Bisalkenyl-substituted nadimide, method for producing same, curable material, curable resin composition, and cured product of same

Abstract

[Problem] To provide a bisalkenyl-substituted nadimide which gives a film that has a low dielectric constant and a low dielectric loss tangent in a GHz band (in particular, in a 10 GHz band) and has excellent flexibility. [Solution] A bisalkenyl-substituted nadimide according to the present invention is represented by general formula (1). (In formula (1), R1 and R2 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and A represents a divalent hydrocarbon group that is derived from a dimer acid skeleton.)

Description

Bisalkenyl-substituted nadimide, its manufacturing method, curable material, curable resin composition, and cured product thereof

[0001] The present invention relates to a bisalkenyl-substituted nadimide, a method for producing the same, a curable material, a curable resin composition, and a cured product thereof.

[0002] With the advancement of science and technology, the materials used are required to have higher performance and functionality, and various materials have been developed to meet these demands. For example, various high-performance polymers known as so-called super engineering plastics (engineering plastics), such as polyether ketone, polyphenylene sulfide, and polyimide, are widely available on the market. In particular, expectations are high for polyimide in terms of its heat resistance, etc.

[0003] Among polyimides, bismaleimides, which have imide skeletons at both ends, are commonly used. Because of their rigid imide rings, bismaleimide resins exhibit high heat resistance and low thermal expansion, exceeding that of epoxy resins. In addition, because they do not emit volatile gases during molding, they are primarily used in fields such as aerospace and electronic materials.

[0004] Furthermore, among these, bisnadiimides having norbornene rings at both ends of the bismaleimide have a higher upper limit of usable temperature than bismaleimides without norbornene rings at both ends. Therefore, they have been attracting attention as raw materials for addition-type polyimide resins with extremely high heat resistance. Some of these have been put to practical use as matrices for so-called advanced composite materials. However, these bisnadiimides are generally difficult to handle due to their high melting points and poor solubility in solvents. Furthermore, due to their poor reactivity, harsh reaction conditions (e.g., high-temperature molding at 300°C) are required to increase their molecular weight.

[0005] However, under these reaction conditions, in addition to the desired polymerization reaction, a retro-Diels-Alder reaction of the norbornene rings also occurs. The highly volatile cyclopentadiene generated under these conditions is said to be the cause of significant voids in the molded product.

[0006] Examples of molding methods that can suppress such foaming include a method of reacting under high temperature and pressure (e.g., autoclave molding) and a method of dissolving the imide raw materials, acid anhydride or ester, and diamine in a solvent to oligomerize the resulting material and use it as a varnish. However, these methods require high temperature and pressure conditions and solvent evaporation, leaving room for improvement.

[0007] On the other hand, in order to suppress this foaming, in addition to adopting the above-mentioned means, various methods have been investigated, such as a method for lowering the curing reaction temperature and a method for introducing an appropriate substituent into the norbornene ring so that volatile components are not produced even if a retro-Diels-Alder reaction occurs.

[0008] Patent Documents 1 to 3 disclose various inventions relating to bisalkenyl-substituted nadimides. Patent Document 1 discloses known bisalkenyl-substituted nadimides such as bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximide)phenyl}methane, and Patent Documents 2 and 3 disclose known bisalkenyl-substituted nadimides such as N,N'-m-xylylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximide).

[0009] Thus, the above-mentioned bisalkenyl-substituted nadimides are characterized by their excellent mechanical strength, heat resistance up to 300°C, and dimensional stability, and are used in heat-resistant adhesives, precoating agents for bonding Teflon to metals, heat resistance improvers for epoxy resins, soldering agents, carbon fiber binders, materials for printed circuit boards, etc.

[0010] JP-A-61-73710 JP-A-7-53516 JP-A-7-224121

[0011] However, due to their hardness and brittleness, the cured products of the bisalkenyl-substituted nadimides cannot be used in fields requiring flexibility, such as films, and their application to thin films and films is difficult. Furthermore, because the nadimides are solid or semi-solid, they require heating to achieve fluidity, which may limit their blending with other resins. Furthermore, their dielectric properties, such as the dielectric constant and dielectric loss tangent in the GHz band, particularly in the high-frequency band of 10 GHz or higher, are poor enough to meet the needs of the 5G era.

[0012] SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide a bisalkenyl-substituted nadimide which provides a film having a low dielectric constant and a low dielectric loss tangent in the GHz band, particularly in the high frequency band of 10 GHz or higher, and which is excellent in flexibility.

[0013] As a result of intensive research aimed at achieving the above object, the present inventors have found that the above problems can be solved by synthesizing a novel bis(alkenyl)-substituted nadimide having a specific structure, and have thus completed the present invention.

[0014] That is, the present invention provides the following inventions: [1] A bisalkenyl-substituted nadimide represented by general formula (1): (In formula (1), R １ and R ２ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and A represents a divalent hydrocarbon group derived from a dimer acid skeleton. [2] The bisalkenyl-substituted nadimide of [1], wherein the divalent hydrocarbon group derived from the dimer acid skeleton contains a structure represented by general formula (2): (In formula (2), m, n, p, and q each represent an integer of 1 or more selected so that m+n=5 to 16 and p+q=8 to 19, and each bond shown by a dashed line independently represents a carbon-carbon single bond or a carbon-carbon double bond. However, when the bond shown by a dashed line is a carbon-carbon double bond, formula (2) has a structure in which the number of hydrogen atoms bonded to each carbon atom constituting the carbon-carbon double bond is subtracted by one from the number shown in formula (2). The wavy line represents the bond to the nitrogen atom of the imide.) [3] A method for producing a bisalkenyl-substituted nadiimide according to [1] or [2], which comprises reacting a dimer diamine with a compound represented by general formula (3) through an addition-dehydration reaction. (In formula (3), R １ and R ２ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.) [4] The method for producing an alkenyl-substituted nadiimide according to [3], wherein the dimer diamine contains a structure represented by general formula (4): (In formula (4), m, n, p, and q each represent an integer of 1 or more selected so that m+n=5 to 16 and p+q=8 to 19, and the bonds shown by dashed lines each independently represent a carbon-carbon single bond or a carbon-carbon double bond. However, when the bond shown by dashed line is a carbon-carbon double bond, formula (4) has a structure in which the number of hydrogen atoms bonded to each carbon atom constituting the carbon-carbon double bond is subtracted by one from the number shown in formula (4).) [5] A curable material comprising a bisalkenyl-substituted nadimide according to [1] or [2]. [6] A curable resin composition comprising: (A) the bisalkenyl-substituted nadimide according to [1] or [2], and (B) at least one compound selected from the group consisting of a maleimide compound, an alkenyl-substituted nadimide (excluding the bisalkenyl-substituted nadimide according to [1] or [2]), an epoxy resin, a phenolic resin, a vinylbenzyl compound, a vinyl compound (excluding vinylbenzyl compounds), a cyclic olefin, a conjugated diene resin having a functional group, or an unsaturated polyester resin. [7] The curable resin composition according to [6], wherein the maleimide compound is a bismaleimide represented by general formula (5): (In formula (5), A' represents a divalent hydrocarbon group.) [8] The curable resin composition according to [7], wherein A' in general formula (5) is a divalent hydrocarbon group derived from a dimer acid skeleton. [9] The curable resin composition according to any one of [6] to [8], wherein the mass ratio (A) / (B) of (A) the bisalkenyl-substituted nadimide according to [1] or [2] to (B) is in the range of 90 / 10 to 10 / 90.

