JP2009209117A - Epoxy compound, method for producing the same, epoxy resin composition and cured product thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aromatic polyfunctional epoxy compound which is a liquid at a normal temperature, and provides a cured product having excellent heat resistance. <P>SOLUTION: The epoxy compound is represented by general formula (1) (wherein, R<SP>1</SP>is one of a hydrogen atom, a halogen atom, an allyl group, an aralkyl group, an alkyl group, an alkoxy group and an aryloxy group; at least one of R<SP>2</SP>is a glycidyloxy group or a β-alkyl glycidyloxy group; and X is one of a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, and an aryloxy group). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an epoxy compound, a method for producing the same, an epoxy resin composition, and a cured product thereof. The present invention relates to a novel epoxy compound that gives a cured product excellent in heat resistance, a method for producing the same, an epoxy resin composition, and a cured product thereof.

  Epoxy resins have various excellent properties such as adhesion, heat resistance and mechanical properties, and are used in electrical / electronic materials, paints, adhesives, various composite materials, civil engineering and building materials. Among them, polyfunctional aromatic ring-containing epoxy resins (generally, novolak-type epoxy resins) are widely used in fields where high heat resistance is required. Since the novolac epoxy resin is based on a repeating structure, it is necessary to increase the number of repetitions in order to obtain a cured product having high heat resistance. However, when the number of repetitions is increased, the melt viscosity of the epoxy resin is increased, causing a problem in workability. For example, a polyglycidyl ether derived from dioxynaphthalene and a predetermined aldehyde and having at least a part of the hydroxyl group derived from the dioxynaphthalene of a novolak resin containing two or more naphthalene nuclei in the molecule is proposed. (Patent Document 1). However, although the glycidyl etherified novolak type epoxy resin has high heat resistance, it is solid at room temperature and must be heated and melted or dissolved in a solvent to be cured. There is a problem in workability.

  On the other hand, an aliphatic epoxy compound such as trimethylolpropane triglycidyl ether is known as a representative example of a polyfunctional epoxy compound that is liquid at room temperature. However, such an aliphatic epoxy compound has excellent workability but has a problem in heat resistance. Moreover, although it is a small number, the aromatic polyfunctional epoxy compound which is liquid at normal temperature has been reported (for example, patent document 2). However, there is a problem with heat resistance as described above.

  Thus, the liquid aromatic polyfunctional epoxy compound excellent in heat resistance and workability has not yet been proposed.

JP-A-61-69826 Japanese Patent Laid-Open No. 8-311154

  Accordingly, an object of the present invention is to provide an aromatic polyfunctional epoxy compound that is liquid at room temperature and gives a cured product having excellent heat resistance, a method for producing the epoxy compound, an epoxy resin composition containing the epoxy compound as an essential component, And a cured product obtained by curing the epoxy resin composition.

  As a result of intensive studies in view of the above problems, the present inventor has obtained an epoxy obtained by glycidylating a 1,2,4-trihydroxynaphthalene derivative obtained by reducing a 2-hydroxy-1,4-naphthoquinone derivative. The compound was found to be a liquid at room temperature and give a cured product excellent in heat resistance, and the present invention was completed.

  That is, the first gist of the present invention resides in an epoxy compound represented by the following general formula (1).

(In General Formula (1), R ¹ represents any ^one of a hydrogen atom, a halogen atom, an allyl group, an aralkyl group, an alkyl group, an alkoxy group, and an aryloxy group, and R ² represents a glycidyloxy group and a β-alkyl. Provided that it is either a glycidyloxy group or a hydroxy group, and at least one of R ² represents a glycidyloxy group or a β-alkylglycidyloxy group, X is a hydrogen atom, a halogen atom, an alkyl group, Indicates an alkoxy group or an aryloxy group.)

  According to a second aspect of the present invention, in the presence of a basic compound, a 1,2,4-trihydroxynaphthalene derivative represented by the following general formula (4) is converted to an epihalohydrin compound represented by the following general formula (5): It reacts, It exists in the manufacturing method of the epoxy compound in any one of Claims 1-5 characterized by the above-mentioned.

(In the general formula (4), R ¹ represents any ^one of a hydrogen atom, a halogen atom, an allyl group, an aralkyl group, an alkyl group, an alkoxy group, and an aryloxy group, and X represents a hydrogen atom, a halogen atom, and an alkyl group. , An alkoxy group or an aryloxy group.)

(In the general formula (5), R ⁴ represents either a hydrogen atom or an alkyl group, and Y represents a halogen atom.)

  The third gist of the present invention resides in an epoxy resin composition comprising the above-described epoxy compound as a component, and the fourth gist of the present invention is the epoxy resin composition according to the third gist. It exists in the hardened | cured material formed by hardening.

  According to the present invention, an aromatic polyfunctional epoxy compound that gives a cured product that is liquid at room temperature and has excellent heat resistance, a method for producing the epoxy compound, an epoxy resin composition containing the epoxy compound as an essential component, and the epoxy resin A cured product obtained by curing the composition is provided.

