Novel benzoxazine compound, resin raw material composition and curable resin composition which contain that compound, and cured product

Abstract

To provide: a benzoxazine compound suitable for forming a cured product; and a resin raw material composition and a curable resin composition which contain the compound.SOLUTION: The benzoxazine compound is represented by the general formula (1) in the figure (where R1 is a hydrocarbon group having 1 to 6 carbon atoms, R2 is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and Z is a carbon atom or a tetravalent hydrocarbon group having 2 to 30 carbon atoms).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a benzoxazine compound that can suitably form a cured product, a resin raw material composition containing the same, and a curable resin composition. [Background technology]

[0002] It is known that benzoxazine compounds undergo ring-opening polymerization of the benzoxazine ring upon heating to form a cured resin product. Furthermore, such benzoxazine compounds can be used alone or in combination with other compounds such as epoxy resins to form cured products, and the cured products are known to have excellent heat resistance, flame retardancy, and the like.

[0003] For example, Patent Document 1 discloses a benzoxazine compound of the following formula: [ka] wherein q is an integer from 1 to 4; Z is selected from the group consisting of a direct bond (when q is 2), hydrogen (when q is 1), alkyl (when q is 1), alkylene (when q is 2 to 4), carbonyl (when q is 2), oxygen (when q is 2), thiol (when q is 1), sulfur (when q is 2), sulfoxide (when q is 2), and sulfone (when q is 2); Y is selected from the group consisting of a hydroxyl group and a nitrogen-containing heterocycle; and R 6 is a straight or branched divalent alkylene group containing 1 to 15 carbon atoms, optionally interrupted by one or more heteroatoms selected from oxygen, nitrogen, and sulfur; R 5 is selected from hydrogen, halogen, alkyl, alkenyl, or R 5 is a divalent residue that creates a naphthoxazine moiety from a benzoxazine structure.

[0004] Patent Document 2 discloses a benzoxazine compound of the following formula and a cured product thereof (benzoxazine resin). [ka] (wherein R is an organic group)

[0005] Furthermore, Patent Document 3 discloses a benzoxazine compound of the following formula: [ka] (In the formula, R1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R2 represents an alkylene group having 1 to 6 carbon atoms, and X represents a cycloalkylidene group having 5 to 20 carbon atoms.) [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 2011-530570 [Patent Document 2] Japanese Patent Application Publication No. 2018-177718 [Patent Document 3] WO 2023 / 026850 A1 Summary of the Invention [Problem to be solved by the invention]

[0007] An object of the present invention is to provide a benzoxazine compound suitable for forming a cured product, a resin raw material composition containing the same, and a curable resin composition. [Means for solving the problem]

[0008] The present invention is presented below. 1. A benzoxazine compound represented by the following general formula (1): [ka] (In the formula, R 1 is a hydrocarbon group having 1 to 6 carbon atoms, and R 2 is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and Z is a carbon atom or a tetravalent hydrocarbon group having 2 to 30 carbon atoms. 2. A resin raw material composition containing the benzoxazine compound according to item 1 above. 3. A curable resin composition containing the benzoxazine compound according to item 1 above. 4. A cured product obtained by curing the benzoxazine compound according to item 1 above or the curable resin composition according to item 3 above. [Effects of the Invention]

[0009] The benzoxazine compound of the present invention can be easily heated to produce a cured product. Furthermore, a resin raw material composition and a curable resin composition containing this compound are suitable for producing adhesives, sealing materials, photosensitive materials, paints (resist inks, etc.), etc. These materials can be used for producing circuit boards, interlayer insulating materials, laminates, printed wiring boards, prepregs, molding materials, various electronic components, etc. [Brief explanation of the drawings]

[0010] [Figure 1] 1 is a DSC curve of a benzoxazine compound (Q1) measured in Example 2-1. [Figure 2] 1 is a DSC curve of a benzoxazine compound (Q3) measured in Example 2-2. [Figure 3] 1 is a DSC curve of a benzoxazine compound (Q4) measured in Example 2-3. [Figure 4] 1 is a DSC curve of a benzoxazine compound (Q5) measured in Example 2-4. [Figure 5] 1 is a DSC curve of a benzoxazine compound (Q6) measured in Example 2-5. DETAILED DESCRIPTION OF THE INVENTION

[0011] The benzoxazine compound of the present invention (hereinafter referred to as "benzoxazine compound (A)") is a compound represented by the above general formula (1) and containing four benzoxazine rings.

