JP7570241B2 - Curable resin composition and cured product thereof - Google Patents

Description

The present invention relates to a curable resin composition having a specific composition and its cured product, which is suitable for use in electrical and electronic components such as semiconductor encapsulants, printed wiring boards, and build-up laminates, lightweight, high-strength materials such as carbon fiber reinforced plastics and glass fiber reinforced plastics, and 3D printing applications.

In recent years, the required characteristics of laminates for mounting electric and electronic components have become more extensive and sophisticated due to the expansion of fields of use. Conventional semiconductor chips were mainly mounted on metal lead frames, but semiconductor chips with high processing power such as central processing units (hereinafter referred to as CPUs) are increasingly being mounted on laminates made of polymer materials.

In particular, semiconductor packages (hereafter referred to as PKGs) used in smartphones and other devices require thinner PKG substrates to meet the demand for smaller size, thinner thickness, and higher density. However, as the PKG substrate becomes thinner, its rigidity decreases, and problems such as large warping occur when the PKG is heated during solder mounting to the motherboard (PCB). To reduce this, there is a demand for PKG substrate materials with a high Tg (260°C, 288°C in recent years) that is higher than the solder mounting temperature.

In addition, the development of the fifth-generation communication system "5G" is currently accelerating, and it is expected that even greater capacity and faster communication will be achieved. This will lead to an increasing need for low dielectric tangent materials, with a dielectric tangent of at least 0.005 or less at 1 GHz.

Furthermore, with the advancement of electronics in the automotive field, precision electronic devices are sometimes placed near the engine drive, requiring higher levels of heat resistance and moisture resistance. SiC semiconductors are beginning to be used in trains and air conditioners, and the encapsulation material for semiconductor elements requires extremely high heat resistance.

In recent years, 3D printing has been attracting attention as a method for three-dimensional modeling, and this 3D printing method is beginning to be applied in fields that require reliability, such as aerospace, automobiles, and even connectors for electronic components used in these. In particular, photocurable and thermosetting resins are being studied for applications such as stereolithography (SLA) and digital light processing (DLP). Therefore, while the main requirements for shape stability and accuracy were the conventional method of transferring from a mold, 3D printing applications require various properties such as heat resistance, mechanical properties, toughness, flame retardancy, moisture absorption, and even electrical properties, and materials development is being promoted to meet these requirements.

In light of this background, polymeric materials with heat resistance and low dielectric tangent properties are being studied. For example, Patent Document 1 proposes a composition containing a maleimide resin and a propenyl group-containing phenolic resin. However, on the other hand, since phenolic hydroxyl groups that do not participate in the curing reaction remain during the curing reaction, the electrical properties are not sufficient. Patent Document 2 discloses an allyl ether resin in which hydroxyl groups are replaced with allyl groups. However, it has been shown that Claisen rearrangement occurs at 190°C, and at 200°C, which is the molding temperature for general substrates, phenolic hydroxyl groups that do not contribute to the curing reaction are generated, so the electrical properties are not satisfactory.

Japanese Patent Application Publication No. 04-359911 International Publication No. 2016/002704 Special Publication No. 4-75222 Special Publication No. 6-37465

The present invention was made in consideration of these circumstances, and aims to provide a curable resin composition and its cured product that exhibit excellent compatibility, excellent heat resistance, and low dielectric properties.

As a result of intensive research conducted by the inventors to solve the above problems, they discovered that a cured product of a curable resin composition having a specific structure with excellent compatibility has excellent heat resistance and low dielectric properties, which led to the completion of the present invention.

That is, the present invention relates to the following [1] to [11].
[1]
A curable resin composition comprising at least one compound selected from the group consisting of (A) a compound composed only of a hydrocarbon and (B) a compound containing at least one fluorine atom in the molecule, and a compound represented by the following formula (1):

(In formula (1), R represents a hydrocarbon group having 1 to 10 carbon atoms or a halogenated alkyl group. m represents an integer of 0 to 3, and n represents 1≦n≦20.)
[2]
The curable resin composition according to the above item [1], wherein in the formula (1), n is 1.1≦n≦20.
[3]
The compound represented by formula (1) contains 90 area % or less of N,N'-(phenylene-di-(2,2-propylidene)-di-p-phenylene)bismaleimide. The curable resin composition according to item [1] or [2] above.
[4]
The curable resin composition according to any one of the above items [1] to [3], wherein the component (A) is a polystyrene compound or a copolymer of a styrene compound and any polymerizable monomer.
[5]
The curable resin composition according to the above item [4], wherein the component (A) is a styrene-butadiene copolymer.
[6]
The curable resin composition according to any one of the above items [1] to [5], wherein the component (B) is a compound having at least one fluoro group or trifluoromethyl group in the molecule.
[7]
The curable resin composition according to any one of the above items [1] to [6], further comprising a curing accelerator.
[8]
The curable resin composition according to any one of the above items [1] to [7], further comprising a flame retardant.
[9]
The curable resin composition according to any one of the above items [1] to [8], further comprising a polymerization inhibitor.
[10]
The curable resin composition according to any one of the above items [1] to [9], wherein the compound represented by formula (1) is represented by the following formula (2):

(In formula (2), R represents a hydrocarbon group having 1 to 10 carbon atoms or a halogenated alkyl group. m represents an integer of 0 to 3, and n represents 1≦n≦20.)
[11]
A cured product obtained by curing the curable resin composition according to any one of the above items [1] to [10].

The curable resin composition of the present invention has excellent compatibility, and the cured product has excellent properties such as high heat resistance and low dielectric properties. Therefore, it is a useful material for sealing electric and electronic components, circuit boards, carbon fiber composites, etc.

1 shows a GPC analysis spectrum of Synthesis Example 3. 4 shows the HPLC analysis spectrum of Synthesis Example 3. 1 shows a GPC analysis spectrum of Synthesis Example 8. 4 shows the HPLC analysis spectrum of Synthesis Example 8.

The present invention will be described in detail below. First, a method for producing the compound represented by formula (1), which is an essential component of the curable resin composition of the present invention, will be described.

[Method of producing aromatic amine resin]
The compound represented by formula (1) can use an aromatic amine resin represented by formula (3) below as a precursor.

(In formula (3), R represents a hydrocarbon group having 1 to 10 carbon atoms or a halogenated alkyl group. m represents an integer from 0 to 3, and n represents 1≦n≦20.)

In the formula (3), m is usually 0 to 3, preferably 0 to 2, and more preferably 0. n is usually 1≦n≦20, preferably 1.1≦n≦20, more preferably 1.1≦n≦10, and particularly preferably 1.1≦n≦5. The value of n can be calculated from the weight average molecular weight (Mw) of the maleimide resin determined by gel permeation chromatography (GPC) measurement.
R is usually a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, and more preferably 1 to 3 carbon atoms. A hydrocarbon having R of 3 or less carbon atoms is less likely to undergo molecular vibration when exposed to high frequency waves, and therefore has excellent electrical properties.

The aromatic amine resin represented by formula (3) is more preferably represented by the following formula (4). This is because the crystallinity is reduced compared to when the substitution position of the propyl group with respect to the benzene ring to which the amino group is not bonded in formula (3) is the para position.

(In formula (4), R represents a hydrocarbon group having 1 to 10 carbon atoms or a halogenated alkyl group. m represents an integer from 0 to 3, and n represents 1≦n≦20.)

In formula (4), the preferred ranges for R, m, and n are the same as those in formula (3).

The method for producing the aromatic amine resin represented by the formula (3) or formula (4) is not particularly limited. For example, in Patent Document 3, aniline and m-diisopropenylbenzene or m-di(α-hydroxyisopropyl)benzene are reacted at 180 to 250°C in the presence of an acid catalyst to obtain the n=1 isomer in the formula (4) as the main component, which contains three isomers: 1,3-bis(p-aminocumyl)benzene, 1-(o-aminocumyl)-3-(p-aminocumyl)benzene, and 1,3-bis(o-aminocumyl)benzene. In addition, n=2 to 5 isomers are also produced as minor components, and in Patent Document 3, these are purified by crystallization to obtain 1,3-bis(p-aminocumyl)benzene with a purity of 98%. In addition, in Patent Document 4, 1,3-bis(p-aminocumyl)benzene is maleimidized to synthesize N,N'-(1,3-phenylene-di-(2,2-propylidene)-di-p-phenylene)bismaleimide to obtain a crystalline product, but heating is required to dissolve this in a solvent, and if left at room temperature after heating, crystals will precipitate within a few hours. Therefore, crystals may also precipitate when preparing a resin composition, and the higher the concentration of N,N'-(1,3-phenylene-di-(2,2-propylidene)-di-p-phenylene)bismaleimide, the higher the possibility of crystallization. In order to create printed wiring boards and composite materials, glass cloth or carbon fiber is impregnated with varnish to attach the resin, but if crystals precipitate, the impregnation process becomes impossible, and on the other hand, raising the temperature to maintain the soluble state accelerates the reaction of the composition, shortening the usable time of the varnish.

