JP2016153476A - Thermosetting resin composition and application thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosetting resin composition used for manufacturing a film-shaped adhesive excellent in shear strength and peel strength.SOLUTION: There is provided a thermosetting resin composition containing at least a compound represented by the following formula (1). In the formula (1), Rrepresents bivalent organic group having at least an amide bond, Rrepresents a bivalent group binding to an aromatic ring and each independently represents a direct bond or a bivalent organic group having no amide bond binding to an aromatic ring, Rrepresents each independently a hydrocarbon group capable of being substituted, Rrepresents a group binding to an aromatic ring and each independently represents a hydrocarbon group capable of being substituted and n represents each independently an integer of 0 to 3.SELECTED DRAWING: None

Description

  The present invention relates to a thermosetting resin composition containing at least a compound having a dihydro-1,3-benzoxazine ring, and a film adhesive, a dihydrobenzoxazine compound, and a laminate using the thermosetting resin composition About.

Since fiber reinforced composite materials are materials that achieve both high strength and light weight, they are often used in ships, automobiles, aircraft, building materials, sports equipment, and the like.
A fiber-reinforced composite material is a film-like structure called a prepreg obtained by impregnating a fiber with a thermosetting resin composition and semi-cured with another member such as a metal such as aluminum as necessary. Are laminated and cured through a film adhesive.

  Film adhesives used in such fiber reinforced composite materials are not only shear stress but stress in various directions, so film adhesives have excellent performance in both shear strength and peel strength. Is required.

  As a thermosetting resin composition used for such a film adhesive, Patent Document 1 discloses at least one kind selected from an epoxy resin containing nanocore-shell particles, an amine-terminated polyethersulfone, and an amine-terminated polysulfone. A thermosetting adhesive composition containing a toughening agent and at least one multifunctional epoxy resin is disclosed. Patent Document 2 discloses a structural adhesive containing a bisphenol-type epoxy resin, a modified epoxy resin containing a blocked isocyanate, a carboxyl group-containing butadiene-acrylonitrile liquid rubber, and a curing agent.

Special table 2013-503249 gazette JP 05-148337 A

  The subject of this invention is the thermosetting resin composition used for manufacture of the film adhesive excellent in shear strength and peel strength, the film adhesive manufactured from this thermosetting resin composition, a laminated body, Another object is to provide a dihydrobenzoxazine compound used in the thermosetting resin composition.

The configuration of the present invention is as follows.
[1] A thermosetting resin composition comprising at least a compound represented by the following formula (1).

(In Formula (1), R ¹ represents a divalent organic group having at least one amide bond. R ² represents a divalent group bonded to an aromatic ring, and each independently represents a direct bond or an aromatic group. A divalent organic group having no amide bond bonded to the ring, R ³ represents a hydrocarbon group that can be independently substituted, R ⁴ represents a group bonded to an aromatic ring, and each independently substituted Each represents a possible hydrocarbon group, and each n independently represents an integer of 0 to 3.)
[2] The thermosetting resin composition according to [1], wherein R ¹ is a divalent organic group represented by the following formula (2).

(In the formula (2), R ⁵ represents an alkanediyl group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, a group represented by —R ⁶ —R ⁷ — (R ⁶ ) _p —, or — R ⁷ —R ⁶ — (R ⁷ ) _p — represents a group represented by R ⁶ , each R ⁶ independently represents an alkanediyl group having 1 to 20 carbon atoms, and R ⁷ represents each independently an arylene having 6 to 20 carbon atoms. And p represents independently 0 or 1. * represents a bond.)
[3] The thermosetting resin composition according to [1] or [2], wherein at least one of R ² is a divalent organic group represented by the following formula (3).

(In formula (3), R ⁸ represents oxygen or sulfur. R ⁹ represents an alkanediyl group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, —R ¹⁰ —R ¹¹ — (R ¹⁰ ). _q - group represented by or ^{-R 11 -R 10 - (R 11} ) q - represents a group represented by .R ¹⁰ shows an alkanediyl group having 1 to 20 carbon atoms each independently .R ¹¹ are each Independently represents an arylene group having 6 to 20 carbon atoms, q independently represents 0 or 1, and * represents a bond.