[10] The curable material according to [5], which is used for electronic material applications.

[11] The curable resin composition according to any one of [6] to [9], which is used for electronic material applications.

[12] A cured product obtained by curing the curable material according to [5] or

[10] .

[13] A cured product obtained by curing the curable resin composition according to any one of [6] to [9] and

[11] .

[0015] According to the present invention, it is possible to provide a bisalkenyl-substituted nadimide that can give a film having a low dielectric constant and a low dielectric loss tangent in the GHz band, particularly in the high frequency band of 10 GHz or more, and excellent flexibility, and a method for producing the same. Therefore, the curable material or curable resin composition containing the bisalkenyl-substituted nadimide of the present invention can be suitably used as a film for 5G-compatible electronic material applications.

[0016] 1 shows the IR spectrum of the bisalkenyl-substituted nadimide A synthesized in Example 1. １ The H-NMR spectrum of the bisalkenyl-substituted nadiimide A synthesized in Example 1 is shown. １３ The C-NMR spectrum is shown.

[0017] (Bisalkenyl-substituted nadimide) The bisalkenyl-substituted nadimide of the present invention is a compound represented by the structure of the following general formula (1).

[0018] In the above formula (1), R １ and R ２are each independently selected hydrogen atoms or alkyl groups having 1 to 6 carbon atoms, preferably each independently selected hydrogen atoms or alkyl groups having 1 to 3 carbon atoms, more preferably each independently selected hydrogen atoms or methyl groups, and even more preferably both are hydrogen atoms.

[0019] In formula (1), A is a divalent hydrocarbon group derived from a dimer acid skeleton. Dimer acids are dibasic acids of dicarboxylic acids produced by dimerization of unsaturated fatty acids derived from natural products such as vegetable oils and fats, and do not have a single structure but multiple structures and isomers. Specific examples of dimer acids include, but are not limited to, the following structures: In formulas (2) and (6), m, n, p, and q each represent an integer of 1 or greater selected so that m+n=5 to 16 and p+q=8 to 19, and the bond represented by a dashed line represents a carbon-carbon single bond or a carbon-carbon double bond. However, when the bond represented by a dashed line is a carbon-carbon double bond, formulas (2) and (6) have a structure in which the number of hydrogen atoms bonded to each carbon atom constituting the carbon-carbon double bond is subtracted by one from the number represented by formulas (2) and (6). The wavy line represents the bond to the nitrogen atom of the imide. In a preferred embodiment of the present invention, A includes a structure represented by formula (2).

[0020] The bisalkenyl-substituted nadimide of the present invention is liquid at room temperature, and therefore easily dispersible with other components when preparing a curable resin composition. Furthermore, when cured, conventional bisalkenyl-substituted nadimides having a structure containing an aromatic ring give hard and brittle cured products, whereas the cured product of the bisalkenyl-substituted nadimide of the present invention is flexible and can be molded into a film. This is thought to be because, when A in formula (1) contains a cyclic structure, it can occupy a larger volume, resulting in liquid properties and excellent flexibility of the cured product. This is merely the inventors' speculation, and the present invention is not bound by this theory.

[0021] [Method for Producing Bisalkenyl-Substituted Nadimide] The bisalkenyl-substituted nadimide of the present invention can be synthesized by subjecting an alkenyl-substituted nadic anhydride represented by the following general formula (3) to an addition-dehydration reaction with a dimer diamine in which the two carboxyl groups of the dimer acid are substituted with primary amino groups or primary aminomethyl groups.

[0022] (Alkenyl-substituted nadic anhydride) The alkenyl-substituted nadic anhydride used in the synthesis of the bisalkenyl-substituted nadimide of the present invention is a compound represented by the structure of the following general formula (3). In formula (3), R １ and R ２ are each independently selected hydrogen atoms or alkyl groups having 1 to 6 carbon atoms, preferably each independently selected hydrogen atoms or alkyl groups having 1 to 3 carbon atoms, more preferably each independently selected hydrogen atoms or methyl groups, and even more preferably both are hydrogen atoms.

[0023] As the alkenyl-substituted nadic anhydride represented by the above formula (3), various known compounds can be used without particular limitation. Representative examples include allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, methacrylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, and methacrylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride. These compounds may be mixtures of their respective geometric isomers. Alkenyl-substituted nadic anhydrides can be easily produced by known methods. For example, allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride can be produced by adding dropwise allylcyclopentadiene obtained from allyl chloride and cyclopentadiene to a methyl ethyl ketone solution of maleic anhydride and allowing the mixture to react.

[0024] (Dimer diamine) Dimer diamine is a compound that derives the divalent hydrocarbon group A of the bisalkenyl-substituted nadimide of the present invention. As described in, for example, JP-A-9-12712, dimer diamine is a compound derived from a dimer acid, which is a dimer of an unsaturated fatty acid such as oleic acid. Dimer acid does not have a single structure but exists as multiple structures and isomers, and dimer diamine, which is a derivative thereof, also does not have a single structure but exists as multiple structures and isomers. Specific examples of the dimer diamine include, but are not limited to, the following structures: In formulas (4) and (7), m, n, p, and q each represent an integer of 1 or greater selected so that m+n=5 to 16 and p+q=8 to 19, and the bond shown by a dashed line represents a carbon-carbon single bond or a carbon-carbon double bond. However, when the bond shown by a dashed line is a carbon-carbon double bond, formulas (4) and (7) have a structure in which the number of hydrogen atoms bonded to each carbon atom constituting the carbon-carbon double bond is reduced by one from the number shown in formulas (4) and (7).

[0025] In this embodiment, known dimer diamines can be used without any particular limitations. The dimer diamine in the present invention preferably contains at least one of a compound represented by formula (4) and a compound represented by formula (7), and more preferably contains a compound represented by formula (4). The known dimer diamine may be a commercially available product. Examples of such commercially available products include "VERSAMINE 551" and "VERSAMINE 552" (all trade names, manufactured by Cognis Japan Co., Ltd.), "PRIAMINE 1073", "PRIAMINE 1074", and "PRIAMINE 1075" (all trade names, manufactured by Croda Japan Co., Ltd.).