In the present invention, attention has been focused on the isomers and polymer components in the aromatic amine resin, which were removed as insoluble components in Patent Document 3, and a maleimide resin having excellent solution stability has been developed by maleimidizing the isomers and polymer components without removing these.
Since the present invention does not require a purification step such as crystallization, it can be produced in a short time and at low cost, thereby increasing the industrial applicability.

When synthesizing the aromatic amine resin represented by formula (3), examples of the acid catalyst used include hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, zinc chloride, ferric chloride, aluminum chloride, p-toluenesulfonic acid, methanesulfonic acid, activated clay, ion exchange resins, and the like. These may be used alone or in combination of two or more. The amount of catalyst used is usually 0.1 to 50% by weight, preferably 1 to 30% by weight, based on the aniline used. If the amount is too large, the viscosity of the reaction solution becomes too high, making stirring difficult, and if the amount is too small, the reaction proceeds slowly.

The reaction may be carried out using an organic solvent such as toluene or xylene, or without a solvent, if necessary. For example, after adding an acidic catalyst to a mixed solution of aniline and a solvent, if the catalyst contains water, it is preferable to remove the water from the system by azeotropy. Thereafter, diisopropenylbenzene or di(α-hydroxyisopropyl)benzene is added, and the reaction is carried out at 140 to 220°C, preferably 160 to 200°C, for 5 to 50 hours, preferably 5 to 30 hours, while removing the solvent from the system. When di(α-hydroxyisopropyl)benzene is used, water is by-produced, so it is removed from the system by azeotropy with the solvent during heating. After the reaction is completed, the acidic catalyst is neutralized with an alkaline aqueous solution, and a water-insoluble organic solvent is added to the oil layer and the wastewater is repeatedly washed with water until it becomes neutral, and then the solvent and excess aniline derivative are removed under heating and reduced pressure. When activated clay or ion exchange resin is used, the reaction liquid is filtered after the reaction is completed to remove the catalyst.
Depending on the reaction temperature and the type of catalyst, diphenylamine is produced as a by-product. Therefore, the diphenylamine derivative is removed to 1% by weight or less, preferably 0.5% by weight or less, and more preferably 0.2% by weight or less under high temperature and high vacuum or by using a means such as steam distillation.

The compound represented by formula (1) is obtained by subjecting the aromatic amine resin represented by formula (3) obtained by the above process to an addition or dehydration condensation reaction with maleic acid or maleic anhydride (hereinafter also referred to as "maleic anhydride") in the presence of a solvent and a catalyst.

[Method of producing maleimide resin]
The solvent used in the reaction is a water-insoluble solvent because water generated during the reaction must be removed from the system. Examples of the solvent include, but are not limited to, aromatic solvents such as toluene and xylene, aliphatic solvents such as cyclohexane and n-hexane, ethers such as diethyl ether and diisopropyl ether, ester solvents such as ethyl acetate and butyl acetate, and ketone solvents such as methyl isobutyl ketone and cyclopentanone. Two or more of these solvents may be used in combination.

In addition to the water-insoluble solvent, an aprotic polar solvent can also be used in combination. Examples include dimethyl sulfone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, and N-methyl-2-pyrrolidone, and two or more of these may be used in combination. When using an aprotic polar solvent, it is preferable to use one that has a higher boiling point than the water-insoluble solvent used in combination.

The catalyst used in the reaction is an acid catalyst, and although there is no particular limitation, examples include p-toluenesulfonic acid, hydroxy-p-toluenesulfonic acid, methanesulfonic acid, sulfuric acid, phosphoric acid, etc. The amount of the acid catalyst used is usually 0.1 to 10% by weight, preferably 1 to 5% by weight, based on the aromatic amine resin.

For example, the aromatic amine resin represented by the formula (3) is dissolved in toluene and N-methyl-2-pyrrolidone, maleic anhydride is added to generate an amic acid, and then p-toluenesulfonic acid is added to carry out the reaction under reflux conditions while removing the generated water from the system.

Alternatively, maleic anhydride is dissolved in toluene, and an N-methyl-2-pyrrolidone solution of the aromatic amine resin represented by formula (3) is added under stirring to generate an amic acid, and then p-toluenesulfonic acid is added to carry out the reaction under reflux conditions while removing the generated water from the system.

Alternatively, maleic anhydride is dissolved in toluene, p-toluenesulfonic acid is added, and the N-methyl-2-pyrrolidone solution of the aromatic amine resin represented by formula (3) is added dropwise under stirring and reflux while the water that forms an azeotropic mixture is removed from the system and the toluene is returned to the system to carry out the reaction (this is the first stage reaction).

In either method, maleic anhydride is usually used in an amount of 1 to 3 equivalents, preferably 1.2 to 2.0 equivalents, relative to the amino groups of the aromatic amine resin represented by formula (3).

To reduce the amount of unclosed amic acid, water is added to the reaction solution after the maleimide reaction listed above, separating it into a resin solution layer and an aqueous layer. Excess maleic acid, maleic anhydride, aprotic polar solvent, catalyst, etc., which are dissolved in the aqueous layer, are removed by liquid separation, and the same operation is repeated to thoroughly remove excess maleic acid, maleic anhydride, aprotic polar solvent, and catalyst. A catalyst is added again to the maleimide resin solution in the organic layer from which the excess maleic acid, maleic anhydride, aprotic polar solvent, and catalyst have been removed, and the dehydration and ring-closing reaction of the remaining amic acid is carried out again under heating and reflux conditions, resulting in a maleimide resin solution with a low acid value (this is the second-stage reaction).

The time for the re-dehydration ring-closing reaction is usually 1 to 5 hours, preferably 1 to 3 hours, and the aforementioned aprotic polar solvent may be added if necessary. After the reaction is completed, the reaction mixture is cooled and repeatedly washed with water until the washing water becomes neutral. Thereafter, the water is removed by azeotropic dehydration under heating and reduced pressure, and the solvent may be distilled off or another solvent may be added to adjust the resin solution to the desired concentration, or the solvent may be completely distilled off to obtain a solid resin.

The compound obtained by the above-mentioned manufacturing method has a structure represented by the following formula (1).

(In formula (1), R represents a hydrocarbon group having 1 to 10 carbon atoms or a halogenated alkyl group. m represents an integer from 0 to 3, and n represents 1≦n≦20.)

In the formula (1), the preferred ranges for R, m, and n are the same as those in the formula (3).

In formula (1), the value of n can be calculated from the number average molecular weight determined by gel permeation chromatography (GPC, detector: RI) of the maleimide resin, but approximately it can be considered to be almost equal to the value of n calculated from the GPC measurement results of the aromatic amine resin represented by formula (3), which is the raw material.

The weight average molecular weight of the compound represented by formula (1) is preferably 200 or more and less than 5000, more preferably 300 or more and less than 3000, and particularly preferably 400 or more and less than 2000. If the weight average molecular weight is less than 5000, purification by washing with water becomes easy, and if it is 200 or more, the target compound does not volatilize in the solvent distillation step.

In the present invention, the content of N,N'-(phenylene-di-(2,2-propylidene)-di-p-phenylene)bismaleimide is determined by the following method.
First, the content (A1) of the n=1 component in formula (1) is determined by gel permeation chromatography (GPC, detector: RI) analysis. Next, the content (A2) of N,N'-(phenylene-di-(2,2-propylidene)-di-p-phenylene)bismaleimide in the n=1 component is determined by high performance liquid chromatography (HPLC) analysis.
The content of N,N'-(phenylene-di-(2,2-propylidene)-di-p-phenylene)bismaleimide in the compound represented by formula (1) is calculated by the formula (A1) x (A2).