[4] The thermosetting resin composition according to [1] to [3], further comprising a compound having an epoxy group.
[5] The thermosetting resin composition according to [4], wherein the compound having an epoxy group is a bisphenol type epoxy resin.
[6] The thermosetting according to [1] to [5], further comprising a curing catalyst that accelerates curing of at least one compound selected from the compound represented by the formula (1) and the compound having an epoxy group. Resin composition.
[7] The thermosetting resin composition according to [1] to [6], further containing organic particles.
[8] A film adhesive obtained by semi-curing at least the thermosetting resin composition according to [1] to [7].
[9] A film adhesive obtained by impregnating the thermosetting resin composition according to any one of [1] to [7] into a fiber and semi-curing the fiber.
[10] A laminate comprising the film adhesive according to [8] or [9].
[11] A dihydrobenzoxazine compound represented by the following formula (4).

(In Formula (4), R ¹ represents a divalent organic group having at least one amide bond. R ² represents a divalent group bonded to an aromatic ring, and each independently represents a direct bond or an aromatic group. A divalent organic group having no amide bond bonded to the ring, R ³ represents a hydrocarbon group that can be independently substituted, R ⁴ represents a group bonded to an aromatic ring, and each independently substituted Each represents a possible hydrocarbon group, and each n independently represents an integer of 0 to 3.)

  The thermosetting resin composition of the present invention can produce a film adhesive having excellent shear strength and peel strength. The film adhesive and laminate of the present invention are excellent in shear strength and peel strength. The dihydrobenzoxazine compound of the present invention can be suitably used for the thermosetting resin composition of the present invention.

The result of ¹ H-NMR of the raw material phenol compound of the compound (A1) synthesized in Example 1 is shown. The result of ¹ H-NMR of the compound (A1) synthesized in Example 1 is shown.

[1] Dihydrobenzoxazine Compound A dihydrobenzoxazine compound (hereinafter also referred to as “compound (A)”) is a compound having a dihydro-3,1-benzoxazine structure represented by the following formula (1).

(In Formula (1), R ¹ represents a divalent organic group having at least one amide bond. R ² represents a divalent group bonded to an aromatic ring, and each independently represents a direct bond or an aromatic group. A divalent organic group having no amide bond bonded to the ring, R ³ represents a hydrocarbon group that can be independently substituted, R ⁴ represents a group bonded to an aromatic ring, and each independently substituted Each represents a possible hydrocarbon group, and each n independently represents an integer of 0 to 3.)

  The thermosetting resin composition of this invention can manufacture the film adhesive excellent in shear strength and peel strength by containing a compound (A) at least. The reason is not clear, but in the two dihydrobenzoxazine structures involved in cross-linking, the spacer site effective for elongation of the cured product has an amide structure effective for adhesion to the metal substrate, thereby increasing the peel strength. It is presumed that an excellent film-like adhesive having excellent shear strength and heat resistance can be obtained.

The amide bond in the divalent organic group having at least one amide bond of R ^{1 represents} a bond represented by —NR ¹¹ —C═O—. R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. Examples of the alkyl group having 1 to 20 carbon atoms of R ¹¹ include a methyl group, an ethyl group, an isopropyl group, a butyl group, a tert-butyl group, and an n-octyl group.

  As the divalent organic group having an amide bond, a divalent organic group represented by the following formula (2) is preferable because a film adhesive having excellent shear strength, peel strength, and heat resistance can be obtained. .

In Formula (2), R ⁵ is an alkanediyl group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, a group represented by —R ⁶ —R ⁷ — (R ⁶ ) _p —, or —R ⁷ -R ⁶ - represents a group represented by - (R ⁷⁾ _p. R ⁶ independently represents an alkanediyl group having 1 to 20 carbon atoms. R ⁷ each independently represents an arylene group having 6 to 20 carbon atoms. p shows 0 or 1 each independently. * Indicates a bond.

