Compound, curable resin composition and cured product thereof, and method for producing compound

Abstract

To provide a compound that has excellent low dielectric characteristics; a curable resin composition; and a cured product thereof.SOLUTION: An allyl ether-modified phenyl aralkyl resin represented by formula (1). In formula (1), R1 and R3 each represent a C1-5 hydrocarbon group. R2 represents a hydrocarbon group represented by formula (a). p represents an integer of 0-4. q is the average number of repetitions and satisfies 1<q≤20. l represents an integer of 0-4. k represents an integer of 0-3, and the average value kave of k satisfies 0<kave≤3. n is the average number of repetitions and represents a number from 0.05 to 20.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a compound having a specific structure, a curable resin composition and a cured product thereof, as well as a method for producing the compound, which are suitable for use in electrical and electronic components such as semiconductor encapsulants, printed wiring boards, build-up laminates, and optical waveguide devices, lightweight, high-strength materials such as carbon fiber reinforced plastics and glass fiber reinforced plastics, and 3D printing applications. [Background technology]

[0002] In recent years, the required characteristics of laminates for mounting electrical and electronic components have become more widespread and sophisticated due to the expansion of their 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.

[0003] The fifth generation communication system "5G", whose development is currently accelerating, is expected to further increase capacity and speed of communication. 5G will use higher frequencies, but reducing transmission loss is important to achieve high-speed communication using high frequencies, and even lower dielectric properties will be required for circuit board materials. Transmission loss that occurs on printed circuit boards comes from conductor loss and dielectric loss. As stated in Non-Patent Document 1, dielectric loss α D is the relative permittivity of the dielectric, ε r and the dielectric loss tangent tanδ, the relative dielectric constant ε r It can be said that improving the dielectric loss tangent tanδ, which has a large contribution to the above, is effective. Low-dielectric materials include thermoplastic materials such as PTFE (polytetrafluoroethylene) and LCP (liquid crystal polymer), but they are less moldable than thermosetting resins. In light of this, there is a need to develop thermosetting resins with excellent low-dielectric properties.

[0004] In light of this background, polymer materials with excellent low dielectric properties have been investigated. For example, Patent Document 1 proposes a thermoplastic resin composition containing an imide compound having a maleimide group and a phenol aralkyl resin having an aliphatic unsaturated bond. However, the electrical properties are not sufficient because phenolic hydroxyl groups that do not participate in the curing reaction remain. Patent Document 2 also discloses an allyl ether-modified biphenyl aralkyl novolac resin to which an allyl group is added along with the phenolic hydroxyl group. However, it has been shown that the Claisen rearrangement occurs in allyl ether-modified biphenyl aralkyl novolac resin at 190°C. At 200°C, the molding temperature for general substrates, phenolic hydroxyl groups that do not participate in the curing reaction are generated, resulting in insufficient electrical properties. [Prior art documents] [Non-patent literature]

[0005] [Non-Patent Document 1] "Signal Loss Factors in High-Speed Signal Transmission on Printed Circuit Boards," 29th Spring Conference of the Japan Institute of Electronics Packaging, Session ID: 16P1-17, 2015 [Patent documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 04-359911 [Patent Document 2] International Publication No. 2016 / 002704 Summary of the Invention [Problem to be solved by the invention]

[0007] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a compound having excellent low dielectric properties, a curable resin composition, and a cured product thereof. [Means for solving the problem]

[0008] That is, the present invention relates to the following [1] to [6]. In the present invention, “(numerical value 1) to (numerical value 2)” indicates that the upper and lower limit values are included. [1] A compound represented by the following formula (1).

[0009]

Chemical formula

[0010] In the above formula (1), a plurality of R1 and R3 each independently represent a hydrocarbon group having 1 to 5 carbon atoms. A plurality of R2 each independently represent a hydrocarbon group represented by the following formula (a). A plurality of p each independently represent an integer of 0 to 4. q is an average value of the number of repetitions, and 1 < q ≦ 20. A plurality of l each independently represent an integer of 0 to 4. A plurality of k each independently represent an integer of 0 to 3, and the average value k of k ave is 0 < k ave ≦ 3. n is an average value of the number of repetitions and represents a number of 0.05 to 20.

[0011]

Chemical formula

[0012] In the above formula (a), * represents the bonding position to the fluorene structure of formula (1). A plurality of R4 each independently represent a hydrocarbon group having 1 to 5 carbon atoms. m each independently represents an integer of 0 to 5. [2] A compound obtained by reacting a compound represented by the following formula (A) with a compound represented by the following formula (B).

[0013]

Chemical formula

[0014] In the above formula (A), when there are a plurality of R2s, each R2 independently represents a hydrocarbon group represented by the following formula (a). When there are a plurality of R3s, each R3 independently represents a hydrocarbon group having 1 to 5 carbon atoms. When there are a plurality of ps, each p independently represents an integer of 0 to 4. q is the average value of the repeating number, and 1 < q ≦ 20. When there are a plurality of ks, each k independently represents an integer of 0 to 3, and the average value k ave of k is such that 0 < k ave ≦ 3. n is the average value of the repeating number and represents a number from 0.05 to 20.

[0015] [Chemical formula]

[0016] In the above formula (a), * represents the bonding position to the fluorene structure of formula (A). When there are a plurality of R4s, each R4 independently represents a hydrocarbon group having 1 to 5 carbon atoms. When there are a plurality of ms, each m independently represents an integer of 0 to 5.

[0017] [Chemical formula]

[0018] In the above formula (B), when there are a plurality of R1s, each R1 independently represents a hydrocarbon group having 1 to 5 carbon atoms. l represents an integer of 0 to 4. X represents a halogen atom. [3] A curable resin composition containing the compound according to the preceding item [1] or [2]. [4] Furthermore, the curable resin composition according to the preceding item [3], which contains at least one or more selected from a curing accelerator, a polymerization initiator, an epoxy resin, an active ester compound, a phenol resin, a polyphenylene ether compound, an amine resin, a compound having an ethylenically unsaturated bond, an isocyanate resin, a polyamide resin, a maleimide compound, a cyanate ester resin, a polyimide resin, polybutadiene and its modified products, polystyrene and its modified products, polyethylene and its modified products, and a benzoxazine compound. [5] A cured product obtained by curing the compound according to the preceding paragraph [1] or [2]. [6] A cured product obtained by curing the curable resin composition according to the preceding paragraph [3] or [4]. [7] A method for producing a compound represented by the following formula (1), which is obtained by reacting a compound represented by the following formula (A) with a compound represented by the following formula (B) in an aprotic polar solvent in the presence of a basic catalyst.

[0019] [Chemical formula]

[0020] In the above formula (A), a plurality of R2 each independently represents a hydrocarbon group represented by the following formula (a). A plurality of R3 each independently represents a hydrocarbon group having 1 to 5 carbon atoms. A plurality of p each independently represents an integer of 0 to 4. q is an average value of the repeating number and 1 < q ≦ 20. A plurality of k each independently represents an integer of 0 to 3, and the average value k ave is 0 < k ave ≦ 3. n is an average value of the repeating number and represents a number of 0.05 to 20.

[0021] [Chemical formula]

[0022] In the above formula (a), * represents the bonding position to the fluorene structure of the formula (A). A plurality of R4 each independently represents a hydrocarbon group having 1 to 5 carbon atoms. A plurality of m each independently represents an integer of 0 to 5.

[0023] [Chemical formula]

[0024] In the above formula (B), when there are a plurality of R1, each independently represents a hydrocarbon group having 1 to 5 carbon atoms. When there are a plurality of l, each independently represents an integer of 0 to 4. X represents a halogen atom.

[0025]

Chemical formula

[0026] In the above formula (1), when there are a plurality of R1 and R3, each independently represents a hydrocarbon group having 1 to 5 carbon atoms. When there are a plurality of R2, each independently represents a hydrocarbon group represented by the following formula (a). When there are a plurality of p, each independently represents an integer of 0 to 4. q is the average value of the repeating number, and 1 < q ≦ 20. When there are a plurality of l, each independently represents an integer of 0 to 4. When there are a plurality of k, each independently represents an integer of 0 to 3, and the average value k of k ave is 0 < k ave ≦ 3. n is the average value of the repeating number and represents a number from 0.05 to 20.

[0027]

Chemical formula

[0028] In the above formula (a), * represents the bonding position to the fluorene structure of formula (1). When there are a plurality of R4, each independently represents a hydrocarbon group having 1 to 5 carbon atoms. When there are a plurality of m, each independently represents an integer of 0 to 5.

Advantages of the Invention

[0029] According to the present invention, it is possible to provide a compound having excellent low dielectric characteristics and a curable resin composition.

Brief Description of the Drawings

[0030] [Figure 1] Shows the HP-LC chart of Example 1. [Figure 2] Shows the 1H-NMR chart of Example 1. [Figure 3]Shows the GPC chart of Example 1. [Figure 4] Shows the HP-LC chart of Comparative Synthesis Example 1. [Figure 5] Shows the 1H-NMR chart of Comparative Synthesis Example 1.

Mode for Carrying Out the Invention

[0031] Hereinafter, embodiments according to the present invention (hereinafter also referred to as "the present embodiment") will be described in more detail.

[0032] The compound of the present embodiment is represented by the following formula (1).

[0033]

Chemical formula

[0034] In the above formula (1), a plurality of R1s each independently represent a hydrocarbon group having 1 to 5 carbon atoms, preferably a hydrocarbon group having 1 to 3 carbon atoms. A plurality of R2s each independently represent a hydrocarbon group represented by the following formula (a). A plurality of R3s each independently represent a hydrocarbon group having 1 to 5 carbon atoms, preferably a hydrocarbon group having 1 to 3 carbon atoms. When the number of carbon atoms is 5 or less, molecular vibration is difficult to occur when exposed to high frequencies, so the electrical properties are excellent. A plurality of ps each independently represent an integer of 0 to 4, more preferably 1 to 4, still more preferably 2 to 3, and most preferably 2. When p is in the range of 1 to 4, molecular rotation is suppressed, leading to improvements in heat resistance and dielectric properties. q is the average value of the repetition number, and 1 < q ≦ 20. From the viewpoints of heat resistance and solvent solubility, q is preferably 1 < q ≦ 10, more preferably 1.1 ≦ q ≦ 7.5, and still more preferably 1.2 ≦ q ≦ 5. A plurality of ks each independently represent an integer of 0 to 3, and the average value k ave is 0 < k ave ≦ 3, and from the viewpoints of solvent solubility and heat resistance, 0 < k aveIt is more preferable that n is ≦2. Multiple l's each independently represent an integer of 0 to 4, preferably 1. n is the average number of repeating units and represents a number of 0.05 to 20. From the viewpoint of heat resistance and solvent solubility, n is preferably 0.05 to 15, more preferably 0.1 to 12.5, even more preferably 0.5 to 10, and particularly preferably 1 to 10.

