JP5973401B2 - Glycidyl glycolurils and their use - Google Patents

Description

  The present invention relates to novel glycidyl glycolurils and their use, particularly to a crosslinking agent for epoxy resins.

  Glycolurils are heterocyclic compounds having 4 urea nitrogens in the ring structure, and are raw materials for various uses and production of new functional compounds using the reactivity of the urea nitrogens. It is used as.

  For example, it has been proposed that glycoluril is reacted with an aldehyde such as dimethoxyethanal to form an aminoplastic resin, which is used as a crosslinking agent for cellulose (see Patent Document 1).

  It has also been proposed to use an emulsion containing a copolymer of vinyl acetate, ethylene and a self-crosslinkable monomer and tetramethylol glycoluril as a binder for a nonwoven fabric (see Patent Document 2). It has also been proposed to use a polyhexamethylene biguanide compound, which is a water-soluble polymer antibacterial agent, as a crosslinking agent for fixing to a fiber (see Patent Document 3).

  On the other hand, compounds having multiple reactive allyl groups in the molecule, such as triallyl isocyanurates, are well known as crosslinking agents for synthetic resins and synthetic rubbers. Tetraallylglycolurils having four allyl groups in a molecule that functions as a crosslinking agent are also known (see Patent Document 4).

  Compounds having a plurality of glycidyl groups in the molecule, for example, triglycidyl isocyanurate having three glycidyl groups in the molecule are well known as crosslinking agents for epoxy resins.

  However, a compound in which a hydrogen atom on at least one nitrogen atom of glycoluril is substituted with a glycidyl group has not been known so far.

  A compound in which a hydrogen atom on at least one nitrogen atom of a glycoluril is substituted with a glycidyl group is useful as an intermediate for the synthesis of an oxygen-containing compound, and a glycoluril having one epoxy group in the molecule. Are useful as reactive diluents in epoxy resins, for example, and glycolurils having two or more epoxy groups in the molecule are expected to be useful as crosslinking agents for epoxy resins, for example. The

JP-A-8-67729 Japanese Patent Laid-Open No. 2-2611851 Japanese Patent Laid-Open No. 7-82665 Japanese Patent Application Laid-Open No. 11-171887

An object of the present invention is to provide a novel glycidyl glycoluril, an epoxy resin crosslinking agent containing the same, and an epoxy resin composition containing the epoxy resin crosslinking agent.

  According to the invention, the general formula (I)

(In the formula, R ¹ and R ² each independently represent a hydrogen atom, a lower alkyl group or a phenyl group, and R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom or a glycidyl group.)
The glycidyl glycoluril represented by these is provided.

  Moreover, according to this invention, the utilization of the said glycidyl glycoluril provides the crosslinking agent for epoxy resins, and also provides the epoxy resin composition containing the crosslinking agent for epoxy resins.

  Furthermore, according to this invention, the manufacturing method of glycidyl glycoluril is provided. That is, according to the present invention, the general formula (a)

(In the formula, R ¹ and R ² are the same as described above, and R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom or an allyl group.)
A method for producing glycidyl glycoluril is provided, which comprises oxidizing an oxidant to epoxidize an allyl glycoluril represented by the formula (I) by oxidizing an oxidant of the carbon-carbon double bond of the allylglycoluril.

  The glycidyl glycoluril according to the present invention is a novel compound in which at least one hydrogen atom of hydrogen atoms bonded to four nitrogen atoms of the glycoluril is substituted with a glycidyl group.

  Accordingly, such compounds are useful as intermediates for the synthesis of novel oxygen-containing compounds, and those having one glycidyl group in the molecule can be used, for example, as reactive diluents for epoxy resins. Useful. Moreover, what has two or more glycidyl groups in a molecule | numerator is useful as a crosslinking agent for epoxy resins, for example.

  In particular, since 1,3,4,6-tetraglycidylglycoluril in which hydrogen atoms on all nitrogen atoms are substituted with glycidyl groups is tetrafunctional, for example, when used as a crosslinking agent for epoxy resins, A cured epoxy resin having a higher crosslinking density than when a conventional bifunctional or trifunctional crosslinking agent is used, and therefore, an epoxy resin cured product superior in hardness, heat resistance, and the like can be obtained. .

