosphonium salt.

  As the onium salt, an onium salt having one or more functional groups containing active hydrogen or a substituent that can be converted into a salt thereof, which has been invented by the present inventors and described in WO2013 / 147092, can also be used. These onium salts exhibit fat solubility during oxidation, but can be converted into water-soluble substances by simple post-treatment such as hydrolysis after the reaction is completed, and the tungsten compound such as tungsten can be more efficiently converted into water. It is preferable at the point which can melt | dissolve in a layer and can isolate | separate.

  Examples of the onium salt include ammonium salts, pyridinium salts, and imidazolinium salts. Among these, ammonium salts are preferable because they can be synthesized easily and are stable under reaction conditions. Specific examples of the substituent that can be converted into a functional group containing active hydrogen or a salt thereof are not particularly limited, but are preferably a hydroxyl group, a carboxyl group, an amino group, a mercapto group, a sulfonic acid group, or a phosphoric acid group. Or a salt thereof, more preferably a hydroxyl group.

  A substituent that can be converted into a functional group containing active hydrogen or a salt thereof is a substituent that can be converted into a functional group containing active hydrogen or a salt thereof by physical and / or chemical manipulation, specifically, Refers to a substituent that can be converted by chemical reaction, heating, photoreaction, enzyme reaction, microwave irradiation, etc., preferably a substituent that can be converted under mild conditions, more preferably, a condition that does not react with an epoxy group The substituent is convertible with More preferably, specifically, for example, ester group, carbonate group, carbamate group, imide group, amide group, ether group, silyl ether group, acetal group, ketal group, hemiacetal group, sulfonic acid ester group, thioether group, thioester group A thiocarbamate group, a thioacetal group, a phosphate ester group, a benzyl group, and the like. Of these, an ester group is particularly preferred because it can be easily removed.

Preferable specific examples of the onium salt include N-methyl-N, N, N-tri [2- (pentylcarbonyloxy) ethyl] ammonium hydrogen sulfate, N-methyl-N, N, N-tri [ 2- (4-t-butylphenylcarbonyloxy) ethyl] ammonium monomethyl hydrogen sulfate, 2,3-bis (4-t-butyl-phenyloxy) -N, N, N-N-triethyl-1-propaneammonium chloride, N-butyl-N, N-di [2- (4-t-butylbenzoyloxy) ethyl-N-methylammonium monomethyl sulfate and the like can be mentioned. Among these, from the viewpoint of easy preparation and analysis, N -Butyl-N, N-di [2- (4-t-butylbenzoyloxy) ethyl-N-methylammonium monomethyl sulfate. In the present invention, onium salts may be used alone or in combination of two or more.

  The anion species of the onium salt used in the present invention is not particularly limited, but specifically, hydrogen sulfate ion, monomethyl sulfate ion, halide ion, nitrate ion, acetate ion, hydrogen carbonate ion, dihydrogen phosphate ion, Monovalent anions such as sulfonate ion, carboxylate ion and hydroxide ion, and divalent anions such as hydrogen phosphate ion and sulfate ion can be mentioned, and monovalent anions are easy to adjust. preferable. Among them, monomethyl sulfate ion, hydrogen sulfate ion, acetate ion, phosphorus ion because the anion species is not added to the epoxy group of the epoxy compound that is the reaction product, the carbon-carbon double bond of the substrate, or the preparation is easy. Acid dihydrogen ions or hydroxide ions are preferred. The anionic species may be used alone or in combination of two or more.

  The amount of the onium salt used can be appropriately adjusted depending on the properties of the allyl compound used as a raw material, and is not particularly limited. However, if the amount used is small, the reaction does not proceed sufficiently, and if the amount used is large, the onium salt is removed. Tend to be difficult. Therefore, with respect to the tungsten compound used in the reaction, it is usually 0.1 equivalent or more, preferably 0.2 equivalent or more, more preferably 0.3 equivalent or more, usually 5.0 equivalent or less, preferably 2. It is 0 equivalent or less, More preferably, it is 1.0 equivalent or less.

The concentration of the hydrogen peroxide solution is not particularly limited, but is usually 10% by weight or more, preferably 20% by weight or more, more preferably 30% by weight or more, and usually 60% by weight or less, more preferably 45% or less. Those in this concentration range are easily available, have a low risk of decomposition, and are low in transportation costs.
Furthermore, it is more preferable from the viewpoint of safety and productivity to keep the amount and concentration of hydrogen peroxide in the system low during the reaction by adding water to the reaction system or sequentially adding hydrogen peroxide. The amount of hydrogen peroxide to be used is not particularly limited and varies depending on the raw material allyl compound, the type of catalyst, reaction conditions, and the like, but is usually about 0.1 to 1 equivalent of the carbon-carbon double bond in the allyl compound used as the raw material. 5 equivalents or more, preferably 1.0 equivalents or more, usually 10 equivalents or less, preferably 3.0 equivalents or less.

  In addition, in the oxidation method ii, it is preferable to use phosphoric acids in addition to tungstic acids and onium salts from the viewpoint of improving the reactivity. Specific examples of the phosphoric acid in the present invention include inorganic phosphoric acids such as phosphoric acid and phosphorous acid; phosphoric acid polymers such as polyphosphoric acid and pyrophosphoric acid; sodium phosphate, potassium phosphate, ammonium phosphate, Inorganic phosphates such as sodium hydrogen phosphate, potassium hydrogen phosphate, ammonium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, calcium dihydrogen phosphate; monomethyl phosphate, dimethyl phosphate, trimethyl phosphate , Phosphoric acid esters such as triethyl phosphoric acid and triphenyl phosphoric acid; Of these, phosphoric acid is preferred.

The amount of phosphoric acid used is not particularly limited, and the amount used can be appropriately adjusted depending on the type of the phosphoric acid compound and the type of the tungsten compound, but preferably the amount used so that the pH of the aqueous layer in the reaction system is within an appropriate range. Adjust. The equivalent amount of phosphorus contained in any of the phosphoric acids and phosphonic acids is usually 0.1 equivalents or more, preferably 0.2 equivalents or more, more preferably 0.3 equivalents to the metal in the tungsten compound to be used. Equivalent or higher, usually 5.0 or lower, preferably 2.0 or lower, more preferably 1.0 or lower.

At least one of the phosphoric acids can be added so that the pH of the aqueous layer of the reaction solution is in an appropriate range, and other acids and bases can be added as necessary to adjust the pH. .
A solvent can also be used for the reaction. Although the solvent to be used is not particularly limited, aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as hexane, heptane and dodecane; alcohols such as methanol, ethanol, isopropanol, butanol, hexanol and cyclohexanol Halogenated solvents such as chloroform, dichloromethane, dichloroethane and chlorobenzene; ethers such as tetrahydrofuran and dioxane; ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and anone; nitriles such as acetonitrile and butyronitrile; ethyl acetate and acetic acid Ester compounds such as butyl and methyl formate; amides such as N, N-dimethylformamide and N, N-dimethylacetamide; ureas such as N, N′-dimethylimidazolidinone; water Beauty mixtures of these solvents. As described above, it is more preferable in terms of safety and productivity to keep the amount and concentration of hydrogen peroxide in the system low during the reaction by adding water to the reaction system. In addition, when this reaction is carried out in a two-layer system in which an aqueous layer and an organic layer are separated, the epoxy resin is dissolved in the organic layer due to the two-layer separation, so that the epoxy ring is opened due to the influence of the acidic aqueous layer. Decomposition due to dislocation or the like can be suppressed. Therefore, a combination of water-insoluble aromatic hydrocarbons, aliphatic hydrocarbons, halogenated solvents or a mixture of these solvents and water is preferable, and among these, aromatics are preferred because they are stable against oxidation reactions. A combination of hydrocarbons or aliphatic hydrocarbons and water is more preferable, a combination of aromatic hydrocarbons having a boiling point higher than the reaction temperature and water is more preferable, and a combination of toluene and water is particularly preferable.

The use mode of the organic solvent is not particularly limited, but the solvent may not be used when the starting allyl compound is liquid under the reaction conditions. When the starting allyl compound is solid, it may be dissolved in a solvent or in a suspended state, but it is usually preferable that it is dissolved in a solvent under reaction temperature conditions.
The amount of the organic solvent used depends on the solubility of the compound, but the reaction rate decreases as the amount of the solvent increases. Therefore, the amount is usually 0 to 10 parts by weight, preferably 0 parts by weight per 1 part by weight of the allyl compound used as a raw material. Part to 5 parts by weight, more preferably 0 part to 3 parts by weight.