[0035] The molecular weight of the compound represented by formula (1) is preferably 100 to 10,000, more preferably 125 to 7,500, and even more preferably 150 to 5,000, as determined by gel permeation chromatography (GPC) analysis using a differential refractive index detector. If the number average molecular weight is less than 100, residual raw materials may reduce heat resistance, and tackiness may occur during B-staging. If the number average molecular weight exceeds 10,000, the viscosity of the compound may increase, impairing circuit embedding properties and reducing solvent solubility. The weight average molecular weight is preferably 100 to 10,000, more preferably 125 to 7,500, and even more preferably 150 to 5,000. If the weight average molecular weight is less than 100, residual raw materials may reduce heat resistance, and tackiness may occur during B-staging. If the weight average molecular weight exceeds 10,000, the viscosity of the compound increases, which may impair the ability to embed circuits or reduce the solubility in solvents.

[0036] [ka]

[0037] In the above formula (a), * represents the bonding position to the fluorene structure of formula (1). Multiple R4s each independently represent a hydrocarbon group having 1 to 5 carbon atoms, preferably a hydrocarbon group having 1 to 3 carbon atoms. When the carbon number is 5 or less, molecular vibration is unlikely to occur when exposed to high frequency waves, resulting in excellent electrical properties. Each m independently represents an integer of 0 to 5, preferably 1 to 3, and more preferably 2 or 3.

[0038] The method for producing the compound represented by the above formula (1) is not particularly limited, but it can be obtained by reacting a compound represented by the following formula (A) with a compound represented by the following formula (B).

[0039] [ka]

[0040] In the above formula (A), R2 and R3 are the same as in the above formula (1), and the values and preferred ranges of p, q, k, and n are the same as in the above formula (1).

[0041] [ka]

[0042] In the above formula (a), * represents the bonding position to the fluorene structure of formula (1). R4 is the same as in the above formula (a). The value and preferred range of m are the same as in the above formula (a).

[0043] [ka]

[0044] In the above formula (B), R1 is the same as in the above formula (1). The value and preferred range of l are the same as in the above formula (1). X represents a halogen atom, and from the viewpoints of reactivity and suppression of waste generation, it is preferably a bromine atom or a chlorine atom, and more preferably a chlorine atom.

[0045] When synthesizing a compound represented by formula (1), where α is the number of moles of the compound represented by formula (A) and β is the number of moles of the compound represented by formula (B), β / α is preferably 1.8 to 2.1, more preferably 1.8 to 2.0 mol, and particularly preferably 1.8 to 1.95. If β / α is less than 1.8, the compound represented by formula (A) remains unreacted, which may reduce the toughness of the cured film and may also deteriorate the dielectric properties. This is because the unreacted compound represented by formula (A) does not have a structure that can be crosslinked, and because oxygen reacts with the methylene structure at the 9-position of the fluorene structure of the compound represented by formula (A) to produce a ketone, increasing polarity. If β / α is greater than 2.1, the halogen element in the compound represented by formula (B) that has not been completely removed by purification may be desorbed during curing (e.g., at temperatures of 175°C or higher) or during high-temperature, high-humidity testing (e.g., at 85°C and 85% humidity, or at 120°C and 100% humidity), potentially resulting in corrosion of the copper wiring. The amount of residual halogen in the mixture containing the compound of this embodiment is preferably 1 to 10,000 ppm, more preferably 1 to 3,000 ppm, and even more preferably 1 to 2,000 ppm. Here, the "residual halogen" refers to unreacted raw material compounds and impurities contained in the reaction product obtained by reacting the compound represented by formula (A) with the compound represented by formula (B) to obtain the compound represented by formula (1).

[0046] The reaction between the compound represented by formula (A) and the compound represented by formula (B) is described in detail below. The compound represented by formula (1) can be obtained by reacting the compound represented by formula (A) with the compound represented by formula (B) in an aprotic polar solvent in the presence of a catalyst. Examples of aprotic polar solvents include dimethyl sulfone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, and N-methylpyrrolidone, and two or more of these may be used in combination. If necessary, a water-insoluble solvent may also be used in combination. Examples of water-insoluble solvents 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, and two or more of these may also be used in combination. The catalyst is not particularly limited, and examples include basic catalysts such as sodium hydroxide, potassium hydroxide, and potassium carbonate. The order of adding the compound represented by the formula (A), the compound represented by the formula (B), and the catalyst can be changed as necessary, but a preferred method is to add the compound represented by the formula (A), the aprotic polar solvent, and the catalyst, sufficiently ionize the compound represented by the formula (A), and then add the compound represented by the formula (B).

[0047] When the reaction is carried out without using an aprotic polar solvent, the reaction rate is significantly reduced. When an aprotic polar solvent is not used, the reaction is generally carried out using a phase transfer catalyst. In this case, the raw materials are dissolved in a non-aqueous solvent such as toluene, and the compound represented by formula (A) and the compound represented by formula (B) are reacted in the presence of a basic catalyst such as aqueous sodium hydroxide solution and a phase transfer catalyst such as tetrabutylammonium bromide. In this case, it is difficult to completely remove the phase transfer catalyst such as tetrabutylammonium bromide, making it difficult to achieve low dielectric properties (low dielectric constant and low dielectric loss tangent). In addition, the remaining phase transfer catalyst may cause problems such as ion migration when a substrate material using the compound of this embodiment is subjected to a long-term wet heat reliability test. For this reason, it is preferable to use an aprotic polar solvent.

[0048] The reaction temperature between the compound represented by formula (A) and the compound represented by formula (B) is preferably 0 to 120°C, more preferably 0 to 100°C, and even more preferably 0 to 80°C. At temperatures higher than 120°C, the compound of this embodiment may undergo self-polymerization, resulting in gelation. At temperatures lower than 0°C, the reaction may not proceed sufficiently. When a basic catalyst is used, post-reaction treatment may involve neutralization with an acid compound. If necessary, the reaction solution may be added with an alcohol compound, water, or the like to recover the target product as crystals. The resulting reaction solution or crystals may be redissolved in a solvent and subjected to an extraction step. For the extraction step, aromatic hydrocarbon solvents such as toluene and xylene may be used alone, or non-aromatic hydrocarbons such as cyclohexane and toluene may be used in combination. After extraction, the organic layer is washed with water until the wastewater becomes neutral, and the target compound is obtained by distilling off the solvent using an evaporator or the like.

[0049] The compound represented by the formula (A) is derived from a compound having a fluorene structure (fluorene or fluorene having a substituent) and an alkylbenzene formaldehyde resin. Here, the alkylbenzene formaldehyde resin refers to a reaction product of alkylbenzene and formaldehyde, such as m-xylene formaldehyde resin (also called xylene resin). Examples of alkylbenzene formaldehyde resins include toluene formaldehyde resin, o-xylene formaldehyde resin, m-xylene formaldehyde resin, p-xylene formaldehyde resin, 1,2,3-trimethylbenzene formaldehyde resin, 1,2,4-trimethylbenzene formaldehyde resin, 1,2,5-trimethylbenzene formaldehyde resin, 1,3,5-trimethylbenzene formaldehyde resin, and 1,2,3,4-tetramethylbenzene formaldehyde. Examples of suitable olefins include, but are not limited to, olefin resins, 1,2,3,5-tetramethylbenzeneformaldehyde resins, 1,2,4,5-tetramethylbenzeneformaldehyde resins, 1,3,5-triethylbenzeneformaldehyde resins, 1,3,5-tripropylbenzeneformaldehyde resins, 1,3,5-triisopropylbenzeneformaldehyde resins, 1,3,5-tributylbenzeneformaldehyde resins, and 1,3,5-tri-t-butylbenzeneformaldehyde resins. These may be used alone or in combination of two or more. From the viewpoint of dielectric properties and heat resistance, the olefins are preferably substituted with a hydrocarbon group having 1 to 5 carbon atoms, more preferably with a hydrocarbon group having 1 to 3 carbon atoms, and even more preferably with a methyl group. As the number of carbon atoms in the hydrocarbon group increases, it becomes more difficult to maintain molecular rigidity and the molecules become more prone to vibration, which can result in a decrease in dielectric properties and heat resistance. The amount of alkylbenzene formaldehyde resin used is usually 0.01 to 5% by weight, preferably 0.1 to 0.3% by weight, more preferably 0.2 to 3% by weight, and even more preferably 0.25 to 2% by weight, per 1% by weight of fluorene used.

[0050] When reacting a fluorene compound with an alkylbenzene formaldehyde resin, acidic catalysts such as hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, p-toluenesulfonic acid, and methanesulfonic acid can be used as catalysts, as needed. These catalysts include Lewis acids such as aluminum chloride and zinc chloride, activated clay, acid clay, white carbon, zeolite, and silica alumina, and acidic ion exchange resins. These catalysts may be used alone or in combination. The amount of catalyst used is preferably 0.1 to 40 wt.%, preferably 0.1 to 20 wt.%, based on the total weight of the fluorene and alkylbenzene formaldehyde resin used. Using too much catalyst can result in a reaction solution with too high a viscosity, making stirring difficult; using too little can slow the reaction. The reaction can be carried out using an organic solvent such as hexane, cyclohexane, methylcyclohexane, octane, toluene, or xylene, or it can be carried out solvent-free. For example, an acidic catalyst is added to a mixed solution of fluorene, xylene formaldehyde resin, and a solvent (or no solvent), and if the catalyst contains water, the water is removed from the system by azeotropy or the like. The reaction is then carried out at 40 to 300°C, preferably 50 to 250°C, for 0.5 to 40 hours. After the reaction is complete, the acidic catalyst may be neutralized with a basic aqueous solution, but the process can also proceed to a water-washing step without neutralization. In the water-washing step, a water-insoluble organic solvent is added to the oil layer, and water washing is repeated until the wastewater becomes neutral.

[0051] Furthermore, the compound represented by formula (A) obtained by the above reaction may be continuously converted into the compound represented by formula (1) by adding a neutralizing agent such as any basic compound and an aprotic polar solvent to the solution after the reaction, followed by adding a basic catalyst and the compound represented by formula (B).

[0052] The softening point of the compound represented by formula (A) is preferably 180°C or lower, more preferably 150°C or lower. If the softening point is 180°C or lower, the viscosity when converted into the compound represented by formula (1) is low. This makes it easier to ensure fluidity, does not impair the impregnation ability into glass cloth or carbon fiber, and facilitates B-stage formation, such as prepreg formation. If the viscosity is reduced by increasing the dilution solvent, the resin may not adhere sufficiently to the fibrous material during the impregnation process.

[0053] The compound represented by the formula (1) can be cured by itself by heating or the like, but performance can also be improved by adding various materials to form a curable resin composition.

[0054] [Curing accelerator] The curability of the curable resin composition of the present embodiment can be improved by adding a curing accelerator. As the curing accelerator, an anionic curing accelerator that accelerates the curing reaction by generating anions upon irradiation with ultraviolet light or visible light or heating, or a cationic curing accelerator that accelerates the curing reaction by generating cations upon irradiation with ultraviolet light or visible light or heating, is preferred.

[0055] Examples of anionic curing accelerators include imidazoles such as 2-methylimidazole, 2-ethylimidazole, and 2-ethyl-4-methylimidazole; trialkylamines such as triethylamine and tributylamine; 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol; and 1,8-diazabicyclo(5,4,0)-undecene, with 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)-undecene being preferred. Other examples include phosphines such as triphenylphosphine; and quaternary ammonium salts such as tetrabutylammonium salt, triisopropylmethylammonium salt, trimethyldecanylammonium salt, cetyltrimethylammonium salt, and hexadecyltrimethylammonium hydroxide, but are not limited thereto. These may be used alone or in combination.

