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

Abstract

Provided are a compound having excellent low dielectric properties, a curable resin composition, and a cured product thereof. 【Solution means】 It is an allyl ether-modified phenyl aralkyl resin represented by the following formula (1). TIFF0007716605000030.tif53170 In formula (1), R1 and R3 represent a hydrocarbon group having 1 to 5 carbon atoms. R2 represents a hydrocarbon group represented by formula (a). p represents an integer of 0 to 4. q is the average value of the number of repetitions, and 1 < q ≦ 20. l represents an integer of 0 to 4. k 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 number of repetitions and represents a number of 0.05 to 20. TIFF0007716605000031.tif11170

Description

Technical Field

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

Background Art

[0002] In recent years, due to the expansion of the application fields of laminated boards on which electrical and electronic components are mounted, the required characteristics have become extensive and sophisticated. Conventionally, semiconductor chips were mainly mounted on metal lead frames, but semiconductor chips with high processing capabilities such as central processing units (hereinafter referred to as CPUs) are increasingly being mounted on laminated boards made of polymer materials.

[0003] In the currently accelerating development of the fifth-generation communication system "5G", further increases in capacity and high-speed communication are expected. In 5G, the frequency used will be increased, but in order to realize high-speed communication using high frequencies, it is important to reduce transmission loss, and further low dielectric characteristics of the substrate material are required. The transmission loss occurring on a printed circuit board is derived from conductor loss and dielectric loss. As described in Non-Patent Document 1, the dielectric loss α D is proportional to the square root of the relative permittivity ε r of the dielectric and the dielectric tangent tanδ. Therefore, it can be said that it is effective to improve the dielectric tangent tanδ having a higher contribution degree than the relative permittivity ε r or more for reducing transmission loss. Examples of low dielectric materials include thermoplastic materials typified by PTFE (polytetrafluoroethylene) and LCP (liquid crystal polymer), but they have poor moldability compared to thermosetting resins. Based on this, the development of thermosetting resins having excellent low dielectric characteristics is desired.

[0004] In view of such a background, polymer materials with excellent low dielectric properties have been studied. 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, on the other hand, since phenolic hydroxyl groups that do not participate in the reaction remain during the curing reaction, the electrical properties are not sufficient. Patent Document 2 discloses an allyl ether-modified biphenyl aralkyl novolak resin to which an allyl group is added together with a phenolic hydroxyl group. However, it has been shown that the allyl ether-modified biphenyl aralkyl novolak resin undergoes a Claisen rearrangement at 190 °C, and at 200 °C, which is the molding temperature of a general substrate, phenolic hydroxyl groups that do not contribute to the curing reaction are generated, so that the electrical properties cannot be satisfied.

Prior Art Documents

Non-Patent Documents

[0005]

Non-Patent Document 1

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0007] The present invention has been made in view of such a situation, and an object thereof is to provide a compound, a curable resin composition, and a cured product thereof having excellent low dielectric properties.

Means for Solving the Problems

[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 the 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 the 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), 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. A plurality of ps each independently represent an integer of 0 to 4. q is the average value of the number of repetitions, and 1 < q ≦ 20. A plurality of ks each independently represent an integer of 0 to 3, and the average value k ave of k is 0 < k ave ≦ 3. n is the average value of the number of repetitions 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). A plurality of R4s each independently represent a hydrocarbon group having 1 to 5 carbon atoms. A plurality of ms each independently represent an integer of 0 to 5.

[0017] [Chemical formula]

[0018] In the above formula (B), a plurality of R1s each independently represent 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 previous item [1] or [2]. [4] Furthermore, at least one 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 is contained in the curable resin composition according to the previous item [3]. [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 of 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 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), the plurality of R1 each independently represents a hydrocarbon group having 1 to 5 carbon atoms. The 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), the plurality of R1 and R3 each independently represents a hydrocarbon group having 1 to 5 carbon atoms. The plurality of R2 each independently represents a hydrocarbon group represented by the following formula (a). The 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. The plurality of l each independently represents an integer of 0 to 4. The 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). The plurality of R4 each independently represents a hydrocarbon group having 1 to 5 carbon atoms. The 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

Figure 2

Figure 3

Figure 4

Figure 5

Mode for Carrying Out the Invention

[0031] Hereinafter, embodiments according to the present invention (hereinafter also referred to as "the present embodiments") 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 R1 each independently represents a hydrocarbon group having 1 to 5 carbon atoms, preferably a hydrocarbon group having 1 to 3 carbon atoms. 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, preferably a hydrocarbon group having 1 to 3 carbon atoms. When the number of carbon atoms is 5 or less, it is difficult for the molecule to vibrate when exposed to high frequencies, so the electrical properties are excellent. A plurality of p each independently represents 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 improvement 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, preferably 1.1 ≦ q ≦ 7.5, and still more preferably 1.2 ≦ q ≦ 5. 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, and from the viewpoints of solvent solubility and heat resistance, 0 < k aveIt is more preferably ≤2. A plurality of l each independently represents an integer of 0 to 4, preferably 1. n is the average value of the number of repetitions and represents a number of 0.05 to 20. From the viewpoints of heat resistance and solvent solubility, n is preferably 0.05 to 15, preferably 0.1 to 12.5, more preferably 0.5 to 10, and particularly preferably 1 to 10.