It is IR spectrum of 1, 3- diallyl glycoluril. It is IR spectrum of 1, 3- diglycidyl glycoluril. It is IR spectrum of 1,3,4,6-tetraglycidyl glycoluril. It is IR spectrum of 1,3,4,6-tetraglycidyl-3a, 6a-dimethylglycoluril.

  The glycidyl glycolurils according to the invention are represented by the general formula (I)

(In the formula, R ¹ and R ² are the same as above, and R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom or a glycidyl group.)
It is represented by

  That is, the glycidyl glycoluril according to the present invention has the general formula (Ia)

(In the formula, R ¹ and R ² are the same as described above.)
Monoglycidyl glycoluril represented by the general formula (Ib)

(In the formula, R ¹ and R ² are the same as described above.)
Diglycidyl glycoluril represented by the general formula (Ic)

(In the formula, R ¹ and R ² are the same as described above.)
Diglycidyl glycoluril represented by the general formula (Id)

(In the formula, R ¹ and R ² are the same as described above.)
Diglycidyl glycoluril represented by the general formula (Ie)

(In the formula, R ¹ and R ² are the same as described above.)
And triglycidyl glycoluril represented by the general formula (If)

(In the formula, R ¹ and R ² are the same as described above.)
It is tetraglycidyl glycoluril represented by these.

In the glycidyl glycolurils represented by the above general formulas (I) and (Ia) to (If), when R ¹ or R ² is a lower alkyl group, the lower alkyl group usually has 1 to 1 carbon atoms. 5, preferably 1-3, most preferably 1, and therefore the most preferred lower alkyl group is a methyl group.

Accordingly, preferred specific examples of glycidyl glycolurils according to the present invention include, for example,
1-glycidyl glycoluril,
1,3-diglycidyl glycoluril,
1,4-diglycidyl glycoluril,
1,6-diglycidyl glycoluril,
1,3,4-triglycidyl glycoluril,
1,3,4,6-tetraglycidylglycoluril,
1-glycidyl-3a-methylglycoluril,
1-glycidyl-6a-methyl-glycoluril,
1,3-diglycidyl-3a-methylglycoluril,
1,4-diglycidyl-3a-methylglycoluril,
1,6-diglycidyl-3a-methylglycoluril,
1,3,4-triglycidyl-3a-methylglycoluril,
1,3,4-triglycidyl-6a-methylglycoluril,
1,3,4,6-tetraglycidyl-3a-methylglycoluril,
1-glycidyl-3a, 6a-dimethylglycoluril,
1,3-diglycidyl-3a, 6a-dimethylglycoluril,
1,4-diglycidyl-3a, 6a-dimethylglycoluril,
1,6-diglycidyl-3a, 6a-dimethylglycoluril,
1,3,4-triglycidyl-3a, 6a-dimethylglycoluril,
1,3,4,6-tetraglycidyl-3a, 6a-dimethylglycoluril,
1-glycidyl-3a, 6a-diphenylglycoluril,
1,3-diglycidyl-3a, 6a-diphenylglycoluril,
1,4-diglycidyl-3a, 6a-diphenylglycoluril,
1,6-diglycidyl-3a, 6a-diphenylglycoluril,
1,3,4-triglycidyl-3a, 6a-diphenylglycoluril,
Examples include 1,3,4,6-tetraglycidyl-3a, 6a-diphenylglycoluril.

  The glycidyl glycoluril represented by the general formula (I) according to the present invention is represented by the general formula (a)

(Wherein R ¹ , R ² , R ⁶ , R ⁷ and R ⁸ are the same as described above.)
It can be obtained by oxidizing and epoxidizing the carbon-carbon double bond of the allyl glycoluril by allowing an oxidant to act on the allylglycoluril represented by formula (1).

In general, a method of oxidizing and epoxidizing a carbon-carbon double bond is already well known, and in the present invention, such a method can be used. Examples of such a method include a method using a peracid such as an oxone reagent, peracetic acid, and metachloroperbenzoic acid, and a method using hydrogen peroxide using sodium tungstate as a catalyst.
When using a peracid as an oxidizing agent, the peracid is preferably used at a ratio of 1.0 to 5.0 equivalents relative to the allyl group of allyl glycoluril.