  Hereinafter, the present invention will be described in detail.

(Epoxy compound)
The epoxy compound of the present invention is represented by the following general formula (1).

(In General Formula (1), R ¹ represents any ^one of a hydrogen atom, a halogen atom, an allyl group, an aralkyl group, an alkyl group, an alkoxy group, and an aryloxy group, and R ² represents a glycidyloxy group and a β-alkyl. Provided that it is either a glycidyloxy group or a hydroxy group, and at least one of R ² represents a glycidyloxy group or a β-alkylglycidyloxy group, X is a hydrogen atom, a halogen atom, an alkyl group, Indicates an alkoxy group or an aryloxy group.)

In the present invention, an epoxy compound in which the general formula (1) is the following general formula (2) is preferable. This compound is an epoxy compound in which two of R ^{2 in} the general formula (1) are a glycidyloxy group or a β-alkylglycidyloxy group.

(In General Formula (2), R ¹ represents any ^one of a hydrogen atom, a halogen atom, an allyl group, an aralkyl group, an alkyl group, an alkoxy group, and an aryloxy group, and R ³ represents any one of a hydrogen atom and an alkyl group. X represents any of a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, and an aryloxy group.)

Moreover, in this invention, the epoxy compound whose general formula (1) is the following general formula (3) is preferable. This compound is an epoxy compound in which three of R ^{2 in} the general formula (1) are glycidyloxy groups or β-alkylglycidyloxy groups.

(In General Formula (3), R ¹ represents any ^one of a hydrogen atom, a halogen atom, an allyl group, an aralkyl group, an alkyl group, an alkoxy group, and an aryloxy group, and R ³ represents any one of a hydrogen atom and an alkyl group. X represents any of a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, and an aryloxy group.)

Specific examples of the substituent for R ¹ (other than hydrogen) in the general formulas (1) to (3) are as follows. That is, for example, halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom; allyl groups such as allyl group, methallyl group, crotyl group; benzyl group, p-methylbenzyl group, o-methylbenzyl group, p-chloro Aralkyl groups such as benzyl group, o-chlorobenzyl group, p-methoxybenzyl group, o-methoxybenzyl group, phenethyl group; methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i -Alkyl groups such as butyl group, n-pentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, 2-ethylhexyl group, dodecyl group; methoxy group, ethoxy group, n-propoxy group, n-butoxy group, alkoxy groups such as n-hexyloxy group; phenoxy group, p-methylphenoxy group, o-methylphenoxy group, p- Rorofenokishi group, an aryloxy group such as o- chlorophenoxy group.

  Specific examples of the substituent for X (other than a hydrogen atom) in the general formulas (1) to (3) are as follows. That is, for example, halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom; methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, n-pentyl group, alkyl groups such as n-hexyl group, cyclohexyl group, n-heptyl group, 2-ethylhexyl and dodecyl group; alkoxy groups such as methoxy group, ethoxy group, n-propoxy group, n-butoxy group and n-hexyloxy group; Examples thereof include aryloxy groups such as phenoxy group, p-methylphenoxy group, o-methylphenoxy group, p-chlorophenoxy group, o-chlorophenoxy group.

Specific examples of the substituent for R ³ in the general formulas (2) and (3) (other than a hydrogen atom) include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i Examples thereof include alkyl groups such as -butyl group, n-pentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, 2-ethylhexyl group and dodecyl group.

  Specific examples of the compounds represented by the general formulas (1) to (3) include the following compounds. That is, 1,2,4-triglycidyloxynaphthalene, 1,4-diglycidyloxy-2-hydroxynaphthalene, 2,4-diglycidyloxy-1-hydroxynaphthalene, 1,2-diglycidyloxy-4-hydroxy Naphthalene, 3-fluoro-1,2,4-triglycidyloxynaphthalene, 3-chloro-1,2,4-triglycidyloxynaphthalene, 3-bromo-1,2,4-triglycidyloxynaphthalene, 3-iodo -1,2,4-triglycidyloxynaphthalene, 3-allyl-1,2,4-triglycidyloxynaphthalene, 1,2,4-triglycidyloxy-3-methallylnaphthalene, 3-crotyl-1,2 , 4-triglycidyloxynaphthalene, 3-benzyl-1,2,4-triglycidyloxynaphthal 1,2,4-triglycidyloxy-3-p-methylbenzylnaphthalene, 1,2,4-triglycidyloxy-3-o-methylbenzylnaphthalene, 3-p-chlorobenzyl-1,2,4 -Triglycidyloxynaphthalene, 3-o-chlorobenzyl-1,2,4-triglycidyloxynaphthalene, 1,2,4-triglycidyloxy-3-p-methoxybenzylnaphthalene, 1,2,4-triglycidyl Oxy-3-o-methoxybenzylnaphthalene, 1,2,4-triglycidyloxy-3-phenethylnaphthalene, 1,2,4-triglycidyloxy-3-methylnaphthalene, 3-ethyl-1,2,4- Triglycidyloxynaphthalene, 1,2,4-triglycidyloxy-3-n-propylnaphthalene, 1,2,4-to Glycidyloxy-3-n-propylnaphthalene, 3-n-butyl-1,2,4-triglycidyloxynaphthalene, 3-n-butyl-1,2,4-triglycidyloxynaphthalene, 1,2,4- Triglycidyloxy-3-n-pentylnaphthalene, 1,2,4-triglycidyloxy-3-n-hexylnaphthalene, 3-cyclohexyl-1,2,4-triglycidyloxynaphthalene, 1,2,4-tri Examples thereof include glycidyloxy-3-n-heptylnaphthalene, 3- (2-ethylhexyl) -1,2,4-triglycidyloxynaphthalene, 3-dodecyl-1,2,4-triglycidyloxynaphthalene and the like.