[0035] As the molecular weight of the compound represented by the above formula (1), in the analysis result using a differential refractive index detector in GPC (gel permeation chromatography) analysis, the number average molecular weight is preferably 100 to 10,000, more preferably 125 to 7,500, and even more preferably 150 to 5,000. When the number average molecular weight is less than 100, there is a risk that the heat resistance may decrease due to the remaining of raw materials, etc., and tackiness may occur during B-stage formation. When the number average molecular weight exceeds 10,000, due to the increase in the viscosity of the compound, there is a risk that the circuit embedding property may be impaired and the solvent solubility may decrease. Also, as the weight average molecular weight, it is preferably 100 to 10,000, preferably 125 to 7,500, and even more preferably 150 to 5,000. When the weight average molecular weight is less than 100, there is a risk that the heat resistance may decrease due to the remaining of raw materials, etc., and tackiness may occur during B-stage formation. When the weight average molecular weight exceeds 10,000, due to the increase in the viscosity of the compound, there is a risk that the circuit embedding property may be impaired and the solvent solubility may decrease.

[0036] [Chemical formula]

[0037] In the above formula (a), * represents the bonding position to the fluorene structure of formula (1). A plurality of R4 each independently represents 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, it is difficult for molecular vibration to occur when exposed to high frequencies, so the electrical properties are excellent. m each independently represents an integer of 0 to 5, preferably 1 to 3, and more preferably 2 to 3.

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

[0039]

Chemical formula

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

[0041]

Chemical formula

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

[0043]

Chemical formula

[0044] In the above formula (B), R1 is the same as that in the above formula (1). The value and preferred range of l are the same as those 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 the compound represented by the above formula (1), when the number of moles of the compound represented by the above formula (A) is α and the number of moles of the compound represented by the above formula (B) is β, it is preferable that β / α is 1.8 or more and 2.1 or less, more preferably 1.8 or more and 2.0 mol or less, and particularly preferably 1.8 or more and 1.95 or less. When β / α is less than 1.8, the compound represented by the above 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 the above formula (A) does not have a cross-linkable structure, and oxygen reacts with the methylene structure at the 9-position of the fluorene structure of the compound represented by the above formula (A) to form a ketone, increasing the polarity. When β / α is greater than 2.1, the halogen element of the compound represented by the above formula (B) that could not be completely removed by purification may desorb during curing (for example, at a temperature of 175 °C or higher) or during a high-temperature and high-humidity test (85 °C, humidity 85% or 120 °C, humidity 100%, etc.), leading to corrosion of the copper wiring. The residual halogen content in the mixture containing the compound of this embodiment is preferably 1 to 10000 ppm, more preferably 1 to 3000 ppm, and even more preferably 1 to 2000 ppm. Here, "residual halogen" is 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), and is derived from unreacted raw material compounds and impurities contained in the raw material compounds.

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

[0047] When the reaction is carried out without using an aprotic polar solvent, the reaction rate significantly decreases. When an aprotic polar solvent is not used, generally the reaction is carried out using an interphase transfer catalyst. In this case, the raw materials are dissolved in a water-insoluble solvent such as toluene, and the compounds represented by the above formula (A) and the compounds represented by the above formula (B) are reacted in the presence of a basic catalyst such as an aqueous sodium hydroxide solution and an interphase transfer catalyst such as tetrabutylammonium bromide. In this case, it is difficult to completely remove the interphase transfer catalyst such as tetrabutylammonium bromide, and it is difficult to achieve low dielectric characteristics (low dielectric constant · low dielectric tangent). In addition, due to the remaining interphase transfer catalyst, when the substrate material using the compound of this embodiment is subjected to a long-term damp heat reliability test or the like, problems such as ion migration may occur. Therefore, it is preferable to use an aprotic polar solvent.

[0048] The reaction temperature between the compound represented by the above formula (A) and the compound represented by the above formula (B) is preferably 0 to 120 °C, more preferably 0 to 100 °C, and even more preferably 0 to 80 °C. At a temperature higher than 120 °C, self-polymerization of the compound of this embodiment may proceed and gelation may occur. At a temperature lower than 0 °C, the reaction may not proceed sufficiently. When a basic catalyst is used, as a post-treatment after the reaction, neutralization may be carried out with an arbitrary acid compound. Further, if necessary, an alcohol compound, water, etc. may be added to the reaction solution to recover the target product as crystals. Further, the obtained reaction solution or crystals may be redissolved in an arbitrary solvent and an extraction step may be carried out. For the extraction step, an aromatic hydrocarbon solvent such as toluene or xylene may be used alone, or a non-aromatic hydrocarbon 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 solvent is distilled off using an evaporator or the like to obtain the target compound.