[0026] The addition-dehydration reaction of the alkenyl-substituted nadic anhydride and dimer diamine in the present invention is essentially a stoichiometric reaction of the two components. For example, 1.5 to 3.0 moles, more preferably 1.7 to 2.5 moles, of alkenyl-substituted nadic anhydride are added to 1.0 mole of dimer diamine compound in the presence or absence of a solvent, and the mixture is heated at 20 to 220°C, preferably 100 to 160°C, for 0.5 to 20 hours, preferably 2 to 10 hours, while removing the water generated during the reaction. The reaction is preferably carried out in the presence of a solvent. Examples of the solvent used include aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, halides of these hydrocarbons, oxygen-, nitrogen-, or sulfur-containing compounds of these hydrocarbons, and mixtures thereof. Specific examples thereof include, but are not limited to, aliphatic hydrocarbons such as hexane and heptane; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, methylnaphthalene, and tetralin; halogenated hydrocarbons such as chloroform, trichlene, tetrachloroethylene, chlorobenzene, and o-dichlorobenzene; oxygen-containing compounds such as dioxane, tetrahydrofuran, anisole, acetone, methyl ethyl ketone, methyl isobutyl ketone, and acetophenone; nitrogen-containing compounds such as N-methyl-2-pyrrolidone and N,N-dimethylformamide; and sulfur-containing compounds such as dimethyl sulfoxide.

[0027] [Method for Curing Bisalkenyl-Substituted Nadimide] The bisalkenyl-substituted nadimide of the present invention undergoes a crosslinking reaction upon heating. Meanwhile, a retro-Diels-Alder reaction of alkenylnorbornene is also thought to occur, resulting in the generation of detached components as gas, which may cause voids in the cured product. Because the bisalkenyl-substituted nadimide of the present invention has a low viscosity up to approximately 200°C, it is preferable to preheat it within this temperature range and degas it in advance to prevent voids from forming in the cured product. It is also preferable to use a reduced-pressure oven for heating to promote degassing. The heating time is preferably continued until the generation of bubbles is almost completely eliminated. Further increasing the temperature thereafter rapidly promotes gelation and curing. For full curing, the product is further heated to a temperature of 200°C or higher and 400°C or lower, preferably 200°C or higher and 300°C or lower. In order to prevent uneven curing, volumetric shrinkage, and the occurrence of voids in the cured product, it is preferable to raise the temperature in stages, and by curing at the final curing temperature for 1 hour or more, preferably 5 hours or more, more preferably 10 hours or more, and even more preferably 20 hours or more, a cured product with excellent heat resistance, mechanical properties, and electrical properties can be obtained. Furthermore, a curing catalyst may be added to promote the crosslinking reaction during curing.

[0028] (Curing Catalyst) In order to promote the crosslinking reaction, a curing catalyst such as an organic peroxide, an onium salt, a cationic catalyst, an organic group-containing metal compound, or an amine compound may be added to cure the bisalkenyl-substituted nadimide of the present invention.

[0029] Examples of organic peroxides include, but are not limited to, di-t-butyl peroxide, di-t-amyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, diacetyl peroxide, dipropionyl peroxide, di-i-butyryl peroxide, benzoyl peroxide, peroxysuccinic acid, t-butyl hydroperoxide, cyclohexyl hydroperoxide, cumene hydroperoxide, t-butyl peroxybenzoate, t-butyl peroxypivalate, 1,1-di-t-butylperoxycyclohexane, di-t-butylperoxyisophthalate, t-butyl peroxymaleate, t-butylperoxyisopropyl carbonate, and 2,2-di-t-butylperoxybutane.

[0030] Examples of onium salts include ammonium compounds such as benzyltriethylammonium chloride, benzyltriethylammonium bromide, phenyltrimethylammonium bromide, tetra-n-butylammonium chloride, tetra-n-butylammonium perchlorate, tetraethylammonium tetrafluoroborate, m-trifluoromethylphenyltrimethylammonium bromide, and tetra-n-butylammonium trifluoromethanesulfonate; phosphonium compounds such as methyltriphenylphosphonium iodide, methyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, and 3-bromopropyltriphenylphosphonium bromide; arsonium compounds such as benzyltriphenylarsonium chloride, tetraphenylarsonium bromide, and tetra-n-butylarsonium chloride; stibonium compounds such as benzyltriphenylstibonium chloride and tetraphenylstibonium bromide; and oxonium compounds such as triphenyloxonium chloride and triphenyloxonium bromide. sulfonium compounds such as triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluoroarsenate, tri(p-methoxyphenyl)sulfonium hexafluorophosphate, tri(p-tolyl)sulfonium tetrafluoroborate, dimethylphenacylsulfonium hexafluorophosphate, and dimethylphenacylsulfonium tetrafluoroborate; triphenylselenonium tetrafluoroborate, triphenylselenonium hexafluoroarsenate, triphenylselenonium hexafluorophosphate, and selenonium compounds such as diphenylselenonium chloride, triphenylstannonium bromide, tri-n-butylstannonium bromide, and benzyldiphenylstannonium chloride; diphenyliodonium chloride, diphenyliodonium bromide, diphenyliodonium perchlorate, diphenyliodonium tetrafluoroborate, and diphenyliodonium hexafluoroarsenate;Examples of iodonium compounds include, but are not limited to, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, (p-methoxyphenyl)phenyliodonium tetrafluoroborate, di(2-nitrophenyl)iodonium hexafluoroarsenate, di(p-tolyl)iodonium hexafluorophosphate, and di(p-chlorophenyl)iodonium hexafluoroarsenate.

[0031] Examples of the cationic catalyst include sulfuric acid, dimethyl sulfate, diethyl sulfate, pyridine sulfate, phosphoric acid, phosphorous acid, phenylphosphonic acid, phenylphosphinic acid, triethyl phosphate, dimethyl phosphate, phenyl phosphite, methanesulfonic acid, trifluoromethanesulfonic acid, m-xylene-4-sulfonic acid, p-xylene-2-sulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, p-toluenesulfonic acid-triphenylamine complex, p-toluenesulfonic acid-pyridine complex, m-nitrobenzenesulfonic acid, Examples of the Lewis acidic acid include, but are not limited to, acids or Bronsted acids that liberate acids, or esters thereof, and amine complexes, such as sulfonic acid-pyridine complex, naphthalenesulfonic acid, methyl benzenesulfonate, and ethyl p-toluenesulfonate; and halides exhibiting Lewis acidity or complexes thereof with bases, such as boron trichloride, boron trifluoride, boron trifluoride-ether complex, iron trichloride, tin tetrachloride, titanium tetrachloride, aluminum chloride, aluminum chloride-pyridine complex, aluminum bromide, zinc chloride, and antimony pentachloride.

[0032] Examples of organic group-containing metal compounds include, but are not limited to, acetylacetone salts, carboxylates, metallocenes, alcoholates, chelate compounds, or organometallic compounds of transition elements such as magnesium, zinc, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zirconium, molybdenum, ruthenium, rhodium, lanthanum, cerium, hafnium, tantalum, or tungsten, preferably magnesium, zinc, vanadium, manganese, iron, or cerium, more preferably acetylacetone salts or carboxylates of magnesium, zinc, vanadium, manganese, iron, or cerium.