  The compounds represented by the following formulas (A) and (B) are representative epoxy compounds of the present invention.

(Method for producing epoxy compound)
In the method for producing an epoxy compound according to the present invention, in the presence of a basic compound, a 1,2,4-trihydroxynaphthalene derivative represented by the following general formula (4) is converted to an epihalohydrin represented by the following general formula (5). It is characterized by reacting with a compound.

(In the general formula (4), R ¹ represents any ^one of a hydrogen atom, a halogen atom, an allyl group, an aralkyl group, an alkyl group, an alkoxy group, and an aryloxy group, and X represents a hydrogen atom, a halogen atom, and an alkyl group. , An alkoxy group or an aryloxy group.)

(In the general formula (5), R ⁴ represents either a hydrogen atom or an alkyl group, and Y represents a halogen atom.)

Specific examples of the substituent for R ¹ (other than a hydrogen atom) and the substituent for X in the general formula (4) are the same as those in the general formula (1). As the general formula (5) in the substituent group ^{R 4} (other than a hydrogen atom), a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl group, i- butyl, n- pentyl Group, an n-hexyl group, a cyclohexyl group, an n-heptyl group, a 2-ethylhexyl group, a dodecyl group and the like. Specific examples of Y include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Can be mentioned.

  The 1,2,4-trihydroxynaphthalene derivative represented by the general formula (4) can be obtained, for example, by reducing a 2-hydroxy-1,4-naphthoquinone derivative. Accordingly, the epoxy compound of the present invention is a first reaction for reducing a 2-hydroxy-1,4-naphthoquinone derivative, and the resulting 1,2,4-trihydroxynaphthalene derivative is converted to an epihalohydrin compound in the presence of a basic compound. A second reaction in which two of the three hydroxyl groups are glycidylated or β-alkylglycidylated, and the resulting diglycidyloxyhydroxynaphthalene derivative is glycidylated or β-substituted with an epihalohydrin compound in the presence of a basic compound. -Obtained by a third reaction to alkyl glycidylation.

(First reaction)
In the first reaction, the reduction reaction uses hydrogen reduction using a noble metal as a catalyst. Usable noble metal catalysts include palladium on activated carbon, palladium on alumina, platinum on activated carbon and the like. In particular, 5% palladium / carbon is preferably used.

  The amount of the noble metal catalyst added to the 2-hydroxy-1,4-naphthoquinone derivative is usually 0.01 to 10% by weight, preferably 0.2 to 5% by weight. When the addition amount of the catalyst is less than 0.01% by weight, the hydrogenation rate is slow, and when it exceeds 10% by weight, the hydrogenation of the aromatic ring tends to occur simultaneously as a side reaction.

  Other reducing agents can also be used. Any reducing agent may be used as long as it can reduce the carbonyl group of the 2-hydroxy-1,4-naphthoquinone derivative. For example, sodium borohydride, lithium aluminum hydride, sodium dithionite, thio peroxide Urea or the like is used.

  The solvent to be used is not particularly limited, but alcohol solvents such as methanol and ethanol; ketone solvents such as acetone and methyl isobutyl ketone; ether solvents such as tetrahydrofuran and 1,4-dioxane; aromatics such as toluene and xylene Group solvents; halogen solvents such as dichloromethane and chloroform; amide solvents such as dimethylformamide and dimethylacetamide; water and the like. Two or more of these solvents may be used in combination.

  The amount of the solvent used may be an amount capable of dissolving the raw material 2-hydroxy-1,4-naphthoquinone derivative, or the 1,2,4-trimethyl to be produced even in a slurry state. An amount of a solvent sufficient to dissolve the hydroxynaphthalene derivative may be added. The specific amount used is usually 1 to 30% by weight, preferably 5 to 20% by weight, as the concentration of the 2-hydroxy-1,4-naphthoquinone derivative in the solvent.