[0056] Examples of cationic curing accelerators include quaternary phosphonium salts such as triphenylbenzylphosphonium salt, triphenylethylphosphonium salt, and tetrabutylphosphonium salt (the counter ion of the quaternary salt may be a halogen, an organic acid ion, a hydroxide ion, or the like, and is not particularly specified, but organic acid ions and hydroxide ions are particularly preferred), and transition metal compounds (transition metal salts) such as tin octoate, zinc carboxylate (zinc 2-ethylhexanoate, zinc stearate, zinc behenate, zinc myristate), and zinc phosphate ester (zinc octylphosphate, zinc stearylphosphate), but are not limited to these. These may be used alone or in combination.

[0057] The curing accelerator is used in an amount of 0.01 to 5.0 parts by mass based on 100 parts by mass of the curable resin composition, as needed.

[0058] [Inorganic filler] The curable resin composition of this embodiment may contain an inorganic filler. Examples of inorganic fillers include, but are not limited to, 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, and glass powder, as well as inorganic fillers obtained by forming these into spherical or crushed shapes. These fillers may be used alone or in combination.

[0059] When a curable resin composition for semiconductor encapsulation is obtained, the amount of inorganic filler used is preferably 80 to 92 parts by mass, and more preferably 83 to 90 parts by mass, per 100 parts by mass of the curable resin composition. When a curable resin composition for interlayer insulating layer formation, copper-clad laminates, prepregs, RCC (Resin Coated Copper), and other substrate materials is obtained, the amount of inorganic filler used is preferably 5 to 80 parts by mass, and more preferably 10 to 60 parts by mass, per 100 parts by mass of the curable resin composition.

[0060] [Polymerization initiator] The curability of the curable resin composition of this embodiment can be improved by adding a polymerization initiator. The polymerization initiator is a compound capable of polymerizing an olefin functional group such as an ethylenically unsaturated bond, and examples thereof include an olefin metathesis polymerization initiator, an anionic polymerization initiator, a cationic polymerization initiator, and a radical polymerization initiator. Among these, it is preferable to use a radical polymerization initiator that has curability and appropriate stability. The radical polymerization initiator is a compound that generates radicals upon irradiation with ultraviolet or visible light or heating, thereby initiating a chain polymerization reaction. Usable radical polymerization initiators include organic peroxides, azo compounds, and benzopinacols. Organic peroxides are preferred because they are effective in controlling the curing temperature, suppress outgassing, and minimize the impact of decomposition products on electrical properties.

[0061] Examples of the organic peroxides 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-butyl peroxybenzoate and 1,1-di-t-butylperoxycyclohexane, α-cumylperoxyneodecanoate, t-butylperoxyneodecanoate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, t-butylperoxymethyl ... Examples of the peroxycarbonates include, but are not limited to, alkyl peresters such as di-2-ethylhexyl peroxydicarbonate, t-amylperoxy-3,5,5-trimethylhexanoate, t-butylperoxy-3,5,5-trimethylhexanoate, and t-amylperoxybenzoate, peroxycarbonates such as di-2-ethylhexyl peroxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, t-butylperoxyisopropyl carbonate, and 1,6-bis(t-butylperoxycarbonyloxy)hexane, t-butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxyoctoate, and lauroyl peroxide. These peroxycarbonates may be used alone or in combination. Among the above organic peroxides, ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, alkyl peresters, peroxycarbonates, etc. are preferred, with dialkyl peroxides being more preferred.

[0062] Examples of the azo compounds include, but are not limited to, azobisisobutyronitrile, 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2,4-dimethylvaleronitrile), etc. These compounds may be used alone or in combination.

[0063] The amount of polymerization initiator added is preferably 0.01 to 5 parts by mass, and particularly preferably 0.01 to 3 parts by mass, relative to 100 parts by mass of the curable resin composition. If the amount of polymerization initiator used is less than 0.01 part by mass, there is a risk that the molecular weight will not be sufficiently elongated during the polymerization reaction, and if it is more than 5 parts by mass, there is a risk that the dielectric properties such as the dielectric constant and dielectric loss tangent will be impaired.

[0064] [Polymerization inhibitor] The curable resin composition of this embodiment may contain a polymerization inhibitor. The inclusion of a polymerization inhibitor improves storage stability and enables control of the reaction initiation temperature. Controlling the reaction initiation temperature makes it easier to ensure fluidity, prevents impregnation into glass cloth and the like from being impaired, and facilitates B-staging, such as prepreg formation. If the polymerization reaction proceeds too much during prepreg formation, problems such as difficulty in lamination during the lamination process are likely to occur.

[0065] The polymerization inhibitor may be added during or after the synthesis of the compound of this embodiment. The amount of the polymerization inhibitor used is 0.008 to 1 part by mass, preferably 0.01 to 0.5 parts by mass, per 100 parts by mass of the compound of this embodiment.

[0066] Examples of the polymerization inhibitor include phenol-based, sulfur-based, phosphorus-based, hindered amine-based, nitroso-based, and nitroxyl radical-based. One type of polymerization inhibitor may be used alone, or multiple types may be used in combination. Among these, in this embodiment, phenol-based, hindered amine-based, nitroso-based, and nitroxyl radical-based inhibitors are preferred.

[0067] Examples of the phenolic polymerization inhibitor include 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, 2,4-bis[(octylthio)methyl]-o ...butylated hydroxyanisole, butylated hydroxyanisole, butylated hydroxyanisole, butylated hydroxyanisole, butylated hydroxyanisole, butylated hydroxyanisole, butylated hydroxyanisole, butylated hydroxyanisole, butylated hydroxyanisole, butylated hydroxyanisole, butylated hydroxyanisole, butylated hydroxyanisole, butylated hydroxyanisole, butylated hydroxyanisole, butylated hydroxyanisole, butylated hydroxyanisole, butylated hydroxyanisole, butylated hydroxyanisole, butylated hydroxyani Monophenols such as resol, 2,2'-methylenebis(4-methyl-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 Bisphenols such as calcium ethyl-4-hydroxybenzylsulfonate, 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-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,Examples of the polymerizable phenols include, but are not limited to, 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.

[0068] Examples of the sulfur-based polymerization inhibitor include, but are not limited to, dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, and distearyl-3,3'-thiodipropionate.

[0069] Examples of the phosphorus-based polymerization inhibitor include triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, tris(nonylphenyl) phosphite, diisodecyl pentaerythritol phosphite, tris(2,4-di-t-butylphenyl) phosphite, cyclic neopentane tetrayl bis(octadecyl) phosphite, cyclic neopentane tetrayl bis(2,4-di-t-butylphenyl) phosphite, cyclic neopentane tetrayl bis(2,4-di-t-butyl-4-methylphenyl) phosphite, bis[2- Examples of suitable phosphites include 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, but are not limited to these.

[0070] Examples of the hindered amine polymerization inhibitor include ADK STAB (registered trademark) LA-40MP, ADK STAB LA-40Si, ADK STAB LA-402AF, ADK STAB LA-87, ADK STAB LA-82, ADK 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, and ADK STAB LA-52 (all manufactured by ADK STAB Corporation). Examples of suitable ethylene glycol acrylate crosspolymers include, but are not limited to, ethylene glycol acrylate crosspolymers manufactured by BASF, Chimassorb (registered trademark) 2020FDL, Chimassorb 944FDL, Chimassorb 944LD, Tinuvin (registered trademark) 622SF, Tinuvin PA144, Tinuvin 765, Tinuvin 770DF, Tinuvin XT55FB, Tinuvin 111FDL, Tinuvin 783FDL, and Tinuvin 791FB (all manufactured by BASF).

[0071] Examples of the nitroso-based polymerization inhibitor include, but are not limited to, p-nitrosophenol, N-nitrosodiphenylamine, and the ammonium salt (cupferron) of N-nitrosophenylhydroxyamine. Of these, the ammonium salt (cupferron) of N-nitrosophenylhydroxyamine is preferred.

[0072] Examples of the nitroxyl radical polymerization inhibitor include di-tert-butyl nitroxide, 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-amino-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-acetoxy-2,2,6,6-tetramethylpiperidine-1-oxyl, and 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl, but are not limited to these.

[0073] [Flame retardant] The curable resin composition of the present embodiment may contain a flame retardant. Examples of the flame retardant include halogen-based flame retardants, inorganic flame retardants (antimony compounds, metal hydroxides, nitrogen compounds, boron compounds, etc.), and phosphorus-based flame retardants. From the viewpoint of achieving halogen-free flame retardancy, phosphorus-based flame retardants are preferred.

[0074] The phosphorus-based flame retardant may be either a reactive type or an additive type. Specific examples include phosphate esters such as trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylenyl phosphate, 1,3-phenylenebis(dixylenyl phosphate), 1,4-phenylenebis(dixylenyl phosphate), and 4,4'-biphenyl(dixylenyl phosphate); phosphanes such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 10(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide; phosphorus-containing epoxy compounds obtained by reacting epoxy resins with the active hydrogen of the phosphanes; and red phosphorus. These may be used alone or in combination. Of the above-mentioned exemplified substances, phosphate esters, phosphanes, and phosphorus-containing epoxy compounds are preferred, and 1,3-phenylenebis(dixylenyl phosphate), 1,4-phenylenebis(dixylenyl phosphate), 4,4'-biphenyl(dixylenyl phosphate), and phosphorus-containing epoxy compounds are particularly preferred.

[0075] The content of the flame retardant is preferably in the range of 0.1 to 0.6 parts by mass relative to 100 parts by mass of the curable resin composition. If the content is less than 0.1 part by mass, the flame retardancy may be insufficient, and if the content is more than 0.6 part by mass, the moisture absorption and dielectric properties of the cured product may be adversely affected.

[0076] [Light stabilizer] The curable resin composition of this embodiment may contain a light stabilizer, and preferred examples of the light stabilizer include hindered amine light stabilizers (Hidered Amine Light Stabilizers, HALS). Examples of HALS include the reaction product 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, the reaction product of dimethyl succinate-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, and 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) Examples of suitable hydroxybenzyl compounds include, but are not limited to, 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, and bis(1,2,2,6,6-pentamethyl-4-piperidyl) 2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-n-butylmalonate. These compounds may be used alone or in combination.

[0077] The content of the light stabilizer is preferably in the range of 0.001 to 0.1 parts by mass relative to 100 parts by mass of the curable resin composition. If the content is less than 0.001 part by mass, the light stabilizing effect may be insufficient, and if the content is more than 0.1 part by mass, the moisture absorption and dielectric properties of the cured product may be adversely affected.

[0078] [Binder resin] The curable resin composition of this embodiment may contain a binder resin. 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, and silicone resins. These may be used alone or in combination.

[0079] The amount of binder resin to be added 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 curable resin composition, as needed.

[0080] [Additives] The curable resin composition of the present embodiment may contain additives, such as modified acrylonitrile copolymers, polyethylene, fluororesins, silicone gels, silicone oils, surface treatment agents for fillers such as silane coupling agents, release agents, and colorants such as carbon black, phthalocyanine blue, and phthalocyanine green.