[0049] The compound represented by the above 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 an alkylbenzene and formaldehyde typified by m-xylene formaldehyde resin (also called xylene resin). Examples of the alkylbenzene formaldehyde resin include, but are not limited to, 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, 1,2,3,4-tetramethylbenzene formaldehyde resin, 1,2,3,5-tetramethylbenzene formaldehyde resin, 1,2,4,5-tetramethylbenzene formaldehyde resin, 1,3,5-triethylbenzene formaldehyde resin, 1,3,5-tripropylbenzene formaldehyde resin, 1,3,5-triisopropylbenzene formaldehyde resin, 1,3,5-tributylbenzene formaldehyde resin, 1,3,5-tri-t-butylbenzene formaldehyde resin, etc. These may be used alone or in combination of two or more. From the viewpoints of dielectric properties and heat resistance, it is preferably substituted with a hydrocarbon group having 1 to 5 carbon atoms, more preferably substituted with a hydrocarbon group having 1 to 3 carbon atoms, and still more preferably substituted with a methyl group. As the number of carbon atoms of the hydrocarbon group increases, it becomes difficult to ensure the molecular rigidity, and the molecule is likely to vibrate, which causes a decrease in dielectric properties and heat resistance. The amount of the 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 still more preferably 0.25 to 2% by weight based on 1% by weight of the fluorene used.

[0050] When reacting a fluorene-based compound with an alkylbenzene formaldehyde resin, if necessary, in addition to hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, Lewis acids such as aluminum chloride and zinc chloride, solid acids such as activated clay, acid clay, white carbon, zeolite, and silica alumina, and acidic catalysts such as acidic ion exchange resins can be used. These can be used alone or in combination of two or more. The amount of the catalyst used is preferably added in an amount of 0.1 to 40% by weight, preferably 0.1 to 20% by weight, based on the total weight of the fluorene and the alkylbenzene formaldehyde resin used. If the amount of the catalyst used is too large, the viscosity of the reaction solution may be too high and stirring may become difficult. If it is too small, the progress of the reaction may be slow. The reaction may be carried out by selectively using an organic solvent such as hexane, cyclohexane, methylcyclohexane, octane, toluene, xylene, etc. if necessary, or without a solvent. For example, after adding an acidic catalyst to a mixed solution of fluorene, xylene formaldehyde resin, and a solvent (or without a solvent), if the catalyst contains water, the water is removed from the system by azeotropy or the like. Thereafter, the reaction is carried out at 40 to 300 ° C, preferably 50 to 250 ° C for 0.5 to 40 hours. After the reaction is completed, the acidic catalyst may be neutralized with a basic aqueous solution, or the process may proceed to the water washing step without neutralization. For the water washing step, a water-insoluble organic solvent is added to the oil layer and the water washing is repeated until the waste water becomes neutral.

[0051] Regarding the compound represented by the above formula (A) obtained by the above reaction, after adding a neutralizing agent such as an arbitrary basic compound and an aprotic polar solvent to the solution after the reaction, a basic catalyst and the compound represented by the above formula (B) are added, and it may be continuously induced to the compound represented by the above formula (1).

[0052] The softening point of the compound represented by the above formula (A) is preferably 180 °C or lower, more preferably 150 °C or lower. When the softening point is 180 °C or lower, the viscosity when derived into the compound represented by the above formula (1) becomes low. As a result, it becomes easy to ensure fluidity, the impregnation property into glass cloth, carbon fiber, etc. is not impaired, and B-stage formation such as prepreg formation becomes easy. When the dilution solvent is increased to lower the viscosity, there is a possibility that the resin may not sufficiently adhere to the fibrous material in the impregnation step.

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

[0054] [Curing accelerator] The curable resin composition of the present embodiment can also improve the curability by adding a curing accelerator. As the curing accelerator, an anionic curing accelerator that promotes the curing reaction by generating anions by irradiation with ultraviolet rays, visible light, or heating, or a cationic curing accelerator that promotes the curing reaction by generating cations by irradiation with ultraviolet rays, visible light, or heating is preferable.

[0055] Examples of the anionic curing accelerator include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, etc., and 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)-undecene are preferable. In addition, phosphines such as triphenylphosphine, quaternary ammonium salts such as tetrabutylammonium salt, triisopropylmethylammonium salt, trimethyldecanylammonium salt, cetyltrimethylammonium salt, hexadecyltrimethylammonium hydroxide, etc. are included, but are not limited thereto. Further, these may be used alone or in combination of a plurality.

[0056] Examples of cationic curing accelerators include quaternary phosphonium salts such as triphenylbenzylphosphonium salts, triphenylethylphosphonium salts, and tetrabutylphosphonium salts (the counterions of the quaternary salts are halogens, organic acid ions, hydroxide ions, etc., and there is no particular specification, but organic acid ions and hydroxide ions are particularly preferred), tin octylate, zinc carboxylates (zinc 2-ethylhexanoate, zinc stearate, zinc behenate, zinc myristate), zinc phosphate esters (zinc octyl phosphate, zinc stearyl phosphate), and other transition metal compounds (transition metal salts), etc., but are not limited thereto. These may be used alone or in combination of two or more.

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

[0058] [Inorganic filler] The curable resin composition of this embodiment may contain an inorganic filler. Examples of the inorganic filler include powders such as fused silica, crystalline silica, porous silica, alumina, zircon, calcium silicate, calcium carbonate, quartz powder, silicon carbide, silicon nitride, boron nitride, zirconia, aluminum nitride, graphite, forsterite, steatite, spinel, mullite, titania, talc, clay, iron oxide, asbestos, glass powder, etc., or inorganic fillers obtained by shaping these into spherical or crushed forms, etc., but are not limited thereto. These may be used alone or in combination of two or more.