  The pressure of hydrogen used for hydrogen reduction is usually 2 to 10 atm, preferably 3 to 7 atm. If the hydrogen pressure is too low, the reaction time for hydrogen reduction becomes long, and if the hydrogen pressure is too high, hydrogenation of the aromatic ring may occur as a side reaction.

  The reaction temperature for hydrogen reduction is usually 0 to 100 ° C., preferably 20 to 80 ° C., although it depends on the solvent used. When the reaction temperature is less than 0 ° C., hydrogen reduction is slow and takes a long time for the reaction. When the reaction temperature is higher than 100 ° C., hydrogenation of the aromatic ring occurs in the side reaction and a by-product is formed. The purity of some 1,2,4-trihydroxynaphthalene derivatives decreases. The reaction time for hydrogen reduction under such reaction conditions is usually about 0.5 to 3 hours.

(Second reaction)
In the second reaction, the inside of the reactor containing the solution of the 1,2,4-trihydroxynaphthalene derivative obtained in the first reaction is replaced with an inert gas, and the solvent is removed in the presence of a basic compound at normal pressure. In the presence or absence, the corresponding diglycidyloxyhydroxynaphthalene derivative or di (β-alkylglycidyloxy) hydroxynaphthalene derivative is obtained by reacting with the epihalohydrin compound represented by the general formula (5). Depending on the reaction conditions, 1,2,4-triglycidyloxynaphthalene derivatives or 1,2,4-tri (β-alkylglycidyloxy) naphthalene derivatives are also produced.

(Third reaction)
In the third reaction, the diglycidyloxyhydroxynaphthalene derivative or di (β-alkylglycidyloxy) hydroxynaphthalene derivative obtained in the second reaction is reacted again in the same manner as in the second reaction, whereby the corresponding 1,2 , 4-triglycidyloxynaphthalene derivative or 1,2,4-tri (β-alkylglycidyloxy) naphthalene derivative can be obtained.

  The inert gas used in the second and third reactions is, for example, nitrogen, argon, or the like, and the reaction is preferably performed in the presence of the inert gas. When the second reaction is carried out in the presence of molecular oxygen such as air, the raw material 1,2,4-trihydroxynaphthalene derivative may be oxidized to produce a 2-hydroxy-1,4-naphthoquinone derivative. . The oxygen concentration inside the reaction vessel is not particularly limited, but is usually 2 vol% or less.

  Examples of the 1,2,4-trihydroxynaphthalene derivative that can be used as a raw material in the second reaction include the following compounds. That is, 1,2,4-trihydroxynaphthalene, 3-fluoro-1,2,4-trihydroxynaphthalene, 3-chloro-1,2,4-trihydroxynaphthalene, 3-bromo-1,2,4- Trihydroxynaphthalene, 3-iodo-1,2,4-trihydroxynaphthalene, 3-allyl-1,2,4-trihydroxynaphthalene, 1,2,4-trihydroxy-3-methallylnaphthalene, 3-crotyl -1,2,4-trihydroxynaphthalene, 3-benzyl-1,2,4-trihydroxynaphthalene, 1,2,4-trihydroxy-3-p-methylbenzylnaphthalene, 1,2,4-trihydroxy -3-o-methylbenzylnaphthalene, 3-p-chlorobenzyl-1,2,4-trihydroxynaphthalene, 3-o-chlorobenzyl- , 2,4-trihydroxynaphthalene, 1,2,4-trihydroxy-3-p-methoxybenzylnaphthalene, 1,2,4-trihydroxy-3-o-methoxybenzylnaphthalene, 1,2,4-tri Hydroxy-3-phenethylnaphthalene, 1,2,4-trihydroxy-3-methylnaphthalene, 3-ethyl-1,2,4-trihydroxynaphthalene, 1,2,4-trihydroxy-3-n-propylnaphthalene 1,2,4-trihydroxy-3-n-propylnaphthalene, 3-n-butyl-1,2,4-trihydroxynaphthalene, 3-n-butyl-1,2,4-trihydroxynaphthalene, , 2,4-Trihydroxy-3-n-pentylnaphthalene, 1,2,4-trihydroxy-3-n-hexylnaphthalene, 3-cyclohex 1,2,4-trihydroxynaphthalene, 1,2,4-trihydroxy-3-n-heptylnaphthalene, 3- (2-ethylhexyl) -1,2,4-trihydroxynaphthalene, 3-dodecyl- 1,2,4-trihydroxynaphthalene and the like can be mentioned.

  Examples of the epihalohydrin compound represented by the general formula (5) used in the second and third reactions include epichlorohydrin, epibromohydrin, β-methylepichlorohydrin, and the like. It is chlorohydrin or β-methylepichlorohydrin, and more preferably epichlorohydrin because it is easily available. The epihalohydrin compound can also be used as a solvent.