[0012] In the above general formula (1) representing the benzoxazine compound (A) of the present invention, R 2 If is not a hydrogen atom, R 1 and R 2 and may be the same or different and may be hydrocarbon groups having 1 to 6 carbon atoms. This hydrocarbon group may be any of an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group, and may be selected from a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, a cyclopentyl group, a 1,1-dimethylpropyl group, a 1-methylbutyl group, an n-hexyl group, an isohexyl group, a cyclohexyl group, a 1,1-dimethylbutyl group, and an aryl group.

[0013] In the above general formula (1) representing the benzoxazine compound (A) of the present invention, Z is a carbon atom bonded to a carbon atom constituting a benzoxazine ring, or a tetravalent hydrocarbon group having 2 to 30 carbon atoms. When Z is a tetravalent hydrocarbon group, it may be any of an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group.

[0014] The benzoxazine compound (A) of the present invention is a compound in which the carbon atom constituting the benzoxazine ring bonded to Z in the case where Z is a tetravalent hydrocarbon group in the above general formula (1) is C 1 Then, one carbon atom in Z is connected to two C atoms that make up two benzoxazine rings. 1 The other carbon atoms in Z are bonded to the two Cs that make up the other two benzoxazine rings. 1 It is preferred that the structure be bonded to

[0015] In the present invention, preferred benzoxazine compounds (A) are exemplified below. The following compounds (A1), (A2) and (A3) are compounds having the same structure as R in the above general formula (1). 1 is set to R, and R 2 is replaced with a hydrogen atom. [ka] [ka] [ka] (In each formula, R is a hydrocarbon group having 1 to 6 carbon atoms.)

[0016] The method for producing the benzoxazine compound (A) of the present invention is not particularly limited. For example, when producing the compounds (A1), (A2), and (A3) in which all R are butyl groups, a method can be used in which n-butylamine, a compound having four hydroxy groups (a tetraol compound), such as 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, 2,2-bis[4,4-bis(4-hydroxyphenyl)-cyclohexyl]propane, or α,α,α′,α′-tetrakis(4-hydroxyphenyl)-p-xylene, and a formaldehyde are subjected to a dehydration condensation reaction to form a benzoxazine ring through cyclization. That is, the benzoxazine compound (A) of the present invention can be produced using a primary amine represented by R-NH, a tetraol compound, and a formaldehyde.

[0017] When producing the above compounds (A1), (A2), and (A3) in which R is a hydrocarbon group other than a butyl group, the primary amine that can be used includes methylamine, ethylamine, n-propylamine, isopropylamine, isobutylamine, sec-butylamine, tert-butylamine, n-pentylamine, isopentylamine, neopentylamine, cyclopentylamine, 1,1-dimethylpropylamine, 1-methylbutylamine, n-hexylamine, isohexylamine, 1,1-dimethylbutylamine, cyclohexylamine, aniline, and the like.

[0018] The amount of primary amine used is usually 4 moles or more, more preferably 4 to 20 moles, and even more preferably 4 to 10 moles, per mole of the tetraol compound. Since most primary amines also function as a reaction solvent in the dehydration condensation reaction, when the primary amine is used in excess of more than 4 moles, it functions as a reaction solvent as well as a raw material for forming a benzoxazine ring.

[0019] Examples of formaldehydes include aqueous formaldehyde solutions, 1,3,5-trioxane, and paraformaldehyde.

[0020] The amount of formaldehyde used is preferably 8 moles or more, more preferably 8 to 12 moles, and even more preferably 8 to 10 moles, per mole of the tetraol compound.