Examples of the alkanediyl group having 1 to 20 carbon atoms of R ⁵ include a methylene group, an ethylene group, an ethane-1,1-diyl group, a propane-1,1-diyl group, a propane-1,2-diyl group, and propane. -1,3-diyl group, propane-2,2-diyl group, butane-1,2-diyl group, butane-1,3-diyl group, butane-1,4-diyl group, pentane-1,4- Diyl group, pentane-1,5-diyl group, hexane-1,5-diyl group, hexane-1,6-diyl group, octane-1,8-diyl group, decane-1,10-diyl group, etc. Can be mentioned.

Examples of the arylene group having 1 to 20 carbon atoms of R ⁵ include a 1,2-phenylene group, a 1,3-phenylene group, a 1,4-phenylene group, and a 1,5-naphthylene group.
Examples of the alkanediyl group having 1 to 20 carbon atoms of R ⁶ include groups represented by the alkanediyl group having 1 to 20 carbon atoms of R ⁵ . R ⁶ may be the same or different.

Examples of the arylene group having 6 to 20 carbon atoms of R ⁷ include the groups represented by the arylene group having 1 to 20 carbon atoms of R ⁵ .
R ² in the formula (1) represents a divalent organic group having no direct bond or an amide bond bonded to an aromatic ring.
It is preferable that at least one of R ² is a divalent organic group represented by the following formula (3).

(Equation (3), R ⁸ is oxygen, or .R ⁹ showing a sulfur alkanediyl group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon ^{atoms, -R 10 -R 11 - (R} 10 ) _q -, a group represented by or ^{-R 11 -R 10 - (R 11} ) q - represents a group represented by .R ¹⁰ shows an alkanediyl group having 1 to 20 carbon atoms each independently .R ¹¹ is Each independently represents an arylene group having 6 to 20 carbon atoms, wherein q independently represents 0 or 1, and * represents a bond.

R ⁸ may be bonded to an aromatic ring or R ¹ .
R ⁹ may be bonded to an aromatic ring or R ¹ .
Examples of the alkanediyl group having 1 to 20 carbon atoms of R ⁹ and R ¹⁰ include groups represented by the alkanediyl group having 1 to 20 carbon atoms of R ⁵ . R ¹⁰ may be the same or different.

Examples of the arylene group having 6 to 20 carbon atoms of R ⁹ and R ¹¹ include groups represented by the arylene group having 1 to 20 carbon atoms of R ⁵ .
R ³ in the formula (1) represents a substitutable hydrocarbon group. Examples of the substitutable hydrocarbon group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, and one or more hydrogen atoms of these groups. Are groups substituted with any group selected from an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a hydroxyl group.

Examples of the alkyl group having 1 to 20 carbon atoms of R ³ include a methyl group, an ethyl group, an isopropyl group, a butyl group, a tert-butyl group, and an n-octyl group.
Examples of the cycloalkyl group having 3 to 12 carbon atoms of R ³ include a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group.

Examples of the aryl group having 6 to 20 carbon atoms of R ³ include a phenyl group, a naphthyl group, a tolyl group, a xylyl group, a pyridyl group, and a pyrrole group.
In the formula (1), R ⁴ represents a group bonded to an aromatic ring, and each independently represents a substitutable hydrocarbon group. Examples of R ⁴ include the substitutable hydrocarbon group represented by R ³ .

[Production of dihydrobenzoxazine compound]
The dihydrobenzoxazine compound of the present invention is synthesized using, for example, a bisphenol compound represented by the following formula (5) (hereinafter also referred to as “bisphenol compound”), a primary amine represented by R ³ NH ₂ , and formaldehyde as raw materials. It is obtained by reacting. In the synthesis reaction, the raw material is usually used in an amount of 2 to 40 mol of primary amine and 4 to 80 mol of formaldehyde with respect to 1 mol of the bisphenol compound.

(In the formula (5), R ¹ , R ² , R ⁴ and n are the same as those in the formula (1).)