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

[0060] [Polymerization initiator] The curable resin composition of this embodiment can also improve curability by adding a polymerization initiator. A polymerization initiator is a compound capable of polymerizing olefin functional groups such as ethylenically unsaturated bonds, and examples include olefin metathesis polymerization initiators, anionic polymerization initiators, cationic polymerization initiators, radical polymerization initiators, and the like. Among these, it is preferable to use a radical polymerization initiator having curability and appropriate stability. A radical polymerization initiator refers to a compound that generates radicals upon irradiation with ultraviolet rays, visible light, or heating and initiates a chain polymerization reaction. Examples of radical polymerization initiators that can be used include organic peroxides, azo compounds, benzopinacols, etc., and it is preferable to use organic peroxides because they have less influence on the control of curing temperature, outgas suppression, and the electrical properties of decomposition products.

[0061] Examples of the above-mentioned organic peroxides include, but are not limited to, 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; alkyl peresters such as α-cumyl peroxyneodecanoate, t-butyl peroxyneodecanoate, t-butyl peroxy pivalate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, t-amyl peroxy-2-ethylhexanoate, t-butyl peroxy-2-ethylhexanoate, t-amyl peroxy-3,5,5-trimethylhexanoate, t-butyl peroxy-3,5,5-trimethylhexanoate, and t-amyl peroxybenzoate; peroxycarbonates such as di-2-ethylhexyl peroxydicarbonate, bis(4-t-butylcyclohexyl) peroxydicarbonate, t-butyl peroxyisopropyl carbonate, and 1,6-bis(t-butylperoxycarbonyloxy)hexane; and t-butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxy octoate, lauroyl peroxide, etc. These may be used alone or in combination. Among the above-mentioned organic peroxides, ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, alkyl peresters, peroxycarbonates, etc. are preferred, and dialkyl peroxides are more preferred.

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

[0063] As the addition amount of the polymerization initiator, 0.01 to 5 parts by mass, preferably 0.01 to 3 parts by mass, is preferable with respect to 100 parts by mass of the curable resin composition. If the amount of the polymerization initiator used is less than 0.01 part by mass, the molecular weight may not be sufficiently extended during the polymerization reaction, and if it is more than 5 parts by mass, the dielectric properties such as the dielectric constant and the dielectric loss tangent may be impaired.

[0064] [Polymerization inhibitor] The curable resin composition of the present embodiment may contain a polymerization inhibitor. By containing a polymerization inhibitor, the storage stability is improved, and the reaction start temperature can be controlled. By controlling the reaction start temperature, it becomes easy to ensure fluidity, the impregnation property into a glass cloth or the like is not impaired, and B-stage formation such as prepreg formation becomes easy. If the polymerization reaction proceeds too much during prepreg formation, problems such as difficulty in lamination in the lamination process are likely to occur.

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

[0066] Examples of the polymerization inhibitor include phenolic, sulfur-based, phosphorus-based, hindered amine-based, nitroso-based, nitroxyl radical-based, and the like. Further, the polymerization inhibitor may be used alone or in combination of a plurality of kinds. Among these, in the present embodiment, phenolic, hindered amine-based, nitroso-based, and nitroxyl radical-based are preferable.

[0067] Examples of the phenolic polymerization inhibitor include monophenols such as 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, stearyl-β-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, 2,4-bis[(octylthio)methyl]-o-cresol; bisphenols such as 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, calcium bis(3,5-di-t-butyl-4-hydroxybenzylsulfonic acid ethyl); and polyphenols such as 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 such high-molecular 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, tocopherol, etc.

[0068] Examples of the sulfur-based polymerization inhibitors include, but are not limited to, dilauryl-3,3’-thiodipropionate, dimyristyl-3,3’-thiodipropionate, distearyl-3,3’-thiodipropionate, etc.

[0069] Examples of the phosphorus-based polymerization inhibitors include, but are not limited to, phosphites such as triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris(nonylphenyl) phosphite, diisodecyl pentaerythritol phosphite, tris(2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetrayl bis(octadecyl) phosphite, cyclic neopentanetetrayl bis(2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetrayl bis(2,4-di-t-butyl-4-methylphenyl) phosphite, bis[2-t-butyl-6-methyl-4-{2-(octadecyloxycarbonyl)ethyl}phenyl] hydrogen phosphite; and oxaphosphaphenanthrene oxides such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(3,5-di-t-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, etc.

[0070] Examples of the hindered amine polymerization inhibitor include, but are not limited to, AdekaStab (registered trademark) LA-40MP, AdekaStab LA-40Si, AdekaStab LA-402AF, AdekaStab LA-87, AdekaStab LA-82, AdekaStab LA-81, AdekaStab LA-77Y, AdekaStab LA-77G, AdekaStab LA-72, AdekaStab LA-68, AdekaStab LA-63P, AdekaStab LA-57, AdekaStab LA-52 (manufactured by ADEKA CORPORATION); Chimassorb (registered trademark) 2020FDL, Chimassorb944FDL, Chimassorb944LD; Tinuvin (registered trademark) 622SF, TinuvinPA144, Tinuvin765, Tinuvin770DF, TinuvinXT55FB, Tinuvin111FDL, Tinuvin783FDL, Tinuvin791FB (manufactured by BASF), etc.