[0021] The dehydration condensation reaction can be carried out in a solvent or without a solvent. When the dehydration condensation reaction is carried out in a solvent, the reaction solvent is not particularly limited as long as it does not inhibit the dehydration condensation reaction, and examples of the reaction solvent that can be used include ethers, hydrocarbons, alcohols, and esters.

[0022] Examples of ethers include dimethyl ether, diethyl ether, dipropyl ether, diisopropyl ether, di-n-butyl ether, diisobutyl ether, diisoamyl ether, ethyl propyl ether, isopropyl ethyl ether, methyl tert-butyl ether, cyclopentyl methyl ether, cyclohexyl methyl ether, anisole, phenetole, diphenyl ether, dimethyl glycol, 1,2-diethoxyethane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 4-methyltetrahydropyran, 1,4-dioxane, and 1,3-dioxolane.

[0023] Examples of hydrocarbons include hydrocarbons such as pentane, hexane, heptane, octane, nonane, decane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, 1,2,4-trimethylbenzene, and 1,3,5-trimethylbenzene; and substituted hydrocarbons such as methylene chloride, dichloromethane, trichloromethane, carbon tetrachloride, fluorobenzene, chlorobenzene, bromobenzene, and dichlorobenzene.

[0024] Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, and 2-butanol.

[0025] Examples of esters include methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, ethyl propionate, propyl propionate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate, propylene carbonate, and butylene carbonate.

[0026] When the dehydration condensation reaction is carried out using a reaction solvent, the reaction may be carried out in a state in which all raw materials and the reaction solvent are placed in a reactor. The method of using the raw materials is not particularly limited. For example, after dissolving a tetraol compound in a reaction solvent, the remaining raw material, a primary amine (R 1 The dehydration condensation reaction may be initiated by adding —NH2) and formaldehydes.

[0027] The temperature for the dehydration condensation reaction is preferably 30°C to 150°C, more preferably 50°C to 130°C, since this improves the reaction efficiency while suppressing gelation of the resulting reaction liquid. The atmosphere for the dehydration condensation reaction is not particularly limited, but is preferably an inert gas atmosphere using nitrogen or the like.

[0028] Since the dehydration condensation reaction generates water in the reaction system, it may be carried out under reflux or, if necessary, while removing water from the reaction system by azeotropy with the reaction solvent.

[0029] After the completion of the dehydration condensation reaction, if necessary, the unreacted raw materials, the reaction solvent and by-products can be removed to obtain a purified benzoxazine compound (A).

[0030] The by-product is not clear, but gel permeation chromatography (GPC) has revealed that it is a component with a higher molecular weight than the benzoxazine compound (A) of the present invention, and the present inventors presume that it is a ring-opening polymer (low molecular weight polymer) of benzoxazine compounds.

[0031] The benzoxazine compound (A) of the present invention can easily produce a cured product made of a benzoxazine resin by ring-opening polymerization upon heating without using a curing agent (hereinafter referred to as a "curing accelerator"). The heating temperature is preferably 150°C to 250°C, more preferably 170°C to 220°C. A conventionally known curing accelerator may be used in combination to lower the curing temperature.

[0032] The resin raw material composition of the present invention is a composition containing the benzoxazine compound (A) of the present invention, and is preferably a composition containing an organic solvent. Note that the resin raw material composition of the present invention is a composition that does not contain other benzoxazine compounds, curable resins, and curing accelerators, and a composition that contains other benzoxazine compounds, curable resins, and curing accelerators is a curable resin composition described below.

[0033] The resin raw material composition of the present invention can be in the following embodiments. (X1) A compound consisting of a benzoxazine compound (A) and a solvent for dissolving it. (X2) A reaction solution obtained by the above production method using a reaction solvent, from which unreacted raw materials and by-products have been removed, i.e., a solution consisting of benzoxazine compound (A) and the reaction solvent. (X3) A reaction solution obtained by removing unreacted raw materials and the reaction solvent from the reaction solution obtained by the above production method using a reaction solvent, and then dissolving the benzoxazine compound (A) and by-products in the solvent.