[0081] The amount of the additives to be added is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and particularly preferably 10 parts by mass or less, per 100 parts by mass of the curable resin composition.

[0082] The curable resin composition of this embodiment may further contain other compounds such as epoxy resins, active ester compounds, phenolic resins, polyphenylene ether compounds, amine resins, compounds having an ethylenically unsaturated bond, isocyanate resins, polyamide resins, maleimide compounds, cyanate ester resins, polyimide resins, polybutadiene and modified products thereof, polystyrene and modified products thereof, polyethylene and modified products thereof, and benzoxazine compounds. These may be used alone or in combination. Among these other compounds, polyphenylene ether compounds, compounds having an ethylenically unsaturated bond, cyanate ester resins, polybutadiene and modified products thereof, and polystyrene and modified products thereof are preferred in terms of the balance of heat resistance, adhesion, and dielectric properties. The inclusion of these compounds can improve the brittleness of the cured product and adhesion to metals, thereby suppressing package cracking during reliability tests such as solder reflow and thermal cycling.

[0083] Unless otherwise specified, the total amount of compounds other than the compound represented by formula (1) is preferably 10 times or less by mass, more preferably 5 times or less by mass, and particularly preferably 3 times or less by mass relative to the compound represented by formula (1) of this embodiment. The lower limit is preferably 0.1 times or more by mass, more preferably 0.25 times or more by mass, and even more preferably 0.5 times or more by mass. By being within the above range, the effects of each compound added can be enhanced while taking advantage of the low dielectric properties of the compound represented by formula (1) of this embodiment. The following examples of these components can be used.

[0084] [Epoxy resin] Preferred examples of epoxy resins include, but are not limited to, the following. The epoxy resin may be liquid or solid, and may be used alone or in combination.

[0085] Examples of liquid epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, phenol novolac type epoxy resins, alicyclic epoxy resins having an ester skeleton, cyclohexane type epoxy resins, cyclohexanedimethanol type epoxy resins, and epoxy resins having a butadiene structure. Specific examples include "RE310S" and "RE410S" (all manufactured by Nippon Kayaku Co., Ltd., bisphenol A type epoxy resin), "RE303S", "RE304S", "RE403S", and "RE404S" (all manufactured by Nippon Kayaku Co., Ltd., bisphenol F type epoxy resin), "HP4032", "HP4032D", and "HP4032SS" (all manufactured by DIC Corporation, naphthalene type epoxy resin), "jER (registered trademark) 828US", "jER828EL", "825", and "828EL" (all manufactured by Mitsubishi Chemical Corporation, bisphenol A type epoxy resin), "jER807" and "jER1750" (all manufactured by Mitsubishi Chemical Corporation, bisphenol F type epoxy resin), and "jER152" (manufactured by Mitsubishi Chemical Corporation, phenol Examples of epoxy resins include bisphenol A epoxy resin, jER630, and jER630LSD (all manufactured by Mitsubishi Chemical Corporation; glycidylamine epoxy resin), ZX1059 (manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.; a mixture of bisphenol A epoxy resin and bisphenol F epoxy resin), EX-721 (manufactured by Nagase ChemteX Corporation; glycidyl ester epoxy resin), CELLOXIDE (registered trademark) 2021P (manufactured by Daicel Corporation; alicyclic epoxy resin having an ester skeleton), PB-3600 (manufactured by Daicel Corporation; epoxy resin having a butadiene structure), ZX1658, and ZX1658GS (manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.; liquid 1,4-glycidylcyclohexane epoxy resin). These may be used alone or in combination of two or more.

[0086] Preferred examples of solid epoxy resins include bixylenol-type epoxy resins, naphthalene-type epoxy resins, naphthalene-type tetrafunctional epoxy resins, cresol novolac-type epoxy resins, dicyclopentadiene-type epoxy resins, trisphenol-type epoxy resins, naphthol-type epoxy resins, biphenyl-type epoxy resins, naphthylene ether-type epoxy resins, anthracene-type epoxy resins, bisphenol A-type epoxy resins, bisphenol AF-type epoxy resins, and tetraphenylethane-type epoxy resins, and examples of such solid epoxy resins include naphthol-type epoxy resins, bisphenol AF-type epoxy resins, naphthalene-type epoxy resins, and biphenyl-type epoxy resins.Specific examples include "HP4032H" (manufactured by DIC Corporation, naphthalene-type epoxy resin), "HP-4700", "HP-4710" (all manufactured by DIC Corporation, naphthalene-type tetrafunctional epoxy resin), "N-690" (manufactured by DIC Corporation, cresol novolac-type epoxy resin), "N-695" (manufactured by DIC Corporation, cresol novolac-type epoxy resin), "HP-7200", "HP-7200HH", "HP-7200H" (all manufactured by DIC Corporation, dicyclopentadiene-type epoxy resin), "EXA-7311", "EXA-7311-G3 "," "EXA-7311-G4," "EXA-7311-G4S," "HP-6000" (all manufactured by DIC, naphthylene ether type epoxy resin), "EPPN-502H" (manufactured by Nippon Kayaku, trisphenol type epoxy resin), "NC-7000L," "NC-7300" (all manufactured by Nippon Kayaku, naphthol-cresol novolac type epoxy resin), "NC-3000H," "NC-3000," "NC-3000L," "NC-3100" (all manufactured by Nippon Kayaku, biphenyl aralkyl type epoxy resin), "XD- 1000-2L, "XD-1000-L", "XD-1000-H", "XD-1000-H" (all manufactured by Nippon Kayaku Co., Ltd., dicyclopentadiene type epoxy resin), "ESN475V" (manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., naphthol type epoxy resin), "ESN485" (manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., naphthol novolac type epoxy resin), "YX-4000H", "YX-4000", "YL6121" (all manufactured by Mitsubishi Chemical Corporation, biphenyl type epoxy resin), "YX-4000HK" (manufactured by Mitsubishi Chemical Corporation, bixylenol type epoxy resin) resin), "YX-8800" (manufactured by Mitsubishi Chemical Corporation, anthracene-type epoxy resin), "PG-100", "CG-500" (manufactured by Osaka Gas Chemicals Co., Ltd., fluorene-based epoxy resin), "YL-7760" (manufactured by Mitsubishi Chemical Corporation, bisphenol AF-type epoxy resin), "YL-7800" (manufactured by Mitsubishi Chemical Corporation, fluorene-type epoxy resin), "jER1010" (manufactured by Mitsubishi Chemical Corporation, solid bisphenol A-type epoxy resin), "jER1031S" (manufactured by Mitsubishi Chemical Corporation, tetraphenylethane-type epoxy resin), etc. These may be used alone or in combination of two or more.

[0087] [Active ester compounds] An active ester compound refers to a compound containing at least one ester bond in its structure, with an aliphatic chain, an aliphatic ring, or an aromatic ring bonded to both sides of the ester bond. Examples of active ester compounds include phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, which have two or more highly reactive ester groups per molecule. These compounds are obtained by a condensation reaction between at least one of a carboxylic acid compound, an acid chloride, or a thiocarboxylic acid compound and at least one of a hydroxy compound or a thiol compound. From the viewpoint of improving heat resistance, active ester compounds are preferably obtained from a carboxylic acid compound or an acid chloride and a hydroxy compound, with phenol compounds or naphthol compounds being preferred as the hydroxy compound. Active ester compounds may be used singly or in combination of two or more.

[0088] 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.

[0089] Examples of the acid chloride include acetyl chloride, acrylic acid chloride, methacrylic acid chloride, malonyl chloride, succinic acid dichloride, diglycolyl chloride, glutaric acid dichloride, suberic acid dichloride, sebacic acid dichloride, adipic acid dichloride, dodecandioyl dichloride, azelaic acid chloride, 2,5-furandicarbonyl dichloride, phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, trimesic acid chloride, bis(4-chlorocarbonylphenyl) ether, 4,4'-diphenyldicarbonyl chloride, and 4,4'-azodibenzoyl dichloride.

[0090] Examples of the phenol compound and naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalene, 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, phloroglucinol, benzenetriol, dicyclopentadiene-type diphenol compounds, phenol novolak, and the phenolic resins described below. Here, the term "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing one dicyclopentadiene molecule with two phenol molecules.

[0091] Preferred specific examples of the active ester compound include active ester compounds containing a dicyclopentadiene-type diphenol structure, active ester compounds containing a naphthalene structure, active ester compounds containing an acetylated product of phenol novolac, active ester compounds containing a benzoylated product of phenol novolac, the compound described in Example 2 of WO 2020 / 095829, and the compounds disclosed in WO 2020 / 059625. Among these, active ester compounds containing a naphthalene structure and active ester compounds 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.

[0092] Commercially available active ester compounds include, for example, active ester compounds containing a dicyclopentadiene-type diphenol structure such as "EXB9451," "EXB9460," "EXB9460S," "HPC-8000-65T," "HPC-8000H-65™," "EXB-8000L-65™," and "EXB-8150-65T" (manufactured by DIC Corporation); an active ester compound containing a naphthalene structure such as "EXB9416-70BK" (manufactured by DIC Corporation); an active ester compound containing an acetylated phenol novolac such as "DC808" (manufactured by Mitsubishi Chemical Corporation); an active ester compound containing a benzoylated phenol novolac such as "YLH1026," "YLH1030," and "YLH1048" (manufactured by Mitsubishi Chemical Corporation); and a phosphorus-containing active ester curing agent such as "EXB-9050L-62M" (manufactured by DIC Corporation).

[0093] Regarding the compounding ratio of the active ester compound and the epoxy resin, the ratio (α / β) of the active ester equivalent (α) to the epoxy equivalent (β) is preferably 0.5 to 1.5, more preferably 0.8 to 1.2, and even more preferably 0.90 to 1.10. If the ratio is outside this range, excess epoxy groups or active ester groups may remain in the system, which may deteriorate the properties in high-temperature storage tests (e.g., 150°C, 1000 hours) or long-term reliability tests under high-temperature and high-humidity conditions (e.g., temperature: 85°C, humidity: 85%).

[0094] [Phenol resin] A phenolic resin is a compound having two or more phenolic hydroxyl groups in the molecule. Examples of phenolic resins include, but are not limited to, reaction products of phenols and aldehydes, reaction products of phenols and diene compounds, reaction products of phenols and ketones, reaction products of phenols and substituted biphenyls, reaction products of phenols and substituted phenyls, and reaction products of bisphenols and aldehydes. These may be used alone or in combination. Specific examples of the above raw materials are given below, but are not limited to these. <Phenols> Phenol, alkyl-substituted phenol, aromatic-substituted phenol, hydroquinone, resorcinol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc. <Aldehydes> Formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, furfural, and the like. <Diene compounds> Dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, and the like. <Ketones> Acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, fluorenone, etc. <Substituted biphenyls> 4,4'-bis(chloromethyl)-1,1'-biphenyl, 4,4'-bis(methoxymethyl)-1,1'-biphenyl, 4,4'-bis(hydroxymethyl)-1,1'-biphenyl and the like. <Substituted phenyls> 1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene, 1,4-bis(hydroxymethyl)benzene and the like.