[0033] Examples of the amine compound include heterocyclic amines, aliphatic tertiary amines, aromatic tertiary amines, and Lewis acid complexes thereof, dihydrazide compounds, etc. Examples of heterocyclic amines include imidazole, pyridine, dimethylaminopyridine, piperidine, piperazine, and alkyl, alkenyl, phenyl, benzyl, or N-acyl substituted derivatives thereof. Examples of the substituted imidazoles include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-vinylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-(3-aminopropyl)imidazole, 1-(2,4,6-trimethylbenzoyl)-2-phenylimidazole, 1-(2,6-dichlorobenzoyl)-2-methylimidazole, 1-(2,6-dichlorobenzoyl)-2-phenyl ... benzoyl)-2-ethyl-4-methylimidazole, 1-(2,6-dichlorobenzoyl)-4-phenylimidazole, 1-(2-chloro-6-nitrobenzoyl)-2-ethylimidazole, 1-pentachlorobenzoyl-2-methylimidazole, 1-pentachlorobenzoyl-2-phenylimidazole, 1-propenyl-2-phenylimidazole, and 1-propenyl-4-phenylimidazole. Examples of aliphatic tertiary amines include triethylamine, diethylaminopropylamine, diethylaminoethylamine, dimethylaminobenzylamine, 1,6-bis(dimethylamino)hexane, and triethanolamine. Examples of aromatic tertiary amines include, but are not limited to, N,N-dimethylaniline, N,N-dimethylbenzylamine, N,N-diethylbenzylamine, N,N-dimethylaminobenzaldehyde, and tris(dimethylaminomethyl)phenol. Examples of Lewis acids in the Lewis acid complexes of tertiary amines include, for example, BF ３ , BCl ３ , AlCl ３ , FeCl ３ , TiCl ４ , SnCl ４ etc., especially BF ３ , BCl ３Examples of the dihydrazide compound include, but are not limited to, the following: A typical dihydrazide compound is represented by the following general formula (8). (In formula (8), Z represents a single bond or a divalent organic group, in particular an aliphatic, cycloaliphatic, or aromatic dicarboxylic acid group.)

[0034] Specific examples of the above formula (8) include, for example, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, pimelic acid dihydrazide, suberic acid dihydrazide, sebacic acid dihydrazide, cyclohexanedicarboxylic acid dihydrazide, terephthalic acid dihydrazide, isophthalic acid dihydrazide, 2,6- and 2,7-naphthalenedicarboxylic acid dihydrazide, and the like, but are not limited to these, and mixtures thereof may also be used.

[0035] In addition to the above, the amine compound may also include dicyandiamide and compounds represented by the following formula: (CH ３ ) ２ N-(CH ２ ) ３ -NH(CH ２ ) ３ -NH ２ , (CH ３ ) ２ N-(CH ２ ) ３ -NH(CH ２ ) ３ -CN, or (CH ３ ) ２ N-(CH ２ ) ３ -N(CH ２ CH ２ CN) ２ The content of these catalysts is not particularly limited and may be appropriately selected depending on the type of use.

[0036] [Curable Material] The curable material of the present invention contains the bisalkenyl-substituted nadimide of the present invention and may further contain other components such as a curing catalyst. The bisalkenyl-substituted nadimide of the present invention can be used alone as a curable material without being combined with other resins.

[0037] [Curable Resin Composition] As described above, the bisalkenyl-substituted nadimide of the present invention can be used alone as a curable material in various applications, and can also be combined with various other compounds, resins, etc. to form curable resin compositions. In particular, a curable resin composition containing the bisalkenyl-substituted nadimide of the present invention as component (A) and at least one compound selected from the group consisting of a maleimide compound, an alkenyl-substituted nadimide (excluding the bisalkenyl-substituted nadimide of the present invention), an epoxy resin, a phenolic resin, a vinylbenzyl compound, a vinyl compound (excluding vinylbenzyl compounds), a cyclic olefin, a conjugated diene resin having a functional group, and an unsaturated polyester resin as component (B) can provide a cured product that is particularly useful in laminate materials, molding materials, and composite materials, in addition to excellent dielectric properties, flexibility, and low water absorption, and also excellent heat resistance and toughness.

[0038] Examples of the maleimide compound of component (B) used in the curable resin composition include aliphatic maleimides, aromatic maleimides, aliphatic citraconic imides, aromatic citraconic imides, and bismaleimides. Among these, examples of aliphatic maleimides include maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-laurylmaleimide, N-(2-hydroxyethyl)maleimide, and N-cyclohexylmaleimide. Examples of aromatic maleimides include N-phenylmaleimide, N-(2-methylphenyl)maleimide, N-(3-ethylphenyl)maleimide, N-(4-methylphenyl)maleimide, N-(2,6-diethylphenyl)maleimide, N-(2,4,6-trimethylphenyl)maleimide, N-(2-chlorophenyl)maleimide, N-(4-chlorophenyl)maleimide, N-(4-hydroxyphenyl)maleimide, and N-(4-hydroxymethylphenyl)maleimide. Examples of aliphatic citraconic imides include citraconic imide, N-(4-carboxyphenyl)maleimide, N-(4-ethoxycarbonylphenyl)maleimide, N-(4-benzylphenyl)maleimide, and N-(4-phenoxyphenyl)maleimide; examples of aromatic citraconic imides include N-phenylcitraconimide, N-(3-ethylphenyl)citraconimide, N-(2,6-dimethylphenyl)citraconimide, N-(4-chlorophenyl)citraconimide, N-(4-hydroxyphenyl)citraconimide, and N-(4-benzylphenyl)citraconimide. In particular, by adding a bismaleimide compound represented by the following general formula (5) to the bisalkenyl-substituted nadiimide of the present invention, it is possible to achieve even lower temperature curing properties of the curable resin composition. (In formula (5), A′ represents a divalent hydrocarbon group.)

[0039] Examples of bismaleimides include bis(4-maleimidophenyl)methane, N,N'-phenylene bismaleimide, bis(4-maleimidophenyl)ether, bis(4-maleimidophenyl)sulfone, bis(4-maleimidocyclohexyl)methane, N,N'-tolylene bismaleimide, N,N'-dimethylphenylene bismaleimide, N,N'-xylylene bismaleimide, bis(4-maleimidophenyl)cyclohexane, N,N Examples of the bismaleimide include N,N'-dichlorobiphenylene bismaleimide, bis[4-(methylmaleimide)phenyl]methane, bis[4-(methylmaleimide)phenyl]ether, bis[4-(methylmaleimide)phenyl]sulfone, N,N'-ethylene bismaleimide, N,N'-hexamethylene bismaleimide, and N,N'-hexamethylene bismethylmaleimide, and A' may also be a structure derived from a dimer acid skeleton, but is not limited to these. These bismaleimides may be used alone or in combination, and may also be used as an oligomer.

[0040] Furthermore, as the alkenyl-substituted nadimide of component (B), those other than the novel alkenyl-substituted nadimide represented by the general formula (1) according to the present invention can be used, i.e., a reaction product of an amine other than dimer diamine with an alkenyl-substituted nadic anhydride. Specific examples of bisalkenyl-substituted nadimides synthesized using diamines other than dimer diamine include N-allyl-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(3'-hydroxyphenyl)-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(4'-carboxyphenyl)-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N,N'-ethylene-bis (allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximide), N,N'-hexamethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximide), N,N'-m-phenylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximide), N,N'-m-xylylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximide), N,N'-p-xylylene bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximide), bis[4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximide)phenyl]methane, bis[4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximide)phenyl]ether, bis[4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximide)phenyl]sulfone, 1,6-bis(aryl Examples of such an alkyl ester include, but are not limited to, N,N'-2,5-dimethylene-bicyclo[2.2.1]heptane-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximide)-3-hydroxy-hexane, N,N'-2,5-dimethylene-bicyclo[2.2.1]heptane-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximide), N,N'-3,8-dimethylene-tricyclo[5.2.1.0]decane-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximide).Although allyl-substituted nadimides have been exemplified above, methallyl-, allylmethyl-, and methallylmethyl-substituted nadimides may also be used. The alkenyl-substituted nadimides having such structures may be used alone or as a mixture or oligomer thereof.