The content of N,N'-(phenylene-di-(2,2-propylidene)-di-p-phenylene)bismaleimide in the maleimide resin represented by the formula (1) is usually 90 area % or less, preferably 10 to 80 area %, more preferably 20 to 80 area %, and even more preferably 30 to 70 area %. When the content of N,N'-(phenylene-di-(2,2-propylidene)-di-p-phenylene)bismaleimide is 90 area % or less, crystallinity decreases, and solvent solubility improves. On the other hand, the lower limit of N,N'-(phenylene-di-(2,2-propylidene)-di-p-phenylene)bismaleimide may be 0 area %, but when it is 10 area % or more, the decrease in reactivity can be suppressed.

The content of n=1 in the compound represented by formula (1) by GPC analysis (RI) is preferably 98 area% or less, more preferably 20 to 98 area%, even more preferably 30 to 90 area%, and particularly preferably 40 to 80 area%. When the content of n=1 is 98 area% or less, the heat resistance is good. On the other hand, the lower limit of n=1 may be 0 area%, but when it is 20 area% or more, the viscosity of the resin solution decreases and the impregnation property is good.

The softening point of the compound represented by formula (1) is preferably 50°C to 150°C, more preferably 80°C to 120°C, even more preferably 90°C to 110°C, and particularly preferably 95°C to 100°C. The melt viscosity at 150°C is 0.05 to 100 Pa·s, preferably 0.1 to 40 Pa·s.

The compound represented by formula (1) preferably has a structure represented by formula (2). This is because the crystallinity is reduced compared to when the substitution position of the propyl group with respect to the benzene ring to which the maleimide group is not bonded in formula (1) is para-position.

(In formula (1), R represents a hydrocarbon group having 1 to 10 carbon atoms or a halogenated alkyl group. m represents an integer from 0 to 3, and n represents 1≦n≦20.)

In formula (2), the preferred ranges for R, m, and n are the same as those in formula (3).

The curable resin composition of the present invention contains, in addition to the compound represented by formula (1), one or more compounds selected from the group consisting of (A) compounds composed only of hydrocarbons, and (B) compounds containing at least one fluorine atom in the molecule.
The component (A) is not limited as long as it is a compound composed of only hydrocarbons. For example, in addition to polypropylene and polyethylene, copolymers of a styrene compound and any polymerizable monomer, such as cycloolefin copolymer, polybutadiene, polystyrene, poly-α-methylstyrene, and styrene-butadiene copolymer, can be mentioned. Among these, it is preferable to use a styrene-butadiene copolymer from the viewpoints of curability, dielectric properties, and compatibility.
Said component (B) is not limited as long as it is a compound having at least one or more fluoro or trifluoromethyl groups in the molecule.For example, it can be polytetrafluoroethylene, polychlorotrifluoroethylene, vinylidene fluoride, polyvinyl fluoride, perfluoroalkoxy fluororesin, tetrafluoroethylene-hexafluoropropylene copolymer, ethylene-tetrafluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer, fluorinated polyimide, etc., and it is preferable that it is a compound having at least one or more fluoro or trifluoromethyl groups in the molecule.

The curable resin composition of the present invention may further use any known material as a curable resin. Specifically, phenolic resin, epoxy resin, amine resin, active alkene-containing resin, isocyanate resin, polyamide resin, polyimide resin, cyanate ester resin, propenyl resin, methallyl resin, active ester resin, etc. may be mentioned, and one kind may be used or a plurality of kinds may be used in combination. In addition, it is preferable to contain an epoxy resin, an active alkene-containing resin, or a cyanate ester resin from the viewpoint of the balance of heat resistance, adhesion, and dielectric properties. By containing these curable resins, it is possible to improve the brittleness of the cured product and improve adhesion to metals, and it is possible to suppress cracks in the package during solder reflow and reliability tests such as thermal cycles.
The amount of the curable resin used is preferably 10 times by mass or less, more preferably 5 times by mass or less, and particularly preferably 3 times by mass or less, relative to the compound represented by formula (1). The preferred lower limit is 0.5 times by mass or more, and more preferably 1 time by mass or more. If the amount is 10 times by mass or less, the effects of the heat resistance and dielectric properties of the compound represented by formula (1) can be utilized.

Examples of phenolic resins, epoxy resins, amine resins, active alkene-containing resins, isocyanate resins, polyamide resins, polyimide resins, cyanate ester resins, and active ester resins that can be used include the following:

Phenolic resins: Polycondensates of phenols (phenol, alkyl-substituted phenols, aromatic-substituted phenols, hydroquinone, resorcinol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, furfural, etc.), polycondensates of phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydrofuran, etc.) Polymers of phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), phenolic resins obtained by polycondensation of phenols and substituted biphenyls (4,4'-bis(chloromethyl)-1,1'-biphenyl and 4,4'-bis(methoxymethyl)-1,1'-biphenyl, etc.) or substituted phenyls (1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene and 1,4-bis(hydroxymethyl)benzene, etc.), polycondensates of bisphenols and various aldehydes, polyphenylene ether.

Epoxy resins: glycidyl ether epoxy resins obtained by glycidylating the above-mentioned phenolic resins and alcohols, alicyclic epoxy resins such as 4-vinyl-1-cyclohexene diepoxide and 3,4-epoxycyclohexylmethyl-3,4'-epoxycyclohexanecarboxylate, glycidyl amine epoxy resins such as tetraglycidyldiaminodiphenylmethane (TGDDM) and triglycidyl-p-aminophenol, and glycidyl ester epoxy resins.

Amine resins: diaminodiphenylmethane, diaminodiphenylsulfone, isophoronediamine, naphthalenediamine, aniline novolac, orthoethylaniline novolac, aniline resins obtained by reacting aniline with xylylene chloride, aniline and substituted biphenyls (4,4'-bis(chloromethyl)-1,1'-biphenyl and 4,4'-bis(methoxymethyl)-1,1'-biphenyl, etc.) or substituted phenyls (1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene, 1,4-bis(hydroxymethyl)benzene, etc.) described in Japanese Patent No. 6429862.

Active alkene-containing resins: Polycondensates of the above-mentioned phenolic resins and halogen-based compounds containing active alkenes (chloromethylstyrene, allyl chloride, methallyl chloride, acrylic acid chloride, allyl chloride, etc.), polycondensates of active alkene-containing phenols (2-allylphenol, 2-propenylphenol, 4-allylphenol, 4-propenylphenol, eugenol, isoeugenol, etc.) and halogen-based compounds (4,4'-bis(methoxymethyl)-1,1'-biphenyl, 1,4-bis(chloromethyl)benzene, 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-dibromobenzophenone, cyanuric chloride, etc.), epoxy resins Or polycondensates of alcohols and substituted or unsubstituted acrylates (acrylates, methacrylates, etc.), maleimide resins (4,4'-diphenylmethane bismaleimide, polyphenylmethane maleimide, m-phenylene bismaleimide, 2,2'-bis[4-(4-maleimidophenoxy)phenyl]propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 4,4'-diphenylether bismaleimide, 4,4'-diphenylsulfone bismaleimide, 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene).

Isocyanate resins: Aromatic diisocyanates such as p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and naphthalene diisocyanate; aliphatic or alicyclic diisocyanates such as isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, norbornene diisocyanate, and lysine diisocyanate; polyisocyanates such as one or more biuret forms of isocyanate monomers or isocyanate forms obtained by trimerizing the above diisocyanate compounds; and polyisocyanates obtained by the urethane reaction of the above isocyanate compounds with polyol compounds.

Polyamide resin: Amino acids (6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, paraaminomethylbenzoic acid, etc.), lactams (ε-caprolactam, ω-undecanelactam, ω-laurolactam) and aliphatic diamines such as diamines (ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decanediamine, undecanediamine, dodecanediamine, tridecanediamine, tetradecanediamine, pentadecanediamine, hexadecanediamine, heptadecanediamine, octadecanediamine, nonadecanediamine, eicosanediamine, 2-methyl-1,5-diaminopentane, 2-methyl-1,8-diaminooctane, etc. Polymers made from one or more of the following main raw materials: alicyclic diamines such as cyclohexanediamine, bis-(4-aminocyclohexyl)methane, and bis(3-methyl-4-aminocyclohexyl)methane; aromatic diamines such as xylylenediamine, and mixtures of dicarboxylic acids (aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, and dodecanedioic acid; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; dialkyl esters of these dicarboxylic acids, and dichlorides).