  The reaction conditions in the synthesis reaction are as follows. The reaction temperature is generally 0 ° C to 250 ° C, preferably 50 ° C to 150 ° C. The reaction time is usually 0.5 to 40 hours, preferably 1 to 30 hours. During the reaction, the reaction conditions can be appropriately changed. For example, a method of heating at 50 to 100 ° C. for 12 hours, then heating at 100 to 150 ° C. for 5 hours, and then heating at 50 to 100 ° C. for 12 hours can be mentioned. The reaction may be performed under any atmospheric pressure. In particular, the reaction is preferably performed under reduced pressure while removing water.

  The synthesis reaction is usually performed in a reaction solvent. Examples of the reaction solvent include halogen solvents such as chloroform and dichloromethane; ether solvents such as tetrahydrofuran and dioxane; aromatic solvents such as xylene and toluene; N-methyl-2-pyrrolidone; and the like.

  The reaction can be performed in the presence of a catalyst. Examples of the catalyst include an acid catalyst and a base catalyst. Examples of the acid catalyst include inorganic acids such as hydrochloric acid and sulfuric acid; organic acids such as p-toluenesulfonic acid, xylenesulfonic acid and methanesulfonic acid; Lewis acids such as aluminum chloride and zinc chloride; activated clay, acidic clay and white carbon And solid acids such as zeolite and silica alumina; and acidic ion exchange resins. Examples of the base catalyst include diazabicycloundecene and pyridine.

  The bisphenol compound can be synthesized, for example, by the methods described in JP2003-104965A, JP2004002332A, and the like. Specifically, a compound represented by the following formula (6) and a compound represented by the following formula (7) are mixed with triethylamine, sodium hydroxide, 1,4-diazabicyclo [5] in an organic solvent such as dimethyl sulfoxide or acetonitrile. , 4,0] unde-7-ene and the like in the presence of a base.

(In the formula (6), R ¹ and R ² are the same as those in the formula (1). X represents a halogen atom such as a chlorine atom, a bromine atom or an iodine atom)

(In the formula (7), R ⁴ and n are the same as those in the formula (1). The thiol group is a group bonded to the benzene ring.)

R ³ in the primary amine represented by R ³ NH ₂ is the same as R ³ in the formula (1). Examples of the primary amine represented by R ³ NH ₂ include methylamine, ethylamine, phenylamine, aniline, cyclohexylamine, butylamine, hexylamine, allylamine, and propylenediamine. A primary amine may be used individually by 1 type, and may be used in combination of 2 or more type. The formaldehyde used for the synthesis can also be used as paraformaldehyde.

  The dihydrobenzoxazine compound of the present invention can be produced by reacting the primary amine and formaldehyde with the bisphenol compound of formula (5). In addition, the dihydrobenzoxazine compound of the present invention can be prepared by synthesizing tetrahydrotriazines from the primary amine and formaldehyde according to the synthesis route shown in the following formula (8) and reacting the tetrahydrotriazine with the bisphenol compound of formula (5). Can be manufactured.

(In formula (8), R ³ is the same as R ^{3 in} formula (1)).

  After completion of the reaction, the reaction solution contains various compounds such as the raw material and a compound in which the dihydro-3,1-benzoxazine structure is opened in addition to the compound of the present invention. For this reason, after completion | finish of reaction, it is preferable to refine | purify by a well-known purification method, for example, a reprecipitation method and a liquid washing method.

[2] Thermosetting resin composition The thermosetting resin composition according to the present invention contains at least the dihydrobenzoxazine compound of the present invention. If necessary, an epoxy group-containing compound (hereinafter also referred to as “compound (B)”), a curing catalyst (hereinafter also referred to as “catalyst (C)”), organic particles (hereinafter referred to as “particle (D)”). Or a component selected from a solvent (hereinafter also referred to as “solvent (E)”).