[0041] As the epoxy resin of component (B), various known epoxy resins can be used, such as bisphenol-type epoxy resins obtained by the reaction of bisphenol with epichlorohydrin, novolak-type epoxy resins obtained by the reaction of phenol novolak resin or cresol novolak resin with epichlorohydrin, polyhydroxybenzene-type epoxy resins obtained by the reaction of polyhydric phenols such as resorcinol or hydroquinone with epichlorohydrin, and polyhydroxybenzene-type epoxy resins obtained by the reaction of aromatic amines such as toluidine or aniline with epichlorohydrin. Examples of the resulting nitrogen-containing epoxy resin include, but are not limited to, alicyclic epoxy resins made from cyclohexene, vinylcyclohexene, cyclopentadiene, dicyclopentadiene, etc. as starting materials, epoxy resins having a fluorene skeleton, di- or polyglycidyl ethers of butanediol, hexanediol, glycerin, trimethylolpropane, pentaerythritol, etc., silicon-containing epoxy resins obtained by reacting epoxy resins with silanol, and nitrogen-containing heterocyclic epoxy resins obtained from isocyanuric acid or cyanamide. These epoxy resins may also be used as a mixture of two or more types.

[0042] The phenolic resin of component (B) may be any of a variety of known phenolic resins, including common phenolic resins prepared from phenolic compounds and formaldehyde-producing substances, aromatic hydrocarbon resins such as xylene-formaldehyde resins, reaction products of xylene resins and phenol, phenol alkyl resins synthesized by the reaction of phenol and dimethoxyxylene, phenol-dicyclopentadiene resins obtained by the reaction of phenol and dicyclopentadiene, and resins obtained by polymerizing paravinylphenol, isopropylphenol, etc. Modified versions of each type may also be used, or several types may be mixed and used. Furthermore, while both novolac and resol types of phenolic resins can be used, novolac types are preferred in terms of compatibility with component (A) and other components (B). The number-average molecular weight of the phenolic resin is 200 to 2,000, preferably 300 to 900. Examples of phenolic compounds that are common raw materials for phenolic resins include phenol, cresol, xylenol, ethylphenol, p-t-butylphenol, p-octylphenol, p-nonylphenol, p-cumylphenol, p-phenylphenol, hydroquinone, resorcinol, catechol, bisphenol A, bisphenol F, methylcatechol, butylcatechol, cresorcinol, methylhydroquinone, pyrogallol, dihydroxynaphthalene, trihydroxynaphthalene, and mixtures thereof.

[0043] The vinylbenzyl compound of component (B) is represented by the general formula (9): In formula (9), n is an integer of 1 or 2, and when n=1, X is C ６ ~C １８ a residue in which one hydrogen atom has been removed from the amino group of a monovalent aromatic primary or secondary amine (e.g., aniline, naphthylamine, N-ethylaniline, diphenylamine, N-methylnaphthylamine, N-phenylnaphthylamine, dinaphthylamine, carbazole, etc.), C ２ ~C １２a residue in which one hydrogen atom has been removed from the amino group of a monovalent aliphatic primary or secondary amine (e.g., ethylamine, propylamine, hexylamine, decylamine, diethylamine, dibutylamine, N-propylhexylamine, cyclohexylamine, cyclooctylamine, N-ethylcyclohexylamine, etc.), or C ６ ~C １８ A residue obtained by removing hydrogen from the hydroxyl group of a monohydric phenol (e.g., phenol, ethylphenol, naphthol, methylnaphthol, p-phenylphenol, etc.), when n=2, X is oxygen, C ６ ~C １８ Monovalent aromatic primary amines (e.g., aniline and naphthylamine) or C ２ ~C １２ a residue in which two hydrogen atoms have been removed from the amino group of a monovalent aliphatic primary amine (e.g., ethylamine, propylamine, hexylamine, decylamine, cyclohexylamine, cyclooctylamine, etc.), C ６ ~C １８ a residue in which two hydrogen atoms have been removed from the amino group of a polyvalent aromatic primary or secondary amine (e.g., phenylenediamine, diaminonaphthalene, benzidine, N-methylphenylenediamine, N-phenyldiaminonaphthalene, N-methylbenzidine, etc.) (i.e., a residue in which two hydrogen atoms have been removed from one amino group, or a residue in which one hydrogen atom has been removed from each of two amino groups), C ２ ~C １２ a residue in which two hydrogen atoms have been removed from the amino group of a polyvalent aliphatic primary or secondary amine (e.g., ethylenediamine, hexamethylenediamine, diaminocyclohexane, N-methylethylenediamine, etc.) (i.e., a residue in which two hydrogen atoms have been removed from one amino group, or a residue in which one hydrogen atom has been removed from each of two amino groups) or C ６ ~C １８(e.g., hydroquinone, resorcinol, catechol, biphenol, bisphenol A, bisphenol F, dihydroxybenzophenone, methylcatechol, butylcatechol, cresorcinol, methylhydroquinone, pyrogallol, dihydroxynaphthalene, trihydroxynaphthalene, etc.), where hydrogen atoms are removed from two hydroxyl groups.) Various known vinylbenzyl compounds represented by the formula {can be used, and examples thereof include N-vinylbenzylaniline, N,N'-bis(vinylbenzyl)aniline, bis(vinylbenzyl)ether, N,N'-bis(vinylbenzyl)piperazine, 2,2-bis[4'-(vinylbenzyloxy)phenyl]propane, etc., but are not limited thereto.