The reaction temperature is not particularly limited as long as the reaction is not inhibited, but if it is too low, the reaction rate may be slow, and if it is too high, decomposition of hydrogen peroxide and hydrolysis of the formed epoxy ring tend to be promoted. Therefore, it is usually 10 ° C to 90 ° C, preferably 35 ° C to 80 ° C, and more preferably 60 ° C to 75 ° C.
The reaction time varies depending on the reaction scale and the like, but is usually 1 hour or more, preferably 3 hours or more, more preferably 5 hours or more, and usually 48 hours or less, preferably 36 hours or less, more preferably 24 hours or less. It is.

  As described above, in the oxidation method ii, an allyl compound as a raw material is oxidized with an onium salt and an aqueous hydrogen peroxide solution in the presence of tungstic acids to produce an epoxy resin. The order in which these compounds are added is not particularly limited, but in a normal reaction, firstly, the starting materials such as allyl compounds, tungstic acid, onium salts, and phosphoric acids are mixed in a reaction solvent to keep the temperature of the mixture constant. Then, hydrogen peroxide solution may be dropped and stirred. After the reaction, the remaining hydrogen peroxide is quenched with a reducing agent such as an aqueous sodium thiosulfate solution, and an ordinary operation such as washing with water or concentration is performed to obtain an epoxy resin. If necessary, purification by crystallization or column chromatography may be carried out.

<2.6. Oxidation method iii>
The oxidation method iii will be described. The oxidation method iii is a method of oxidizing using an organic peracid. Organic peracids used in the reaction include peracetic acid, perpropionic acid, m-chloroperbenzoic acid,
Examples thereof include perbenzoic acid and perphthalic acid. Among them, peracetic acid and m-chloroperbenzoic acid are preferable, and peracetic acid is more preferable because it is industrially inexpensive, liquid, and easy to handle. These may be used individually by 1 type and may use 2 or more types together by arbitrary combinations.

  When the organic peracids are used alone, the amount used is not particularly limited, but is preferably 0.5 equivalents or more, more preferably 1 equivalent, relative to 1 equivalent of the carbon-carbon double bond in the allyl compound used as a raw material. More preferably, it is 1.1 equivalents or more, preferably 5 equivalents or less, more preferably 2 equivalents or less, and even more preferably 1.5 equivalents or less. When the amount used is less than 1 equivalent, the reaction tends not to proceed sufficiently, and when the amount used is more than 5 equivalents, there is a tendency that the excess organic peracids decompose and cause a reaction runaway.

When organic peracids are used in combination with hydrogen peroxide, since the organic acid acts catalytically, it may be a small amount with respect to hydrogen peroxide, preferably 0.05 equivalent or more, more preferably 0.1 Equivalents or more, more preferably 0.2 equivalents or more, and preferably 5 equivalents or less, more preferably 2 equivalents or less, and even more preferably 1.5 equivalents or less.
The concentration of the hydrogen peroxide solution is not particularly limited, but is usually 10% by weight or more, preferably 20% by weight or more and usually 60% by weight or less, and more preferably, availability, risk of decomposition, transportation cost, etc. Is considered, it is 30 mass% or more and 45 mass% or less. The amount of hydrogen peroxide used is not particularly limited, but is preferably 0.5 equivalents or more, more preferably 1 equivalents or more, even more preferably, with respect to 1 equivalent of the carbon-carbon double bond in the allyl compound used as a raw material. Is 1.1 equivalents or more, preferably 5 equivalents or less, more preferably 2 equivalents or less, and even more preferably 1.5 equivalents or less. When the amount used is less than 1 equivalent, the reaction tends not to proceed sufficiently, and when the amount used is more than 5 equivalents, there is a tendency that the excess organic peracids decompose and cause a reaction runaway.

Since organic peracids and hydrogen peroxide may cause rapid reaction and decomposition when the concentration in the system is high, it is preferable to add them in several portions or continuously from the viewpoint of safety. .
A solvent can also be used for the reaction. Although the solvent to be used is not particularly limited, for example, aromatic hydrocarbons such as benzene, toluene, xylene; aliphatic hydrocarbons such as hexane, heptane, dodecane; methanol, ethanol, isopropanol, butanol, hexanol, cyclohexanol, etc. Alcohols such as chloroform, dichloromethane, dichloroethane and chlorobenzene; ethers such as tetrahydrofuran and dioxane; ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and cyclohexanone; nitriles such as acetonitrile and butyronitrile; acetic acid Ester compounds such as ethyl, butyl acetate and methyl formate; organic acids such as acetic acid and propionic acid; amides such as N, N-dimethylformamide and N, N-dimethylacetamide; N , N′-dimethylimidazolidinone and the like; water and mixtures of these solvents. Of these, aromatic hydrocarbons, halogenated solvents and mixtures of these solvents are preferred from the viewpoints of solubility of organic peracids and resistance to oxidation reactions.

Although the usage-amount of a solvent is not specifically limited, Preferably it is 1 weight part-100 weight part with respect to 1 weight part of allyl compounds used as a raw material, More preferably, it is 2 weight part-50 weight part or more. When the amount of the solvent is small, the substrate does not mix well in the system and the reactivity tends to decrease. Moreover, when there are many solvents, the density | concentration of the reaction substrate in a system will fall, and there exists a tendency for reaction rate to fall.
Although reaction temperature is not specifically limited, Preferably it is 0 degreeC or more, More preferably, it is 20 degreeC or more, Preferably it is 100 degrees C or less, More preferably, it is 80 degrees C or less, More preferably, it is 50 degrees C or less. When it exceeds 100 ° C., decomposition of hydrogen peroxide and hydrolysis of the formed epoxy ring tend to be promoted. If it is less than 0 ° C., a sufficient reaction rate cannot be obtained, and the reaction tends not to proceed completely.

The reaction time varies depending on the reaction scale and the like, but is usually 1 hour or longer, preferably 2 hours or longer, and is usually 72 hours or shorter, preferably 24 hours or shorter.
As described above, in the oxidation method iii, the raw material allyl compound is oxidized using an organic peracid to produce an epoxy resin. The order of addition of these compounds is not particularly limited, but in a normal reaction, first, the starting allyl compound is dissolved or suspended in a reaction solvent, and organic peracids are added while paying attention to the temperature of the mixture. When organic acids and hydrogen peroxide are used in combination, hydrogen peroxide is added after paying attention to the temperature of the mixture after adding the organic acids. After the reaction, the remaining hydrogen peroxide is quenched with a reducing agent such as an aqueous sodium thiosulfate solution, and an ordinary operation such as washing with water or concentration is performed to obtain an epoxy resin. If necessary, purification by crystallization or column chromatography may be carried out.

[3. Synthetic intermediates]
<3.1. General formula (2)>
A method for synthesizing the allyl compound represented by the general formula (2) will be described.

(In the formula, A, m ₁ , m ₂ , n ₁ and n ₂ are the same as those in the general formula (1), and Y represents a 2-allyl group or a 2-allyloxy group.)
In the general formula (2), when Y is a 2-allyl group, it can be produced, for example, by the following method.

In general formula (7-1), general formula (7-2), general formula (8-1), and general formula (8-2), A, R, m ₁ and m ₂ are the same as those in general formula (1). It is the same.
The bisallylphenol compound represented by the general formula (7-1) as a starting material is substituted with a carbonyl group at the bonding position of A with the benzene ring by, for example, the method described in JP2010-128820A. The resulting ketone and two phenol molecules can be condensed using an acid catalyst, and allylated and Claisen rearranged by the method described in JP-A-10-077338. Then, the allyl compound represented by General formula (8-1) is obtained by allylating the hydroxyl group of General formula (7-1). Furthermore, if the Claisen rearrangement and the allylation of the hydroxyl group are repeated, an allyl compound represented by the following can be obtained.
When Y is a 2-allyloxy group, the general formula (9) can be produced, for example, by the following method.

In general formula (5) and general formula (9), A, R, m ₁ , m _2, n ₁ , and n ₂ are the same as in general formula (1).
First, the phenol compound represented by the general formula (5) as a starting material is, for example, a ketone in which the bonding position to the benzene ring of A is substituted with a carbonyl group by the method described in JP-A-3-291250. It can be produced by condensing two molecules of polyphenol using an acid catalyst. Then, the allyl compound represented by General formula (9) is obtained by allylating the hydroxyl group of General formula (5).

  The method for the allylation of the hydroxyl group is not particularly limited, but for example, a method described in JP-A-10-077338 in which an allyl halide such as allyl bromide or allyl chloride is allowed to act on a base is used. Moreover, the method of making allyl acetate react in presence of transition metal catalysts, such as palladium and ruthenium, described in Unexamined-Japanese-Patent No. 2014-240377 is used. Among these, in order to reduce the halogen content of the epoxy resin of the present invention represented by the general formula (1), it is preferable to avoid the use of allyl halides.

As described above, the allyl compound represented by the general formula (9) is a raw material for the polyfunctional epoxy resin of the present invention represented by the general formula (6) in which X is a glycidyloxy group in the general formula (1). However, since it has a plurality of allyl groups as crosslinking points, the general formula (9) itself is also useful as a low-viscosity curable resin material, and the cured product is expected to have excellent heat resistance. Is done.
Specific examples of general formula (9) are shown below.