[0095] [Polyphenylene ether compounds] From the viewpoints of heat resistance and electrical properties, the polyphenylene ether compound is preferably a polyphenylene ether compound having an ethylenically unsaturated bond, and more preferably a polyphenylene ether compound having an acrylic group, a methacrylic group, or a styrene structure. Commercially available products include SA-9000 (manufactured by SABIC, a polyphenylene ether compound having a methacrylic group) and OPE-2St 1200 (manufactured by Mitsubishi Gas Chemical Company, a polyphenylene ether compound having a styrene structure). The number-average molecular weight (Mn) of the polyphenylene ether compound is preferably 500 to 5000, more preferably 2000 to 5000, and even more preferably 2000 to 4000. If the number-average molecular weight is less than 500, the heat resistance of the cured product tends to be insufficient. On the other hand, if the number-average molecular weight is greater than 5000, the melt viscosity increases, and sufficient fluidity cannot be obtained, which tends to result in molding defects. In addition, the reactivity decreases, the curing reaction takes a long time, and the amount of unreacted material not incorporated into the curing system increases, which tends to lower the glass transition temperature of the cured product and reduce the heat resistance of the cured product. When the number average molecular weight of the polyphenylene ether compound is 500 to 5000, it is possible to maintain excellent dielectric properties while exhibiting excellent heat resistance, moldability, etc. The number average molecular weight here can be specifically measured using gel permeation chromatography, etc.

[0096] The polyphenylene ether compound may be obtained by a polymerization reaction or by a redistribution reaction of a high-molecular-weight polyphenylene ether compound having a number-average molecular weight of approximately 10,000 to 30,000. Alternatively, these compounds may be used as raw materials and reacted with a compound having an ethylenically unsaturated bond, such as methacrylic acid chloride, acrylic acid chloride, or chloromethylstyrene, to impart radical polymerizability. A polyphenylene ether compound obtained by a redistribution reaction may be obtained, for example, by heating a high-molecular-weight polyphenylene ether compound in a solvent such as toluene in the presence of a phenolic compound and a radical initiator to cause a redistribution reaction. Such polyphenylene ether compounds obtained by a redistribution reaction are preferred because they have hydroxyl groups derived from phenolic compounds at both ends of the molecular chain that contribute to curing, thereby maintaining even higher heat resistance. Furthermore, functional groups can be introduced at both ends of the molecular chain even after modification with a compound having an ethylenically unsaturated bond. Furthermore, polyphenylene ether compounds obtained by a polymerization reaction are preferred because they exhibit excellent fluidity.

[0097] In the case of polyphenylene ether compounds obtained by polymerization, the molecular weight of the polyphenylene ether compound can be adjusted by adjusting the polymerization conditions, etc. Furthermore, in the case of polyphenylene ether compounds obtained by redistribution, the molecular weight of the resulting polyphenylene ether compound can be adjusted by adjusting the conditions, etc. of the redistribution reaction. More specifically, adjusting the amount of the phenolic compound used in the redistribution reaction can be considered. That is, the greater the amount of the phenolic compound, the lower the molecular weight of the resulting polyphenylene ether compound. In this case, poly(2,6-dimethyl-1,4-phenylene ether) or the like can be used as the high-molecular-weight polyphenylene ether compound that undergoes the redistribution reaction. Furthermore, the phenolic compound used in the redistribution reaction is not particularly limited, but preferred are, for example, polyfunctional phenolic compounds having two or more phenolic hydroxyl groups per molecule, such as bisphenol A, phenol novolac, and cresol novolac. These compounds may be used alone or in combination of two or more.

[0098] The content of the polyphenylene ether compound is not particularly limited, but is preferably 5 to 1000 parts by mass, and more preferably 10 to 750 parts by mass, relative to 100 parts by mass of the curable resin composition. When the content of the polyphenylene ether compound is within the above range, it is preferable in that a cured product not only has excellent heat resistance and the like, but also fully exhibits the excellent dielectric properties of the polyphenylene ether compound.

[0099] [Amine resin] Amine resins are compounds that have two or more amino groups in the molecule. Examples of amine resins include diaminodiphenylmethane, diaminodiphenyl sulfone, isophoronediamine, naphthalenediamine, aniline novolak (a reaction product of aniline and formaldehyde), N-methylaniline novolak (a reaction product of N-methylaniline and formaldehyde), orthoethylaniline novolak (a reaction product of orthoethylaniline and formaldehyde), a reaction product of 2-methylaniline and formaldehyde, a reaction product of 2,6-diisopropylaniline and formaldehyde, a reaction product of 2,6-diethylaniline and formaldehyde, a reaction product of 2-ethyl-6-ethylaniline and formaldehyde, a reaction product of 2,6-dimethylaniline and formaldehyde, and aniline and xylylene chloride. Examples of suitable aniline resins include, but are not limited to, aniline resins obtained by reacting aniline with amines, reaction products of aniline and substituted biphenyls (such as 4,4'-bis(chloromethyl)-1,1'-biphenyl and 4,4'-bis(methoxymethyl)-1,1'-biphenyl) as described in Japanese Patent No. 6429862, reaction products of aniline and substituted phenyls (such as 1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene and 1,4-bis(hydroxymethyl)benzene), 4,4'-(1,3-phenylenediisopropylidene)bisaniline, 4,4'-(1,4-phenylenediisopropylidene)bisaniline, reaction products of aniline and diisopropenylbenzene, and dimer diamine. These may be used singly or in combination.

[0100] [Compounds containing ethylenically unsaturated bonds] A compound containing an ethylenically unsaturated bond is a compound that has one or more ethylenically unsaturated bonds in the molecule that can be polymerized by heat or light, regardless of whether a polymerization initiator is used or not. Examples of compounds containing ethylenically unsaturated bonds include, but are not limited to, reaction products of the above-mentioned phenolic resins with ethylenically unsaturated bond-containing halogen-based compounds (chloromethylstyrene, allyl chloride, methallyl chloride, acrylic acid chloride, methacrylic acid chloride, etc.), reaction products of ethylenically unsaturated bond-containing phenols (2-allylphenol, 2-propenylphenol, 4-allylphenol, 4-propenylphenol, eugenol, isoeugenol, etc.) with halogen-based compounds (1,4-bis(chloromethyl)benzene, 4,4'-bis(chloromethyl)biphenyl, 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-dibromobenzophenone, cyanuric chloride, etc.), reaction products of epoxy resins or alcohols with (meth)acrylic acids (acrylic acid, methacrylic acid, etc.), and acid-modified products thereof. These compounds may be used alone or in combination.

[0101] [Isocyanate resin] An isocyanate resin is a compound that has two or more isocyanate groups in its molecule. Examples of the isocyanate resin include, but are not limited to, aromatic diisocyanates such as p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylene diisocyanate, m-xylene 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-mentioned diisocyanate compounds; and polyisocyanates obtained by a urethanization reaction between the above-mentioned isocyanate compounds and polyol compounds. These may be used alone or in combination.

[0102] [Polyamide resin] Examples of polyamide resins include reaction products of one or more of diamines, diisocyanates, and oxazolines with dicarboxylic acids, reaction products of diamines with acid chlorides, and ring-opening polymerization products of lactam compounds. These may be used alone or in combination. Specific examples of the above raw materials are given below, but are not limited to these. <Diamine> 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, dimer diamine, cyclohexanediamine, bis-(4-aminocyclohexyl)methane, bis(3-methyl-4-aminocyclohexyl)methane, xylylenediamine, norbornanediamine, isophoronediamine, bisaminomethyltricyclodecane, phenylenediamine, diethyltoluenediamine, naphthalenediamine, diaminodiphenylmethane, bis(4-amino-3,5-dimethylphenyl)methane, bis(4-amino-3,5-diethylphenyl)methane aniline, 4,4'-methylenebis-o-toluidine, 4,4'-methylenebis-o-ethylaniline, 4,4'-methylenebis-2-ethyl-6-methylaniline, 4,4'-methylenebis-2,6-diisopropylaniline, 4,4-ethylenedianiline, diaminodiphenyl sulfone, diaminodiphenyl ether, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 4,4-bis(4-aminophenoxy)biphenyl, 2,2-bis[4-(4-amino 4,4'-(1,3-phenylenediisopropylidene)bisaniline, 4,4'-(1,4-phenylenediisopropylidene)bisaniline, 9,9-bis(4-aminophenyl)fluorene, 2,7-diaminofluorene, aminobenzylamine, diaminobenzophenone, and the like. <Diisocyanate> Benzene diisocyanate, toluene diisocyanate, 1,3-bis(isocyanatomethyl)benzene, 1,3-bis(isocyanatomethyl)cyclohexane, bis(4-isocyanatophenyl)methane, isophorone diisocyanate, 1,3-bis(2-isocyanato-2-propyl)benzene, 2,2-bis(4-isocyanatophenyl)hexafluoropropane, dicyclohexylmethane-4,4'-diisocyanate, and the like. <Dicarboxylic acid> Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, 5-hydroxyisophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, cyclohexanedicarboxylic acid, biphenyldicarboxylic acid, naphthalenedicarboxylic acid, benzophenonedicarboxylic acid, furandicarboxylic acid, 4,4'-dicarboxydiphenyl ether, 4,4'-dicarboxydiphenyl sulfide, etc. <Acid chloride> Acetyl chloride, acrylic acid chloride, methacrylic acid chloride, malonyl chloride, succinic acid dichloride, diglycolyl chloride, glutaric acid dichloride, suberic acid dichloride, sebacic acid dichloride, adipic acid dichloride, dodecandioyl dichloride, azelaic acid chloride, 2,5-furandicarbonyl dichloride, phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, trimesic acid chloride, bis(4-chlorocarbonylphenyl) ether, 4,4'-diphenyldicarbonyl chloride, 4,4'-azodibenzoyl dichloride and the like. <Lactam> ε-caprolactam, ω-undecanelactam, ω-laurolactam, and the like.

[0103] [Polyimide resin] Examples of polyimide resins include, but are not limited to, reaction products of the above diamines with the following tetracarboxylic dianhydrides. These may be used alone or in combination. <Tetracarboxylic acid dianhydride> 4,4'-(Hexafluoroisopropylidene)diphthalic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-cyclohexene-1,2dicarboxylic 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 acid 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]meth 2,2-bis[3-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 2,2-bis[4-(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-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3,4,9,10-Perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, ethylenetetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride tetracarboxylic acid dianhydride, 3,3',4,4'-bicyclohexyltetracarboxylic acid 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(cyclohexane-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), 9,9'-bis(3,4-dicarboxyphenyl)fluorene dianhydride, etc.,

[0104] [Maleimide compounds] The curable resin composition of this embodiment may contain a maleimide compound. A maleimide compound is a compound having one or more maleimide groups in the molecule. Examples of maleimide compounds include 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), and Xylox-type maleimide compounds (anilix). Maleimide, manufactured by Mitsui Chemicals Fine Co., Ltd.), biphenylaralkyl-type maleimide compounds (solidified by distilling off the solvent under reduced pressure from a resin solution containing the maleimide compound (M2) described in Example 4 of JP 2009-001783 A), bisaminocumylbenzene-type maleimide (maleimide compounds described in WO 2020 / 054601 A), maleimide compounds having an indane structure described in Japanese Patent No. 6629692 or WO 2020 / 217679, MATERIAL STAGE Vol. 18, No. 12 2019 "Continued Story of Epoxy Resin CAS Numbers - Hardener CAS Number Memorandum No. 31 Bismaleimide (1)" and MATERIAL STAGE Vol. 19, No. 2 2019 "Continued Story of Epoxy Resin CAS Numbers - Hardener CAS Number Memorandum No. 32" Bismaleimide (2) and the like can be used, but are not limited to these. These can be used alone or in combination.