[0044] Furthermore, as the vinyl compound (excluding vinylbenzyl compounds) of component (B), various known compounds having one or more vinyl groups can be used, such as unsaturated aromatic hydrocarbons, unsaturated carboxylic acids, esters of unsaturated carboxylic acids and saturated alcohols, esters of saturated and / or unsaturated carboxylic acids and unsaturated alcohols, esters of isocyanuric acid and unsaturated alcohols, ether compounds, nitrogen-containing compounds, sulfur-containing compounds, zinc-containing compounds, and silicon-containing compounds. Specific examples thereof include unsaturated aromatic hydrocarbons such as styrene, α-methylstyrene, ethylvinylbenzene, o-, m-, p-divinylbenzene, and divinylnaphthalene; unsaturated carboxylic acids such as acrylic acid, methacrylic acid, {hereinafter, compounds of acrylic acid and methacrylic acid will be commonly represented by "(meth)]}, maleic acid, maleic anhydride, fumaric acid, itaconic acid, and itaconic anhydride; and esters of unsaturated carboxylic acids and saturated alcohols such as methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, and the like. acrylate, isodecyl (meth)acrylate, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, glycidyl (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, propoxylated neopentyl glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,Examples of esters of saturated and / or unsaturated carboxylic acids and unsaturated alcohols include vinyl acetate, vinyl benzoate, vinyl phthalate, divinyl adipate, allyl (meth)acrylate, 1,2-benzenedicarboxylate di-2-propenyl, 1,3-benzenedicarboxylate di-2-propenyl, diallyl phthalate, diallyl isophthalate, diallyl maleate, and diethylene glycol bisallyl carbonate. Examples of esters of isocyanuric acid and unsaturated alcohols include triallyl isocyanurate and trimethallyl isocyanurate. Examples of the ether compounds include 1,1'-oxybisethene and 3,3'-oxybis-1-propene. Examples of the nitrogen-containing compounds include acrylonitrile, N-2-propenyl-2-propen-1-amine and 2,2-dichloro-N,N-di(2-propenyl)acetamide. Examples of the sulfur-containing compounds include 1,1'-thiobisethene, 1,1'-sulfonylbisethene and di-1-propenyl disulfide. Examples of the zinc-containing compounds include zinc diacrylate and zinc dimethacrylate. Examples of the silicon-containing compounds include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane. Other examples include, but are not limited to, 3,9-divinyl-2,4,8,10-tetraoxaspiro[5.5]undecane and dialkenylbisphenol A. Among these, o-, m-, p-divinylbenzene, 1,3-benzenedicarboxylate di-2-propenyl, 1,2-benzenedicarboxylate di-2-propenyl, diallyl phthalate, and triallyl isocyanurate are preferably used in view of the reactivity of the resulting composition and the workability during the preparation of the composition.

[0045] Furthermore, the cyclic olefin of component (B) may be any of various known cyclic olefins, including, but not limited to, cyclopentene, cyclohexene, 4-vinylcyclohexene, cycloheptene, cyclooctene, cyclododecene, cyclopentadiene, dicyclopentadiene, 1,3-cyclohexadiene, 1,3-cycloheptadiene, 1,5-cyclooctadiene, and indene.

[0046] As the conjugated diene resin having a functional group of component (B), various known conjugated diene resins having a functional group can be used, for example, C ４ ~C １２ Examples of the conjugated diene monomer include polymers of 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,2-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, etc. into which a hydroxyl group, an epoxy group, a carboxyl group, or a cyano group has been introduced, and copolymers of these conjugated diene monomers with polar vinyl monomers such as acrylonitrile, acrylic acid, and acrylic acid esters.

[0047] As the unsaturated polyester resin of component (B), various known unsaturated polyester resins can be used, and generally, C ２ ~C １２ and a low molecular weight diol of C ３ ~C １２ Examples of suitable diols include esterification products of 1,2-propylene glycol, ethylene glycol, 1,3-propylene glycol, diethylene glycol, di-1,2-propylene glycol, 1,4-butanediol, neopentyl glycol, and the like, used alone or in mixtures. Examples of suitable acids include, but are not limited to, maleic acid, fumaric acid, phthalic acid, terephthalic acid, isophthalic acid, adipic acid, glutaric acid, and / or their anhydrides, and often mixtures thereof.

[0048] The blending ratio of component (A) and component (B) in the curable resin composition is usually 98 to 5 parts by weight of component (A) and 2 to 95 parts by weight of component (B), preferably 90 to 10 parts by weight of component (A) and 10 to 90 parts by weight of component (B), more preferably 60 to 10 parts by weight of component (A) and 40 to 90 parts by weight of component (B), and even more preferably 55 to 15 parts by weight of component (A) and 45 to 85 parts by weight of component (B).

[0049] Furthermore, the curable resin composition containing the above-mentioned components (A) and (B) can be cured by heating alone, but in order to accelerate the curing rate, a curing catalyst can be used in combination as component (C) as necessary. As this curing catalyst, the curing catalyst that can be used when curing the above-mentioned bisalkenyl-substituted nadimide of the present invention can be used, and the content of the catalyst is not particularly limited and may be selected appropriately depending on the type of use.

[0050] The composition is also useful as a matrix for composite materials, and during curing, 10 to 500 parts by weight of various inorganic fillers, such as glass fiber, carbon fiber, metal fiber, ceramic fiber, calcium phosphate, calcium carbonate, magnesium carbonate, aluminum hydroxide, magnesium hydroxide, antimony oxide, gypsum, silica, alumina, clay, talc, quartz powder, carbon black, etc. may be mixed, if necessary, with respect to 100 parts by weight of the bisalkenyl-substituted nadimide.

[0051] The cured product of the curable resin composition containing component (A) and component (B) has the same heat resistance and mechanical properties as those of a curable resin composition using a conventional alkenyl-substituted nadimide, but provides a cured product with improved low dielectric constant, flexibility, and low water absorption.

[0052] Furthermore, the bisalkenyl-substituted nadimide of the present invention may be formed into a curable resin composition containing component (A) and component (D) consisting of at least one of a silicone resin, a modified silicone resin, a polysulfone resin, a polyphenylene sulfide resin, and a fluororesin. The curable resin composition can be used as a stain-resistant coating material that forms a stain-resistant cured coating on a substrate.

[0053] As the silicone resin, modified silicone resin, polysulfone resin, polyphenylene sulfide resin and fluororesin used as component (D), various known materials can be widely used, and specific examples thereof include silicone resins such as methylpolysiloxane resin, methylphenylpolysiloxane resin and methylhydrogenpolysiloxane resin, modified silicone resins such as epoxy-modified silicone resin, polyester-modified silicone resin, acrylic-modified silicone resin and phenol-modified silicone resin, polysulfone resins such as polysulfone resin, polyallylsulfone resin and polyethersulfone resin, and fluororesin such as polytetrafluoroethylene resin, tetrafluoroethylene-perfluoroalkylvinylether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-hexafluoropropylene-perfluoroalkylvinylether copolymer, tetrafluoroethylene-ethylene copolymer, polychlorotrifluoroethylene resin and polyvinylidene fluoride resin. Each of these resins may be used alone or in combination.

[0054] The blending ratio of component (A) and component (D) in the curable resin composition is usually 98 to 5 parts by weight of component (A) and 2 to 95 parts by weight of component (D), but preferably 80 to 20 parts by weight of component (A) and 20 to 80 parts by weight of component (D).

[0055] [Method of Curing Curable Resin Composition] The curable resin composition of the present invention can be cured by melt-mixing the alkenyl-substituted nadimide of the present invention with the above-mentioned components, followed by molding by a method such as cast molding, injection molding, or compression molding, or by applying the composition to an object, removing the solvent as necessary, drying to form a film, and then heating. The curing temperature and curing time can be adjusted appropriately depending on the components to be mixed and their blending ratios, and are generally from 80°C to 280°C, preferably from 80°C to 220°C, and from 0.01 to 5 hours, preferably from 0.05 to 2 hours. When an inorganic filler or the like is mixed, the composition may be further heat-treated at 150 to 350°C for 0.5 to 30 hours, if necessary.