<3.2. General formula (3)>
The manufacturing method of the diglycidyl ether represented by General formula (3) is demonstrated.
The general formula (3) can be produced, for example, by glycidylating the hydroxyl group of the bisallylphenol compound represented by the general formula (7) as a starting material.

(In the formula, A, m ₁ , m _2, n ₁ , and n ₂ are the same as those in the general formula (1).)
About glycidylation, it can carry out similarly to the method as described in the term of manufacturing method III.

[4. Properties of epoxy resin]
The polyfunctional epoxy resin of the present invention represented by the above general formula (1) further includes _{1 to} n of ₂ + n ₁ + n ₂ epoxy groups of the epoxy resin of the present invention represented by the general formula (1). An epoxy resin in which ₁ + n ₂ pieces form a carbon-carbon double bond instead of an epoxy group may be included. The mixing ratio is not particularly limited as long as the effects of the present invention are not impaired, and can be appropriately set depending on the purpose of use. In the above oxidation reaction, the raw material allyl compound is sequentially oxidized to produce an epoxy resin. Therefore, in any oxidation method, the epoxy group and the carbon-carbon double bond are controlled by controlling the equivalent of the oxidizing agent. The content ratio and epoxy equivalent can be controlled. The mixing ratio is preferably higher in order to improve heat resistance, while it is preferably lower in order to reduce viscosity and toxicity. The content of other impurities can also be estimated by the epoxy equivalent, but the smaller the impurities, the better the processability of the composition containing the polyfunctional epoxy resin of the present invention and the heat resistance of the cured product of the present invention. . Therefore, the ratio of the epoxy equivalent of the polyfunctional epoxy resin of the present invention to the theoretical epoxy equivalent (epoxy equivalent of the mixture / theoretical epoxy equivalent) is usually preferably 1.00 to 1.40, and preferably 1.00 to 1.20. More preferably, 1.00 to 1.10.

  The shear viscosity at 150 ° C. of the polyfunctional epoxy resin of the present invention is preferably high from the viewpoint of being less likely to volatilize, and preferably low from the viewpoint of excellent moldability and processability. Specifically, it is preferably 5 mPa · s or more, more preferably 20 mPa · s or more, and further preferably 35 mPa · s or more. On the other hand, it is preferably 200 mPa · s or less, more preferably 100 mPa · s or less, and even more preferably 70 mPa · s or less.

In addition, when the polyfunctional epoxy resin of the present invention is solid at 25 ° C., it is preferable that the melting point is not higher than the curing temperature because of good workability and moldability. Specifically, it is preferably 160 ° C. or lower, more preferably 150 ° C. or lower, and further preferably 130 ° C. or lower. On the other hand, from the viewpoint of ease of handling, 30 ° C or higher is preferable, 40 ° C or higher is more preferable, and 60 ° C or higher is more preferable.

  Further, the chlorine content in the polyfunctional epoxy resin of the present invention is preferably 1000 ppm by mass or less, more preferably 500 ppm by mass or less, and particularly preferably 100 ppm by mass or less in terms of Cl. When the content ratio of the chlorine component is large, the chlorine component remains in the obtained cured product, which may reduce the insulation of the cured product or corrode the metal wiring or the like that comes into contact.

[5. Epoxy resin composition]
The polyfunctional epoxy resin composition of the present invention contains the polyfunctional epoxy resin of the present invention. The polyfunctional epoxy resin composition of the present invention is excellent in that it has low toxicity and protects the safety of workers. Moreover, by containing the polyfunctional epoxy resin of this invention, it is excellent in workability and moldability sufficient for applying to processes, such as film shaping | molding, application | coating, and injection | pouring, with low viscosity. Furthermore, when cured, it tends to exhibit heat resistance. Therefore, it is suitable for adhesives, paints, civil engineering and building materials, electrical / electronic materials, and the like.

  The polyfunctional epoxy resin composition of the present invention is an epoxy resin other than the polyfunctional epoxy resin of the present invention (hereinafter, “ It may be referred to as “another epoxy resin”), a curing agent, a filler, other additives, a solvent, and the like. When the polyfunctional epoxy resin composition of the present invention contains a component other than the polyfunctional epoxy resin of the present invention, the content does not significantly hinder the effect expressed by containing the polyfunctional epoxy resin of the present invention. If it is a range, it will not specifically limit.

  The content ratio of the polyfunctional epoxy resin of the present invention with respect to the total solid content contained in the polyfunctional epoxy resin composition of the present invention is often high in that the characteristics of the polyfunctional epoxy resin of the present invention can be sufficiently expressed. It is preferable that the number of components other than the polyfunctional epoxy resin of the present invention is small in that the characteristics of the components can be sufficiently expressed. Therefore, it is usually 0.1% by weight or more, preferably 1% by weight or more, and particularly preferably 10% by weight or more. Moreover, it is 95 weight% or less normally, 90 weight% or less is preferable, 80 weight% or less is more preferable, and 70 weight% or less is especially preferable. In addition, the polyfunctional epoxy resin composition of the present invention may contain two or more polyfunctional epoxy resins of the present invention. In that case, the total amount is preferably in the above range.

<5.1. Other epoxy resins>
Specific examples of other epoxy resins that may be contained in the polyfunctional epoxy resin composition of the present invention include bisphenol A type epoxy resins, bisphenol F type epoxy resins, naphthalene type epoxy resins, and phenol novolac type epoxy resins. And various epoxy resins such as a cresol novolac type epoxy resin, a phenol aralkyl type epoxy resin, a biphenyl type epoxy resin, a triphenylmethane type epoxy resin and a dicyclopentadiene type epoxy resin. Specifically, for example, bisphenol A, bisphenol F, 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 , Phenols (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, Derived from polycondensates with 4-bis (chloromethyl) benzene, 1,4-bis (methoxymethyl) benzene, etc., and their modified products, halogenated bisphenols such as tetrabromobisphenol A, or alcohols Glycidyl etherified product of alicyclic epoxy resin, glycidylamine epoxy resin, glycidyl ester epoxy resin, silsesquioxane epoxy resin (chain, cyclic, ladder, or a mixture of at least two of them) Siloxane structure with glycidyl group and / or epoxycyclohexa It includes solid or liquid epoxy resin having an epoxy resin) having the structure. These may be used alone or in combination of two or more in any ratio.

  When another epoxy resin is contained in the polyfunctional epoxy resin composition of the present invention, the content of the polyfunctional epoxy resin of the present invention relative to the total amount of the epoxy resin including the polyfunctional epoxy resin of the present invention in the composition Is more likely to exhibit the excellent moldability and processability of the polyfunctional epoxy resin of the present invention, and the heat resistance effect when a composition containing the same is cured, but the lesser is the other epoxy Effects such as process controllability of the resin and controllability of physical properties when a composition containing the resin is cured are easily exhibited. Therefore, specifically, the content of the polyfunctional epoxy resin of the present invention relative to the total amount of the epoxy resin in the composition is usually 0.1 to 100% by weight, preferably 10 to 100% by weight, and more preferably 20%. -100% by weight, particularly preferably 40-100% by weight.

  Moreover, the total content of the epoxy resin including the polyfunctional epoxy resin of the present invention relative to the total solid content contained in the polyfunctional epoxy resin composition of the present invention is large in that the characteristics of the epoxy resin are easily expressed sufficiently. It is preferable that the amount of the component other than the epoxy resin is small in that the physical properties of the component can be sufficiently expressed. Therefore, it is usually 1% by weight or more, preferably 3% by weight or more, particularly preferably 5% by weight or more, and usually 95% by weight or less, preferably 80% by weight or less, particularly preferably 70% by weight or less. That is good.

<5.2. Curing agent>
The curing agent that may be contained in the polyfunctional epoxy resin composition of the present invention may be any substance that contributes to the crosslinking reaction of the epoxy group of the polyfunctional epoxy resin of the present invention, and is generally an epoxy resin curing agent. In addition to the curing agent said to be included, those generally known as curing accelerators are also included. That is, the curing agent according to the present invention is a substance that contributes to a crosslinking reaction between epoxy groups of the epoxy resin contained in the polyfunctional epoxy resin composition of the present invention, or an epoxy contained in the polyfunctional epoxy resin composition of the present invention. It is a substance that exhibits a function of promoting a crosslinking reaction between resins and an addition reaction between an epoxy resin and a curing agent.