  In the second and third reactions, the charged molar ratio of the epihalohydrin compound to the 1,2,4-trihydroxynaphthalene compound is usually 2.0 to 30, preferably 3.0 to 15. If the latter feed molar ratio with respect to the former is less than 2.0, unreacted hydroxynaphthalene derivative remains, and if the feed mole ratio exceeds 30, it takes time to remove the unreacted epihalohydrin compound, resulting in inefficiency. Is.

  Examples of the basic compound used as the dehydrohalogenating agent in the second and third reactions include trimethylamine, triethylamine, tripropylamine, tributylamine, diethylamine, dibutylamine, piperidine, pyridine, α-picoline, γ- Examples thereof include organic bases such as picoline; inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, and potassium bicarbonate. Among these, sodium hydroxide or potassium hydroxide is preferable because it is easily available.

  The usage-amount of a basic compound is 2.0-9 normally as a preparation molar ratio with respect to a 1,2,4-trihydroxy naphthalene derivative. When the charged molar ratio is less than 2.0, the 1,2,4-trihydroxynaphthalene derivative remains unreacted, whereas when the basic compound is too much, the epihalohydrin compound or epoxy group polymerization or Cleavage occurs, causing a rapid exotherm during the reaction and a decrease in product purity.

  In the second and third reactions, a solvent is used as necessary. Examples of usable solvents include alcohol solvents such as ethanol and 2-propanol; ketone solvents such as acetone and methyl isobutyl ketone; dioxane and tetrahydrofuran. Ether solvents such as: aprotic polar solvents such as dimethylformamide and N-methylpyrrolidone; halogen solvents such as chloroform and dichloromethane. Two or more of these organic solvents may be combined.

  In the second and third reactions, a catalyst is used as necessary. Catalysts that can be used include quaternary ammonium salts such as tetramethylammonium chloride and tetrabutylammonium bromide; tertiary amines such as triethylamine and benzyldimethylamine; imidazoles such as 2-phenylimidazole; and phosphines such as triphenylphosphine. Etc.

  Next, the reaction conditions for the second and third reactions will be described. The reaction temperature of the second reaction is usually not higher than the boiling point of the solvent or epihalohydrin compound. For example, when epichlorohydrin is used, the temperature is in the range of 10 to 100 ° C. When adding an aqueous solution of an inorganic base as the dehydrohalogenating agent described above, it is preferable to add the aqueous solution of the inorganic base continuously or intermittently in small portions over 1 to 8 hours in order to prevent a rapid reaction.

  After completion of the reaction, the basic compound and by-product salt are removed by washing with water and / or filtered. Next, the diglycidyloxyhydroxynaphthalene derivative is obtained in the second reaction by removing the solvent and unreacted epihalohydrin by distilling off under reduced pressure, and the 1,2,4-triglycidyloxynaphthalene derivative is obtained in the third reaction. can get. The obtained diglycidyloxyhydroxynaphthalene derivative or 1,2,4-triglycidyloxynaphthalene derivative may be separated and purified by silica gel column chromatography or the like, if necessary.

  On the other hand, in the second reaction, when the catalyst is used together with an aqueous solution of an inorganic base such as sodium hydroxide as the basic compound, the reaction temperature is 10 to 50 ° C. in the presence of the catalyst such as a quaternary ammonium salt. A diglycidyloxyhydroxynaphthalene derivative or di (β-alkylglycidyl) in which two of the three hydroxy groups of the 1,2,4-trihydroxynaphthalene derivative are glycidylated or β-alkylglycidylated by adding a base Oxy) hydroxynaphthalene derivatives can be selectively produced. Moreover, when not using a catalyst, it can manufacture similarly by adding an inorganic base with reaction temperature of 10-60 degreeC. When the reaction temperature is set to 50 ° C. or higher using a catalyst, or when the reaction temperature is set to 60 ° C. or higher without using a catalyst, the 1,2,4-triglycidyloxynaphthalene derivative or 1,2,4-tri There is a tendency for (β-alkylglycidyloxy) naphthalene derivatives to increase.

(Epoxy resin composition)
The epoxy resin composition of the present invention is characterized by containing the aforementioned epoxy compound as a component.

  The epoxy resin composition of this invention can use another epoxy resin together as needed. It does not specifically limit as an epoxy resin to use together, All the conventionally well-known epoxy resins can be used. For example, bisphenol A type, bisphenol F type, biphenyl type, phenol novolak type, cresol novolak type, bisphenol A novolak type, phenol aralkyl type, naphthalene type, and the like, alicyclic epoxy resin, aliphatic epoxy resin, etc. Can be mentioned. Two or more of these epoxy resins may be used in combination.