Polyimide resin: The above diamine and tetracarboxylic dianhydride (4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-cyclohexene-1,2 dicarboxylic anhydride, pyromellitic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4, 4'-diphenylsulfonetetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, methylene-4,4'-diphthalic dianhydride, 1,1-ethylidene-4,4'-diphthalic dianhydride, 2,2'-propylidene-4,4'-diphthalic dianhydride, 1,2-ethylene-4,4'-diphthalic dianhydride, 1,3-trimethylene-4,4'-diphthalic dianhydride, 1,4-tetramethylene-4,4'-diphthalic dianhydride, 1,5-pentamethylene-4,4'-diphthalic dianhydride, 4,4'-oxydiphthalic dianhydride , thio-4,4'-diphthalic dianhydride, sulfonyl-4,4'-diphthalic dianhydride, 1,3-bis(3,4-dicarboxyphenyl)benzene dianhydride, 1,3-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 1,3-bis[2-(3,4-dicarboxyphenyl)-2-propyl]benzene dianhydride, 1,4-bis[2-(3,4-dicarboxyphenyl)-2-propyl]benzene dianhydride, bis[3-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride, bis[4-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride, 2,2-bis[3-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride 1,3-bis(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, bis(3,4-dicarboxyphenoxy)dimethylsilane dianhydride, 1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldisiloxane dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 3,4,9,10-perylene tetracarboxylic dianhydride, 2,3,6,7-anthracene tetracarboxylic dianhydride, 1,2,7,8-phenanthrene tetracarboxylic dianhydride, ethylene tetracarboxylic dianhydride, 1,2,3,4-butane tetracarboxylic dianhydride, 1,2,3,4-cyclobutane tetracarboxylic dianhydride), cyclopentane tetracarboxylic acid Dianhydrides, cyclohexane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, 3,3',4,4'-bicyclohexyltetracarboxylic dianhydride, carbonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, methylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,2-ethylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,1-ethylidene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 2,2-propylidene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, oxy-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, thio-4,4'-bis(cyclo hexane-1,2-dicarboxylic acid) dianhydride, sulfonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, rel-[1S,5R,6R]-3-oxabicyclo[3,2,1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride, ethylene glycol-bis-(3,4-dicarboxylic acid anhydride phenyl) ether, 4,4'-biphenyl bis(trimellitic acid monoester acid anhydride), polycondensation with 9,9'-bis(3,4-dicarboxyphenyl)fluorene dianhydride.

Cyanate ester resin: a cyanate ester compound obtained by reacting a phenol resin with a cyanogen halide. Specific examples include dicyanatobenzene, tricyanatobenzene, dicyanatonaphthalene, dicyanatobiphenyl, 2,2'-bis(4-cyanatophenyl)propane, bis(4-cyanatophenyl)methane, bis(3,5-dimethyl-4-cyanatophenyl)methane, 2,2'-bis(3,5-dimethyl-4-cyanatophenyl)propane, 2,2'-bis(4-cyanatophenyl)ethane, 2,2'-bis(4-cyanatophenyl)hexafluoropropane, bis(4-cyanatophenyl)sulfone, bis(4-cyanatophenyl)thioether, phenol novolac cyanate, and phenol-dicyclopentadiene co-condensates in which the hydroxyl groups have been converted to cyanate groups, but are not limited thereto.
Furthermore, the cyanate ester compound, the synthesis method of which is described in JP-A-2005-264154, is particularly preferred as the cyanate ester compound because it has low moisture absorption, excellent flame retardancy, and excellent dielectric properties.
The cyanate resin may contain a catalyst such as zinc naphthenate, cobalt naphthenate, copper naphthenate, lead naphthenate, zinc octoate, tin octoate, lead acetylacetonate, dibutyltin maleate, etc., in order to trimerize the cyanate group to form a sym-triazine ring, if necessary. The catalyst is usually used in an amount of 0.0001 to 0.10 parts by mass, preferably 0.00015 to 0.0015 parts by mass, per 100 parts by mass of the total mass of the curable resin composition.

Active ester resin: A compound having one or more active ester groups in one molecule can be used as a curing agent for a curable resin other than the compound represented by the formula (1) of the present invention, such as an epoxy resin, if necessary. As the active ester curing agent, a compound having two or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, is preferred. The active ester curing agent is preferably one obtained by a condensation reaction between at least one compound of a carboxylic acid compound and a thiocarboxylic acid compound and at least one compound of a hydroxy compound and a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester curing agent obtained from a carboxylic acid compound and at least one compound of a phenol compound and a naphthol compound is preferred.
Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.
Examples of phenol compounds or naphthol compounds include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene-type diphenol compounds, phenol novolak, etc. Here, the term "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.
Preferred specific examples of the active ester curing agent include an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and an active ester compound containing a benzoylated product of phenol novolac. Among them, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene-type diphenol structure are more preferred. The "dicyclopentadiene-type diphenol structure" refers to a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.
Commercially available active ester curing agents include, for example, active ester compounds containing a dicyclopentadiene-type diphenol structure such as "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "HPC-8000H-65TM", "EXB-8000L-65TM", and "EXB-8150-65T" (manufactured by DIC Corporation); active ester compounds containing a naphthalene structure such as "EXB9416-70BK" (manufactured by DIC Corporation); and phenolic Examples of active ester compounds containing an acetylated phenol novolac include "DC808" (manufactured by Mitsubishi Chemical Corporation); active ester compounds containing a benzoylated phenol novolac include "YLH1026", "YLH1030", and "YLH1048" (manufactured by Mitsubishi Chemical Corporation); "DC808" (manufactured by Mitsubishi Chemical Corporation) is an active ester curing agent which is an acetylated phenol novolac; and "EXB-9050L-62M" (manufactured by DIC Corporation) is a phosphorus atom-containing active ester curing agent.

The curable resin composition of the present invention can further be improved in curability by using a curing accelerator in combination. As a specific example of a curing accelerator that can be used, it is preferable to use a radical polymerization initiator for the purpose of promoting self-polymerization of a radically polymerizable curable resin such as an olefin resin or a maleimide resin, or radical polymerization with other components. Examples of the radical polymerization initiator that can be used include ketone peroxides such as methyl ethyl ketone peroxide and acetylacetone peroxide, diacyl peroxides such as benzoyl peroxide, dialkyl peroxides such as dicumyl peroxide and 1,3-bis-(t-butylperoxyisopropyl)-benzene, peroxyketals such as t-butylperoxybenzoate and 1,1-di-t-butylperoxycyclohexane, α-cumylperoxyneodecanoate, t-butylperoxyneodecanoate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, and t-amylperoxy-3,5,5-trimethylhexanoate. peroxycarbonates such as di-2-ethylhexyl peroxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, t-butylperoxyisopropyl carbonate, 1,6-bis(t-butylperoxycarbonyloxy)hexane; organic peroxides such as t-butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxyoctoate, lauroyl peroxide; and known curing accelerators such as azo compounds such as azobisisobutyronitrile, 4,4'-azobis(4-cyanovaleric acid), and 2,2'-azobis(2,4-dimethylvaleronitrile). However, the curing accelerator is not particularly limited to these. Ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, alkyl peresters, percarbonates, etc. are preferred, with dialkyl peroxides being more preferred. The amount of radical polymerization initiator added is preferably 0.01 to 5 parts by mass, and particularly preferably 0.01 to 3 parts by mass, per 100 parts by mass of the curable resin composition. If a large amount of radical polymerization initiator is used, the molecular weight does not extend sufficiently during the polymerization reaction.

If necessary, a curing accelerator other than the radical polymerization initiator may be added or used in combination. Specific examples of curing accelerators that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, and 2-ethyl-4-methylimidazole, tertiary amines such as 2-(dimethylaminomethyl)phenol and 1,8-diaza-bicyclo(5,4,0)undecene-7, phosphines such as triphenylphosphine, quaternary ammonium salts such as tetrabutylammonium salt, triisopropylmethylammonium salt, trimethyldecanylammonium salt, cetyltrimethylammonium salt, and hexadecyltrimethylammonium hydroxide, Examples of the additive include quaternary phosphonium salts such as triphenylbenzylphosphonium salt, triphenylethylphosphonium salt, and tetrabutylphosphonium salt (the counter ions of the quaternary salts can be halogens, organic acid ions, hydroxide ions, etc., but are not particularly specified, and organic acid ions and hydroxide ions are particularly preferred), transition metal compounds (transition metal salts) such as zinc compounds such as tin octylate, zinc carboxylate (zinc 2-ethylhexanoate, zinc stearate, zinc behenate, zinc myristylate), and zinc phosphate esters (zinc octylphosphate, zinc stearylphosphate, etc.). The amount of the curing accelerator to be used is 0.01 to 5.0 parts by weight per 100 epoxy resin, as necessary.