[0034] Examples of solvents for dissolving the benzoxazine compound (A) include acetone, N-methyl-2-pyrrolidone, 2-propanol, 2-acetoxy-1-methoxypropane, 1-methoxy-2-propanol, N,N-dimethylformamide, N,N-dimethylacetamide, acetonitrile, propylene carbonate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, γ-butyrolactone, ethyl lactate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, cyclopentanone, cyclohexanone, etc. When dissolving the benzoxazine compound (A), these organic solvents can be used alone or in combination of two or more.

[0035] The concentration of the benzoxazine compound (A) contained in the resin raw material composition of the present invention is preferably 5 to 90% by mass, more preferably 10 to 80% by mass.

[0036] The resin raw material composition of the present invention can be used, for example, as a raw material for producing a curable resin composition described below, a resin modifier, etc.

[0037] The curable resin composition of the present invention contains the benzoxazine compound (A) of the present invention, and may further contain other benzoxazine compounds, a curable resin, a curing accelerator, an additive, an organic solvent, etc.

[0038] Other benzoxazine compounds include those represented by the general formula (1) above, 1 and R 2 or a benzoxazine compound in which either one of the above is a hydrocarbon group having 7 or more carbon atoms; or a benzoxazine compound in which the number of benzoxazine rings is 1, 2, 3, or 5 or more. When the curable resin composition of the present invention contains other benzoxazine compounds, the other benzoxazine compounds contained may be one type only or two or more types.

[0039] Examples of the curable resin include epoxy resin, phenol resin, cyanate resin, imide resin, maleimide resin, silicone resin, acrylic resin, fluororesin, and urea resin. When the curable resin composition of the present invention contains a curable resin, the curable resin contained may be one type or two or more types.

[0040] Examples of epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, 2,2'-diallyl bisphenol A type epoxy resins, hydrogenated bisphenol type epoxy resins, propylene oxide-added bisphenol A type epoxy resins, resorcinol type epoxy resins, biphenyl type epoxy resins, sulfide type epoxy resins, diphenyl ether type epoxy resins, dicyclopentadiene type epoxy resins, naphthalene type epoxy resins, fluorene type epoxy resins, anthracene dihydride type epoxy resins, brominated novolac type epoxy resins, naphthylene ether type epoxy resins, phenol novolac type epoxy resins, ortho-cresol novolac type epoxy resins, dicyclopentadiene novolac type epoxy resins, biphenyl novolac type epoxy resins, naphthalene phenol novolac type epoxy resins, glycidyl amine type epoxy resins, alkyl polyol type epoxy resins, rubber-modified epoxy resins, and glycidyl ester compounds.

[0041] Examples of phenolic resins include novolac-type phenolic resins such as phenol novolac resin, cresol novolac resin, naphthol novolac resin, aminotriazine novolac resin, and trisphenylmethane-type phenol novolac resin; modified phenolic resins such as terpene-modified phenolic resin and dicyclopentadiene-modified phenolic resin; aralkyl-type resins such as phenol aralkyl resins having a phenylene skeleton and / or biphenylene skeleton and naphthol aralkyl resins having a phenylene skeleton and / or biphenylene skeleton; and resol-type phenolic resins.

[0042] Examples of the curing accelerator include amine compounds, phenol compounds, thiol compounds, acid anhydride compounds, cyanate compounds, active ester compounds, imidazole compounds, sulfonium salt compounds, and phosphine compounds.

[0043] Examples of additives include fillers, flame retardants, ultraviolet absorbers, antioxidants, coupling agents, antifoaming agents, dispersants, storage stabilizers, bleed inhibitors, fluxing agents, leveling agents, and colorants.