  Furthermore, the epoxy resin composition of this invention can use a hardening | curing agent as needed. It does not specifically limit as a hardening | curing agent, All the compounds generally used as a hardening | curing agent of an epoxy resin can be used. For example, polyphenols such as bisphenol A, bisphenol F, bisphenol S, thiodiphenol, hydroquinone, biphenol, dihydroxynaphthalene; various aldehydes such as phenol novolac resin, cresol novolac resin, bisphenol A novolac resin, naphthol novolac resin Phenol resins obtained by the condensation reaction of; acid anhydrides such as methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyrometic acid, and methylnadic acid; latent amine curing agents such as dicyandiamide, imidazole, and guanidine derivatives And aromatic amines such as metaphenylenediamine and xylylenediamine. Two or more of these curing agents may be used in combination.

  In the epoxy resin composition of the present invention, the blending ratio of the epoxy resin and the curing agent is not particularly limited, but the amount of the active hydrogen group of the curing agent with respect to 1 equivalent of the epoxy group in the epoxy resin is usually 0.3 to 2. 0 equivalents, preferably 0.7-1.2 equivalents.

  Furthermore, the epoxy resin composition of the present invention can use a curing accelerator. The curing accelerator is not particularly limited, and all compounds generally used as an epoxy resin curing accelerator can be used. For example, phosphines such as triphenylphosphine and tributylphosphine; imidazoles such as 2-ethyl-4-methylimidazole and 2-methylimidazole; 4-dimethylaminopyridine, 2,4,6-tris (dimethylaminomethyl) phenol And diazabicyclo compounds such as 1,8-diazabicyclo [5,4,0] -7-undecene; Lewis acids, amine complex salts and the like. Two or more of these curing accelerators may be used in combination.

  In the epoxy resin composition of the present invention, the mixing ratio of the epoxy resin and the curing accelerator is not particularly limited, but is usually 0.1 to 7.0% by weight, preferably 0.2 to 5.0% with respect to the epoxy resin. % By weight.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to the following description examples, unless the meaning is exceeded.

Synthesis Example 1 (Synthesis of 1,2,4-trihydroxynaphthalene):
2-hydroxy-1,4-naphthoquinone 20 g (0.11 mol), water 100 g, 5% palladium-carbon was charged into a 200 ml autoclave, and the inside of the container was replaced with nitrogen three times with stirring at a pressure of 0.4 MPa. The reactor was heated to 70 ° C. Thereafter, stirring was stopped, and the inside of the container was replaced with hydrogen three times at a pressure of 0.4 MPa, and then stirring was performed to start a hydrogen reduction reaction. After the reaction for 2 hours, the hydrogen in the vessel was released, the inside of the vessel was replaced with nitrogen at a pressure of 0.4 MPa, and 5% palladium-carbon was filtered under a nitrogen atmosphere. To the filtrate, 127.4 g (1.38 mol) of epichlorohydrin and 20 g of methyl isobutyl ketone were added, 1,2,4-trihydroxynaphthalene was extracted into the organic layer, the aqueous layer was separated, and 1,2,4 -About 167 g of trihydroxynaphthalene solution was obtained.

Synthesis Example 2 (Synthesis of diglycidyloxyhydroxynaphthalene):
In a nitrogen atmosphere, about 167 g of the 1,2,4-trihydroxynaphthalene solution obtained in Synthesis Example 1 was added to a reactor equipped with a dropping funnel, a condenser, and a thermometer, and then 1.8 g of tetrabutylammonium bromide ( 0.006 mol) of a 50 wt% aqueous solution was added to the solution, and with stirring, a 40 wt% aqueous solution of 15.1 g (0.38 mol) of sodium hydroxide was added dropwise over 2 hours at room temperature (20 ° C.). At this time, the temperature in the reactor was controlled so as not to exceed 40 ° C. Further, after stirring for 3 hours, 80 g of methyl isobutyl ketone and 100 g of water were added to separate into two layers, the aqueous layer was extracted, and the organic layer was further washed with 50 g of water. Methyl isobutyl ketone and unreacted epichlorohydrin in the organic layer were distilled off under reduced pressure to obtain 20.8 g of brown, liquid crude diglycidyloxyhydroxynaphthalene. Gel permeation chromatography (GPC) purity was 59%. The crude product was purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate = 1/1 to 2/3 (vol / vol)) to produce a light yellow, liquid purified diglycidyloxyhydroxynaphthalene (E-1). Got. The GPC purity was 92% and the epoxy equivalent was 299 g / eq.

  For GPC measurement, a separation column: TSKgel G1000 + G2000 + G3000HXL (7.8 mm ID × 300 mm, 3, manufactured by Tosoh Corporation), eluent: tetrahydrofuran, detector: differential refractometer (manufactured by JASCO Corporation) did. The eluent conditions were flow rate: 1.0 mL / min, temperature: 40 ° C. Moreover, the epoxy equivalent measurement was based on JISK7236: 2001.

About the compound obtained above, the following physical property was measured.
(1) IR spectrum by infrared (IR) spectrophotometer (manufactured by JASCO Corporation, model: IR-810)

(2) ¹ H-NMR analysis by nuclear magnetic resonance apparatus (NMR) (manufactured by JEOL Ltd., model: GSX FT NMR Spectrometer)

(3) Mass spectrum (manufactured by Shimadzu Corporation, mass spectrometer, model: GCMS-QP5000)

  The results of physical property measurement are as follows, and it was confirmed that the compound obtained in Synthesis Example 2 was diglycidyloxyhydroxynaphthalene.