The curable resin composition of the present invention may further include a flame retardant. Examples of the flame retardant include phosphorus-containing compounds, which may be reactive or additive. Specific examples of phosphorus-containing compounds include phosphoric acid esters such as trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylyleneyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylyleneyl phosphate, 1,3-phenylene bis(dixylyleneyl phosphate), 1,4-phenylene bis(dixylyleneyl phosphate), and 4,4'-biphenyl(dixylyleneyl phosphate); 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10(2,5- Phosphanes such as dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide; phosphorus-containing epoxy compounds obtained by reacting epoxy resins with active hydrogen of the phosphanes, red phosphorus, etc. are included, but phosphates, phosphanes, or phosphorus-containing epoxy compounds are preferred, and 1,3-phenylenebis(dixylyl phosphate), 1,4-phenylenebis(dixylyl phosphate), 4,4'-biphenyl(dixylyl phosphate), or phosphorus-containing epoxy compounds are particularly preferred. The content of the phosphorus-containing compound is preferably in the range of 0.1 to 0.6 (weight ratio) (phosphorus-containing compound)/(total epoxy resin). If it is 0.1 or less, the flame retardancy is insufficient, and if it is 0.6 or more, there is a concern that it may have an adverse effect on the moisture absorption and dielectric properties of the cured product.

The curable resin composition of the present invention may further contain a polymerization inhibitor. Examples of polymerization inhibitors that can be used include phenol-based, sulfur-based, phosphorus-based, hindered amine-based, nitroso-based, and nitroxyl radical-based polymerization inhibitors. The polymerization inhibitor may be added when synthesizing the compound represented by formula (1) or after synthesis. The polymerization inhibitor may be used alone or in combination of two or more kinds. The amount of the polymerization inhibitor used is usually 0.008 to 1 part by weight, preferably 0.01 to 0.5 parts by weight, based on 100 parts by weight of the resin component. These polymerization inhibitors may be used alone, or may be used in combination of two or more kinds. In the present invention, phenol-based, hindered amine-based, nitroso-based, and nitroxyl radical-based are preferred.

Specific examples of phenol-based polymerization inhibitors include monophenols such as 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, stearyl-β-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, and 2,4-bis[(octylthio)methyl]-o-cresol; -6-t-butylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol), 4,4'-thiobis(3-methyl-6-t-butylphenol), 4,4'-butylidenebis(3-methyl-6-t-butylphenol), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 2,2-thio-diethylenebis[ 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, 3,9-bis[1,1-dimethyl-2-{β-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}ethyl]2,4,8,10-tetraoxaspiro[5,5]undecane, bis(3,5-di-t-butyl-4-hydroxybenzylsulfonate ethyl)calcium bisphenols; 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5-trimethyl-2,4, Examples include polymeric phenols such as 6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, tetrakis-[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methane, bis[3,3'-bis-(4'-hydroxy-3'-t-butylphenyl)butyric acid]glycol ester, tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-tris(3',5'-di-t-butyl-4'-hydroxybenzyl)-S-triazine-2,4,6-(1H,3H,5H)trione, and tocopherol.

Specific examples of sulfur-based polymerization inhibitors include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, and distearyl-3,3'-thiodipropionate.

Specific examples of phosphorus-based polymerization inhibitors include triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, tris(nonylphenyl)phosphite, diisodecyl pentaerythritol phosphite, tris(2,4-di-t-butylphenyl)phosphite, cyclic neopentane tetraylbis(octadecyl)phosphite, cyclic neopentane tetraylbi(2,4-di-t-butylphenyl)phosphite, cyclic neopentane tetraylbi(2,4-di-t-butyl-4-methylphenyl)phosphite, Examples include phosphites such as bis[2-t-butyl-6-methyl-4-{2-(octadecyloxycarbonyl)ethyl}phenyl]hydrogen phosphite; and oxaphosphaphenanthrene oxides such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(3,5-di-t-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.

Specific examples of hindered amine polymerization inhibitors include ADK STAB LA-40MP, ADK STAB LA-40Si, ADK STAB LA-402AF, ADK STAB LA-87, DEKA STAB LA-82, DEKA STAB LA-81, ADK STAB LA-77Y, ADK STAB LA-77G, ADK STAB LA-72, ADK STAB LA-68, ADK STAB LA-63P, ADK STAB LA-57, ADK STAB Examples include, but are not limited to, LA-52, Chimassorb 2020FDL, Chimassorb 944FDL, Chimassorb 944LD, Tinuvin 622SF, Tinuvin PA144, Tinuvin 765, Tinuvin 770DF, Tinuvin XT55FB, Tinuvin 111FDL, Tinuvin 783FDL, Tinuvin 791FB, etc.

Specific examples of nitroso-based polymerization inhibitors include p-nitrosophenol, N-nitrosodiphenylamine, ammonium salt of N-nitrosophenylhydroxyamine, (cupferron), etc., with the ammonium salt of N-nitrosophenylhydroxyamine (cupferron) being preferred.

Specific examples of nitroxyl radical polymerization inhibitors include, but are not limited to, TEMPO free radical, 4-hydroxy-TEMPO free radical, etc.

Furthermore, a light stabilizer may be added to the curable resin composition of the present invention as necessary. As the light stabilizer, a hindered amine light stabilizer, particularly HALS, etc., is preferred. Although there is no particular limitation on the HALS, representative ones include a polycondensate of dibutylamine/1,3,5-triazine/N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine and N-(2,2,6,6-tetramethyl-4-piperidyl)butylamine, a polycondensate of dimethyl succinate-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, poly[{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidyl)imino}hexamethylene{(2,2,6,6-tetramethyl-4-piperidyl) bis(1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butyl malonate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, 2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-n-butylmalonate bis(1,2,2,6,6-pentamethyl-4-piperidyl), and the like. Only one type of HALS may be used, or two or more types may be used in combination.

Furthermore, the curable resin composition of the present invention can also contain a binder resin as needed. Examples of binder resins include, but are not limited to, butyral resins, acetal resins, acrylic resins, epoxy-nylon resins, NBR-phenol resins, epoxy-NBR resins, polyamide resins, polyimide resins, and silicone resins. The amount of binder resin to be used is preferably within a range that does not impair the flame retardancy and heat resistance of the cured product, and is preferably 0.05 to 50 parts by mass, and more preferably 0.05 to 20 parts by mass, per 100 parts by mass of the resin component, as needed.

Furthermore, to the curable resin composition of the present invention, powders such as fused silica, crystalline silica, porous silica, alumina, zircon, calcium silicate, calcium carbonate, quartz powder, silicon carbide, silicon nitride, boron nitride, zirconia, aluminum nitride, graphite, forsterite, steatite, spinel, mullite, titania, talc, clay, iron oxide asbestos, glass powder, etc., or inorganic fillers in the form of spherical or crushed powders thereof, can be added as necessary. In particular, when obtaining a curable resin composition for semiconductor encapsulation, the amount of the inorganic filler used is usually 80 to 92% by mass, preferably 83 to 90% by mass, in the curable resin composition.

The curable resin composition of the present invention can contain known additives as necessary. Specific examples of additives that can be used include modified acrylonitrile copolymers, polyphenylene ether, polystyrene, polyethylene, polyimide, fluororesin, silicone gel, silicone oil, surface treatment agents for fillers such as silane coupling agents, mold release agents, and colorants such as carbon black, phthalocyanine blue, and phthalocyanine green. The amount of these additives to be added is preferably 1,000 parts by mass or less, more preferably 700 parts by mass or less, per 100 parts by mass of the curable resin composition.

The curable resin composition of the present invention can be obtained by uniformly mixing the above components in a predetermined ratio, and is usually pre-cured at 130 to 180°C for 30 to 500 seconds, and then post-cured at 150 to 200°C for 2 to 15 hours to allow the curing reaction to proceed sufficiently and obtain the cured product of the present invention. Alternatively, the components of the curable resin composition can be uniformly dispersed or dissolved in a solvent, etc., and cured after removing the solvent.