Examples of general epoxy resin curing agents include phenolic curing agents, ester curing agents, benzoxazine curing agents, acid anhydride curing agents, primary and secondary amine curing agents, and mercaptan curing agents. Amide type curing agent, block isocyanate type curing agent and the like. It is also possible to use a phenoxy resin as a curing agent.
Various known phenolic curing agents can be used as the phenolic curing agent. Specific examples include bisphenol A, bisphenol F, bisphenol S, bisphenol AD, hydroquinone, resorcin, methylresorcin, biphenol, tetramethylbiphenol, dihydroxynaphthalene, dihydroxydiphenyl ether, thiodiphenols, phenol novolac resin, cresol novolac resin, phenol Polyhydric phenols such as aralkyl resins, biphenyl aralkyl resins, naphthol aralkyl resins, terpene phenol resins, dicyclopentadiene phenol resins, bisphenol A novolac resins, naphthol novolac resins, brominated bisphenol A, brominated phenol novolac resins; Benzaldehyde, hydroxybenzaldehyde, crotonaldehyde, glyoxy Polyhydric phenol resins obtained by condensation reaction with aldehydes such as alcohol; polyhydric phenol resins obtained by condensation reaction of xylene resin and phenols; heavy oils and pitches, phenols and formaldehydes And phenol resins such as co-condensation resins. Of these, phenol novolac resin, phenol aralkyl resin, trisphenol methane resin, biphenyl aralkyl resin, naphthol aralkyl resin, phenol / benzaldehyde / xylylene dimethoxide polycondensate, phenol / benzaldehyde / 4,4′-dimethoxybiphenyl polycondensation A thing etc. are preferable.

The ester curing agent is generally roughly classified into an active ester curing agent and a cyanate ester resin.
The active ester curing agent has a highly reactive ester group such as a phenol ester compound, a thiophenol ester compound, an N-hydroxyamine ester compound, a compound in which a heterocyclic hydroxy group is esterified, and has a curing action on an epoxy resin. Say the substance you have. The active ester curing agent is preferably a compound having two or more active ester groups. In particular, from the viewpoint of improving the heat resistance of a cured product obtained by curing the epoxy group resin composition of the present invention, an active ester compound obtained from a carboxylic acid compound and a hydroxy compound is more preferable, and the carboxylic acid compound and the phenol compound or An active ester compound obtained from a naphthol compound is more preferred. Further, an aromatic compound having two or more active ester groups obtained from a carboxylic acid compound and an aromatic compound having a phenolic hydroxyl group is more preferable, and has at least two compounds having a carboxylic acid and a phenolic hydroxyl group. Particularly preferred are aromatic compounds having two or more active ester groups obtained from aromatic compounds. The active ester curing agent may be linear or hyperbranched. Here, if the compound having at least two carboxylic acids is a compound containing an aliphatic chain, the compatibility with the epoxy resin can be increased, and if the compound has an aromatic ring, the compound of the present invention can be used. The heat resistance of the cured product obtained by curing the polyfunctional epoxy resin composition can be increased. Specific examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Of these, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, and terephthalic acid are preferred from the viewpoint of improving the heat resistance of a cured product obtained by curing the polyfunctional epoxy resin composition of the present invention. Terephthalic acid is more preferred. Specific examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o -Cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetra Hydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadienyl diphenol, phenol novolac and the like. Among these, bisphenol A, bisphenol F, bisphenol S, methylated bisphenol A, and methylated bisphenol F from the viewpoint of improving solubility and improving heat resistance of a cured product obtained by curing the polyfunctional epoxy resin composition of the present invention. Methylated bisphenol S, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, Benzenetriol, dicyclopentadienyl diphenol, and phenol novolak are preferable, and catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxy More preferred are phthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadienyldiphenol, phenol novolac, α-naphthol, β-naphthol, 1,5 -Dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyldiphenol, phenol novolac are more preferable, α-naphthol, β-naphthol , Dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopenta Enildiphenol and phenol novolak are particularly preferred, α-naphthol, β-naphthol, dicyclopentadienyl diphenol and phenol novolak are particularly preferred, and α-naphthol, β-naphthol and dicyclopentadienyl diphenol are most preferred. . Moreover, as an active ester compound, the active ester compound currently disclosed by Unexamined-Japanese-Patent No. 2004-277460 may be used, and various commercial items may be used. Commercially available products include, for example, “EXB-9451” and “EXB-9460” manufactured by DIC Corporation, as those containing a dicyclopentadienyl diphenol structure, as acetylated products of phenol novolac, Mitsubishi Chemical Corporation “DC808” manufactured by Mitsubishi Electric Corporation, and “YLH1026” manufactured by Mitsubishi Chemical Co., Ltd. can be cited as benzoylated products of phenol novolac.

  Specific examples of the cyanate ester resin include, for example, bisphenol A dicyanate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), 4,4′-methylenebis (2,6-dimethylphenyl cyanate), 4, 4'-ethylidenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), bis (4-cyanate-3,5- Bifunctional cyanate resins such as dimethylphenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, bis (4-cyanatephenyl) ether; phenol Novolac, cle Polyfunctional cyanate resin derived from Runoborakku like; these cyanate resins and partially triazine of prepolymer. As a commercially available cyanate ester resin, a phenol novolak type polyfunctional cyanate ester resin (“PT30” manufactured by Lonza Japan Co., Ltd., cyanate equivalent 124) and a part or all of bisphenol A dicyanate were triazine to form a trimer. Prepolymers (“BA230” manufactured by Lonza Japan Co., Ltd., cyanate equivalent 232) and the like can be mentioned.

Specific examples of the benzoxazine-based curing agent include Fa, Pd (manufactured by Shikoku Kasei Co., Ltd.), HFB2006M (manufactured by Showa Polymer Co., Ltd.), and the like.
Specific examples of acid anhydride curing agents include dodecenyl succinic anhydride, polyadipic acid anhydride, polyazeline acid anhydride, polysebacic acid anhydride, poly (ethyloctadecanedioic acid) anhydride, poly (phenylhexadecanedioic acid) Anhydride, Methyltetrahydrophthalic anhydride, Methylhexahydrophthalic anhydride, Hexahydrophthalic anhydride, Methylhymic anhydride, Tetrahydrophthalic anhydride, Trialkyltetrahydrophthalic anhydride, Methylcyclohexene dicarboxylic anhydride, Methylcyclohexene tetracarboxylic Acid anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bistrimellitic dianhydride, het anhydride, nadic anhydride, methyl nadic anhydride, 5- ( 2, -Dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexane-1,2-dicarboxylic anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene-2-succinic acid Anhydride, 1-methyl-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, etc. are mentioned.
Specific examples of the primary and secondary amine curing agents include aliphatic amines, polyether amines, alicyclic amines, aromatic amines and the like. Aliphatic amines include ethylenediamine, 1,3-diaminopropane, 1,4-diaminopropane, hexamethylenediamine, 2,5-dimethylhexamethylenediamine, trimethylhexamethylenediamine, diethylenetriamine, iminobispropylamine, bis ( Hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-hydroxyethylethylenediamine, tetra (hydroxyethyl) ethylenediamine, and the like. Examples of polyether amines include triethylene glycol diamine, tetraethylene glycol diamine, diethylene glycol bis (propylamine), polyoxypropylene diamine, and polyoxypropylene triamines. Cycloaliphatic amines include isophorone diamine, metacene diamine, N-aminoethylpiperazine, bis (4-amino-3-methyldicyclohexyl) methane, bis (aminomethyl) cyclohexane, 3,9-bis (3-amino). Propyl) -2,4,8,10-tetraoxaspiro (5,5) undecane, norbornenediamine and the like. Aromatic amines include tetrachloro-p-xylenediamine, m-xylenediamine, p-xylenediamine, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, 2,4-diaminoanisole, 2,4 -Toluenediamine, 2,4-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diamino-1,2-diphenylethane, 2,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone , M-aminophenol, m-aminobenzylamine, benzyldimethylamine, 2-dimethylaminomethyl) phenol, triethanolamine, methylbenzylamine, α- (m-aminophenyl) ethylamine, α- (p-aminophenyl) Ethylamine, diaminodiethyl Methyl diphenyl methane, alpha,. Alpha .'- bis (4-aminophenyl)-p-diisopropylbenzene and the like.

  A known phenoxy resin can be used as the phenoxy resin. The phenoxy resin is preferably an epoxy resin having a weight average molecular weight of 5,000 to 200,000 and an epoxy equivalent of 2,000 g / equivalent to 100,000 g / equivalent. By including the phenoxy resin in the polyfunctional epoxy resin composition of the present invention, the flexibility can be improved when the cured product obtained by curing the polyfunctional epoxy resin composition of the present invention is a film. . Specific examples of the phenoxy resin include “FX280” and “FX293” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., “YX8100”, “YX6954 (YL6954)” and “YL6974” manufactured by Mitsubishi Chemical Corporation.