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

[0072] Examples of the nitroxyl radical polymerization inhibitor include, but are not limited to, 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, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl, etc.

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

[0074] The above phosphorus-based flame retardant may be 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-phenylene bis(dixylenyl phosphate), 1,4-phenylene bis(dixylenyl phosphate), 4,4'-biphenyl (dixylenyl phosphate), etc., phosphanes such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, etc. In addition, phosphorus-containing epoxy compounds obtained by reacting epoxy resins with the active hydrogen of the above phosphanes, red phosphorus, etc. can be mentioned, but are not limited thereto. Also, these may be used alone or in combination of a plurality. Among the above exemplified substances, phosphate esters, phosphanes or phosphorus-containing epoxy compounds are preferred, and 1,3-phenylene bis(dixylenyl phosphate), 1,4-phenylene bis(dixylenyl phosphate), 4,4'-biphenyl (dixylenyl phosphate) or 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 with respect to 100 parts by mass of the curable resin composition. If it is less than 0.1 part by mass, the flame retardancy may be insufficient, and if it is more than 0.6 part by mass, it may adversely affect the hygroscopicity and dielectric properties of the cured product.

[0076] [Light stabilizer] The curable resin composition of the present embodiment may use a light stabilizer. As the light stabilizer, a hindered amine light stabilizer (HALS) or the like is suitable. 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, 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)imino}], bis(1,2,2,6,6-pentamethyl-4-piperidyl)[[(3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl)methyl]butyl malonate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, 2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-n-butyl malonic acid bis(1,2,2,6,6-pentamethyl-4-piperidyl), etc., but are not limited thereto. Also, these may be used alone or in combination of two or more.

[0077] The content of the light stabilizer is preferably in the range of 0.001 to 0.1 parts by mass with respect to 100 parts by mass of the curable resin composition. If it is less than 0.001 part by mass, there is a risk that the light stabilizing effect may not be sufficiently exhibited, and if it is more than 0.1 part by mass, it may adversely affect the hygroscopicity and dielectric properties of the cured product.

[0078] [Binder resin] The curable resin composition of this embodiment may use a binder resin. Examples of the binder resin include, but are not limited to, butyral resins, acetal resins, acrylic resins, epoxy-nylon resins, NBR-phenol resins, epoxy-NBR resins, silicone resins, etc. These may be used alone or in combination of two or more.

[0079] The blending amount of the binder resin is preferably in 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, more preferably 0.05 to 20 parts by mass, with respect to 100 parts by mass of the curable resin composition, and is used as needed.

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

[0081] The blending amount of the additives 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 with respect to 100 parts by mass of the curable resin composition.

[0082] The curable resin composition of this embodiment may further use other compounds such as epoxy resins, active ester compounds, phenolic resins, polyphenylene ether compounds, amine resins, compounds having ethylenically unsaturated bonds, isocyanate resins, polyamide resins, maleimide compounds, cyanate ester resins, polyimide resins, polybutadiene and its modified products, polystyrene and its modified products, polyethylene and its modified products, benzoxazine compounds, etc. These may be used alone or in combination of two or more. Among these other compounds, from the balance of heat resistance, adhesion, and dielectric properties, it is preferable to contain polyphenylene ether compounds, compounds having ethylenically unsaturated bonds, cyanate ester resins, polybutadiene and its modified products, polystyrene and its modified products. By containing these compounds, the brittleness of the cured product can be improved and the adhesion to metals can be enhanced, and cracks in the package during reliability tests such as solder reflow and thermal cycling can be suppressed.

[0083] When there is no particular notice, the total usage amount of other compounds other than the compound represented by the above formula (1) is preferably 10 mass times or less, more preferably 5 mass times or less, and particularly preferably 3 mass times or less with respect to the compound represented by the above formula (1) of this embodiment. Also, the preferable lower limit is 0.1 mass times or more, more preferably 0.25 mass times or more, and still more preferably 0.5 mass times or more. By being within the above range, while taking advantage of the low dielectric property effect of the compound represented by the above formula (1) of this embodiment, the effects of each added compound can be added. For these components, those exemplified below can be used.

[0084] [Epoxy Resin] Preferred epoxy resins are exemplified below, but are not limited thereto. The property of the epoxy resin may be liquid or solid, and it may be used alone or in combination of two or more.