[0044] Examples of fillers include inorganic fillers such as silica, alumina, magnesium oxide, titanium oxide, boehmite, talc, clay, mica, calcium carbonate, magnesium carbonate, hydrotalcite, barium sulfate, calcium sulfate, calcium sulfite, boron nitride, aluminum nitride, silicon nitride, zinc borate, barium metaborate, aluminum borate, calcium borate, sodium borate, strontium titanate, barium titanate, carbon fiber, glass fiber, boron fiber, and steel fiber; and organic fillers such as acrylic rubber particles, urethane rubber particles, silicone rubber particles, polyamide particles, polyamideimide particles, polyimide particles, and benzoguanamine particles.

[0045] Examples of the flame retardant include metal hydroxides such as aluminum hydroxide and magnesium hydroxide, halogen compounds, phosphorus compounds, and nitrogen compounds.

[0046] The curable resin composition of the present invention can have the following aspects. (Y1) A composition comprising a benzoxazine compound (A), a curable resin, and optionally a curing accelerator, additives, and an organic solvent. (Y2) A composition comprising a benzoxazine compound (A), a curing accelerator, and optionally an additive and an organic solvent. (Y3) A composition comprising a benzoxazine compound (A), an additive, and an organic solvent, if necessary.

[0047] The method for producing the curable resin composition of the present invention is not particularly limited, and examples thereof include a method of mixing prepared raw materials, a method of mixing the resin raw material composition of the present invention with a curable resin, a curing accelerator, additives, etc. A homodisper, a Banbury mixer, a kneader, etc. may be used for mixing.

[0048] The curable resin composition of the present invention is suitable for producing adhesives, sealing materials, photosensitive materials, paints (resist inks, etc.), etc., and these materials can be used for producing circuit boards, interlayer insulating materials, laminates, printed wiring boards, prepregs, molding materials, various electronic components, etc.

[0049] The cured product of the present invention is an article obtained by curing the benzoxazine compound (A) or curable resin composition of the present invention. The heating temperature when obtaining a cured product of the benzoxazine compound (A) is as described above. Heating is also preferred when curing the curable resin composition, and the temperature is preferably 150°C or higher. The benzoxazine compound (A) and the curable resin composition can be heated by a constant temperature heat treatment or a multi-stage temperature increase heat treatment, and the atmosphere during heating is not particularly limited.

[0050] Specific methods for producing the cured product of the present invention include, for example, a method of heating the benzoxazine compound (A) or curable resin composition that has been applied or placed in a mold, and a method of applying a resin raw material composition containing the benzoxazine compound (A) and an organic solvent to a substrate or the like, removing the organic solvent from the coating film, and then heating the coating film. [Example]

[0051] The present invention will be specifically described below with reference to examples.

[0052] 1. Synthesis of benzoxazine compounds Example 1-1 Into a 300 mL three-neck flask equipped with a thermometer, a stirrer, and a condenser, 20.0 g of 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, 13.1 g of 92% paraformaldehyde, 14.7 g of n-butylamine, and 80.0 g of diethylene glycol dimethyl ether (reaction solvent) were placed and heated to 80°C for reaction. After 24 hours, the resulting reaction liquid was cooled to room temperature and added dropwise to pure water. The precipitate was collected and dried at 60°C to obtain 28.5 g of a reaction product. The reaction product is then 1 1 H NMR measurement confirmed that the compound contained the compound (Q1) represented by the following formula. [ka]

[0053] This compound (Q1) 1 The 1 H NMR spectrum data is as follows: 1 H NMR (400MHz, (CD3)2CO): 0.20-1.00(12H, m), 1.00-1.82(16H, m), 2.10-2.71(8H, t), 3.58-4.20(8H, s), 4.28-4.99(10H, m), 5.86-7.83(12H, m)

[0054] The reaction product was subjected to gel permeation chromatography, and in the resulting chromatogram, the area ratio of the peak of compound (Q1) to the total area of ​​detected peaks was 69%.