The curable resin composition of the present invention thus obtained has moisture resistance, heat resistance, and high adhesion. Therefore, the curable resin composition of the present invention can be used in a wide range of fields where moisture resistance, heat resistance, and high adhesion are required. Specifically, it is useful as a material for all electrical and electronic components, such as insulating materials, laminates (printed wiring boards, BGA substrates, build-up substrates, etc.), sealing materials, and resists. It can also be used in fields such as molding materials and composite materials, as well as paint materials, adhesives, and 3D printing. In particular, solder reflow resistance is beneficial in semiconductor sealing.

The semiconductor device is encapsulated with the curable resin composition of the present invention. Examples of semiconductor devices include DIP (dual in-line package), QFP (quad flat package), BGA (ball grid array), CSP (chip size package), SOP (small outline package), TSOP (thin small outline package), TQFP (thin quad flat package), etc.

The method for preparing the curable resin composition of the present invention is not particularly limited, but each component may be mixed uniformly or may be prepolymerized. For example, the curable resin of the present invention is prepolymerized by heating in the presence or absence of a catalyst and in the presence or absence of a solvent. Similarly, in addition to the curable resin of the present invention, a curing agent such as an epoxy resin, an amine compound, a maleimide compound, a cyanate ester compound, a phenolic resin, or an acid anhydride compound and other additives may be added to prepolymerize. For mixing or prepolymerization of each component, for example, an extruder, kneader, or roll is used in the absence of a solvent, and a reaction kettle with a stirrer is used in the presence of a solvent.

As a method of uniform mixing, the mixture is kneaded at a temperature in the range of 50 to 100°C using a device such as a kneader, roll, or planetary mixer to obtain a uniform resin composition. The obtained resin composition is crushed and then molded into a cylindrical tablet using a molding machine such as a tablet machine, or into a granular powder or powder molded body, or these compositions can be melted on a surface support and molded into a sheet having a thickness of 0.05 mm to 10 mm to obtain a molded curable resin composition. The obtained molded body is a non-sticky molded body at 0 to 20°C, and even if stored at -25 to 0°C for one week or more, the flowability and curability are hardly reduced.
The obtained molded article can be molded into a cured product using a transfer molding machine or a compression molding machine.

An organic solvent can be added to the curable resin composition of the present invention to form a varnish-like composition (hereinafter simply referred to as varnish). The curable resin composition of the present invention can be dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, or N-methylpyrrolidone as necessary to form a varnish, which can then be impregnated into a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, or paper, and dried by heating to obtain a prepreg, which can then be hot-press molded to form a cured product of the curable resin composition of the present invention. The solvent used in this case usually accounts for 10 to 70% by weight, preferably 15 to 70% by weight, of the mixture of the curable resin composition of the present invention and the solvent. If the composition is in a liquid form, a cured product of the curable resin containing carbon fiber can be obtained as is, for example, by the RTM method.

The curable composition of the present invention can also be used as a modifier for film-type compositions. Specifically, it can be used to improve flexibility in the B-stage. Such a film-type resin composition can be obtained as a sheet-like adhesive by applying the curable resin composition of the present invention as the curable resin composition varnish onto a release film, removing the solvent under heating, and then performing B-stage formation. This sheet-like adhesive can be used as an interlayer insulating layer in multilayer substrates, etc.

The curable resin composition of the present invention can be heated and melted to reduce the viscosity, and impregnated into reinforcing fibers such as glass fibers, carbon fibers, polyester fibers, polyamide fibers, and alumina fibers to obtain a prepreg. Specific examples include glass fibers such as E glass cloth, D glass cloth, S glass cloth, Q glass cloth, spherical glass cloth, NE glass cloth, and T glass cloth, inorganic fibers other than glass, polyparaphenylene terephthalamide (Kevlar (registered trademark), manufactured by DuPont Co., Ltd.), fully aromatic polyamide, polyester; and organic fibers such as polyparaphenylene benzoxazole, polyimide, and carbon fibers, but are not limited to these. The shape of the substrate is not particularly limited, but examples include woven fabric, nonwoven fabric, roving, chopped strand mat, and the like. In addition, plain weave, sash weave, twill weave, and the like are known as weaving methods for woven fabrics, and these known methods can be appropriately selected and used depending on the intended use and performance. In addition, woven fabrics that have been subjected to fiber opening treatment and glass woven fabrics that have been surface-treated with a silane coupling agent or the like are preferably used. The thickness of the substrate is not particularly limited, but is preferably about 0.01 to 0.4 mm. Prepregs can also be obtained by impregnating reinforcing fibers with the varnish and drying them by heating.

The laminate of this embodiment comprises one or more of the prepregs. The laminate is not particularly limited as long as it comprises one or more prepregs, and may have any other layer. The method for producing the laminate can be appropriately applied by a generally known method, and is not particularly limited. For example, when forming the metal foil-clad laminate, a multi-stage press machine, a multi-stage vacuum press machine, a continuous molding machine, an autoclave molding machine, etc. can be used, and the prepregs are laminated together and heated and pressurized to obtain a laminate. At this time, the heating temperature is not particularly limited, but is preferably 65 to 300 ° C, and more preferably 120 to 270 ° C. In addition, the pressure to be applied is not particularly limited, but if the pressure is too high, it is difficult to adjust the solid content of the resin of the laminate, and the quality is not stable, and if the pressure is too low, air bubbles and adhesion between the laminates are deteriorated, so that 2.0 to 5.0 MPa is preferable, and 2.5 to 4.0 MPa is more preferable. The laminate of this embodiment comprises a layer made of metal foil, and can be suitably used as a metal foil-clad laminate described later.
The prepreg is cut into a desired shape and laminated with copper foil or the like as necessary. The laminate is then heated and cured while applying pressure thereto by press molding, autoclave molding, sheet winding molding or the like, to obtain an electrical and electronic laminate (printed wiring board) or a carbon fiber reinforced material.

The cured product of the present invention can be used in various applications such as molding materials, adhesives, composite materials, and coating materials. The cured product of the curable resin composition described in the present invention exhibits excellent heat resistance and dielectric properties, and is therefore suitable for use in electrical and electronic components such as encapsulants for semiconductor devices, encapsulants for liquid crystal display devices, encapsulants for organic EL devices, printed wiring boards, and build-up laminates, as well as composite materials for lightweight, high-strength structural materials such as carbon fiber reinforced plastics and glass fiber reinforced plastics.

The present invention will be described in detail below with reference to examples and comparative examples. In the text, "parts" and "%" represent "parts by weight" and "% by weight", respectively. The softening point and melt viscosity were measured by the following methods.
Softening point: Measured according to JIS K-7234 Acid value: Measured according to JIS K-0070:1992

GPC (gel permeation chromatography) analysis columns: SHODEX GPC KF-601 (2 columns), KF-602, KF-602.5, KF-603
Flow rate: 0.5ml/min.
Column temperature: 40°C
Solvent used: THF (tetrahydrofuran)
Detector: RI (Differential Refraction Detector)

・HPLC (High Performance Liquid Chromatography) analytical column: Inertsil ODS-2
Flow rate: 1.0ml/min.
Column temperature: 40°C
Solvent used: acetonitrile/water Detector: photodiode array (200 nm)

[Synthesis Example 1]
A flask equipped with a thermometer, a cooling tube, a Dean-Stark azeotropic distillation trap, and a stirrer was charged with 279 parts of aniline, 100 parts of toluene, 146 parts of m-di(α-hydroxyisopropyl)benzene, and 50 parts of activated clay. The temperature in the system was raised to 170°C over 6 hours while distilling off water and toluene, and the reaction was carried out at this temperature for 13 hours. The mixture was then cooled to room temperature, 230 parts of toluene was added, and the activated clay was removed by filtration. Next, 241 parts of aromatic amine resin (A1) was obtained by distilling off excess aniline and toluene from the oil layer using a rotary evaporator under reduced pressure with heating. The amine equivalent of the aromatic amine resin (A1) was 179 g/eq, and the softening point was 46.5°C. GPC analysis (RI) revealed that the content of n=1 was 73%, and HPLC analysis revealed that the content of 1,3-bis(p-aminocumyl)benzene in the n=1 was 49%, so that the content of 1,3-bis(p-aminocumyl)benzene in the aromatic amine resin was 36%.