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

[0086] Examples of the solid epoxy resin include a bixylenol type epoxy resin, a naphthalene type epoxy resin, a naphthalene type tetrafunctional epoxy resin, a cresol novolak type epoxy resin, a dicyclopentadiene type epoxy resin, a trisphenol type epoxy resin, a naphthol type epoxy resin, a biphenyl type epoxy resin, a naphthylene ether type epoxy resin, an anthracene type epoxy resin, a bisphenol A type epoxy resin, a bisphenol AF type epoxy resin, and a tetraphenylethane type epoxy resin. Preferred examples include a naphthol type epoxy resin, a bisphenol AF type epoxy resin, a naphthalene type epoxy resin, and a biphenyl type epoxy resin.Specific examples include "HP4032H" (manufactured by DIC, naphthalene-type epoxy resin), "HP-4700", "HP-4710" (both manufactured by DIC, naphthalene-type tetrafunctional epoxy resin), "N-690" (manufactured by DIC, cresol novolak-type epoxy resin), "N-695" (manufactured by DIC, cresol novolak-type epoxy resin), "HP-7200", "HP-7200HH", "HP-7200H" (all manufactured by DIC, 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 Co., Ltd., tris-phenol-type epoxy resin), "NC-7000L", "NC-7300" (both manufactured by Nippon Kayaku Co., Ltd., naphthol-cresol novolak-type epoxy resin), "NC-3000H", "NC-3000", "NC-3000L", "NC-3100" (all manufactured by Nippon Kayaku Co., Ltd., 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 & Sumikin Chemical Co., Ltd., naphthol-type epoxy resin), "ESN485" (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., naphthol novolak-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), "YX-8800" (manufactured by Mitsubishi Chemical Corporation, anthracene-type epoxy resin), "PG-100", "CG-500" (manufactured by Osaka Gas Chemical 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), and the like. These may be used alone or in combination of two or more.

[0087] [Active ester compound] The active ester compound refers to a compound containing at least one ester bond in its structure and having an aliphatic chain, an aliphatic ring, or an aromatic ring bonded to both sides of the ester bond. Examples of the active ester compound include compounds having two or more highly reactive ester groups such as phenolic esters, thiophenolic esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds, etc. in one molecule, and can be obtained by a condensation reaction of at least one of a carboxylic acid compound, an acid chloride, or a thiocarboxylic acid compound with at least one of a hydroxy compound or a thiol compound. In particular, from the viewpoint of improving heat resistance, it is preferably obtained from a carboxylic acid compound or an acid chloride and a hydroxy compound, and as the hydroxy compound, a phenol compound or a naphthol compound is preferred. The active ester compound may be used alone or in combination of two or more.

[0088] Examples of the above-mentioned carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, etc.

[0089] Examples of the above-mentioned acid chloride include acetyl chloride, acryloyl chloride, methacryloyl chloride, malonyl chloride, succinyl dichloride, diglycolyl chloride, glutaric acid dichloride, suberic acid dichloride, sebacic acid dichloride, adipic acid dichloride, dodecanedioyl dichloride, azelaoyl 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, etc.

[0090] Examples of the phenolic compound and the naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene-type diphenol compounds, phenol novolac, phenolic resins described below, and the like. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

[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, compounds described in Example 2 of International Publication No. 2020 / 095829, compounds disclosed in International Publication No. 2020 / 059625, and the like. Among them, 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 represents a divalent structural unit composed of phenylene-dicyclopentylene-phenylene.

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

[0093] Regarding the mixing ratio of the active ester compound and the epoxy resin, it is preferable that the ratio (α / β) of the active ester equivalent (α) to the epoxy equivalent (β) is 0.5 to 1.5, more preferably 0.8 to 1.2, and even more preferably 0.90 to 1.10. If outside the above range, there is a possibility that the excessive epoxy groups or active ester groups may remain in the system, and the characteristics may deteriorate in long-term reliability tests such as high-temperature storage tests (150 °C, 1000 hours, etc.) or under high-temperature and high-humidity conditions (temperature: 85 °C, humidity: 85%, etc.).

[0094] [Phenolic 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, reaction products of bisphenols and aldehydes, etc. Also, these may be used alone or in combination of two or more. Specific examples of the above raw materials are exemplified below, but are not limited thereto. <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, etc. <Diene compounds> Dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc. <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, etc. <Substituted phenyls> 1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene, 1,4-bis(hydroxymethyl)benzene, etc.

[0095] [Polyphenylene ether compound] As the polyphenylene ether compound, from the viewpoints of heat resistance and electrical properties, it 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. Examples of 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. When the number average molecular weight is less than 500, sufficient heat resistance of the cured product tends not to be obtained. Also, when the number average molecular weight is greater than 5000, the melt viscosity becomes high and sufficient fluidity cannot be obtained, so there is a tendency for molding defects to easily occur. Also, the reactivity decreases, the curing reaction takes a long time, the unreacted materials increase without being incorporated into the curing system, the glass transition temperature of the cured product decreases, and the heat resistance of the cured product tends to decrease. If the number average molecular weight of the polyphenylene ether compound is 500 to 5000, excellent heat resistance, moldability, etc. can be exhibited while maintaining excellent dielectric properties. Here, the number average molecular weight can be specifically measured using gel permeation chromatography or the like.