[0105] [Cyanate ester resin] Cyanate ester resins are cyanate ester compounds obtained by reacting phenolic resins with cyanogen halides. Specific examples include, but are not limited to, 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. These compounds may be used alone or in combination. 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, flame retardancy, and excellent dielectric properties. The cyanate ester resin may optionally contain a catalyst such as zinc naphthenate, cobalt naphthenate, copper naphthenate, lead naphthenate, zinc octoate, tin octoate, lead acetylacetonate, or dibutyltin maleate to trimerize the cyanate group to form a sym-triazine ring.

[0106] The catalyst is preferably used in an amount of 0.0001 to 0.10 parts by mass, and more preferably 0.00015 to 0.0015 parts by mass, per 100 parts by mass of the cyanate ester resin and the curable resin composition.

[0107] [Polybutadiene and its modified products] Polybutadiene and its modified products are polybutadiene or compounds having a structure derived from polybutadiene in the molecule. The unsaturated bonds in the polybutadiene-derived structure may be partially or entirely converted to single bonds by hydrogenation. Examples of polybutadiene and its modified products include, but are not limited to, polybutadiene, hydroxyl-terminated polybutadiene, (meth)acrylate-terminated polybutadiene, carboxylic acid-terminated polybutadiene, amine-terminated polybutadiene, and styrene-butadiene rubber. These may be used alone or in combination. Among these, polybutadiene or styrene-butadiene rubber is preferred from the viewpoint of dielectric properties. Examples of styrene-butadiene rubber (SBR) include RICON-100, RICON-181, and RICON-184 (all manufactured by Cray Valley Corporation), and 1,2-SBS (manufactured by Nippon Soda Co., Ltd.). Examples of polybutadiene include B-1000, B-2000, and B-3000 (all manufactured by Nippon Soda Co., Ltd.). The molecular weight of polybutadiene and styrene-butadiene rubber is preferably a weight-average molecular weight of 500 to 10,000, more preferably 750 to 7,500, and even more preferably 1,000 to 5,000. Below the lower limit of the above range, the amount of evaporation is large, making it difficult to adjust the solids content during prepreg production, while above the upper limit of the above range, compatibility with other curable resins is impaired. Generally, in the case of compounds containing heteroatoms such as oxygen or nitrogen, such as bismaleimides and polymaleimides, it is difficult to ensure compatibility with low-polarity compounds, such as compounds composed mainly of hydrocarbons or compounds composed only of hydrocarbons, due to their polarity. On the other hand, the compound of this embodiment does not have a skeleton design that actively incorporates heteroatoms such as oxygen or nitrogen, and therefore has excellent compatibility with materials having low polarity and low dielectric properties, as well as compounds composed only of hydrocarbons.

[0108] [Polystyrene and its modified products] Polystyrene and its modified products are polystyrene or compounds having a structure derived from polystyrene in the molecule. Examples of polystyrene and modified products thereof include polystyrene, styrene-2-isopropenyl-2-oxazoline copolymer (Epocross RPS-1005, RP-61, both manufactured by Nippon Shokubai Co., Ltd.), SEP (styrene-ethylene-propylene copolymer: Septon 1020, manufactured by Kuraray Co., Ltd.), SEPS (styrene-ethylene-propylene-styrene copolymer: Septon 2002, Septon 2004F, Septon 2005, Septon 2006, Septon 2063, Septon 2104, all manufactured by Kuraray Co., Ltd.), SEEPS (styrene-ethylene / ethylene-propylene-styrene block copolymer: Septon 4003, Septon 4044, Septon 4055, Septon 4077, Septon 4099, all manufactured by Kuraray Co., Ltd.), SEBS (styrene-ethylene-butylene-styrene copolymer: Septon 4003, Septon 4044, Septon 4055, Septon 4077, Septon 4099, all manufactured by Kuraray Co., Ltd.), Examples of suitable block copolymers include Septon 8004, Septon 8006, and Septon 8007L (all manufactured by Kuraray Co., Ltd.), SEEPS-OH (a styrene-ethylene / ethylene-propylene-styrene block copolymer having a terminal hydroxyl group: Septon HG252, manufactured by Kuraray Co., Ltd.), SIS (styrene-isoprene-styrene block copolymer: Septon 5125 and Septon 5127, both manufactured by Kuraray Co., Ltd.), hydrogenated SIS (hydrogenated styrene-isoprene-styrene block copolymer: Hybrar 7125F and Hybrar 7311F, both manufactured by Kuraray Co., Ltd.), and SIBS (styrene-isobutylene-styrene block copolymer: SIBSTAR 073T, SIBSTAR 102T, and SIBSTAR 103T (all manufactured by Kaneka Corporation), and Septon V9827 (manufactured by Kuraray Co., Ltd.)), but are not limited to these. These may be used alone or in combination. Polystyrene and its modified products are preferably free of unsaturated bonds, since they have higher heat resistance and are less susceptible to oxidative degradation. The weight-average molecular weight of polystyrene and its modified products is not particularly limited as long as it is 10,000 or more, but if it is too large, compatibility with not only polyphenylene ether compounds but also low-molecular-weight components with a weight-average molecular weight of about 50 to 1,000 and oligomer components with a weight-average molecular weight of about 1,000 to 5,000 deteriorates, making it difficult to ensure mixing and solvent stability. Therefore, the weight-average molecular weight is preferably about 10,000 to 300,000.

[0109] [Polyethylene and its modified products] Polyethylene and its modified products are polyethylene or compounds having a polyethylene-derived structure in the molecule. Examples of polyethylene and its modified products include, but are not limited to, ethylene-propylene copolymers, ethylene-styrene copolymers, ethylene-propylene-ethylidene norbornene copolymers (EBT: K-8370EM, K-9330M, etc., manufactured by Mitsui Chemicals, Inc.), ethylene-propylene-vinyl norbornene copolymers (VNB-EPT: PX-006M, PX-008M, PX-009M, etc., manufactured by Mitsui Chemicals, Inc.), ethylene-vinyl alcohol copolymers, and ethylene-vinyl acetate copolymers. From the viewpoint of improving heat resistance, it is preferable to use ethylene-propylene-ethylidene norbornene copolymers or ethylene-propylene-vinyl norbornene copolymers containing a crosslinkable structure. These may be used alone or in combination. There are no particular restrictions on the weight-average molecular weight of polyethylene and modified polyethylenes thereof as long as it is 10,000 or more. However, if it is too large, compatibility with not only polyphenylene ether compounds but also low-molecular-weight components with a weight-average molecular weight of about 50 to 1,000 and oligomer components with a weight-average molecular weight of about 1,000 to 5,000 deteriorates, making it difficult to ensure mixing and solvent stability. Therefore, it is preferably about 10,000 to 300,000.

[0110] [Benzoxazine compounds] Any benzoxazine compound may be used as long as it is a compound obtained by reacting a compound having a phenolic hydroxyl group, a compound having an amino group, or a compound having an aldehyde group. The compound having a phenolic hydroxyl group is not particularly limited, but examples thereof include the aforementioned phenolic resins, phenols (which may have a substituent such as an alkenyl group or an alkyl group), and bisphenols. The compound having an amino group is not particularly limited, but examples thereof include the aforementioned amine resins, diamines, and anilines (which may have a substituent such as an alkenyl group or an alkyl group). The aldehyde compound may be, for example, the aforementioned aldehydes, but formaldehyde is preferred. Commercially available benzoxazine compounds may be used, such as benzoxazine Pd, Fa, and ALP-d (all manufactured by Shikoku Chemical Industry Co., Ltd.), JBZ-BA100N, JBZ-FA100N, JBZ-DP100N, JBZ-OP100N, JBZ-OP100D, and JBZ-OP100I (all manufactured by JFE Chemical Corporation), and BTBz (manufactured by Japan Material Technology Co., Ltd.).

[0111] The curable resin composition of this embodiment can be obtained by preparing the above components in a predetermined ratio, pre-curing the composition at 130 to 180°C for 30 to 500 seconds, and then post-curing the composition at 150 to 200°C for 2 to 15 hours, thereby allowing the curing reaction to proceed sufficiently and producing the cured product of this embodiment. Alternatively, the components of the curable resin composition can be uniformly dispersed or dissolved in a solvent or the like, and the solvent can be removed before curing.

[0112] The method for preparing the curable resin composition of this embodiment is not particularly limited, and the components may be simply mixed uniformly, or may be prepolymerized. For example, a mixture containing the compound of this embodiment is heated in the presence or absence of a curing accelerator or a polymerization initiator, and in the presence or absence of a solvent, to form a prepolymer. Similarly, compounds such as amine compounds, compounds having ethylenically unsaturated bonds, maleimide compounds, cyanate ester compounds, polybutadiene and modified products thereof, polystyrene and modified products thereof, inorganic fillers, and other additives may be added to form a prepolymer. The components may be mixed or prepolymerized using, for example, an extruder, kneader, or rolls in the absence of a solvent, or a reaction kettle equipped with a stirrer in the presence of a solvent.

[0113] To achieve uniform mixing, the materials are 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 resulting resin composition is then pulverized and molded into cylindrical tablets using a molding machine such as a tablet machine, or into granular powder or powder-like molded products. Alternatively, these compositions can be melted on a surface support and molded into a sheet with a thickness of 0.05 mm to 10 mm to obtain a molded curable resin composition. The resulting molded product is non-sticky at 0 to 20°C, and exhibits little loss of fluidity or curability even when stored at -25 to 0°C for one week or more. The resulting molded article can be molded into a cured product using a transfer molding machine or a compression molding machine.

[0114] The curable resin composition of this embodiment can also be made into a varnish-like composition (hereinafter simply referred to as varnish) by adding an organic solvent. The curable resin composition of this embodiment can be dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, or N-methylpyrrolidone as needed to form a varnish. This varnish can then be impregnated into a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, or paper, and heated and dried to obtain a prepreg. This prepreg can then be hot-press molded to form a cured product of the curable resin composition of this embodiment. The solvent used here accounts for 10 to 70 wt %, preferably 15 to 70 wt %, of the mixture of the curable resin composition of this embodiment and the solvent. Furthermore, if the composition is in liquid form, a cured product containing carbon fiber can be obtained directly, for example, by the RTM method.

[0115] The curable resin composition of this embodiment can also be used as a modifier for film-type compositions. Specifically, it can be used to improve flexibility and the like 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 this embodiment as a 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 a multilayer substrate or the like.