  The content of these curing agents contained in the polyfunctional epoxy resin composition of the present invention is sufficient in a short time because the epoxy groups contained in the polyfunctional epoxy resin composition of the present invention do not easily remain unreacted. In terms of easy curing, a larger amount is preferable. On the other hand, it is preferable that there are few in the site | part which reacts with the epoxy group of a hardening | curing agent to the hardened | cured material which hardened | cured the polyfunctional epoxy resin composition of this invention with the unreacted residue. Specifically, the epoxy group contained in the polyfunctional epoxy resin composition of the present invention and the reaction site in the curing agent (hydroxyl group of phenolic curing agent, ester group of ester curing agent, NO group of benzoxazine curing agent) The acid anhydride group of the acid anhydride-based curing agent, the amino group of the amine-based curing agent, etc.), and preferably used so as to be 0.3 or more, and 0.8 or more. More preferably, it is particularly preferably used so as to be 0.9 or more. On the other hand, it is preferably used so as to be 1.5 or less, and more preferably used so as to be 1.2 or less. Note that only one type of curing agent may be used, or two or more types may be used in any combination and ratio. As for the content in the case of using 2 or more types of hardening | curing agents, it is preferable that the total amount is said preferable range.

Curing agents that are often referred to as curing accelerators generally include imidazole curing accelerators, tertiary amine curing accelerators, organic phosphine curing accelerators, phosphonium salt curing accelerators, and tetraphenylboron salt salts. Examples thereof include a curing accelerator, a metal curing accelerator, an organic acid dihydrazide, and a boron halide amine complex.
Specific examples of the imidazole curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2 -Phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2 -Ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino- 6- [2 ' -Methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino- 6- [2′-Ethyl-4′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s -Triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl Imidazoles such as -5 hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 2-phenylimidazoline Compounds and imidazole compounds and adducts with epoxy resins.

  Specific examples of the tertiary amine curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6, -tris (dimethylaminomethyl) Examples thereof include tertiary amine compounds such as phenol and 1,8-diazabicyclo [5,4,0] -7-undecene, and adducts of these tertiary amine compounds and epoxy resins.

  The content of the imidazole curing accelerator and the amine curing accelerator contained in the polyfunctional epoxy resin composition of the present invention is that the polyfunctional epoxy resin composition of the present invention is sufficiently cured in a short time. A large amount is preferable. On the other hand, the storage stability of the polyfunctional epoxy resin composition of the present invention, the low coefficient of thermal expansion, and the effect of the curing agent on the cured product are preferably small. Specifically, it is preferably used in an amount of 0.1 parts by weight or more, and 0.2 parts by weight or more with respect to 100 parts by weight of the epoxy resin contained in the polyfunctional epoxy resin composition of the present invention. In addition, it is preferably used so as to be 20 parts by weight or less, more preferably 10 parts by weight or less.

  Organic phosphine-based curing accelerators include triphenylphosphine, diphenyl (p-tolyl) phosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, tris (alkylalkoxyphenyl) phosphine, tris (dialkylphenyl) phosphine , Tris (trialkylphenyl) phosphine, tris (tetraalkylphenyl) phosphine, tris (dialkoxyphenyl) phosphine, tris (trialkoxyphenyl) phosphine, tris (tetraalkoxyphenyl) phosphine, trialkylphosphine, dialkylarylphosphine, alkyl Organic phosphines such as diarylphosphine; complexes of these organic phosphines with organic borons; 1,4-benzoquinone, 2,5- Ruquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, Examples include quinones such as phenyl-1,4-benzoquinone and compounds to which a compound such as diazophenylmethane is added. Phosphonium salt curing accelerators include phosphonium salts such as ethyltriphenylphosphonium salt, benzyltriphenylphosphonium salt, tetraphenylphosphonium salt, methyltributylphosphonium salt and counter anions such as chloride ion, bromide ion, and organic phosphate ion. Combinations: Complexes of these organic phosphonium salts and organic borons can be mentioned. Examples of the tetraphenylboron salt-based curing accelerator include a tetraphenylboron salt of 2-ethyl-4-methylimidazole, a tetraphenylboron salt of N-methylmorpholine, and the like.

  The content of these curing accelerators contained in the polyfunctional epoxy resin composition of the present invention is 0.001 part by weight or more with respect to 100 parts by weight of the epoxy resin contained in the polyfunctional epoxy resin composition of the present invention. It is preferably used so that it becomes 0.005 parts by weight or more, and on the other hand, it is preferably used so that it becomes 20 parts by weight or less, and so that it becomes 10 parts by weight or less. It is more preferable to use it, and it is especially preferable to use it so that it may become 5 weight part or less.

Examples of the metal curing accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organometallic complex include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. Organic zinc complexes such as iron (III) acetylacetonate, nickel (II)
And organic nickel complexes such as acetylacetonate and manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate. Among these, from the viewpoint of solvent solubility and curability of the polyfunctional epoxy resin composition of the present invention, cobalt (II) acetylacetonate, cobalt (III) acetylacetonate, zinc (II) acetylacetonate, naphthenic acid Zinc and iron (III) acetylacetonate are preferred, and cobalt (III) acetylacetonate and zinc naphthenate are particularly preferred. The content of the metal-based curing accelerator contained in the polyfunctional epoxy resin composition of the present invention is preferably large in that it is easy to form a conductor layer having excellent peel strength on the surface of the low-roughness insulating layer. On the other hand, there are few points in which the polyfunctional epoxy resin composition of this invention is excellent in storage stability and insulation. Therefore, the metal-based curing agent-derived metal is preferably 500 ppm or less, more preferably 200 ppm or less, and on the other hand, preferably 20 ppm or more, and 30 ppm relative to the nonvolatile content in the composition. More preferably, it is the above.

Among these, particularly when using a cyanate ester resin, it is easy to efficiently cure the cyanate ester resin and the epoxy resin, so that a metal curing agent, an imidazole curing agent, an amine curing agent, etc. are used in combination. Is preferred.
Also, "Review Epoxy Resin Vol. 1" (1st edition, Epoxy Resin Technology Association, 2003), pages 119-209 and "Review Epoxy Resin Recent Progress i" (1st edition, Epoxy Resin Technology Association, 2009). ), Pages 43-84, and curing agents and curing accelerators may be used.
The type and combination of the curing agents and the amount thereof may be selected according to the balance of the curing conditions, the shape of the cured product, the physical properties such as the adhesiveness and bending strength of the cured product.

<5.3. Filler>
When the polyfunctional epoxy resin composition of the present invention contains a filler, by curing the polyfunctional epoxy resin composition of the present invention, low linear expansion coefficient, high thermal conductivity, flame retardancy, conductivity, etc. The physical properties of the filler can be imparted to the cured product. Since the polyfunctional epoxy resin of the present invention has a low viscosity, it is easy to maintain excellent processability even if many fillers are added.

  The type of filler may be selected according to desired physical properties. For example, when it is desired to obtain an insulating composition at a low cost, it is preferable to use an insulating filler such as alumina, aluminum nitride, boron nitride, silicon nitride, and silica, and among these, a composition having particularly high thermal conductivity. In the case where it is desired to obtain, alumina, aluminum nitride, boron nitride and the like are preferable. When it is desired to obtain a conductive composition, it is preferable to use an electrically conductive filler such as aluminum, silver, copper, carbon, silicon carbide, etc. Among these, when it is desired to obtain a composition that is particularly excellent in workability. Silver is preferred.

  The shape and particle size of the filler are not particularly limited as long as the desired effect due to the inclusion of the filler is exhibited without significantly impairing the excellent physical properties of the polyfunctional epoxy resin composition of the present invention. However, with regard to the shape of the filler, when it is desired to obtain a composition with excellent processability, a filler having a small surface area such as a sphere is fibrous, etc. in that the functions such as the thermal conductivity of the filler are easily exhibited. A filler having a large surface area is preferably a filler having an intermediate surface area such as a flat shape in that it is easy to balance the two.

The particle size of the filler is preferably small in that voids are not easily generated in a cured product obtained by curing the polyfunctional epoxy resin composition of the present invention. On the other hand, it is preferable that the filler is large in that it does not aggregate and is easily dispersed. Therefore, specifically, the particle size is preferably 0.05 μm or more, more preferably 0.1 μm or more, particularly preferably 0.5 μm or more, and on the other hand, 1000 μm or less. Preferably, it is 200 micrometers or less, It is especially preferable that it is 100 micrometers or less. The particle size can be measured by a method such as a laser diffraction scattering method or a sedimentation method.

  When the polyfunctional epoxy resin composition of the present invention contains a filler, the content of the filler is preferably large in that the effect of using the filler is easily exhibited. On the other hand, it is preferable that the polyfunctional epoxy resin composition of the present invention is small in that it tends to be excellent in processability. Therefore, specifically, the filler content is preferably 10% by weight or more, preferably 20% by weight or more, and on the other hand, preferably 95% by weight or less, 90% by weight. More preferably, it is% or less. A filler may be used only by 1 type, or may use 2 or more types by arbitrary combinations and a ratio. As for the content in the case of using two or more kinds of fillers, the total amount is preferably in the above-mentioned preferable range.