[0096] The polyphenylene ether compound may be obtained by a polymerization reaction or by subjecting a high molecular weight polyphenylene ether compound having a number average molecular weight of about 10,000 to 30,000 to a redistribution reaction. Further, using these as raw materials, radical polymerizability may be imparted by reacting them with a compound having an ethylenically unsaturated bond such as methacrylic acid chloride, acrylic acid chloride, chloromethylstyrene, etc. The polyphenylene ether compound obtained by the redistribution reaction is obtained, for example, by heating a high molecular weight polyphenylene ether compound in a solvent such as toluene in the presence of a phenol compound and a radical initiator and subjecting it to a redistribution reaction. The polyphenylene ether compound thus obtained by the redistribution reaction has hydroxyl groups derived from phenol compounds that contribute to curing at both ends of the molecular chain, so that in addition to being able to maintain higher heat resistance, it is preferable because functional groups can be introduced at both ends of the molecular chain even after modification with a compound having an ethylenically unsaturated bond. Further, the polyphenylene ether compound obtained by the polymerization reaction is preferable in terms of exhibiting 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] An amine resin is a compound having two or more amino groups in the molecule. Examples of amine resins include diaminodiphenylmethane, diaminodiphenylsulfone, isophoronediamine, naphthalenediamine, aniline novolak (reaction product of aniline and formaldehyde), N-methylaniline novolak (reaction product of N-methylaniline and formaldehyde), orthoethylaniline novolak (reaction product of orthoethylaniline and formaldehyde), reaction product of 2-methylaniline and formaldehyde, reaction product of 2,6-diisopropylaniline and formaldehyde, reaction product of 2,6-diethylaniline and formaldehyde, reaction product of 2-ethyl-6-ethylaniline and formaldehyde, reaction product of 2,6-dimethylaniline and formaldehyde, aniline resin obtained by the reaction of aniline and xylylene chloride, reaction product of aniline and substituted biphenyls (such as 4,4'-bis(chloromethyl)-1,1'-biphenyl and 4,4'-bis(methoxymethyl)-1,1'-biphenyl) described in Japanese Patent No. 6429862, reaction product of aniline and substituted benzenes (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 product of aniline and diisopropenylbenzene, dimer diamine, etc., but are not limited thereto. These may be used alone or in combination of two or more.

[0100] [Compound containing ethylenically unsaturated bond] A compound containing an ethylenically unsaturated bond is a compound having one or more ethylenically unsaturated bonds in the molecule that can be polymerized by heat or light regardless of the use or non-use of a polymerization initiator. Examples of the compound containing an ethylenically unsaturated bond include reaction products of the above phenolic resin and a halogen-based compound containing an ethylenically unsaturated bond (such as chloromethylstyrene, allyl chloride, methallyl chloride, acryloyl chloride, methacryloyl chloride, etc.), reaction products of phenols containing an ethylenically unsaturated bond (such as 2-allylphenol, 2-propenylphenol, 4-allylphenol, 4-propenylphenol, eugenol, isoeugenol, etc.) and a halogen-based compound (such as 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 an epoxy resin or alcohols and (meth)acrylic acids (such as acrylic acid, methacrylic acid, etc.), and acid-modified products thereof, etc., but are not limited thereto. Further, these may be used alone or in combination of two or more.

[0101] [Isocyanate resin] An isocyanate resin is a compound having two or more isocyanate groups in the molecule. Examples of the isocyanate resin include 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, naphthalene diisocyanate, etc., aliphatic or alicyclic diisocyanates such as isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, norbornene diisocyanate, lysine diisocyanate, etc., polyisocyanates such as a burette body of one or more kinds of isocyanate monomers, or an isocyanate body obtained by trimerizing the above diisocyanate compound, polyisocyanates obtained by urethanization reaction of the above isocyanate compound and a polyol compound, etc., but are not limited thereto. Further, these may be used alone or in combination of two or more.

[0102] [Polyamide resin] Examples of the polyamide resin include reaction products of any one or more of diamine, diisocyanate, and oxazoline with dicarboxylic acid, reaction products of diamine with acid chloride, and ring-opening polymers of lactam compounds. These may be used alone or in combination of two or more. Specific examples of the above raw materials are illustrated below, but are not limited thereto. <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, 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, diaminodiphenylsulfone, diaminodiphenylether, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 4,4-bis(4-aminophenoxy)biphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(4-aminophenoxy)phenyl]sulfone, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-(1,3-phenylenediisopropylidene)bisaniline, 4,4'-(1,4-phenylenediisopropylidene)bisaniline, 9,9-bis(4-aminophenyl)fluorene, 2,7-diaminofluorene, aminobenzylamine, diaminobenzophenone, etc. <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, etc. <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, acryloyl chloride, methacryloyl chloride, malonyl chloride, succinyl dichloride, diglycolyl chloride, glutaric dichloride, suberic dichloride, sebacic dichloride, adipic dichloride, dodecanedioyl dichloride, azelaoyl 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, etc. <Lactam> ε-Caprolactam, ω-undecanolactam, ω-laurolactam, etc.