[0056] (Other Components) The curable material and curable resin composition of the present invention may contain other components, such as solvents, surface conditioners, surfactants, ultraviolet absorbers, antioxidants, light stabilizers, tackifiers, colloidal silica, antifoaming agents, wetting agents, rust inhibitors, plasticizers, chain transfer agents, photosensitizers, dehydrating agents, weathering agents, heat stabilizers, lubricants, brighteners, colorants, flame retardants, release agents, surface treatment agents, and viscosity modifiers, which are known in the field of electronic materials.

[0057] [Cured Product] The cured product of the present invention is obtained by curing the curable material or curable resin composition of the present invention. The cured product of the present invention can be suitably used for electronic material applications such as circuit boards. In particular, due to its low dielectric properties in the 10 GHz band, it can be suitably used for 5G-compatible electronic material applications, and due to its flexibility, it can be suitably used for film-like members.

[0058] The present invention will be described in more detail below using examples, but the present invention is not limited to the following examples. In the following, "parts" and "%" are all by mass unless otherwise specified.

[0059] Example 1: Synthesis of bisalkenyl-substituted nadimide A 228.0 g of dimer diamine (PRIAMINE 1075, manufactured by Croda Japan Co., Ltd.) and 82.0 g of methylcyclohexane were placed in a reaction vessel equipped with a thermometer, a stirrer, and a water content receiver, and the temperature was raised to 110°C. Next, 180.0 g of allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride was added dropwise, and the mixture was then reacted at 110°C under reflux with methylcyclohexane for 2 hours. During the reaction, the water produced was discharged outside the system. The mixture was then heated to 140°C and distilled under reduced pressure at a reduced pressure of approximately 150 torr for 1 hour, followed by a reduced pressure of approximately 25 torr for 2 hours, to obtain 383.5 g (yield 99.1%) of bisalkenyl-substituted nadimide A, a dark brown viscous liquid.

[0060] IR spectrum of bisalkenyl-substituted nadimide A synthesized in Example 1. １ H-NMR spectrum and １３C-NMR (500 MHz, acetone-d6) are shown in FIGS. 1 to 3, respectively.

[0061] In the IR spectrum, alkene C-H stretching: 3077 cm －１ Alkane C-H stretching: 2922 cm －１ , 2853 cm －１ Imide C=O stretching: 1769 cm －１ , 1697 cm －１ Alkene C=C stretching: 1641 cm －１ Imide C-N stretching (imide II): 1396 cm －１ etc. are attributed.

[0062] The acid value of the synthesized bisalkenyl-substituted nadimide A was determined by neutralization titration with a 0.1 M KOH / ethanol solution using phenolphthalein as an indicator, and was found to be 8.1 (KOH mg / g).

[0063] [Preparation of Cured Bisalkenyl-Substituted Nadimide] (Example 2: Preparation of Cured Bisalkenyl-Substituted Nadimide A) A cured product was prepared using the bisalkenyl-substituted nadimide A synthesized in Example 1 as follows. First, the bisalkenyl-substituted nadimide A was placed in a vacuum oven at 200°C and degassed for 3 hours. Next, the degassed bisalkenyl-substituted nadimide A was poured into a casting mold consisting of two glass plates coated with a mold release agent and a 2 mm-thick silicone rubber spacer secured with clips, and then placed in a vacuum oven at 200°C and degassed overnight. After degassing overnight, the casting mold was transferred to an electric furnace at 200°C under a nitrogen stream, and the temperature was gradually increased to 240°C and maintained there for 24 hours. The cured product was then cooled to approximately room temperature in the oven and removed from the mold.

[0064] Comparative Example 1 Preparation of Cured BANI-M Product The structure of BANI-M is shown in the following formula (10). Instead of the bisalkenyl-substituted nadimide A synthesized in Example 1, bisalkenyl-substituted nadimide BANI-M (brown solid; melting point 75°C) manufactured by Maruzen Petrochemical Co., Ltd. was used, and the mixture was degassed for 3 hours in a 200°C vacuum oven, poured into a casting mold, and degassed overnight in a 200°C vacuum oven in the same manner as in Example 2. After degassing overnight, the casting mold was transferred to an electric furnace at 200°C under a nitrogen stream, and the temperature was gradually increased to 250°C, after which it was maintained there for 24 hours. The mixture was then cooled to approximately room temperature in the furnace, and the cured product was removed from the mold.

[0065] Comparative Example 2: Preparation of Cured BANI-X The structure of BANI-X is shown in the following formula (11). A cured product was prepared in the same manner as in Comparative Example 1, except that bisalkenyl-substituted nadimide BANI-X (light yellow solid; melting point 40°C) manufactured by Maruzen Petrochemical Co., Ltd. was used in place of the bisalkenyl-substituted nadimide A synthesized in Example 1.

[0066] <Evaluation of Physical Properties> The cured products obtained in Example 2, Comparative Example 1 and Comparative Example 2 were subjected to the following measurements, and the results are shown in Table 1.

[0067] [Bending test (maximum stress and apparent modulus of elasticity)] Measurements were carried out in accordance with JIS K7171 under the following conditions. The bending test was carried out by measuring crosshead displacement, and no compliance correction was made. The apparent modulus of elasticity was calculated from the stress gradient in the specified strain range (0.05% to 0.25%). Measurements were carried out five times for each of Example 2 and Comparative Example 2, and three times for Comparative Example 1, and the average values ​​for each were calculated. Measuring device: Instron Model 5966 universal testing machine Test piece dimensions: 50 mm x 25 mm x (thickness) 2 mm Test temperature: 23°C Test speed: 1 mm / min Distance between supports: 32 mm (indenter radius 5 mm, support table radius 2 mm)

[0068] [Water absorption measurement] The test piece was pre-dried at 50°C for 24 hours, and then immersed at 23°C for 24 hours to absorb water. The water absorption was calculated from the mass of the test piece before and after water absorption. Three measurements were taken, and the average value was used as the water absorption.

[0069] [Measurement of dielectric constant and dielectric loss tangent] Measurements were carried out in accordance with IEC 62810 (cavity resonator perturbation method) under the following conditions: Measuring device: PNA network analyzer N5222B manufactured by Keysight Technologies Cavity resonator: CP531 (for 10 GHz) manufactured by Kanto Electronics Application Development Co., Ltd. Test piece dimensions: 80 mm x 1.5 mm x 1.5 mm Measurement frequency: 10 GHz Conditioning: 23°C ± 1°C, RH 50% ± 5% x 24 hours Test environment: 23°C ± 1°C, RH 50% ± 5% Number of measurements: n = 2

[0070] [TMA Measurement (Linear Expansion Coefficient and Glass Transition Point)] TMA measurement was performed under the following conditions. The linear expansion coefficient was calculated from the results obtained in the range of 25°C to 300°C. Measuring device: Rigaku TMA8311 Test piece dimensions: 10 mm x 5 mm x (thickness) 2 mm Temperature range: room temperature to 400°C Heating rate: 5°C / min Atmosphere: N ２ (100 mL / min) Mode: Compression (load 49 mN)

[0071]

[0072] The results in Table 1 above confirm that the water absorption rate of the bisalkenyl-substituted nadimide A of Example 2 is lower than that of the bisalkenyl-substituted nadimide compounds of Comparative Examples 1 and 2. It is also confirmed that the dielectric constant and dielectric dissipation factor of the bisalkenyl-substituted nadimide A of Example 2 in the 10 GHz band are lower than those of the bisalkenyl-substituted nadimide compounds of Comparative Examples 1 and 2, and that good insulating performance can be obtained. Furthermore, the results of the bending test and TMA measurement confirm that the bisalkenyl-substituted nadimide A is softer than the bisalkenyl-substituted nadimide compounds of Comparative Examples 1 and 2, and that good flexibility can be obtained.