  When used, the reaction solvent is not particularly limited as long as it does not inhibit the reaction. For example, water, alcohols such as methanol, ethanol and isopropyl alcohol, aliphatics such as hexane and heptane are used. Hydrocarbons, ketones such as acetone and 2-butanone, esters such as ethyl acetate and butyl acetate, aromatic hydrocarbons such as benzene, toluene and xylene, methylene chloride, chloroform, carbon tetrachloride, chloro Halogenated hydrocarbons such as trifluoromethane, dichloroethane, chlorobenzene, dichlorobenzene, ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane, diethylene glycol dimethyl ether, formamide, N, N-dimethyl Formamide, N, N- dimethylacetamide, amides such as N- methyl-2-pyrrolidone, N- methylpyrrolidinone, hexamethylphosphoric triamide, may be mentioned sulfoxides such as dimethyl sulfoxide and the like. These reaction solvents are used alone or in combination of two or more, and an appropriate amount is used.

  The reaction temperature when oxidizing allyl glycoluril using the peracid is usually in the range of −10 to 150 ° C., and preferably in the range of 0 ° C. to 100 ° C. Moreover, although reaction time is based also on reaction temperature, it is the range of 1 to 24 hours normally, Preferably, it is the range of 1 to 6 hours.

  After completion of the reaction, the desired glycidyl glycoluril can be obtained by extraction from the resulting reaction mixture, or crystallization from an appropriate solvent and filtration.

  When allyl glycoluril is oxidized with hydrogen peroxide using sodium tungstate as a catalyst, the hydrogen peroxide is in a ratio of 1.0 to 5.0 equivalents with respect to the allyl group of allyl glycoluril. Used in In addition, sodium tungstate is preferably used in a proportion of 0.001 to 0.5 equivalent with respect to the allyl group of allyl glycoluril.

  When the reaction solvent is used, it is not particularly limited as long as the reaction is not inhibited. For example, the same reaction solvent as in the above-described oxidation reaction using a peracid can be used.

  The reaction temperature is usually in the range of −10 to 150 ° C., preferably in the range of 0 ° C. to 100 ° C., as in the case of the oxidation reaction using the peracid described above, and the reaction time is also the reaction temperature. However, it is usually in the range of 1 to 24 hours, and preferably in the range of 1 to 6 hours.

  After completion of the reaction, in the same manner as in the case of the oxidation reaction with peracid described above, the objective is obtained by extracting from the obtained reaction mixture, or crystallizing from an appropriate solvent and filtering. Glycidyl glycoluril can be obtained.

  The glycidyl glycoluril thus obtained can be purified as necessary by washing with a solvent such as water, activated carbon treatment, silica gel chromatography and the like.

  Among the glycidyl glycolurils according to the present invention, those having one glycidyl group in the molecule are useful, for example, as a synthetic intermediate for oxygen-containing compounds and as a diluent for epoxy resins. Of the glycidyl glycolurils according to the present invention, those having two or more glycidyl groups in the molecule are useful as, for example, a crosslinking agent for epoxy resins.

  Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolak type epoxy resin such as phenol novolak type epoxy resin and cresol novolak type epoxy resin, alicyclic epoxy resin, 3 ′, 4′- Cycloalicyclic epoxy resins such as epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, nitrogen-containing cyclic epoxies such as triglycidyl isocyanurate, monoallyl diglycidyl isocyanurate, diallyl monoglycidyl isocyanurate and hydantoin type epoxy resins Resin, hydrogenated bisphenol A type epoxy resin, aliphatic epoxy resin, glycidyl ether type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, dicyclo ring type In addition to epoxy resins, naphthalene-type epoxy resins, halogenated epoxy resins, etc., epoxy-modified organopolysiloxane compounds by hydrosilylation addition reaction between organic compounds having carbon-carbon double bonds and glycidyl groups and silicon compounds having SiH groups (for example, And epoxy-modified organopolysiloxane compounds disclosed in JP-A No. 2004-99751 and JP-A 2006-282898.