[0055] Example 1-2 Into a 300 mL three-neck flask equipped with a thermometer, a stirrer, and a condenser, 10.0 g of 2,2-bis[4,4-bis(4-hydroxyphenyl)-cyclohexyl]propane, 4.6 g of 92% paraformaldehyde, 5.1 g of n-butylamine, and 40.0 g of diethylene glycol dimethyl ether (reaction solvent) were placed and heated to 80°C for reaction. After 24 hours, the resulting reaction liquid was cooled to room temperature and added dropwise to pure water. The precipitate was collected and dried at 60°C to obtain 11.8 g of a reaction product. The reaction product is then 1 1 H NMR measurement confirmed that the compound contained the compound (Q2) represented by the following formula. [ka]

[0056] This compound (Q2) 1 The 1 H NMR spectrum data is as follows: 1 H NMR (400MHz, (CD3)2CO): 0.22-0.64(6H, s), 0.64-0.98(12H, t), 1.06-1.26(8H, q), 1.26-1.95(30H, m), 2.53-2.77(12H, m), 3.76-4.12(8H, d), 4.48-4.99(8H, d), 6.4-7.3(12H, m)

[0057] Examples 1-3 A 300 mL three-neck flask equipped with a thermometer, a stirrer, and a condenser was charged with 20.0 g of 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, 13.1 g of 92% paraformaldehyde, 13.1 g of 70% aqueous ethylamine solution, and 80.0 g of ethylene glycol dimethyl ether, and the mixture was heated to 60° C. After 3 hours, the resulting reaction liquid was dried, and 31.2 g of the reaction product was recovered. The reaction product is then 1 1 H NMR measurement confirmed that the compound contained the compound (Q3) represented by the following formula. [ka]

[0058] This compound (Q3) 1 The 1 H NMR spectrum data is as follows: 1 H NMR (400MHz, CDCl3): 0.69-1.42 (20H, m), 3.60-3.95 (8H, s), 4.06-4.51 (2H, s), 4.51-4.98 (8H, s), 6.14-7.19 (12H, m)

[0059] The reaction product was subjected to gel permeation chromatography, and in the resulting chromatogram, the area ratio of the peak of compound (Q3) to the total area of ​​the detected peaks was 99%.

[0060] Examples 1-4 A 300 mL three-neck flask equipped with a thermometer, a stirrer, and a condenser was charged with 20.0 g of 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, 13.1 g of 92% paraformaldehyde, 20.6 g of n-hexylamine, and 80.0 g of ethylene glycol dimethyl ether, and the mixture was heated to 60° C. After 4 hours, the resulting reaction liquid was concentrated, and 11.1 g of the reaction product was recovered. The reaction product is then 1 1 H NMR measurement confirmed that the compound contained the compound (Q4) represented by the following formula. [ka]

[0061] This compound (Q4) 1 The 1 H NMR spectrum data is as follows: 1 H NMR (400MHz, CDCl3): 0.48-1.75 (44H, m), 2.30-2.91 (8H, m), 3.60-3.90 (8H, s), 4.27-4.37 (2H, s), 4.69-4.98 (8H, s), 6.22-7.08 (12H, m)

[0062] The reaction product was subjected to gel permeation chromatography, and in the resulting chromatogram, the area ratio of the peak of compound (Q4) to the total area of ​​detected peaks was 69%.

[0063] Examples 1-5 A 300 mL three-neck flask equipped with a thermometer, a stirrer, and a condenser was charged with 20.0 g of 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, 13.1 g of 92% paraformaldehyde, 20.0 g of cyclohexylamine, and 80.0 g of ethylene glycol dimethyl ether, and the mixture was heated to 70° C. After 2 hours, the resulting reaction liquid was concentrated, and 15.7 g of the reaction product was recovered. The reaction product is then 1 1 H NMR measurement confirmed that the compound contained the compound (Q5) represented by the following formula. [ka]

[0064] This compound (Q5) 1 The 1 H NMR spectrum data is as follows: 1 H NMR (400MHz, CDCl3): 0.42-2.02 (40H, m), 2.28-2.79 (4H, s), 3.69-4.03 (8H, s), 4.17-4.48 (2H, s), 4.59-4.99 (8H, s), 6.10-7.03 (12H, m)

[0065] The reaction product was subjected to gel permeation chromatography, and in the resulting chromatogram, the area ratio of the peak of compound (Q5) to the total area of ​​the detected peaks was 99%.