[Synthesis Example 2]
A flask equipped with a thermometer, a cooling tube, a Dean-Stark azeotropic distillation trap, and a stirrer was charged with 93 parts of aniline, 50 parts of toluene, and 52.1 parts of 35% hydrochloric acid. The temperature was raised while distilling off water and toluene to bring the system to 165-170°C, and 20 parts of 1,3-diisopropenylbenzene was added dropwise at this temperature over 1.5 hours, and the reaction was carried out at the same temperature for 30 hours. Thereafter, while cooling, 87 parts of a 30% aqueous sodium hydroxide solution was slowly added dropwise so as not to cause vigorous reflux in the system, and 50 parts of toluene were added at 80°C or less, and the mixture was allowed to stand at 70°C to 80°C. The separated lower aqueous layer was removed, and the reaction liquid was repeatedly washed with water until the washing liquid became neutral. Next, excess aniline and toluene were distilled off from the oil layer using a rotary evaporator under heating and reduced pressure, 100 parts of toluene were added and the mixture was dissolved by heating, and then 100 parts of cyclohexane were added, followed by crystallization, filtration and drying to obtain 35 parts of 1,3-bis(p-aminocumyl)benzene (A2) which was 100% n=1 by GPC analysis (RI) and had a purity of 98% by HPLC.

[Synthesis Example 3]
A flask equipped with a thermometer, a cooling tube, a Dean-Stark azeotropic distillation trap, and a stirrer was charged with 147 parts of maleic anhydride, 300 parts of toluene, and 4 parts of methanesulfonic acid, and heated to reflux. Next, a resin solution obtained by dissolving 197 parts of aromatic amine resin (A1) in 95 parts of N-methyl-2-pyrrolidone and 100 parts of toluene was added dropwise over 3 hours while maintaining the reflux state. During this time, the condensed water and toluene that were azeotropically formed under reflux conditions were cooled and separated in the Dean-Stark azeotropic distillation trap, and then the toluene, which was the organic layer, was returned to the system, and the water was discharged outside the system. After the dripping of the resin solution was completed, the reaction was carried out for 6 hours while maintaining the reflux state and performing a dehydration operation.
After the reaction was completed, the mixture was washed with water four times to remove methanesulfonic acid and excess maleic anhydride, and water was removed from the system by azeotropic distillation of toluene and water under reduced pressure at 70°C or less. Then, 2 parts of methanesulfonic acid was added, and the reaction was carried out for 2 hours under heated reflux. After the reaction was completed, the mixture was washed with water four times until the washing water became neutral, and water was removed from the system by azeotropic distillation of toluene and water under reduced pressure at 70°C or less, and toluene was completely distilled off under reduced pressure at 70°C or less to obtain a maleimide resin (M1). The softening point of the obtained maleimide resin (M1) was 100°C, and the acid value was 9 mgKOH/g. GPC analysis (RI) revealed that the content of n=1 isomer was 70%, and HPLC analysis revealed that the content of N,N'-(1,3-phenylene-di-(2,2-propylidene)-di-p-phenylene)bismaleimide in the n=1 isomer was 53%, so that the content of N,N'-(1,3-phenylene-di-(2,2-propylidene)-di-p-phenylene)bismaleimide in the maleimide resin (M1) was 37%.
The results of the GPC analysis are shown in Figure 1. The peak at a retention time of 22.3 minutes is the peak of n=1.
The results of the HPLC analysis are shown in Figure 2. The peaks at retention times 22.1 minutes, 24.0 minutes, and 25.3 minutes are peaks of the n=1 form, and the peak at 25.3 minutes is N,N'-(1,3-phenylene-di-(2,2-propylidene)-di-p-phenylene)bismaleimide.

[Synthesis Example 4]
A maleimide resin (M2) was obtained by carrying out the same operation as in Synthesis Example 3, except that 197 parts of the aromatic amine resin (A1) in Synthesis Example 3 was replaced with 36 parts of the aromatic amine resin (A1) and 140 parts of the aromatic amine resin (A2), and a resin solution prepared by dissolving 95 parts of N-methyl-2-pyrrolidone and 95 parts of toluene in 72 parts of N-methyl-2-pyrrolidone and 100 parts of toluene. The softening point of the obtained maleimide resin (M2) was 93° C. and the acid value was 4 mgKOH/g. GPC analysis (RI) revealed that the content of n=1 isomer was 96%, and HPLC analysis revealed that the content of N,N'-(1,3-phenylene-di-(2,2-propylidene)-di-p-phenylene)bismaleimide in the n=1 isomer was 92%, so that the content of N,N'-(1,3-phenylene-di-(2,2-propylidene)-di-p-phenylene)bismaleimide in the maleimide resin (M2) was 88%.

[Synthesis Example 5]
The same operations as in Synthesis Example 3 were carried out, except that 197 parts of the aromatic amine resin (A1) in Synthesis Example 3 was replaced with a resin solution prepared by dissolving 74 parts of the aromatic amine resin (A1) and 107 parts of the aromatic amine resin (A2), and 95 parts of N-methyl-2-pyrrolidone and 95 parts of toluene in 78 parts of N-methyl-2-pyrrolidone and 100 parts of toluene, to obtain a maleimide resin (M3) represented by the formula (2). The softening point of the obtained maleimide resin (M3) was 95° C., and the acid value was 5 mgKOH/g. GPC analysis (RI) revealed that the content of n=1 isomer was 80%, and HPLC analysis revealed that the content of N,N'-(1,3-phenylene-di-(2,2-propylidene)-di-p-phenylene)bismaleimide in the n=1 isomer was 79%, so that the content of N,N'-(1,3-phenylene-di-(2,2-propylidene)-di-p-phenylene)bismaleimide in the maleimide resin (M3) was 63%.

[Synthesis Example 6]
A maleimide resin (M4) was obtained by carrying out the same operation as in Synthesis Example 3, except that 197 parts of the aromatic amine resin (A1) in Synthesis Example 3 was replaced with a resin solution prepared by dissolving 73 parts of the aromatic amine resin (A1) and 114 parts of the aromatic amine resin (A2), and 95 parts of N-methyl-2-pyrrolidone and 95 parts of toluene in 84 parts of N-methyl-2-pyrrolidone and 100 parts of toluene. The softening point of the obtained maleimide resin (M4) was 96° C. and the acid value was 7 mgKOH/g. GPC analysis (RI) revealed that the content of n=1 isomer was 78%, and HPLC analysis revealed that the content of N,N'-(1,3-phenylene-di-(2,2-propylidene)-di-p-phenylene)bismaleimide in the n=1 isomer was 76%, so that the content of N,N'-(1,3-phenylene-di-(2,2-propylidene)-di-p-phenylene)bismaleimide in the maleimide resin (M4) was 59%.

[Synthesis Example 7]
A maleimide resin (M5) was obtained by carrying out the same operations as in Synthesis Example 3, except that 197 parts of the aromatic amine resin (A1) in Synthesis Example 3 was replaced with a resin solution prepared by dissolving 73 parts of the aromatic amine resin (A1) and 114 parts of the aromatic amine resin (A2), and 95 parts of N-methyl-2-pyrrolidone and 95 parts of toluene in 84 parts of N-methyl-2-pyrrolidone and 100 parts of toluene. The softening point of the obtained maleimide resin (M5) was 98° C. and the acid value was 8 mgKOH/g. GPC analysis (RI) revealed that the content of n=1 isomer was 74%, and HPLC analysis revealed that the content of N,N'-(1,3-phenylene-di-(2,2-propylidene)-di-p-phenylene)bismaleimide in the n=1 isomer was 70%, so that the content of N,N'-(1,3-phenylene-di-(2,2-propylidene)-di-p-phenylene)bismaleimide in the maleimide resin (M5) was 52%.