<5.4. Other additives>
Examples of other additives that may be contained in the polyfunctional epoxy resin composition of the present invention include the following additives. The multifunctional epoxy resin composition of the present invention, the adhesion between a cured product obtained by curing the same and the substrate, and the glycidylamine of the present invention when an inorganic filler is contained in the multifunctional epoxy resin composition of the present invention Coupling agents such as silane coupling agents and titanate coupling agents used to improve the adhesion between the compound and this inorganic filler; UV inhibitors, antioxidants, plasticizers used to improve storage stability; Flux for removing oxide film of solder; flame retardant; colorant; dispersant; emulsifier; low elasticity agent; diluent; defoaming agent;

  Examples of silane coupling agents include epoxy silanes such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; γ-amino Propyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane Aminosilanes such as 3-mercaptopropyltrimethoxysilane; p-styryltrimethoxysilane, vinyltrichlorosilane, vinyltris (8-methoxyethoxy) silane, vinyltrimethoxysilane, vinyltriethoxysila , .Gamma.-methacryloxypropyl vinylsilane such as trimethoxysilane, epoxy-based, amino-based, and the like silanes polymer type vinyl system.

  As titanate coupling agents, isopropyl triisostearoyl titanate, isopropyl tri (N-aminoethyl / aminoethyl) titanate, diisopropyl bis (dioctyl phosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl) Examples thereof include phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, and bis (dioctylpyrophosphate) ethylene titanate.

It is preferable that the content of the coupling agent when the polyfunctional epoxy resin composition of the present invention contains a coupling agent is large in that it is easy to obtain an adhesive effect due to the coupling agent blending. On the other hand, it is preferable that the coupling agent is small in that it is difficult to bleed out. Therefore, specifically, the content of the coupling agent with respect to the total solid content in the polyfunctional epoxy resin composition of the present invention is preferably 0.1 wt% or more and 2.0 wt% or less. Coupling agent is 1
You may use only by seed | species or may use 2 or more types by arbitrary combinations and a ratio. As for the content in the case of using 2 or more types of coupling agents, the total amount is preferably within the above-mentioned preferable range.

<5.5. Solvent>
The polyfunctional epoxy resin composition of the present invention may contain a solvent for adjusting the viscosity at the time of processing and handling properties when curing. As the solvent, the solvent used when producing the polyfunctional epoxy resin of the present invention may be used. Examples of the solvent contained in the polyfunctional epoxy resin composition of the present invention include ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, and cyclohexanone; esters such as ethyl acetate; ethers such as ethylene glycol monomethyl ether Amides such as N, N-dimethylformamide and N, N-dimethylacetamide; alcohols such as methanol, ethanol and isopropanol; alkanes such as hexane and cyclohexane; aromatics such as toluene and xylene;
The amount of the solvent used is preferably not used or small because voids are easily formed in the cured product due to residual solvent. On the other hand, it is preferable that the number of cracks accompanying the increase in the viscosity of the composition is less likely to occur. These solvents may be used alone or in combination of two or more in any ratio.

[6. Cured product]
The cured product of the present invention can be obtained by curing the polyfunctional epoxy resin composition of the present invention. The cured product of the present invention is excellent in heat resistance because the polyfunctional epoxy resin composition of the present invention is cured. The curing method and conditions are not particularly defined as long as the polyfunctional epoxy resin composition of the present invention can be cured. However, thermosetting is preferable because it is easy to mold.

  The cured product of the present invention is obtained by curing the composition containing the polyfunctional epoxy resin of the present invention, and has a high glass transition temperature and excellent heat resistance. The glass transition temperature of the cured product of the present invention measured by dynamic viscoelasticity is, for example, Ricacid MH-700 (manufactured by Shin Nippon Chemical Co., Ltd.) and Hishicolin PX-4MP (manufactured by Nippon Chemical Industry Co., Ltd.) or EMI24 as a curing agent. (Mitsubishi Chemical Co., Ltd.) is used as a curing accelerator and cured at 100 ° C. for 3 hours and 140 ° C. for 3 hours, usually 100 ° C. or higher, preferably 150 ° C. or higher, more preferably 200 ° C. or higher, more preferably It is 210 ° C or higher. The upper limit of the glass transition temperature is usually 350 ° C.

[7. Application]
Since the polyfunctional epoxy resin of the present invention and the composition containing the same have a low viscosity, it has sufficient processability to be applied to processes such as coating, mixing, and film forming. Further, it can be preferably used for other resin modifiers, various raw materials for chemicals such as adducts and thermoplastic resins.

  And the hardened | cured material which hardened this composition is excellent in heat resistance. Therefore, it can be applied as materials in various fields such as adhesives, paints, materials for civil engineering and construction, and insulating materials in the electric / electronic field. In particular, it is useful as an insulating casting, laminate material, sealing material, etc. in the electric / electronic field. Examples of the use of the composition containing the polyfunctional epoxy resin of the present invention and the cured product thereof include multilayer printed wiring boards, film adhesives, liquid adhesives, semiconductor sealing materials, underfill materials, and 3D-LSI interfacing. A chip fill, an insulating sheet, a prepreg, a heat dissipation board, etc. are mentioned.

Hereinafter, the present invention will be described more specifically based on experimental examples (synthesis examples, examples), but the present invention is not limited by the following experimental examples unless it exceeds the gist.
Unless otherwise specified, commercially available reagents that are usually available were used in the examples. Moreover, the various analysis methods in an Example and a comparative example are as follows.
⁽¹ H-NMR Analysis Conditions)
Equipment: AVANCE400, 400MHz made by BRUKER
Solvent: 0.03 vol% tetramethylsilane-containing heavy chloroform (epoxy equivalent)
It measured according to JIS K7236: 2001.

(Shear viscosity measurement)
The epoxy resin was melted on a hot plate of a viscometer adjusted to 150 ° C., and the viscosity when measured at a rotational speed of 750 rpm was measured.
Analyzer: Cone plate viscometer (melting point measurement) manufactured by Tokai Yagami Co., Ltd. Analyzer: DSC7020 manufactured by SII Nano Technology
Measurement temperature range: 20 ° C to 250 ° C
Temperature increase rate: 10 ° C / min
(Glass transition temperature (Tg))
Using a test piece obtained by cutting a cured product into a length of 5 cm, a width of 1 cm, and a thickness of 4 mm, the measurement was performed under the following conditions, and the peak top of 1 ″ E ″ and tan δ at the second temperature increase was Tg. It was.

Analyzer: EXSTAR6100 manufactured by Seiko Instruments Inc.
Measurement mode: 3-point bending mode Measurement temperature range: 30 ° C to 280 ° C
Temperature increase rate: 5 ° C / min, Temperature decrease rate: 5 ° C / min

  <Production Example 1: Synthesis of 1,1-bis (3-allyl-4-hydroxyphenyl) cyclododecane (Compound 11)>

  In a 10 L autoclave, 353 g (1.00 mol) of 1,1-bis (4-hydroxyphenyl) cyclododecane (compound 10), 1277 g of N, N-dimethylformamide, 1054 g (7.63 mol) of potassium carbonate, 486 g of allyl chloride (6 .35 mol) was added, and the mixture was heated to 40 ° C. and uniformly dissolved, and then heated to 65 ° C. over 1 hour. After reacting at 65 ° C. for 6 hours, 2200 g of methyl isobutyl ketone was added, and the resulting reaction solution was washed with water. After distilling off excess allyl chloride and methyl isobutyl ketone under reduced pressure, the mixture was heated to 200 ° C. and heated for 6 hours to obtain 1,1-bis (3-allyl-4-hydroxyphenyl) cyclododecane (Compound 11). 520 g (1.20 mol) were obtained.

  <Production Example 2: Synthesis of 1,1-bis (3-allyl-4-glycidyloxyphenyl) cyclododecane (Compound 12)>

  238 g (550 mmol) of 1,1-bis (3-allyl-4-hydroxyphenyl) cyclododecane (Compound 11) synthesized in Production Example 1 in a 3 L four-necked flask, 663 g (7.17 mmol) of epichlorohydrin, 258 g of isopropanol, water After 92 g was charged and the temperature was raised to 40 ° C. and dissolved uniformly, the temperature was raised to 65 ° C. while 106 g (1.29 mmol) of a 48.5 wt% aqueous sodium hydroxide solution was added dropwise over 90 minutes. After completion of the dropwise addition, the mixture was further stirred for 30 minutes, the reaction solution was washed with water, the solvent and epichlorohydrin were distilled off, and crude 1,1-bis (3-allyl-4-glycidyloxyphenyl) cyclododecane (Compound 12 )

This was dissolved in 450 g of methyl isobutyl ketone, 6.00 g (72.8 mmol) of 48.5 wt% sodium hydroxide aqueous solution was added, and the mixture was stirred at 65 ° C. for 1 hour. After neutralizing the reaction solution by adding an aqueous sodium dihydrogen phosphate solution, the reaction solution was washed with water, and then the solvent was distilled off to obtain 1,1-bis (3-allyl-4-glycidyloxyphenyl). ) 280 g of a pale yellow solid mainly composed of cyclododecane (compound 12) was obtained. The yield was 93% when the purity was 100%, and the epoxy equivalent was 288 g / equivalent.