[0073] [Preparation of Cured Products of Bisalkenyl-Substituted Nadimide A / Bismaleimide Compositions] (Examples 3 to 5) Cured products were prepared using compositions prepared by mixing the bisalkenyl-substituted nadimide A synthesized in Example 1 with bismaleimide BMI-689 purchased from DESIGNER MOLECULES Inc. in a predetermined ratio. The respective mixing ratios (parts by mass) are shown in Table 2. A representative structure of BMI-689 is shown in the following formula (12).

[0074] The composition of bisalkenyl-substituted nadimide A and BMI-689 was placed in a vacuum oven at 170°C for degassing, but since almost no foaming was observed, the treatment was only carried out for a few minutes. A long degassing treatment like that in Example 1 (bisalkenyl-substituted nadimide A) was not necessary. Next, the composition was poured into a casting mold secured with clips using two glass plates coated with a release agent and 2 mm-thick silicone rubber as spacers, and preheated at 180°C under atmospheric pressure. Similarly, no foaming was observed. Furthermore, curing of the resin was observed at 180°C. This was transferred to an electric furnace at 200°C under a nitrogen stream, and the temperature was gradually increased to 240°C, after which it was maintained for 24 hours. After cooling to approximately room temperature in the furnace, the cured product was removed from the mold.

[0075] Comparative Example 3: Preparation of a cured product using bismaleimide BMI-689 alone A cured product was prepared in the same manner as in Example 3 using bismaleimide BMI-689. In the case of BMI-689, similar to Examples 3 to 5, no foaming was observed, but the product did not cure at 180°C. The product was then transferred to an electric furnace at 200°C under a nitrogen stream, and the temperature was raised stepwise to 240°C, after which it was maintained there for 24 hours. The product was then cooled to approximately room temperature in the furnace, and the cured product was then removed from the mold.

[0076] For Examples 3 to 5 and Comparative Example 3, the low-temperature curing properties, the presence or absence of foaming, and the physical properties of the products cured at 240°C are summarized in Table 2. With regard to low-temperature curing properties, those that cured with the above-mentioned 180°C preheating were marked with "Good", and those that did not cure were marked with "Poor". With regard to foaming, those that were confirmed to foam with the above-mentioned 180°C preheating were marked with "Poor", and those that were not confirmed to foam were marked with "Good".

[0077]

[0078] It was confirmed that compositions (Examples 3 to 5) prepared by mixing the bisalkenyl-substituted nadimide A of the present invention and the bismaleimide BMI-689 in a specific ratio could be cured at lower temperatures than the bisalkenyl-substituted nadimide A alone (Example 2) and BMI-689 alone (Comparative Example 3). Furthermore, in Examples 3 to 5, no foaming was observed during preheating at 180°C, which was used to evaluate low-temperature curing properties, making it possible to omit the need for prolonged preheating under reduced pressure for degassing. Furthermore, the composition (Example 3) with an A:BMI-689 mass ratio of 50:50 yielded a very soft cured product with extremely low maximum stress, and test specimens were repeatedly bent 180° and restored to their original shape without fracture.

[0079] These results suggest that the bisalkenyl-substituted nadimide of the present invention can be suitably used as a material for insulating films used in high frequency bands. Furthermore, blending with other compounds such as bismaleimide can suppress the generation of bubbles during curing and enable curing at lower temperatures, providing a curable resin composition that has excellent workability while maintaining its insulating performance.

Claims

1. A bisalkenyl-substituted nadimide represented by the general formula (1): (In formula (1), R １ and R ２ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and A represents a divalent hydrocarbon group derived from a dimer acid skeleton.

2. The bisalkenyl-substituted nadimide according to claim 1, wherein the divalent hydrocarbon group derived from the dimer acid skeleton contains a structure represented by general formula (2). (In formula (2), m, n, p, and q each represent an integer of 1 or greater selected so that m+n=5 to 16 and p+q=8 to 19, and each bond shown by a dashed line independently represents a carbon-carbon single bond or a carbon-carbon double bond. However, when the bond shown by a dashed line is a carbon-carbon double bond, formula (2) has a structure in which the number of hydrogen atoms bonded to each carbon atom constituting the carbon-carbon double bond is subtracted by one from the number shown in formula (2). The wavy line represents the bond to the nitrogen atom of the imide.) 3. A method for producing a bisalkenyl-substituted nadimide according to claim 1 or 2, which comprises subjecting dimer diamine and a compound represented by general formula (3) to an addition-dehydration reaction. (In formula (3), R １ and R ２ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

4. The method for producing an alkenyl-substituted nadiimide according to claim 3, wherein the dimer diamine contains a structure represented by general formula (4). (In formula (4), m, n, p, and q each represent an integer of 1 or more selected so that m+n=5 to 16 and p+q=8 to 19, and each bond shown by a dashed line independently represents a carbon-carbon single bond or a carbon-carbon double bond. However, when the bond shown by a dashed line is a carbon-carbon double bond, formula (4) has a structure in which the number of hydrogen atoms bonded to each carbon atom constituting the carbon-carbon double bond is subtracted by one from the number shown in formula (4).) 5. A curable material comprising the bisalkenyl-substituted nadimide of claim 1 or 2.

6. A curable resin composition comprising: (A) the bisalkenyl-substituted nadimide according to claim 1 or 2; and (B) at least one compound selected from the group consisting of maleimide compounds, alkenyl-substituted nadimides (excluding the bisalkenyl-substituted nadimides according to claim 1 or 2), epoxy resins, phenolic resins, vinylbenzyl compounds, vinyl compounds (excluding vinylbenzyl compounds), cyclic olefins, conjugated diene resins having functional groups, and unsaturated polyester resins.

7. The curable resin composition according to claim 6, wherein the maleimide compound is a bismaleimide represented by general formula (5). (In formula (5), A′ represents a divalent hydrocarbon group.) 8. The curable resin composition according to claim 7, wherein A' in the general formula (5) is a divalent hydrocarbon group derived from a dimer acid skeleton.

9. The curable resin composition according to any one of claims 6 to 8, wherein the mass ratio (A) / (B) of (A) the bisalkenyl-substituted nadimide according to claim 1 or 2 to (B) is in the range of 90 / 10 to 10 / 90.

10. The curable material according to claim 5, which is used for electronic materials.

11. The curable resin composition according to any one of claims 6 to 9, which is used as an electronic material.

12. A cured product obtained by curing the curable material according to claim 5 or 10.

13. A cured product obtained by curing the curable resin composition according to any one of claims 6 to 9 and 11.

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