[Compound (B)]
The compound (B) is used for the purpose of adjusting the curing rate of the thermosetting resin composition of the present invention and / or for the purpose of improving the adhesive strength.
The compound (B) refers to a compound having at least one epoxy group, for example, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol type epoxy resin, trisphenol type epoxy resin, tetraphenol type epoxy. Resin, phenol-xylylene type epoxy resin, naphthol-xylylene type epoxy resin, phenol-naphthol type epoxy resin, phenol-dicyclopentadiene type epoxy resin, cycloaliphatic epoxy resin, epoxy resin of aliphatic epoxy resin; resorcinol diglycidyl ether , Pentaerythritol glycidyl ether, trimethylolpropane polyglycidyl ether, glycerol polyglycidyl ether, phenyl glycidyl ether, neopentyl Coal diglycidyl ether, ethylene / polyethylene glycol diglycidyl ether, propylene / polypropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, sorbitol polyglycidyl ether, propylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, etc. An epoxy compound.

Among these compounds having an epoxy group, a bisphenol type epoxy resin is preferable from the viewpoint of adhesive strength.
The compound which has an epoxy group may be used individually by 1 type, and may be used in combination of 2 or more types.

  The content of the compound having an epoxy group in the thermosetting resin composition is usually 1 to 500 parts by mass, preferably 10 to 300 parts by mass, more preferably 100 parts by mass of the compound (A). It is 50-150 mass parts. When the usage-amount of the compound which has an epoxy group is the said range, the hardened | cured material which has the outstanding adhesive strength can be obtained.

[Catalyst (C)]
The catalyst (C) is used for the purpose of accelerating the crosslinking reaction of a crosslinkable group such as a dihydrobenzoxazine ring or an epoxy group and accelerating the curing rate. A curing catalyst usually used in these crosslinkable groups is used. Can be used.

Examples of the catalyst (C) include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and methyl endo. Acid anhydrides such as ethylenetetrahydrophthalic acid and trialkyltetrahydrophthalic anhydride; Triflates such as diethylammonium triflate, triethylammonium triflate, diisopropylammonium triflate, ethyl isopropylammonium triflate; metal fluoroboron complex and boron compounds such as boron trifluoride complex compound, bis (perfluoroalkyl sulfonyl) methane metal _{salts; PCl 5, TiCl 4, AlCl} 3, inorganic acids such as TeOMe; p-toluenesulfonic acid, p- DOO Organic acids such as toluenesulfonic acid esters; dicyandiamide, diethyl toluene diamine, bases such as meta-xylene diamine; and the like.

  Content of the catalyst (C) in a composition is 0.5-50 mass parts normally with respect to a total of 100 mass parts of a compound (A) and a compound (B), Preferably it is 1-30 mass parts. is there. When content of a catalyst (C) is the said range, the hardened | cured material which has the outstanding adhesive strength can be obtained.

[Particle (D)]
The particles (D) are used for the purpose of improving the toughness of the film adhesive produced from the thermosetting resin composition.

  The particles (D) include olefin resin, silicone resin, epoxy resin, melamine resin, urea resin, acrylic resin, polyimide resin, Teflon (registered trademark) resin, polyethylene resin, polyester resin, polyurethane resin, polyamide resin, and cyanamide resin. And the like, which are particles of a resin such as Commercially available particles (D) include Zefiac F-320, F-301, F-340, F-325, F-351 (manufactured by Ganz Kasei Co., Ltd.), acrylic fine particles MP-300 (manufactured by Soken Chemical Co., Ltd.) ) And the like.

  As the particles (D), core-shell particles described in JP2010-084083A, JP2012-224733A, JP2012052051A, and the like can also be used. As the particles (D), one type may be used alone, or two or more types may be used in combination.

The primary particle size of the particles (D) is usually 0.001 to 50 μm. The primary particle size can be measured with a transmission electron microscope.
Content of particle | grains (D) becomes like this. Preferably it is 1-600 mass parts with respect to 100 mass parts of compounds (A), More preferably, it is 10-200 mass parts, More preferably, it is 50-100 mass parts.

[Solvent (E)]
The solvent (E) is used for the purpose of uniformly mixing the compound (A) and other components to improve handleability, adjust the viscosity of the thermosetting resin composition, and improve storage stability. It is done.