(1) IR (KBr, cm ⁻¹ ): 3440, 3075, 3010, 2934, 2888, 1637, 1605, 1471, 1459, 1420, 1397, 1362, 1350, 1278, 1259, 1142, 1102, 1092, 1055 1025, 912, 865, 840, 765.

(2) ¹ H-NMR (CDCl ₃ , ppm): δ 2.25 (bs, 1H, OH), 2.80-3.48 (m, 2H, methylene), 3.95-4.44 (m, 7H, methylene × 3, methine), 6.52 (s, 1H, naphthalene ring), 7.32-7.52 (m, 2H, naphthalene ring), 8.00 (d, 1H, naphthalene ring), 8 .16 (d, 1H, naphthalene ring).

(3) Mass spectrum: (EI-MS) m / z = 288 (M +)

  In remote H—H COSY measurement, remote coupling between the proton at the 3rd position of the naphthalene ring and the methylene proton at the 4th position glycidyloxy group was observed, and 1,4-diglycidyloxy-2-hydroxynaphthalene was observed. Alternatively, it was estimated as 2,4-diglycidyloxy-1-hydroxynaphthalene.

Synthesis Example 3 (Synthesis of 1,2,4-triglycidyloxynaphthalene):
As described below, the synthesis of the above-mentioned compound is a step 1 of diglycidylating 1,2,4-trihydroxynaphthalene and a step of further glycidylating the diglycidyloxyhydroxynaphthalene obtained in step 1. It consists of a total of 3 steps, 2 and step-3.

<Step-1>
In the same manner as in Synthesis Example 2, 20.8 g of crude diglycidyloxyhydroxynaphthalene was obtained.

<Step-2>
20.8 g of crude diglycidyloxyhydroxynaphthalene was dissolved in 20 g of methyl isobutyl ketone, put into a reactor equipped with a dropping funnel, a condenser and a thermometer, and 63.8 g (0.69 mol) of epichlorohydrin, tetrabutyl. A 50% aqueous solution of 0.7 g (0.002 mol) of ammonium bromide was added and stirred, and 40% aqueous solution of 10.2 g (0.26 mol) of sodium hydroxide was added dropwise at room temperature (20 ° C.) over 1 hour. . After further stirring for 4 hours, separation, extraction of the aqueous layer, and distillation under reduced pressure were performed in the same manner as in Step-1.

<Step-3>
Unreacted diglycidyloxyhydroxynaphthalene remains in the crude 1,2,4-triglycidyloxynaphthalene obtained in Step-2. Then, 21.0 g of crude 1,2,4-triglycidylnaphthalene (E-2) as a brown liquid was obtained by reaction, separation, extraction of the aqueous layer, and distillation under reduced pressure in the same manner as in Step-2. The GPC purity was 52% and the epoxy equivalent was 211 g / eq. The crude product was purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate = 1/1 (vol / vol)) to purify a pale yellow liquid, 1,2,4-triglycidyloxynaphthalene (E-3). Got. The GPC purity was 87% and the epoxy equivalent was 179 g / eq.

The obtained compound was confirmed to be 1,2,4-triglycidyloxynaphthalene by IR, ¹ H-NMR and Mass spectrum. The results of each physical property measurement are as follows.

(1) IR (KBr, cm ⁻¹ ): 3075, 3010, 2938, 2896, 1640, 1607, 1475, 1460, 1420, 1396, 1365, 1349, 1377, 1360, 1215, 1150, 1109, 1057, 978, 916, 842, 768

(2) ¹ H-NMR (CDCl ₃ , ppm): δ2.58-2.95 (m, 4H, methylene × 2), 3.14-3.20 (m, 1H, methine), 3.41- 3.51 (m, 2H, methine x 2), 3.75-4.47 (m, 8H, methylene x 4), 6.47 (s, 1H, naphthalene ring), 7.25-7.38 ( m, 1H, naphthalene ring), 7.44-7.50 (m, 1H, naphthalene ring), 8.00 (d, 1H, naphthalene ring), 8.16 (d, 1H, naphthalene ring)

(3) Mass spectrum: (EI-MS) m / z = 344 (M +)

  Test Example 1 (Diglycidyloxyhydroxynaphthalene (E-1) curing method and evaluation of cured product):

  Methyl tetrahydrophthalic anhydride as a curing agent was mixed with 100 parts by weight of diglycidyloxyhydroxynaphthalene (E-1, epoxy equivalent 299 g / eq) obtained in Synthesis Example 2 (an equivalent ratio of anhydride / epoxy value was 0.00). 9/1) Further, 1.0 part by weight of 4-dimethylaminopyridine was mixed as a curing accelerator to obtain an epoxy resin composition. Subsequently, it heated at 100 degreeC for 2 hours, 150 degreeC for 2 hours, and 180 degreeC for 2 hours, and obtained hardened | cured material. Table 1 shows the glass transition temperature (Tg) of the obtained cured product. Tg was measured by DSC according to JIS K 7121 (hereinafter the same).