[Synthesis Example 8]
A flask equipped with a thermometer, a cooling tube, a Dean-Stark azeotropic distillation trap, and a stirrer was charged with 147 parts of maleic anhydride, 300 parts of toluene, and 3.3 parts of methanesulfonic acid, and heated to reflux. Next, a resin solution obtained by dissolving 172 parts of 1,3-bis(p-aminocumyl)benzene (A2) in 66 parts of N-methyl-2-pyrrolidone and 100 parts of toluene was added dropwise over 3 hours while maintaining the reflux state. During this time, the condensed water and toluene that were azeotropically formed under reflux conditions were cooled and separated in the Dean-Stark azeotropic distillation trap, and then the toluene, which was the organic layer, was returned to the system, and the water was discharged outside the system. After the dripping of the resin solution was completed, the reaction was carried out for 2 hours while maintaining the reflux state and performing a dehydration operation.
After the reaction was completed, the mixture was washed with water four times to remove methanesulfonic acid and excess maleic anhydride, and water was removed from the system by azeotropic distillation of toluene and water under reduced pressure at 70°C or less. Then, 1.7 parts of methanesulfonic acid was added, and the reaction was carried out for 2 hours under heated reflux. After the reaction was completed, the mixture was washed with water three times until the washing water became neutral, and water was removed from the system by azeotropic distillation of toluene and water under reduced pressure at 70°C or less, and toluene was completely distilled off under reduced pressure at 70°C or less to obtain 237 parts of maleimide resin (M6). The softening point of the obtained maleimide resin (M6) was 91°C, and the acid value was 3 mgKOH/g. GPC analysis (RI) revealed that the n=1 form was 98%, and HPLC analysis revealed that the N,N'-(1,3-phenylene-di-(2,2-propylidene)-di-p-phenylene)bismaleimide in the n=1 form was 100%, so that the N,N'-(1,3-phenylene-di-(2,2-propylidene)-di-p-phenylene)bismaleimide in the maleimide resin (M6) was 98%.
The results of the GPC analysis are shown in Figure 3. The peak at a retention time of 22.3 minutes is the peak of n=1.
The results of the HPLC analysis are shown in Figure 4. The peak at a retention time of 25.4 minutes is the peak of n=1, and the peak at 25.3 minutes is N,N'-(1,3-phenylene-di-(2,2-propylidene)-di-p-phenylene)bismaleimide.

[Synthesis Example 9]
To a flask equipped with a thermometer, a condenser, a Dean-Stark azeotropic distillation trap, and a stirrer, 21.1 parts of toluene, 22.2 parts of 4,4'-(hexafluoroisopropylidenediphthalic anhydride, 15.6 parts of 2,2'-bis(trifluoromethyl)benzidine, 1.4 parts of 4,4'-(hexafluoroisopropylidene)bis(2-aminophenol), and 1.0 parts of triethylamine were added, and the internal temperature was raised to 165°C while removing toluene and generated water, and the reaction was carried out while maintaining the temperature for 2 hours for azeotropic dehydration. The internal temperature was raised to 180°C under normal pressure, and toluene and triethylamine were recovered, and then 50 parts of NMP were recovered under reduced pressure. Thereafter, the mixture was diluted with NMP to obtain a fluorine-containing polyimide resin solution (FRS1) with a solid content of 40%.

[Synthesis Example 10]
A 300 ml reactor equipped with a thermometer, a reflux condenser, a Dean-Stark azeotropic distillation trap, a raw material inlet, a nitrogen inlet and a stirrer was charged with 8.23 parts of BAFL (9,9-bis(4-aminophenyl)fluorene, manufactured by JFE Chemical Corporation, molecular weight 348.45 g/mol), 14.63 parts of PRIAMINE1075 (C36 dimer diamine, manufactured by Croda Japan Co., Ltd., amine equivalent 534.38 g/mol), 15.51 parts of ODPA (oxydiphthalic anhydride, manufactured by Manac Co., Ltd., molecular weight 310.22 g/mol), 85.41 parts of anisole, 1.01 parts of triethylamine and 21.23 parts of toluene, and heated to 100 ° C. to dissolve the raw materials. The reaction was carried out at 135 ° C. for 4 hours while removing water generated by ring closure of the amic acid by azeotropic distillation with toluene. After the generation of water stopped, the remaining triethylamine and toluene were subsequently removed at 140° C. to obtain a polyimide resin solution (PIS1). The solids concentration of the polyimide resin solution was 30.0%. The molar ratio of the diamine component and the acid anhydride component used in the synthesis of the polyimide resin (moles of diamine component/moles of acid anhydride component) was 1.02.

[Examples 1 and 2, Comparative Example 1]
The maleimide resin (M1) obtained in Synthesis Example 3 was dissolved in toluene so that the resin content was 60%, to prepare a maleimide resin solution (MS1). This was mixed with various materials in the ratios shown in Table 1, and a compatibilization test was carried out to confirm the state of the solution after stirring at room temperature for 30 minutes. The results are shown in Table 1.
FRS1: Synthesized in Synthesis Example 9 BMI: 4,4'-bismaleimide diphenylmethane (Tokyo Chemical Industry Co., Ltd.)
Toluene SA-9000-111: Methacrylic-terminated polyphenylene ether (manufactured by SABIC)
Ricon 134 : butadiene copolymer (manufactured by Cray Valley)

The results in Table 1 confirm that the curable resin composition of the present invention has excellent compatibility.

[Examples 3 and 4, Comparative Examples 2 and 3]
The maleimide resin (M1) obtained in Synthesis Example 3 was dissolved in toluene so that the resin content was 60%, and a maleimide resin solution (MS1) was prepared. This was mixed with various materials in the ratios shown in Tables 2 and 3, and after stirring at room temperature for 30 minutes, each resin solution was applied to a copper foil (T4X, manufactured by Fukuda Metal Copper Foil Co., Ltd.) using an applicator so that the coating thickness after drying was 200 μm, and dried at 120 ° C. for 10 minutes. Then, the film was cured at 250 ° C. for 2 hours to obtain a cured film (resin film). The obtained film was removed by etching, cut to a length of 4 mm and a width of 3 mm, and a dielectric constant test, a dielectric loss tangent test, and a glass transition temperature were measured. The results are shown in Table 2.

<Dielectric constant test/dielectric tangent test>
The test was carried out by the cavity resonator perturbation method using a 1 GHz cavity resonator manufactured by Kanto Electronics Application Development Co., Ltd. Furthermore, the dielectric constant and dielectric loss tangent were also measured after the test piece was immersed in water for 24 hours.
<Glass transition temperature>
The measurement was performed in accordance with JIS K-7244. The peak top temperature of tan δ was taken as Tg.
Dynamic viscoelasticity measuring instrument: TA-instruments, DMA-2980
Heating rate: 2°C/min

FRS1: Synthesized in Synthesis Example 9 PIS1: Synthesized in Synthesis Example 10 SA-9000-111: Methacrylic-terminated polyphenylene ether (manufactured by SABIC)
Ricon 100: Styrene butadiene copolymer (manufactured by Cray Valley)
DCP: Dicumyl peroxide (Tokyo Chemical Industry Co., Ltd.)

From the results in Table 2, it was confirmed that the curable resin composition of the present invention has excellent heat resistance and excellent dielectric properties at the initial stage and after the water absorption test. On the other hand, Comparative Example 2 has a problem with water absorption properties, and Comparative Example 3 has a problem with heat resistance.

Claims (8)

A curable resin composition comprising at least one selected from the group consisting of (A) a compound composed only of a hydrocarbon, and (B) a compound containing at least one fluorine atom in the molecule, and a compound represented by the following formula (1):
The compound (A) composed only of hydrocarbons is a styrene-butadiene copolymer,
The curable resin composition , wherein the compound (B) containing at least one fluorine atom in the molecule is a fluorinated polyimide .
(In formula (1), R represents a hydrocarbon group having 1 to 10 carbon atoms or a halogenated alkyl group. m represents an integer of 0 to 3, and n represents 1≦n≦20.) The curable resin composition according to claim 1, wherein in formula (1), n is 1.1≦n≦20. The curable resin composition according to claim 1 or 2, wherein the compound represented by formula (1) contains 90 area % or less of N,N'-(phenylene-di-(2,2-propylidene)-di-p-phenylene)bismaleimide. The curable resin composition according to any one of claims 1 to 3 further contains a curing accelerator. The curable resin composition according to any one of claims 1 to 4, further comprising a flame retardant. The curable resin composition according to any one of claims 1 to 5, further comprising a polymerization inhibitor. The curable resin composition according to claim 1 , wherein the compound represented by formula (1) is represented by the following formula (2):
(In formula (2), R represents a hydrocarbon group having 1 to 10 carbon atoms or a halogenated alkyl group. m represents an integer of 0 to 3, and n represents 1≦n≦20.) A cured product obtained by curing the curable resin composition according to claim 1 .

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