  Examples of the solvent (E) include ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; propylene glycol such as propylene glycol monomethyl ether, propylene glycol monopropyl ether and propylene glycol monobutyl ether. Monoalkyl ethers; propylene glycol dialkyl ethers such as propylene glycol dimethyl ether and propylene glycol dibutyl ether; propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol monobutyl ether acetate; cellosolves such as butyl cellosolve; Carbitols such as Tol; lactate esters such as ethyl lactate; aliphatic carboxylic acid esters such as ethyl acetate, isopropyl acetate, n-butyl propionate, isobutyl propionate; methyl 3-methoxypropionate, 3-methoxy Other esters such as ethyl propionate, methyl pyruvate, ethyl pyruvate; ketones such as methyl ethyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone; amides such as N-dimethylformamide; γ-butyrolacun And lactones; and aromatic hydrocarbons such as toluene and xylene. Among these, ketones and ethers are preferable because the polymer (A) can be uniformly dissolved.

A solvent (E) may be used individually by 1 type, and may be used in combination of 2 or more type.
The amount of the solvent (E) used is usually such an amount that the solid content concentration of the thermosetting resin composition of the present invention is 1 to 90% by mass, and is appropriately determined depending on the purpose and use of the composition.

[Other ingredients]
In the thermosetting resin composition of the present invention, the compound (A), the compound having an epoxy group (B), the curing catalyst (C), and particles (D) are used within a range not impairing the specification of the thermosetting resin composition. ) And components other than the solvent (E) can be contained.

  Other components include, for example, γ-methacryloxypropyltrimethoxysilane, 1,3,5-N-tris (trimethoxysilylpropyl) isocyanurate, and 1,2, Adhesion aids such as 3-benzotriazole; flame retardants such as phosphazene compounds and bromides to improve the flame retardancy of the cured product; colorants such as dyes and pigments to impart color to the cured product Fibers such as carbon fiber, glass fiber, and synthetic resin fiber; thermoplastic resins such as polyethylene, polystyrene, polyethersulfone and polyurethane; silica, alumina, zirconium oxide, oxidation to improve scratch resistance and crack resistance Titanium, zinc oxide, magnesium oxide, calcium carbonate, magnesium carbonate, barium sulfate, talc, molybdenum Inorganic particles such as Morironaito; and the like.

[Production of thermosetting resin composition]
The thermosetting resin composition of the present invention comprises compound (A) as an essential component, and if necessary, compound (B), catalyst (C), particles (D), solvent (E), and other components are mixed. Can be manufactured. Moreover, you may remove the dust contained in a composition with a filter etc. after mixing.

[3] Film adhesive The film adhesive of the present invention is a film obtained by thermosetting the thermosetting resin composition of the present invention so that the degree of curing is in a semi-cured state (B stage). Semi-cured product. Alternatively, a semi-cured product can be produced by impregnating a thermosetting resin composition into fibers such as non-woven cloth. The curing conditions are usually 50 ° C. or higher and 0.1 to 2 hours. Moreover, you may carry out, pressing at the pressure of about 0.01-1 Mpa at the time of hardening. Prior to the heat curing, heating may be performed at a temperature lower than 150 ° C. as preliminary curing. Moreover, the film adhesive of this invention can also be manufactured by thermosetting the thermosetting resin composition of this invention on a peeling film.

  Since the film adhesive of this invention is manufactured using the thermosetting resin composition of this invention, it is excellent in shear strength and peel strength. Furthermore, the film adhesive of the present invention is excellent in heat resistance.

[4] Laminate The laminate of the present invention is a laminate containing the film adhesive of the present invention. The laminate of the present invention is produced by, for example, laminating and curing other members such as metal members and fiber reinforced plastics via the film adhesive of the present invention. Since the laminate of the present invention uses the thermosetting resin composition of the present invention, the laminate has characteristics of high shear strength and difficulty in delamination.

  Since the laminate of the present invention has the characteristics of high shear strength and resistance to delamination, it can be suitably used for ships, automobiles, aircraft, building materials, sports equipment, and the like.

EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples. In the following description of Examples and the like, “part” is used to mean “part by mass” unless otherwise specified.
1. Synthesis of Compound (A) [Example 1] Synthesis of Compound (A1) In a solution of N, N′-methylenebisacrylamide (10.2 g) and 4-mercaptophenol (25 g) in acetonitrile (700 ml), triethylamine (0 .46 ml) was added dropwise, heated at 60 ° C. for 3 hours, and further heated at 75 ° C. for 10 minutes. A white solid precipitated after heating was taken out, and the white solid was recrystallized with cyclopentanone to obtain a bisphenol compound. The results of ¹ H-NMR (heavy solvent: DMSO-d6) of the bisphenol compound are shown in FIG.

The bisphenol compound (0.50 g) and n-butylamine (0.29 g) were mixed with N, N′-dimethylformamide (0.8 ml) at 50 ° C. Paraformaldehyde (0.24 g) was added dropwise to the mixed solution, heated at 50 ° C. for 1 hour, and further heated at 70 ° C. for 3 hours. After the heated mixture was concentrated, N, N′-dimethylformamide (0.14 ml) and paraformaldehyde (0.12 g) were added, and the mixture was heated at 50 ° C. for 1 hour and further at 70 ° C. for 2.5 hours. Volatile components in the mixed solution were removed by an evaporator and redissolved in chloroform (7 ml), and then the organic layer was washed with a 10% NaOH aqueous solution. After washing, it was washed with water until the organic layer became neutral. The organic layer after washing with water was concentrated and redissolved in toluene, and then purified by reprecipitation with hexane to synthesize compound (A1). From the ¹ H-NMR and ¹³ C-NMR analysis (device name “ECP-400P”, measured by JEOL), the structure of the compound (A1) is represented by the compound (compound (A1)) represented by the following formula (9). It became clear that there was. The result of ¹ H-NMR (deuterated solvent: DMSO-d6) of the compound (A1) is shown in FIG.

2. Production of thermosetting resin composition [Example 1]
By mixing the components shown in Table 1, the thermosetting resin compositions of Example 1 and Comparative Examples 1 and 2 were produced. The details of various components shown in Table 1 are as follows.
A1: Compound (A1) produced in Synthesis Example 1
RA1: Compound represented by the following formula (10)

RA2: Compound represented by the following formula (11)

B1: Trade name “jER1256B40” (Mitsubishi Chemical Corporation, bisphenol A type liquid epoxy resin, epoxy equivalent 6700-8000 g / eq)
C1: Dicyandiamide B2 + D1: Trade name “Kane Ace MX-153” (manufactured by Kaneka Corporation, a composition in which 33% by mass of core-shell rubber particles are dispersed in bisphenol A type liquid epoxy resin)
E1: 2-butanone

3. Production of film adhesive [Example 2]
The composition of Example 1 was dip-coated with a nonwoven fabric (nylon nonwoven fabric manufactured by Nippon Vilene Co., Ltd., film thickness 40 um, basis weight 13 g / m ² ), heated at 50 ° C. for 10 minutes, and then at 0.04 MPa. While pressing, the film-like adhesive of Example 2 was obtained by heating at 70 ° C. for 30 minutes.

  The shear strength of the film adhesive was measured by the following method. The film adhesive of Example 2 was cut into a size of 25 mm × 12.5 mm, and then sandwiched between two chrome-treated aluminum plates (size: 25 mm × 100 mm, thickness: 2 mm) at 180 ° C. A sample for shear strength evaluation was prepared by heating for 2 hours. The shear strength was based on JIS K6850, and the maximum load when the test piece was pulled at a tensile speed of 1 nm / min was defined as the shear strength. The evaluation results are shown in Table 2.

  The peel strength of the film adhesive was measured by the following method. The film-like adhesive of Example 2 was cut to a size of 25 mm × 140 mm, and then sandwiched between two chrome-treated aluminum plates (size: 25 mm × 200 mm, thickness: 0.5 mm) at 180 ° C. A sample for peel strength evaluation was prepared by heating for 2 hours. The peel strength was based on JIS K6854-3, and the average value between 100 and 200 mm when the test piece was pulled at a pulling speed of 100 mm / min was defined as the peel strength. The evaluation results are shown in Table 2.