  The glycidyl glycoluril according to the present invention can be made into an epoxy resin composition by blending it with the above-mentioned epoxy resin together with a curing agent and, if necessary, a curing accelerator.

  In such an epoxy resin composition, the glycidyl glycoluril according to the present invention is usually used in a proportion of 0.1 to 150 parts by weight, preferably 10 to 100 parts by weight, with respect to 100 parts by weight of the epoxy resin. It is used in the ratio.

  Examples of the curing agent include compounds having phenolic hydroxyl groups, acid anhydrides, amines, mercaptan compounds such as mercaptopropionic acid esters and epoxy resin-terminated mercapto compounds, triphenylphosphine, diphenylnaphthylphosphine, diphenylethylphosphine, and the like. Examples thereof include organic phosphine compounds, aromatic phosphonium salts, aromatic diazonium salts, aromatic iodonium salts, and aromatic selenium salts.

  Examples of the compound having a phenolic hydroxyl group include bisphenol A, bisphenol F, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol S, tetrachlorobisphenol A, tetrabromobisphenol A, dihydroxynaphthalene, and phenol. Examples thereof include novolak, cresol novolak, bisphenol A novolak, brominated phenol novolak, and resorcinol.

  Examples of the acid anhydride include methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride, trimellitic anhydride, and nadic acid anhydride. , Hymic acid anhydride, methylnadic acid anhydride, methyldicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride And methylnorbornane-2,3-dicarboxylic acid.

  Further, examples of the amines include diethylenediamine, triethylenetetramine, hexamethylenediamine, dimer acid-modified ethylenediamine, 4,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenol ether, 1,8-diazabicyclo. Examples include [5.4.0] -7-undecene, and imidazole compounds such as 2-methylimidazole, 2-ethyl-4-methylimidazole, and 2-phenylimidazole.

  In the epoxy resin composition according to the present invention, the curing agent is usually used in a ratio of 10 to 300 parts by weight, preferably 100 to 200 parts by weight, with respect to 100 parts by weight of the epoxy resin.

  Examples of the curing accelerator include 1,8-diazabicyclo [5.4.0] -7-undecene, diethylenetriamine, triethylenetetramine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris (dimethylaminomethyl). Amine compounds such as phenol, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, imidazole compounds such as 2-heptadecylimidazole, tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine Organic phosphine compounds such as tetrabutylphosphonium bromide, phosphonium compounds such as tetrabutylphosphonium diethyl phosphorodithioate, tetraphenyl Aliphatic acid metals such as tetraphenylboron salts such as suphonium tetraphenylborate, 2-methyl-4-methylimidazole tetraphenylborate, N-methylmorpholine tetraphenylborate, lead acetate, tin octylate, cobalt hexanoate A salt etc. can be mentioned. It is already known that some of these curing accelerators can also be used as the above-described curing agent.

  In the epoxy resin composition according to the present invention, the curing accelerator is usually used in a proportion of 0.01 to 2.0 parts by weight, preferably 0.1 to 0.5 parts, relative to 100 parts by weight of the epoxy resin. Used in parts by weight.

  In addition, the epoxy resin composition according to the present invention may be filled with an inorganic material such as amorphous silica, crystalline silica, calcium carbonate, magnesium carbonate, alumina, magnesia, clay, talc, calcium silicate, titanium oxide, as necessary. In addition to the materials, various polymers such as phenol resin and unsaturated polyester can be included.

  In addition to the above, the epoxy resin composition according to the present invention can contain various additives. Examples of such additives include aliphatic polyols such as ethylene glycol and propylene glycol, carbon dioxide generation inhibitors such as aliphatic or aromatic carboxylic acid compounds and phenol compounds, flexibility imparting agents such as polyalkylene glycol, and oxidation. Inhibitors, plasticizers, lubricants, silane-based coupling agents, inorganic filler surface treatment agents, flame retardants, antistatic agents, coloring agents, antistatic agents, leveling agents, ion trapping agents, sliding property improving agents , Various rubber, organic polymer beads, glass beads, impact modifiers such as inorganic fillers such as glass fibers, thixotropic agents, surfactants, surface tension reducing agents, antifoaming agents, anti-settling agents, light diffusion Agents, ultraviolet absorbers, antioxidants, release agents, fluorescent agents, conductive fillers and the like.