  <Production Example 3: Synthesis of 1,1-bis (3-glycidyl-4-glycidyloxyphenyl) cyclododecane (Compound 13)>

In a 300 ml three-necked flask, 20.0 g (36.7 mmol) of 1,1-bis (3-allyl-4-glycidyloxyphenyl) cyclododecane (Compound 12) produced in Production Example 2, toluene 40 ml, N-butyl -N, N-di [2- (4-t-butylbenzoyloxy) ethyl] -N-methylammonium monomethyl sulfate 1.71 g (3.67 mmol), 8.1 (w / v)% phosphoric acid 11. 5 mL (9.54 mmol) and 2.42 g (7.34 mmol) of sodium tungstate dihydrate were added, a Dimroth was attached, and the mixture was stirred at 70 ° C. To this mixture, 1.03 ml (4.00 mmol) of 42% by weight hydrogen peroxide was added over 8.5 hours, and the mixture was further stirred for 1 hour for liquid separation. The aqueous layer was re-extracted with 5 ml of toluene and mixed with the toluene layer of the reaction solution. The toluene solution was cooled to 45 ° C., 60 ml of a 5 wt% aqueous sodium thiosulfate solution was added and stirred for 1 hour, and then the aqueous layer was extracted. The aqueous layer was re-extracted with 10 ml of toluene and mixed with the previous toluene layer. To this toluene layer, 20 ml of methanol and 2.02 g (14.7 mmol) of potassium carbonate were added and stirred for 1 hour, and then 20 ml of a 1 mol / L aqueous sodium hydroxide solution was added and stirred for 1 hour, followed by liquid separation. The aqueous layer was re-extracted with 10 ml of toluene and mixed with the previous toluene layer. The obtained toluene solution was washed with 20 ml of a saturated aqueous sodium sulfate solution and then dried over anhydrous sodium sulfate, and the solvent was distilled off.

The obtained white solid was purified with a silica gel column to obtain 10.7 g (18.6 mmol) of 1,1-bis (3-glycidyl-4-glycidyloxyphenyl) cyclododecane (Compound 13) at a yield of 51%. .
¹ H-NMR (400 MHz, CDCl 3) δ 6.98 (2H, dd, J = 2.3, 8.4 Hz), 6.93 (2H, s), 6.70 (2H, dd, J = 0.7 , 8.4 Hz), 4.20 (2H, dd, J = 3.0, 11.1 Hz), 3.92 (2H, ddd, J = 5.6, 9.4, 11.1 Hz), 3. 35-3.32 (2H, m), 3.16-3.11 (2H, m), 2.93-2.86 (4H, m), 2.81-2.70 (6H, m), 2.54-2.49 (2H, m), 1.99 (4H, br. S), 1.36 (10H, br. S), 1.30 (4H, br. S), 0.91 ( 4H, br.s).
The epoxy equivalent of this epoxy resin was 145 g / equivalent, the melting point was 142 ° C., and the shear viscosity at 150 ° C. was 170 mPa · s.

  <Production Example 4: Synthesis of 1,1-bis (3-allyl-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (Compound 15)>

  In a 10 L autoclave, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (compound 14) 317 g (1.02 mol), N, N-dimethylformamide 901 g, potassium carbonate 849 g (6.15 mol) ), 391 g (5.11 mol) of allyl chloride were charged, heated to 40 ° C. and uniformly dissolved, and then heated to 65 ° C. over 1 hour. After reacting at 65 ° C. for 6 hours, 600 g of methyl isobutyl ketone was added, and the resulting reaction solution was washed with water. After distilling off excess allyl chloride and methyl isobutyl ketone under reduced pressure, the temperature was raised to 200 ° C. and heated for 6 hours to obtain 1,1-bis (3-allyl-4-hydroxyphenyl) -3, 3, 5 -350 g (896 mmol) of trimethylcyclohexane (compound 15) was obtained with a yield of 88%.

  <Production Example 5: Synthesis of 1,1-bis (3-allyl-4-glycidyloxyphenyl) -3,3,5-trimethylcyclohexane (Compound 16)>

In a 3 L four-necked flask, 194 g (497 mmol) of 1,1-bis (3-allyl-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (Compound 15) synthesized in Production Example 1 and 552 g of epichlorohydrin (5. 97 mol), 215 g of isopropanol, and 77 g of water were added, and the mixture was heated to 40 ° C. and dissolved uniformly. Then, 95 g (1.15 mol) of 48.5 wt% sodium hydroxide aqueous solution was added dropwise over 90 minutes at 65 ° C. The temperature was raised to. After completion of the dropwise addition, the mixture was further stirred, the reaction solution was washed with water, the solvent and epichlorohydrin were distilled off, and crude 1,1-bis (3-allyl-4-glycidyloxyphenyl) -3, 3, 5 -Trimethylcyclohexane (compound 16) was obtained.

  This was dissolved in 375 g of methyl isobutyl ketone, 5.3 g (64.3 mmol) of 48.5 wt% aqueous sodium hydroxide solution was added, and the mixture was stirred at 65 ° C. for 1 hour. After neutralizing the reaction solution by adding an aqueous sodium dihydrogen phosphate solution, the reaction solution was washed with water, and then the solvent was distilled off to obtain 1,1-bis (3-allyl-4-glycidyloxyphenyl). ) -3,3,5-trimethylcyclohexane (compound 16) 230 g was obtained. The yield was 92% when the purity was 100%, and the epoxy equivalent was 269 g / equivalent.

  <Production Example 6: Synthesis of 1,1-bis (3-glycidyl-4-glycidyloxyphenyl) -3,3,5-trimethylcyclohexane (Compound 17)>

  20.1 g (39.8 mmol) of 1,1-bis (3-allyl-4-glycidyloxyphenyl) -3,3,5-trimethylcyclohexane (Compound 16) prepared in Preparation Example 4 in a 300 ml three-necked flask , Toluene 40 ml, water 1.8 ml, N-butyl-N, N-di [2- (4-t-butylbenzoyloxy) ethyl] -N-methylammonium monomethyl sulfate 1.85 g (3.98 mmol), 11 (Weight / volume)% phosphoric acid 9.22 mL (10.3 mmol) and sodium tungstate dihydrate 2.61 g (7.96 mmol) were added, a Dimroth was attached, and the mixture was stirred at 70 ° C. To this mixture, 7.70 ml (109 mmol) of 42 wt% hydrogen peroxide was added over 6 hours, and the mixture was further stirred for 1.5 hours to separate the layers. The aqueous layer was re-extracted with 10 ml of toluene and mixed with the toluene layer of the reaction solution. The toluene solution was cooled to 40 ° C., 20 ml of a 5 wt% aqueous sodium thiosulfate solution was added and stirred for 1 hour, and then the aqueous layer was extracted. The aqueous layer was re-extracted with 10 ml of toluene and mixed with the previous toluene layer. To this toluene layer, 20 ml of methanol and 2.22 g (15.9 mmol) of potassium carbonate were added and stirred for 1 hour. Then, 20 ml of a 1 mol / L aqueous sodium hydroxide solution was added and stirred for 1 hour, followed by liquid separation. The aqueous layer was re-extracted with 10 ml of toluene and mixed with the previous toluene layer. The obtained toluene solution was washed with 20 ml of a saturated aqueous sodium sulfate solution and then dried over anhydrous sodium sulfate, and the solvent was distilled off.

The obtained reddish brown oily substance was purified with a silica gel column, and 10.1-g (19.3 mmol) of 1,1-bis (3-glycidyl-4-glycidyloxyphenyl) -3,3,5-trimethylcyclohexane (Compound 17) was obtained. Was obtained in a yield of 48%.
¹ H-NMR (400 MHz, CDCl 3) δ 7.15 (1H, d, J = 8.6 Hz), 7.13 (1H, d, J = 8.6 Hz), 7.06-7.03 (1H, m ), 6.98 (1H, ddt, J = 2.5, 2.8, 10.9 Hz), 6.72 (1H, d, J = 8.1 Hz), 6.66 (1H, d, J = 8.8 Hz), 4.25-4.15 (2H, m), 3
. 96-3.85 (2H, m), 3.36-3.29 (2H, m), 3.17-3.11 (2H, m), 3.11-2.70 (10H, m), 2.63 (1H, d, J = 12.9 Hz), 2.55-2.46 (2H, m), 2.44-2.39 (1H, m), 2.02-1.89 (1H) M), 1.87 (1H, d, J = 13.4 Hz), 1.36 (1H, d, J = 12.9 Hz), 1.13 (1H, dd, J = 12.6, 13. 4 Hz), 0.97-0.95 (6 H, m), 0.86 (1 H, dd, J = 12.4, 12.6 Hz), 0.35 (3 H, d, J = 3.6 Hz).
The epoxy equivalent of this epoxy resin was 136 g / equivalent, and the shear viscosity at 150 ° C. was 45 mPa · s.