  The heat resistance of the film adhesive was evaluated at the glass transition temperature. The film adhesive of Example 2 was placed on a polyethylene terephthalate film (PET film) and heated at 180 ° C. for 2 hours or 200 ° C. for 4 hours to prepare a glass transition temperature evaluation sample. The sample was evaluated using a DMS tester as a glass transition temperature, Tan δ when measured under a measurement condition of 1 Hz within a temperature range of 23 ° C. to 350 ° C. The evaluation results are shown in Table 2.

[Comparative Examples 3 to 4]
Using the compositions of Comparative Examples 1 and 2, a film adhesive was produced in the same manner as in Example 2, and the shear strength, peel strength, and glass transition temperature were evaluated. The evaluation results are shown in Table 2. In Table 2, “ND” indicates that the glass transition temperature could not be observed.

Claims (11)

A thermosetting resin composition comprising at least a compound represented by the following formula (1).
(In Formula (1), R ¹ represents a divalent organic group having at least one amide bond. R ² represents a divalent group bonded to an aromatic ring, and each independently represents a direct bond or an aromatic group. A divalent organic group having no amide bond bonded to the ring, R ³ represents a hydrocarbon group that can be independently substituted, R ⁴ represents a group bonded to an aromatic ring, and each independently substituted Each represents a possible hydrocarbon group, and each n independently represents an integer of 0 to 3.) The thermosetting resin composition according to claim 1, wherein R ¹ is a divalent organic group represented by the following formula (2).
(In the formula (2), R ⁵ represents an alkanediyl group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, a group represented by —R ⁶ —R ⁷ — (R ⁶ ) _p —, or — R ⁷ —R ⁶ — (R ⁷ ) _p — represents a group represented by R ⁶ , each R ⁶ independently represents an alkanediyl group having 1 to 20 carbon atoms, and R ⁷ represents each independently an arylene having 6 to 20 carbon atoms. And p represents independently 0 or 1. * represents a bond.) The thermosetting resin composition according to claim 1, wherein at least one of R ² is a divalent organic group represented by the following formula (3).
(In formula (3), R ⁸ represents oxygen or sulfur. R ⁹ represents an alkanediyl group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, —R ¹⁰ —R ¹¹ — (R ¹⁰ ). _q - group represented by or ^{-R 11 -R 10 - (R 11} ) q - represents a group represented by .R ¹⁰ shows an alkanediyl group having 1 to 20 carbon atoms each independently .R ¹¹ are each Independently represents an arylene group having 6 to 20 carbon atoms, q independently represents 0 or 1, and * represents a bond.   Furthermore, the thermosetting resin composition of any one of Claims 1-3 containing the compound which has an epoxy group.   The thermosetting resin composition according to claim 4, wherein the compound having an epoxy group is a bisphenol type epoxy resin.   Furthermore, the thermosetting of any one of Claims 1-5 containing the curing catalyst which accelerates | stimulates hardening of the at least 1 compound chosen from the compound shown to the said Formula (1), and the compound which has the said epoxy group. Resin composition.   Furthermore, the thermosetting resin composition of any one of Claims 1-6 containing an organic particle.   A film adhesive obtained by semi-curing at least the thermosetting resin composition according to any one of claims 1 to 7.   A film-like adhesive obtained by impregnating at least a fiber with the thermosetting resin composition according to any one of claims 1 to 7 and semi-curing the fiber.   The laminated body characterized by including the film adhesive as described in any one of Claim 8 or 9. A dihydrobenzoxazine compound represented by the following formula (4).
(In Formula (4), R ¹ represents a divalent organic group having at least one amide bond. R ² represents a divalent group bonded to an aromatic ring, and each independently represents a direct bond or an aromatic group. A divalent organic group having no amide bond bonded to the ring, R ³ represents a hydrocarbon group that can be independently substituted, R ⁴ represents a group bonded to an aromatic ring, and each independently substituted Each represents a possible hydrocarbon group, and each n independently represents an integer of 0 to 3.)