  Such epoxy resin compositions include paints for printed wiring boards and electronic components, sealing materials, adhesives, resist inks, etc., as well as coating materials for woodwork, optical fibers, plastics, and cans. The use as is expected.

  The present invention will be described below with reference to examples, but the present invention is not particularly limited to these examples.

Reference example 1
(Synthesis of 1,3-diallylglycoluril)
A 100 mL flask equipped with a thermometer was charged with 3.00 g (50.0 mmol) of urea and 8.71 g (60.0 mmol) of 40% aqueous glyoxal solution. Two drops of 40% aqueous sodium hydroxide solution were added to this mixture at room temperature, and the mixture was stirred at 80 ° C. for 1 hour. Subsequently, the reaction mixture was concentrated under reduced pressure. To the resulting concentrate, 7.00 g (50.0 mmol) of diallylurea, 50 mL of acetic acid and 490 mg (5.0 mmol) of sulfuric acid were added, and the mixture was stirred at 110 ° C. overnight. The reaction mixture is then cooled to room temperature and then 50 mL of acetone is added to separate the viscous oil from the reaction mixture, which is dried to give 1,3-diallylglycoluril as a white viscous oil. It was. Yield 39%.

The IR spectrum of the obtained 1,3-diallylglycoluril is shown in FIG. The ¹ H-NMR spectrum (d6-DMSO) δ value: 7.52 (s, 2H), 5.69-5.84 (m, 2H), 5.08-5.23 (m, 6H) , 3.92 ^ 3.97 (m, 2H), 3.52 (dd, 2H)

Reference example 2
(Synthesis of 1,3,4,6-tetraallylglycoluril)
The compound was synthesized according to the method described in JP-A-11-171887.

  Glycoluril (14.2 g, 100 mmol), sodium hydroxide (16.0 g, 400 mmol) and dimethyl sulfoxide (140 mL) were mixed, heated and stirred at 40 ° C. for 1 hour, and then allyl chloride (34.4 g, 400 mmol) was added at the same temperature for 20 minutes. It was dripped over. After completion of the dropwise addition, the mixture was further heated and stirred at 40 ° C. for 2 hours to complete the reaction.

  The resulting reaction mixture was evaporated to dryness. The obtained dried product was subjected to liquid separation extraction with 400 mL of ethyl acetate and 400 mL of water. The ethyl acetate layer was washed with 100 mL of water and then with 100 mL of saturated brine, and then dried over anhydrous sodium sulfate. Ethyl acetate was distilled off under reduced pressure, and 1,3,4,6-tetraallylglycoluril 27. 4 g was obtained as a colorless oil. Yield 90%.

Reference example 3
(Synthesis of 1,3,4,6-tetraallyl-3a, 6a-dimethylglycoluril)
After mixing 17.0 g (100 mmol) of 3a, 6a-dimethylglycoluril, 16.0 g (400 mmol) of sodium hydroxide and 150 mL of dimethyl sulfoxide, the mixture was heated and stirred at 40 ° C. for 1 hour, and then 34.4 g of allyl chloride ( 400 mmol) was added dropwise over 20 minutes. After completion of the dropwise addition, the mixture was further heated and stirred at 40 ° C. for 2 hours to complete the reaction. Thereafter, the same post-treatment as in Reference Example 2 was performed to obtain 26.1 g of 1,3,4,6-tetraallyl-3a, 6a-dimethylglycoluril as crystals. Yield 79%.

Example 1
(Synthesis of 1,3-diglycidyl glycoluril)
A 100 mL flask equipped with a thermometer and a stirrer was charged with 1.11 g (5.0 mmol) of 1,3-diallylglycoluril and 10 mL of dichloromethane, and 2.92 g of metachloroperbenzoic acid (purity 65%) under ice cooling. 11.0 mmol) was added, and the mixture was warmed to room temperature and stirred overnight.

  After adding 20 mL of 10% sodium sulfite aqueous solution to the obtained reaction mixture, it was mixed with 20 mL of chloroform, shaken and allowed to stand, and the resulting organic layer was extracted and separated.