[0066] Examples 1-6 A 300 mL three-neck flask equipped with a thermometer, stirrer, and condenser was charged with 20.0 g of 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, 13.1 g of 92% paraformaldehyde, 18.9 g of aniline, and 80.0 g of ethylene glycol dimethyl ether (reaction solvent), and the mixture was heated to 70°C to react. After 17 hours, the resulting reaction solution was concentrated, dissolved in acetone, and insoluble matter was filtered off. The recovered solution was concentrated, and 10.4 g of reaction product was recovered. The reaction product is then 1 1 H NMR measurement confirmed that the compound contained the compound (Q6) represented by the following formula. [ka]

[0067] This compound (Q6) 1 The 1 H NMR spectrum data is as follows: 1 H NMR (400MHz, CDCl3): 4.08-4.55 (10H, m), 4.89-5.72 (8H, s), 6.23-7.47 (32H, m)

[0068] The reaction product was subjected to gel permeation chromatography, and in the resulting chromatogram, the area ratio of the peak of compound (Q6) to the total area of ​​the detected peaks was 90%.

[0069] 2. Manufacturing of cured product Example 2-1 The benzoxazine compound (Q1) obtained in Example 1-1 above was subjected to differential scanning calorimetry (DSC), and the DSC curve shown in Figure 1 was obtained. As is clear from Figure 1, an exothermic peak was detected, confirming that a cured product was formed. [DSC measurement conditions] Equipment: Rigaku differential scanning calorimeter "Thermo plus EVO2 / " (model name) Heating rate: 5℃ / min Temperature range: 30℃~300℃ Atmosphere: Nitrogen 50ml / min Sample amount: 10 mg

[0070] Example 2-2 The benzoxazine compound (Q3) obtained in Example 1-3 above was subjected to differential scanning calorimetry (DSC), and an exothermic peak was detected in the DSC curve shown in Figure 2, confirming that a cured product had been formed.

[0071] Example 2-3 The benzoxazine compound (Q4) obtained in Example 1-4 above was subjected to differential scanning calorimetry (DSC), and an exothermic peak was detected in the DSC curve shown in Figure 3, confirming that a cured product had been formed.

[0072] Examples 2-4 The benzoxazine compound (Q5) obtained in Example 1-5 above was subjected to differential scanning calorimetry (DSC), and an exothermic peak was detected in the DSC curve shown in Figure 4, confirming that a cured product had been formed.

[0073] Examples 2-5 The benzoxazine compound (Q6) obtained in Example 1-6 above was subjected to differential scanning calorimetry (DSC), and an exothermic peak was detected in the DSC curve shown in Figure 5, confirming that a cured product had been formed. [Industrial Applicability]

[0074] The benzoxazine compound of the present invention and the resin raw material composition and curable resin composition containing the same are suitable as raw materials for producing circuit boards, interlayer insulating materials, printed wiring boards, laminates, prepregs, molding materials, various electronic components, etc. The benzoxazine compound of the present invention can also be used as a raw material for producing adhesives, sealants, photosensitive materials, paints (resist inks, etc.), matrix resins for composites, etc.

Claims

1. A benzoxazine compound represented by the following general formula (1): 【Chemistry 1】 (In the formula, R １ is a hydrocarbon group having 1 to 6 carbon atoms, and R ２ is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and Z is a carbon atom or a tetravalent hydrocarbon group having 2 to 30 carbon atoms.

2. A resin raw material composition containing the benzoxazine compound according to claim 1.

3. A curable resin composition comprising the benzoxazine compound according to claim 1.

4. A cured product obtained by curing the benzoxazine compound according to claim 1 or the curable resin composition according to claim 3.

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