[0116] The curable resin composition of this embodiment can also be used to obtain a prepreg by heating and melting it to reduce its viscosity and impregnating it into reinforcing fibers such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, and alumina fiber. 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; and organic fibers such as polyparaphenylene terephthalamide (Kevlar®, manufactured by DuPont), wholly aromatic polyamide, polyester, polyparaphenylene benzoxazole, polyimide, and carbon fiber, but are not limited thereto. The shape of the substrate is not particularly limited, but examples include woven fabric, nonwoven fabric, roving, and chopped strand mat. Known weaving methods for woven fabrics include plain weave, saddle-weave, and twill weave, and these known methods can be appropriately selected depending on the intended application and performance. Also suitable are woven fabrics that have been opened or glass woven fabrics that have been surface-treated with a silane coupling agent or the like. The thickness of the substrate is not particularly limited, but is preferably about 0.01 to 0.4 mm. Also, a prepreg can be obtained by impregnating reinforcing fibers with the varnish and drying them by heating.

[0117] A laminate can also be manufactured using the prepreg. The laminate is not particularly limited as long as it includes one or more prepregs, and may also include any other layers. The method for manufacturing the laminate can be any generally known method, and is not particularly limited. For example, when molding a metal foil-clad laminate, a multi-stage press, a multi-stage vacuum press, a continuous molding machine, an autoclave molding machine, or the like can be used. The prepregs are laminated together and then heated and pressure molded to obtain a laminate. The heating temperature is not particularly limited, but is preferably 65 to 300°C, more preferably 120 to 270°C. The pressure applied is also not particularly limited, but if the pressure is too high, it becomes difficult to adjust the resin solid content of the laminate, resulting in unstable quality. If the pressure is too low, air bubbles will form and adhesion between the laminate layers will be poor. Therefore, a pressure of 2.0 to 5.0 MPa is preferred, and 2.5 to 4.0 MPa is more preferred. The laminate of this embodiment, having a layer made of metal foil, can be suitably used as a metal foil-clad laminate, as described below. The prepreg is cut into a desired shape and laminated with copper foil or the like as needed. The laminate is then heated and cured while applying pressure 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.

[0118] The curable resin composition of this embodiment can also be made into a resin sheet. A method for obtaining a resin sheet from the curable resin composition of this embodiment includes, for example, applying the curable resin composition to a support film (support) and then drying to form a resin composition layer on the support film. When the curable resin composition of this embodiment is used for a resin sheet, it is essential that the film softens under the lamination temperature conditions (70°C to 140°C) in a vacuum lamination method and exhibits fluidity (resin flow) that allows resin filling of via holes or through holes present in the circuit board simultaneously with lamination of the circuit board. It is preferable to blend the above-mentioned components so as to exhibit such properties. The resulting resin sheet or circuit board (e.g., copper-clad laminate) is required to have a uniform appearance in order to exhibit consistent performance at any location without causing phenomena such as locally varying property values due to phase separation.

[0119] Here, the diameter of the through-holes in the circuit board is 0.1 to 0.5 mm, and the depth is 0.1 to 1.2 mm, and it is preferable to make it possible to fill the resin within this range. When laminating both sides of the circuit board, it is desirable to fill about half of the through-holes.

[0120] A specific method for producing the resin sheet includes preparing a resin composition varnished by blending an organic solvent, applying the varnished resin composition to the surface of a support film (Y), and then drying the organic solvent by heating or blowing hot air, etc., to form a resin composition layer (X).

[0121] The organic solvent used here preferably includes, for example, ketones such as acetone, methyl ethyl ketone, and cyclohexanone; acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; dimethylformamide, dimethylacetamide, and N-methylpyrrolidone; and it is preferable to use the organic solvent in such a proportion that the nonvolatile content is 30 to 60% by mass of the total.

[0122] The thickness of the resin composition layer (X) to be formed must be equal to or greater than the thickness of the conductor layer of the circuit board to which the resin composition layer (X) is laminated. Since the thickness of the conductor layer of the circuit board is in the range of 5 to 70 μm, the thickness of the resin composition layer (X) is preferably 10 to 100 μm. The resin composition layer (X) in this embodiment may be protected with a protective film, which will be described later. Protection with a protective film can prevent the adhesion of dust and the like to the surface of the resin composition layer (X) and scratches.

[0123] Examples of the support film (Y) and protective film include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride; polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate; polycarbonate; polyimide; and release paper and metal foils such as copper foil and aluminum foil. The support film (Y) and protective film may be subjected to a mud treatment, a corona treatment, or a release treatment. The thickness of the support film (Y) is not particularly limited, but is generally in the range of 10 to 150 μm, preferably 25 to 50 μm. The thickness of the protective film is preferably 1 to 40 μm.

[0124] The support film (Y) is peeled off after laminating the resin composition layer (X) onto a circuit board, or after forming an insulating layer by heat-curing the resin composition layer (X). Peeling off the support film (Y) after the resin composition layer (X) constituting the resin sheet has been heat-cured can prevent the adhesion of dust and the like during the curing process. When peeling off the support film (Y) after curing the resin composition layer (X), the support film (Y) is previously subjected to a release treatment.

[0125] The resin sheet obtained as described above can be used to produce a multilayer printed circuit board. For example, when the resin composition layer (X) is protected with a protective film, the protective film is peeled off, and then the resin composition layer (X) is laminated onto one or both sides of the circuit board so as to be in direct contact with the circuit board, for example, by a vacuum lamination method. The lamination method may be a batch method or a continuous method using a roll. If necessary, the resin sheet and the circuit board may be heated (preheated) before lamination. The lamination conditions are preferably a pressure bonding temperature (lamination temperature) of 70 to 140°C and a pressure bonding pressure of 1 to 11 kgf / cm. 2 (9.8×10 4 ~107.9×10 4 N / m 2 ), and lamination is preferably carried out under reduced air pressure of 20 mmHg (26.7 hPa) or less.

[0126] The curable resin composition of the present embodiment can be used to manufacture semiconductor devices, such as dual in-line packages (DIPs), quad flat packages (QFPs), ball grid arrays (BGAs), chip size packages (CSPs), small outline packages (SOPs), thin small outline packages (TSOPs), and thin quad flat packages (TQFPs).

[0127] The curable resin composition and the cured product thereof according to this embodiment can be used in a wide range of fields. Specifically, it can be used for various applications such as molding materials, adhesives, composite materials, paints, etc. Since the cured product of the curable resin composition described in this embodiment exhibits excellent heat resistance and dielectric properties, it is used as a sealing material for semiconductor elements, a sealing material for liquid crystal display elements, a sealing material for organic EL elements, a laminate (printed wiring board, substrate for BGA, build-up substrate, etc.), etc. It is preferably used for electrical and electronic components, composite materials for lightweight and high-strength structural materials such as carbon fiber reinforced plastics and glass fiber reinforced plastics, and 3D printing.

Examples

[0128] Next, the present invention will be described more specifically with reference to examples. Hereinafter, unless otherwise specified, "parts" refers to parts by mass. Note that this embodiment is not limited to these examples.

[0129] The following describes various analysis methods used in the examples. <High Performance Liquid Chromatography (HP-LC)> HP-LC: Liquid delivery unit (LC-20AB), online degasser (DGU-20A3), autosampler (SIL-20A), column oven (CTO-20A), system controller (CBM-20A), absorbance detector (SPD-M20A) (all manufactured by Shimadzu Corporation) Column: ODS-2 (manufactured by GL Sciences Inc.) Linked eluent: Tetrahydrofuran: Water = 3:1 (no gradient) Flow rate: 0.5 ml / min. Column temperature: 40°C Detection: PDA (Photodiode Array Detector) <GPC (Gel Permeation Chromatography) Analysis> Column: SHODEX GPC KF-601 (2 pieces), KF-602, KF-602.5, KF-603 Flow rate: 1.5 ml / min. Column temperature: 40°C Solvent used: THF (Tetrahydrofuran) Detector: Differential refractive index detector (RID-20A, manufactured by Shimadzu Corporation)

[0130] [Example 1] A flask equipped with a thermometer, a condenser, a stirrer, and a Dean-Stark tube was purged with nitrogen, and 16.6 parts of fluorene, 8.3 parts of xylene formaldehyde resin (Nikanol (registered trademark) LL, manufactured by Fudow Co., Ltd.), 16.6 parts of methylcyclohexane, and 1.2 parts of p-toluenesulfonic acid were added, heated to 100 ° C., and the reaction was continued for 2 hours while removing the generated water from the system by azeotropic dehydration using a Dean-Stark tube. The internal temperature was then cooled to 80 ° C., and 0.3 parts of sodium hydroxide was added. Thereafter, methylcyclohexane was recovered until the internal temperature reached 140 ° C., and the mixture was cooled to an internal temperature of 80 ° C., followed by the addition of 100 parts of dimethyl sulfoxide and 12 parts of sodium hydroxide, and the mixture was stirred at 60 ° C. for 30 minutes. Thereafter, while maintaining the internal temperature at 65°C or below, 29.0 parts of CMS-14 (AGC Seimi Chemical Co., Ltd., mixture of 4-chloromethylstyrene and 3-chloromethylstyrene, 4-chloromethylstyrene:3-chloromethylstyrene=95:5 (molar ratio), purity 96.87% by weight) was added dropwise over 30 minutes, and the reaction was carried out at 65°C for 2 hours. 150 parts of toluene was added, and the organic layer was washed five times with 100 parts of water. The obtained organic layer was concentrated to obtain 17.6 parts of compound (F1) represented by the following formula (f-1). The HPLC chart of the obtained compound (F1) is shown in Figure 1. 1 The H-NMR data (deuterated chloroform) is shown in Figure 2. 1In the H-NMR chart, a signal derived from the terminal hydrogen of the vinyl group (two hydrogens per vinyl group) was observed at 4.90-5.56 ppm, a signal derived from the methylene bond derived from the n repeating unit was observed at 3.76-4.26 ppm, a signal derived from the methylene bond derived from the q repeating unit was observed at 3.40-3.76 ppm, and a signal derived from the methylene structure of R2 was observed at 3.04-3.26 ppm. The integral value of the peak derived from the terminal hydrogen of the vinyl group was 8.00, the integral value of the peak derived from the hydrogen of the methylene site modified with R2 was 1.03, the sum of the integral values of the peaks derived from each hydrogen of the methylene bond site derived from the q repeating unit was 0.56, and the integral value of the peak derived from each hydrogen of the methylene bond site derived from the n repeating unit was 2.10. The average value k of k in the following formula (f-1) calculated from this was ave The value of was 0.17, the value of q was 1.53, and the value of n was 0.53. The GPC chart of the obtained compound (F1) is shown in Figure 3. The number average molecular weight Mn of compound (F1) was 447, and the weight average molecular weight Mw was 619.

[0131] [ka]

[0132] In the above formula (f-1), multiple R2s represent hydrocarbon groups represented by the following formula (fa).

[0133] [ka]

[0134] In the above formula (fa), * represents the bonding position to the fluorene structure of formula (f-1).