  This extraction operation with chloroform was further performed twice, and the resulting extracts were combined, dried over sodium sulfate, and then volatile components were distilled off. The residue thus obtained was purified by silica gel chromatography (chloroform / methanol = 10/1 (volume ratio)) to obtain 1.80 g of 1,3-diglycidylglycoluril as a white viscous oil. Yield 98%.

The IR spectrum of the obtained 1,3-diglycidyl glycoluril is shown in FIG. The δ value in the ¹ H-NMR spectrum (CDCl ₃ ) was as follows.

  7.36 (br, 2H), 5.12-5.37 (m, 8H), 4.77-4.82 (m, 2H), 4.54-4.57 (m, 2H)

Example 2
(Synthesis of 1,3,4,6-tetraglycidyl glycoluril)
A 100 mL flask equipped with a thermometer and a stirrer was charged with 1.51 g (5.0 mmol) of 1,3,4,6-tetraallylglycoluril and 10 mL of dichloromethane. Under ice cooling, metachloroperbenzoic acid (purity 65 %) 5.84 g (22.0 mmol) was added, and the mixture was warmed to room temperature and stirred overnight.

  20 mL of 10% aqueous sodium sulfite solution was added to the resulting reaction mixture, mixed with 20 mL of chloroform, shaken and allowed to stand, and the resulting organic layer was extracted and separated.

  This extraction operation with chloroform was further performed twice, and the resulting extracts were combined, dried over sodium sulfate, and then volatile components were distilled off. The residue thus obtained was purified by silica gel chromatography (chloroform / methanol = 40/1 (volume ratio)) to obtain 1.80 g of 1,3,4,6-tetraglycidylglycoluril as a colorless oil. It was. Yield 98%.

The IR spectrum of the obtained 1,3,4,6-tetraglycidyl glycoluril is shown in FIG. The δ value in the ¹ H-NMR spectrum (CDCl ₃ ) was as follows.

  5.37-5.69 (m, 2H), 4.23-4.27 (m, 1H), 4.03-4.06 (m, 1H), 3.61-3.81 (m, 3H) ), 3.45-3.46 (m, 1H), 3.01-3.23 (m, 6H), 2.78-2.84 (m, 4H), 2.59-2.63 (m) , 4H)

Example 3
(Synthesis of 1,3,4,6-tetraglycidyl-3a, 6a-dimethylglycoluril)
1,100,4,6-Tetraallyl-3a, 6a-dimethylglycoluril (1.51 g, 5.0 mmol) and dichloromethane (10 mL) were placed in a 100 mL flask equipped with a thermometer and a stirrer. After adding acid (purity 65%) 5.84g (22.0mmol), it heated up to room temperature and stirred all night.

  20 mL of 10% aqueous sodium sulfite solution was added to the resulting reaction mixture, mixed with 20 mL of chloroform, shaken and allowed to stand, and the resulting organic layer was extracted and separated.

  This extraction operation with chloroform was further performed twice, and the obtained extracts were combined, dried over sodium sulfate, and then volatile components were distilled off. The residue thus obtained was purified by silica gel chromatography (chloroform / methanol = 40/1 (volume ratio)) to obtain 1.81 g of 1,3,4,6-tetraglycidyl-3a, 6a-dimethylglycoluril. Was obtained as a colorless liquid. Yield 92%.

FIG. 4 shows the IR spectrum of the obtained 1,3,4,6-tetraglycidyl-3a, 6a-dimethylglycoluril. The δ value in the ¹ H-NMR spectrum (CDCl ₃ ) was as follows.