  <Production Example 7: Synthesis of 2,2-bis (3-glycidyl-4-glycidyloxyphenyl) propane (Compound 19)>

In a 100 ml reaction vessel, 4.00 g (10.3 mmol) of 2,2-bis (3-allyl-4-allyloxyphenyl) propane (Compound 18), toluene 16 ml, water 2 ml, N-butyl-N, N- 417 mg (0.62 mmol) of di [2- (4-t-butylbenzoyloxy) ethyl] -N-methylammonium monomethyl sulfate, 154 mg (130 mmol) of 85% (w / v) aqueous phosphoric acid solution, sodium tungstate dihydrate 410 mg (1.24 mol) of the Japanese product was added, and a Dimroth was attached, followed by stirring at 70 ° C. To this mixture, 44.84 ml (68.2 mmol) of 42 wt% aqueous hydrogen peroxide was added over 6 hours, and the mixture was further stirred for 3 hours for liquid separation.

  To the obtained toluene layer, 8 ml of toluene was added, and washed with 4 ml of water and 8 ml of a 5 wt% aqueous sodium thiosulfate solution. 4 ml of methanol and 1.42 g (10.2 mmol) of potassium carbonate were added, and the mixture was treated at an internal temperature of 40 ° C. for 1 hour. Further, 4 ml of a 1 mol / L sodium hydroxide aqueous solution was added and stirred at an internal temperature of 40 ° C. for 1 hour. Thereafter, liquid separation was performed. The obtained toluene solution was washed with 4 ml of water, and then the solvent was distilled off.

The obtained reddish brown oily substance was purified with a silica gel column to obtain 9.34 g of 2,2-bis (3-glycidyl-4-glycidyloxyphenyl) propane (Compound 19) in a yield of 44%.
¹ H-NMR (400 MHz, CDCl 3) δ 7.00-7.08 (4H, m), 6.72-6.76 (2H, m), 4.19-4.26 (2H, m), 3. 90-3.98 (2H, m), 3.32-3.38 (2H, m), 3.13-3.20 (2H, m), 2.86-2.94 (4H, m), 2.72-2.83 (6H, m), 2.52-2.56 (2H, m), 1.63 (6H, s).
The epoxy equivalent of this epoxy resin was 115 g / equivalent, and the shear viscosity at 150 ° C. was 30 mPa · s.

  <Production Example 8: Synthesis of 2,2-bis (3,4-diallyloxyphenyl) cyclohexane (Compound 21)>

  In a reaction vessel, 9.4 g (31 mmol) of 2,2-bis (3,4-dihydroxyphenyl) cyclohexane (Compound 20) was dissolved in 120 ml of ethanol. To this were added 16.7 g (138 mmol) of allyl bromide and 19.0 g (138 mmol) of potassium carbonate, and the mixture was heated to reflux for 12 hours. The reaction solution was returned to room temperature and then filtered, and the solvent of the filtrate was distilled off.

The obtained oil was purified with a silica gel column to obtain 13.0 g of 2,2-bis (3,4-allyloxyphenyl) cyclohexane (Compound 21) in a yield of 91%.
¹ H-NMR (400 MHz, CDCl 3) δ 6.79 (4H, s), 5.97-6.12 (4H, m), 5.40 (2H, dd, J = 1.5, 17.3 Hz), 5.34 (2H, dd, J = 1.5, 17.3 Hz), 5.25 (2H, dd, J = 1.5, 10.5 Hz), 5.22 (2H, dd, J = 1. 5, 10.5 Hz), 4.57 (4H, d, J = 5.3), 4.52 (4H, d, J = 5.3 Hz), 2.12-2.22 (4H, m), 1.42-1.61 (6H, m).

  <Production Example 9: Synthesis of 2,2-bis (3,4-diglycidyloxyphenyl) cyclohexane (Compound 22)>

  In a reaction container, 1.0 g (2.2 mmol) of 2,2-bis (3,4-diallylphenyl) cyclohexane (Compound 21) was dissolved in 1.5 ml of toluene, and then 72.6 mg of sodium tungstate dihydrate. (2.2 mmol) Methyl trioctyl ammonium hydrogen sulfate (2.2 mmol), 85% phosphoric acid 10.6 mg (929 μmol), 98% sulfuric acid 10.6 mg (1.06 mmol), and toluene 0.5 ml were added. Further, 2.49 g (22.0 mmol) of 30% hydrogen peroxide was added dropwise at room temperature over 5 minutes. The reaction mixture was stirred at 50 ° C. for 4 hours and at 70 ° C. for 3 hours, cooled to room temperature, and ethyl acetate was added. The organic layer was washed with 10% aqueous sodium bisulfite solution and water, dried over sodium sulfate, and then the solvent was distilled off.

The obtained reddish brown oily substance was purified with a silica gel column to obtain 0.28 g of 2,2-bis (3,4-diglycidyloxyphenyl) cyclohexane (Compound 22) in a yield of 25%.
¹ H-NMR (500 MHz, CDCl 3) δ 6.82-6.85 (6H, m), 4.16-4.23 (4H, m), 3.91-3.98 (4H, m), 3. 32-3.36 (2H, m), 3.28-3.32 (2H, m), 2.83-2.87 (4H, m), 2.72-2.73 (2H, m), 2.71-2.69 (2H, m), 2.12-2.21 (4
H, m), 1.43-1.55 (6H, m).

<Examples 1-3, Comparative Example 1: Production and evaluation of cured product>
4-Methylhexahydrophthalic anhydride / hexahydrophthalic anhydride = 70/30 as a curing agent for each epoxy resin at the ratio shown in Table 1 below (Rikacid MH-700 manufactured by Shin Nippon Rika Co., Ltd.)
) At 60 ° C. until uniform, followed by methyltributylphosphonium dimethyl phosphate (Hishicolin (registered trademark) PX-4MP manufactured by Nippon Chemical Industry Co., Ltd.) or 2-ethyl-4 (5)- Methylimidazole (EMI24, manufactured by Mitsubishi Chemical Corporation) was added and stirred until uniform to obtain an epoxy resin composition. A casting plate adjusted to a thickness of 2 mm was prepared using two glass plates with a release PET film on the inside, and the composition liquid was cast on the casting plate for 3 hours at 100 ° C. and at 140 ° C. for 3 hours. Heated for hours to obtain a cured product. The Tg of the obtained cured product is shown in Table 1.

  From the above results, in the polyfunctional epoxy resin of the present invention, the number of epoxy groups contained in one molecule of epoxy resin is the same four as in Comparative Example 1 and shows the same Tg. It was shown that since the equivalent weight is large, the toxicity is small and the viscosity that does not affect the processability and moldability can be maintained. Therefore, it can be said that the polyfunctional epoxy resin of the present invention is an epoxy resin that balances the low toxicity and the physical properties that are generally easy to conflict with each other, such as low viscosity and high heat resistance.

Claims (8)

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

(In the formula, A is an optionally substituted monocyclic alicyclic hydrocarbon having 3 to 20 carbon atoms, X is independently a glycidyl group or a glycidyloxy group, and R is independently an alkyl group having 1 to 4 carbon _atoms, m 1, _{m 2} represents an integer of 0 to _2, n 1, _{n 2} is 1 or 2.)   The polyfunctional epoxy resin of Claim 1 whose A in the said General formula (1) is the C7-20 monocyclic alicyclic hydrocarbon which may be substituted.   The polyfunctional epoxy resin of Claim 1 whose A in the said General formula (1) is a C4-C20 monocyclic alicyclic hydrocarbon which has an alkyl group as a substituent.   The polyfunctional epoxy resin as described in any one of Claims 1-3 whose X in the said General formula (1) is a glycidyl group.   The polyfunctional epoxy resin according to any one of claims 1 to 3, wherein X in the general formula (1) is a glycidyloxy group. An allyl compound represented by the following general formula (9).

(In the formula, A and m ₁ , m ₂ , n ₁ and n ₂ are the same as those in the general formula (1).)   The epoxy resin composition characterized by including the polyfunctional epoxy resin as described in any one of Claims 1-5.   Hardened | cured material formed by hardening | curing the epoxy resin composition of Claim 7.