[0135] [Comparative Synthesis Example 1] A flask equipped with a thermometer, a condenser, and a stirrer was purged with nitrogen. 133 parts of methyl isobutyl ketone (hereinafter also referred to as MIBK), 33.3 parts of fluorene, 1.9 parts of tetrabutylammonium bromide, 0.49 parts of hydroquinone, and 64 parts of 50 wt% aqueous sodium hydroxide solution were added, and the internal temperature was raised to 60 ° C. Subsequently, 71.2 parts of CMS-P (AGC Seimi Chemical Co., Ltd., mixture of 4-chloromethylstyrene and 3-chloromethylstyrene, 4-chloromethylstyrene:3-chloromethylstyrene = 1:1 (molar ratio), purity 95.59 wt%) was added dropwise over 1 hour, and the reaction was allowed to proceed at 60 ° C. for 9 hours. The mixture was neutralized with 41.6 parts of 35 wt% aqueous hydrochloric acid, and the organic layer was washed three times with 100 parts of water. Recrystallization with toluene and methanol yielded 35.6 parts of compound (F2) represented by the following formula (f-2). The HPLC chart of the obtained compound (F2) is shown in Figure 4. 1 The H-NMR data (deuterated chloroform) is shown in Figure 5.

[0136] [ka]

[0137] [Example 2, Comparative Examples 1 and 2] The compounds (F1, F2) obtained in Example 1 and Comparative Synthesis Example 1, and OPE-2St (a polyphenylene ether compound manufactured by Mitsubishi Gas Chemical Co., Ltd.) were used in the amounts shown in Table 1, and were sandwiched between mirror-finished copper foils (T4X, manufactured by Fukuda Metal Copper Foil Co., Ltd.) and vacuum-press molded, followed by curing at 220°C for 2 hours. A 250 μm-thick piece of cushion paper with a 150 mm x 150 mm hole cut out from the center was used as a spacer. For evaluation, test pieces were cut to the desired size using a laser cutter as needed, and evaluation was performed.

[0138] <Dielectric constant test / dielectric loss tangent test> Tests were conducted at 25°C using a 10 GHz cavity resonator manufactured by AET Co., Ltd. using the cavity resonator perturbation method. The sample size was 1.7 mm wide x 100 mm long, and 0.3 mm thick. The evaluation results are shown in Table 1.

[0139] [Table 1]

[0140] From the results in Table 1, it was confirmed that the compounds of the present invention have smaller dielectric loss tangents than those of Comparative Examples 1 and 2, and are excellent in low dielectric properties.

[0141] <Curing test> [Reference example 1] 5 parts of the compound (F1) obtained in Example 1, 20 parts of NC-3000 (manufactured by Nippon Kayaku Co., Ltd., biphenylaralkyl type epoxy resin), 0.5 parts of MDEA: 4,4'-methylenebis(2-ethyl-6-methylaniline) (manufactured by Tokyo Chemical Industry Co., Ltd., amine compound), 1 part of DICY: dicyandiamide (manufactured by Tokyo Chemical Industry Co., Ltd., amide compound), 0.5 parts of KAYAHARD MCD (manufactured by Nippon Kayaku Co., Ltd., acid anhydride compound), KAYAHARD 0.5 parts of GPH-65 (manufactured by Nippon Kayaku Co., Ltd., biphenyl aralkyl type phenol resin), 0.5 parts of Unifiner W-575 (manufactured by Unitika Ltd., activated ester resin), 0.5 parts of G4-142MHR (manufactured by Nippon Kayaku Co., Ltd., carboxylic acid compound), 2.5 parts of MIR-3000-70MT (manufactured by Nippon Kayaku Co., Ltd., maleimide compound), 2.5 parts of MIZ-001 (manufactured by Nippon Kayaku Co., Ltd., maleimide compound), 0.5 parts of phenylmaleimide (manufactured by Tokyo Chemical Industry Co., Ltd., maleimide compound), 0.5 parts of SYTESTER TA (manufactured by Mitsubishi Gas Chemical Co., Ltd., bisphenol A type cyanate resin), 60 parts of OPE-2st 2200 (manufactured by Mitsubishi Gas Chemical Co., Ltd., polyphenylene ether compound), 3 parts of STR-2000 (manufactured by Nippon Kayaku Co., Ltd., compound having an ethylenic unsaturated bond), KAYARAD R-684 (manufactured by Nippon Kayaku Co., Ltd., compound having an ethylenically unsaturated bond) 1 part, acenaphthylene (manufactured by Tokyo Chemical Industry Co., Ltd., compound having an ethylenically unsaturated bond) 0.5 parts, 1 part of a polyimide compound obtained by the method described in WO2023 / 013224A1, TAIC: triallyl isocyanurate (manufactured by Mitsubishi Chemical Corporation, allyl compound) 1 part, Septon 2104 (manufactured by Kuraray Co., Ltd., modified polystyrene) 1 part, Pd-type benzoxazine (manufactured by Shikoku Chemical Industry Co., Ltd., benzoxazine compound) 1 part, 2E4MZ: 2-ethyl-4-methylimidazole (manufactured by Shikoku Chemical Industry Co., Ltd., curing accelerator) 0.5 parts, TPP: triphenylphosphine (manufactured by Hokko Chemical Industry Co., Ltd., curing accelerator) 0.5 parts, Octope Zn (manufactured by Hope Pharmaceutical Co., Ltd., curing accelerator) 0.1 parts, San-Aid 0.1 parts of SI-B5 (Sanshin Chemical Co., Ltd., curing accelerator), 1 part of DCP: dicumyl peroxide (Kayaku Nouryon Co., Ltd., polymerization initiator), 99.2 parts of toluene as a solvent, 49.The mixture was mixed at a ratio of 6 parts and heated at 110°C for 10 minutes and then at 220°C for 1 hour in a nitrogen atmosphere to obtain a cured product.

[0142] [Reference example 2] A mixture of 5 parts of the compound (F1) obtained in Example 1, 50 parts of NC-3000 (a biphenylaralkyl epoxy resin manufactured by Nippon Kayaku Co., Ltd.), 10 parts of MIZ-001 (a maleimide compound manufactured by Nippon Kayaku Co., Ltd.), 5 parts of STR-2000 (a compound having an ethylenically unsaturated bond manufactured by Nippon Kayaku Co., Ltd.), 45 parts of KAYARAD R-684 (a compound having an ethylenically unsaturated bond manufactured by Nippon Kayaku Co., Ltd.), 1 part of Irgacure OXE-04 (a polymerization initiator manufactured by BASF), and 1 part of Irgacure 290 (a polymerization initiator manufactured by BASF) was applied to a PET film to a thickness of 100 μm. A PET film was also attached to the side not in contact with the film, and the mixture was exposed to light of 3000 mJ / cm 2 using a high-pressure mercury lamp (365 nm). 2 A cured product was obtained by irradiating the composition with ultraviolet light. [Industrial Applicability]

[0143] The compound of the present invention is suitably used in electric and electronic parts such as semiconductor encapsulants, printed wiring boards, build-up laminates, and optical waveguide devices.

Claims

1. A compound represented by the following formula (1): 【Chemical 1】 In the above formula (1), there are multiple R １ and R ３ Each of R independently represents a hydrocarbon group having 1 to 5 carbon atoms. ２ Each independently represents a hydrocarbon group represented by the following formula (a). Multiple p's each independently represent an integer of 0 to 4. q is the average number of repetitions, and 1<q≦20. Multiple l's each independently represent an integer of 0 to 4. Multiple k's each independently represent an integer of 0 to 3, and the average k's k ａｖｅ is 0<k ａｖｅ ≦3. n is the average number of repetitions and represents a number from 0.05 to 20. 【Chemistry 2】 In the above formula (a), * represents the bonding position to the fluorene structure of formula (1). ４ each independently represents a hydrocarbon group having 1 to 5 carbon atoms, and each m independently represents an integer of 0 to 5.

2. A compound obtained by reacting a compound represented by the following formula (A) with a compound represented by the following formula (B): 【Chemistry 3】 In the above formula (A), there are multiple R ２ Each of R independently represents a hydrocarbon group represented by the following formula (a): ３ Each of the plural p's independently represents an integer of 0 to 4. The symbol q represents the average number of repeats, and 1<q≦20. Each of the plural k's independently represents an integer of 0 to 3, and the average value of k's is k ａｖｅ is 0<k ａｖｅ ≦3. n is the average number of repetitions and represents a number from 0.05 to 20. 【Chemistry 4】 In the above formula (a), * represents the bonding position to the fluorene structure of formula (A). ４ each independently represents a hydrocarbon group having 1 to 5 carbon atoms, and each m independently represents an integer of 0 to 5. 【Chemistry 5】 In the above formula (B), there are multiple R １ each independently represents a hydrocarbon group having 1 to 5 carbon atoms, l represents an integer of 0 to 4, and X represents a halogen atom.

3. A curable resin composition containing the compound according to claim 1 or 2.

4. The curable resin composition according to claim 3, further comprising at least one selected from the group consisting of a curing accelerator, a polymerization initiator, an epoxy resin, an active ester compound, a phenolic resin, a polyphenylene ether compound, an amine resin, a compound having an ethylenically unsaturated bond, an isocyanate resin, a polyamide resin, a maleimide compound, a cyanate ester resin, a polyimide resin, polybutadiene and modified products thereof, polystyrene and modified products thereof, polyethylene and modified products thereof, and a benzoxazine compound.

5. A cured product obtained by curing the compound according to claim 1 or 2.

6. A cured product obtained by curing the curable resin composition according to claim 3.

7. A method for producing a compound represented by the following formula (1), which is obtained by reacting a compound represented by the following formula (A) with a compound represented by the following formula (B) in an aprotic polar solvent in the presence of a basic catalyst. 【Chemistry 6】 In the above formula (A), there are multiple R ２ Each of R independently represents a hydrocarbon group represented by the following formula (a): ３ Each of the plural p's independently represents an integer of 0 to 4. The symbol q represents the average number of repeats, and 1<q≦20. Each of the plural k's independently represents an integer of 0 to 3, and the average value of k's is k ａｖｅ is 0<k ａｖｅ ≦3. n is the average number of repetitions and represents a number from 0.05 to 20. 【Chemistry 7】 In the above formula (a), * represents the bonding position to the fluorene structure of formula (A). ４ each independently represents a hydrocarbon group having 1 to 5 carbon atoms. A plurality of m's each independently represents an integer of 0 to 5. 【Chemistry 8】 In the above formula (B), there are multiple R １ each independently represents a hydrocarbon group having 1 to 5 carbon atoms, l represents an integer of 0 to 4, and X represents a halogen atom. 【Chemistry 9】 In the above formula (1), there are multiple R １ and R ３ Each of R independently represents a hydrocarbon group having 1 to 5 carbon atoms. ２ Each independently represents a hydrocarbon group represented by the following formula (a). Multiple p's each independently represent an integer of 0 to 4. q is the average number of repetitions, and 1<q≦20. Multiple l's each independently represent an integer of 0 to 4. Multiple k's each independently represent an integer of 0 to 3, and the average k's k ａｖｅ is 0<k ａｖｅ ≦3. n is the average number of repetitions and represents a number from 0.05 to 20. 【Chemistry 10】 In the above formula (a), * represents the bonding position to the fluorene structure of formula (1). ４ Each of R independently represents a hydrocarbon group having 1 to 5 carbon atoms. ２ In formula (a), m's each independently represent an integer of 0 to 5.

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