  3.40-4.37 (m, 8H), 3.03-3.18 (m, 3H), 2.78-2.85 (m, 3H), 2.55-2.62 (m, 3H) ), 2.55-2.62 (m, 3H), 1.45-1.70 (m, 9H)

Example 4
As shown in Table 1, hydrogenated bisphenol A type epoxy resin (YX8000 manufactured by Mitsubishi Chemical Co., Ltd., abbreviated as YX8000 in Table 1) is used as a curing agent in 80 parts by weight of 4-methylhexahydrophthalic anhydride / hexahydro. 120 parts by weight of phthalic anhydride (mixture with a weight ratio of 70/30, Rikacid MH-700 manufactured by Shin Nippon Rika Co., Ltd., abbreviated as MH-700 in Table 1), tetra-n-butylphosphonium as a curing accelerator -O, o-diethyl phosphorodithionate (Hishicolin PX-4ET manufactured by Nippon Chemical Industry Co., Ltd., abbreviated as PX-4ET in Table 1) 0.5 parts by weight and 1,3,4,4 as a crosslinking agent An epoxy resin composition was prepared by blending and kneading 20 parts by weight of 6-tetraglycidylglycoluril (abbreviated as TG-G in Table 1).

  This epoxy resin composition was heated at a temperature of 120 ° C. for 6 hours to obtain a cured product. About this hardened | cured material, the glass transition point (Tg), the bending elastic modulus, and the bending strength were measured, and the result shown in Table 1 was obtained. Tg was measured by DSC according to JISK7121. The flexural modulus and flexural strength were measured according to JISK7203.

Comparative Example 1
As shown in Table 1, 100 parts by weight of hydrogenated bisphenol A type epoxy resin (YX8000 manufactured by Mitsubishi Chemical Corporation) as a curing agent, 4-methylhexahydrophthalic anhydride / hexahydrophthalic anhydride (70/30 mixture, new 80 parts by weight of Nippon Rika Co., Ltd. Rikacid MH-700) and tetra-n-butylphosphonium-o, o-diethylphosphorodithionate (Hishicolin PX-4ET, Nippon Chemical Industry Co., Ltd.) as a curing accelerator 5 parts by weight was blended and kneaded to prepare an epoxy resin composition.

  In the same manner as in Example 4, this epoxy resin composition was heated to obtain a cured product, and the glass transition point (Tg), bending elastic modulus and bending strength of this cured product were measured, and the results shown in Table 1 were obtained. Got.

Comparative Example 2
In Example 4, instead of 20 parts by weight of the crosslinking agent 1,3,4,6-tetraglycidylglycoluril, triglycidyl isocyanuric acid (triglycidyl isocyanurate manufactured by Tokyo Chemical Industry Co., Ltd., in Table 1, TG-ICA) An epoxy resin composition was prepared in the same manner as in Example 4 except that 20 parts by weight was used.

  In the same manner as in Example 4, this epoxy resin composition was heated to obtain a cured product, and the glass transition point (Tg), bending elastic modulus and bending strength of this cured product were measured, and the results shown in Table 1 were obtained. Got.

  As is apparent from the results shown in Table 1, the epoxy resin composition containing glycidyl glycoluril as a crosslinking agent according to the present invention is a cured product of an epoxy resin composition not containing a crosslinking agent (Comparative Example 1) or a crosslinking agent. As compared with the cured epoxy resin composition containing triglycidyl isocyanuric acid (Comparative Example 2), it has excellent heat resistance and excellent mechanical strength.

Among the glycidyl glycolurils according to the present invention, those having one glycidyl group in the molecule are useful, for example, as a synthetic intermediate for oxygen-containing compounds and as a diluent for epoxy resins. Among the glycidyl glycolurils according to the present invention, those having two or more glycidyl groups in the molecule are useful as, for example, a crosslinking agent for epoxy resins.

Claims (5)

General formula ( If )
(In the formula, R ¹ and R ² each independently represent a hydrogen atom, a lower alkyl group or a phenyl group. )
Tetraglycidyl glycolurils represented in. The crosslinking agent for epoxy resins containing the tetraglycidyl glycoluril of Claim 1.   The epoxy resin composition containing the crosslinking agent for epoxy resins of Claim 2. General formula ( a1 )
(In the formula, R ¹ and R ² are the same as above, and R ⁶ , R ⁷ and R ⁸ all represent an allyl group .)
In by the action of an oxidizing agent to tetraallyl glycolurils represented, the tetraallyl glycolurils to oxidize the double bond between carbon atoms of the tetraglycidyl glycol according to claim 1, comprising epoxidizing uril Manufacturing method. The method for producing tetraglycidylglycolurils according to claim 4, wherein the oxidizing agent is a peracid.