Test Example 2 (Crude 1,2,4-triglycidyloxynaphthalene (E-2) curing method and evaluation of cured product):
In Test Example 1, the same as Test Example 1 except that crude 1,2,4-triglycidyloxynaphthalene (E-2, epoxy equivalent 211 g / eq) obtained in Synthesis Example 3 was used instead of E-1. Through the operations, an epoxy resin composition and a cured product were obtained. Table 1 shows Tg of the obtained cured product.

Test Example 3 (Purification method of purified 1,2,4-triglycidyloxynaphthalene (E-3) and evaluation of cured product):
In Test Example 1, the same procedure as in Test Example 1 except that purified 1,2,4-triglycidyloxynaphthalene (E-3, epoxy equivalent of 179 g / eq) obtained in Synthesis Example 3 was used instead of E-1. Through the operations, an epoxy resin composition and a cured product were obtained. Table 1 shows Tg of the obtained cured product.

Comparative Test Example 1 (Trimethylolpropane triglycidyl ether curing method and evaluation of cured product):
In Test Example 1, the same operation as in Test Example 1 was conducted except that trimethylolpropane triglycidyl ether (E-4, epoxy equivalent of 145 g / eq, Sigma-Aldrich Japan Co., Ltd. reagent) was used instead of E-1. Thus, an epoxy resin composition and a cured product were obtained. Table 1 shows Tg of the obtained cured product.

  From Table 1, the following is clear. That is, the glass transition temperature of the cured product of 1,2,4-triglycidyloxynaphthalene (E-2, E-3) of the present invention is the cured product of the epoxy compound (E-4) obtained in Comparative Example 1. Since it is higher than the glass transition temperature, it has excellent heat resistance. As described above, 1,2,4-triglycidyloxynaphthalene is liquid at room temperature and is easy to handle.

Claims (10)

An epoxy compound represented by the following general formula (1).

(In General Formula (1), R ¹ represents any ^one of a hydrogen atom, a halogen atom, an allyl group, an aralkyl group, an alkyl group, an alkoxy group, and an aryloxy group, and R ² represents a glycidyloxy group and a β-alkyl. Provided that it is either a glycidyloxy group or a hydroxy group, and at least one of R ² represents a glycidyloxy group or a β-alkylglycidyloxy group, X is a hydrogen atom, a halogen atom, an alkyl group, Indicates an alkoxy group or an aryloxy group.) The epoxy compound according to claim 1, wherein the general formula (1) is the following general formula (2).

(In General Formula (2), R ¹ represents any ^one of a hydrogen atom, a halogen atom, an allyl group, an aralkyl group, an alkyl group, an alkoxy group, and an aryloxy group, and R ³ represents any one of a hydrogen atom and an alkyl group. X represents any of a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, and an aryloxy group.) The epoxy compound according to claim 2, wherein R ¹ , R ³ , and X in the general formula (2) are hydrogen atoms. The epoxy compound according to claim 1, wherein the general formula (1) is the following general formula (3).

(In General Formula (3), R ¹ represents any ^one of a hydrogen atom, a halogen atom, an allyl group, an aralkyl group, an alkyl group, an alkoxy group, and an aryloxy group, and R ³ represents any one of a hydrogen atom and an alkyl group. X represents any of a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, and an aryloxy group.) The epoxy compound according to claim 4, wherein R ¹ , R ³ , and X in the general formula (3) are hydrogen atoms. A 1,2,4-trihydroxynaphthalene derivative represented by the following general formula (4) is reacted with an epihalohydrin compound represented by the following general formula (5) in the presence of a basic compound. The manufacturing method of the epoxy compound in any one of 1-5.

(In the general formula (4), R ¹ represents any ^one of a hydrogen atom, a halogen atom, an allyl group, an aralkyl group, an alkyl group, an alkoxy group, and an aryloxy group, and X represents a hydrogen atom, a halogen atom, and an alkyl group. , An alkoxy group or an aryloxy group.)

(In the general formula (5), R ⁴ represents either a hydrogen atom or an alkyl group, and Y represents a halogen atom.) A method for producing an epoxy compound according to claim 6, a manufacturing method of R ^1, R ^3, and X is an epoxy compound which is a hydrogen atom in the general formula (2). Method for producing a method for producing an epoxy compound according to claim ^6, R ^1, R 3, and X is an epoxy compound which is a hydrogen atom in the general formula (3).   An epoxy resin composition comprising the epoxy compound according to any one of claims 1 to 5 as a component.   A cured product obtained by curing the epoxy resin composition according to claim 9.