[0103] [Polyimide resin] Examples of the polyimide resin include, but are not limited to, reaction products of the above diamine and tetracarboxylic dianhydrides exemplified below. These may be used alone or in combination of two or more. <tetracarboxylic dianhydride> 4,4'-(Hexafluoroisopropylidene)diphthalic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-cyclohexene-1,2-dicarboxylic anhydride, pyromellitic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, methylene-4,4'-diphthalic dianhydride, 1,1-ethylidene-4,4'-diphthalic dianhydride, 2,2'-propylidene-4,4'-diphthalic dianhydride, 1,2-ethylene-4,4'-diphthalic dianhydride, 1,3-trimethylene-4,4'-diphthalic dianhydride, 1,4-tetramethylene-4,4'-diphthalic dianhydride, 1,5-pentamethylene-4,4'-diphthalic dianhydride, 4,4'-oxydiphthalic dianhydride, thio-4,4'-diphthalic dianhydride, sulfonyl-4,4'-diphthalic dianhydride, 1,3-bis(3,4-dicarboxyphenyl)benzene dianhydride, 1,3-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 1,3-bis[2-(3,4-dicarboxyphenyl)-2-propyl]benzene dianhydride, 1,4-bis[2-(3,4-dicarboxyphenyl)-2-propyl]benzene dianhydride, bis[3-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride, bis[4-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride, 2,2-bis[3-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 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 - Perylene tetracarboxylic dianhydride, 2,3,6,7 - anthracene tetracarboxylic dianhydride, 1,2,7,8 - phenanthrene tetracarboxylic dianhydride, ethylene tetracarboxylic dianhydride, 1,2,3,4 - butane tetracarboxylic dianhydride, 1,2,3,4 - cyclobutane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, cyclohexane - 1,2,3,4 - tetracarboxylic dianhydride, cyclohexane - 1,2,4,5 - tetracarboxylic dianhydride, 3,3’,4,4’ - bicyclohexyltetracarboxylic dianhydride, carbonyl - 4,4’ - bis(cyclohexane - 1,2 - dicarboxylic acid) dianhydride, methylene - 4,4’ - bis(cyclohexane - 1,2 - dicarboxylic acid) dianhydride, 1,2 - ethylene - 4,4’ - bis(cyclohexane - 1,2 - dicarboxylic acid) dianhydride, 1,1 - ethylidene - 4,4’ - bis(cyclohexane - 1,2 - dicarboxylic acid) dianhydride, 2,2 - propylidene - 4,4’ - bis(cyclohexane - 1,2 - dicarboxylic acid) dianhydride, oxy - 4,4’ - bis(cyclohexane - 1,2 - dicarboxylic acid) dianhydride, thio - 4,4’ - bis(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 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 anhydride, ethylene glycol - bis-(3,4 - dicarboxylic anhydride phenyl) ether, 4,4’ - biphenylbis(trimellitic monoester anhydride), 9,9’ - bis(3,4 - dicarboxyphenyl)fluorene dianhydride, etc.,

[0104] [Maleimide compound] 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'-diphenyl ether bismaleimide, 4,4'-diphenyl sulfone bismaleimide, 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene, a zairok-type maleimide compound (anilix maleimide, manufactured by Mitsui Chemicals Fine Chemicals Co., Ltd.), a biphenyl aralkyl-type maleimide compound (solidified by distilling off the solvent under reduced pressure from a resin solution containing the maleimide compound (M2) described in Example 4 of JP-A-2009-001783), a bisaminocumylbenzene-type maleimide (the maleimide compound described in International Publication No. 2020 / 054601), a maleimide compound having an indane structure described in Patent No. 6629692 or International Publication No. 2020 / 217679, the maleimide compounds described in MATERIAL STAGE Vol.18, No.12 2019 "~Continued: The Story of Epoxy Resin CAS Numbers~ Hardener CAS Number Memorandum, No. 31 Bismaleimide (1)" and MATERIAL STAGE Vol.19, No.2 2019 "~Continued: The Story of Epoxy Resin CAS Numbers~ Hardener CAS Number Memorandum, No. 32 Bismaleimide (2)", etc., but are not limited thereto. These may be used alone or in combination of two or more.

[0105] [Cyanate Ester Resin] The cyanate ester resin is a cyanate ester compound obtained by reacting a phenolic resin with a cyanogen halide. Specific examples include dicyanate benzene, tricyanate benzene, dicyanate naphthalene, dicyanate biphenyl, 2,2'-bis(4-cyanate phenyl) propane, bis(4-cyanate phenyl) methane, bis(3,5-dimethyl-4-cyanate phenyl) methane, 2,2'-bis(3,5-dimethyl-4-cyanate phenyl) propane, 2,2'-bis(4-cyanate phenyl) ethane, 2,2'-bis(4-cyanate phenyl) hexafluoropropane, bis(4-cyanate phenyl) sulfone, bis(4-cyanate phenyl) thioether, phenol novolac cyanate, and those obtained by converting the hydroxyl groups of a phenol-dicyclopentadiene co-condensate into cyanate groups, etc., but are not limited thereto. Also, these may be used alone or in combination of two or more. In addition, the cyanate ester compound described in JP-A-2005-264154 is particularly preferable as a cyanate ester compound because it has excellent low hygroscopicity, flame retardancy, and dielectric properties. The cyanate ester resin can also contain a catalyst such as zinc naphthenate, cobalt naphthenate, copper naphthenate, lead naphthenate, zinc octylate, tin octylate, lead acetylacetonate, dibutyltin maleate, etc. in order to trimerize the cyanate groups to form a sym-triazine ring as needed.

[0106] The catalyst is preferably used in an amount of 0.0001 to 0.10 parts by mass, preferably 0.00015 to 0.0015 parts by mass, based on 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 compounds having polybutadiene or a structure derived from polybutadiene in the molecule. The structure derived from polybutadiene may have some or all of the unsaturated bonds 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, styrene-butadiene rubber, etc. These may be used alone or in combination. From the perspective of dielectric properties, polybutadiene or styrene-butadiene rubber is preferred. Examples of styrene-butadiene rubber (SBR) include RICON-100, RICON-181, RICON-184 (all manufactured by Kray Valley), 1,2-SBS (manufactured by Nippon Soda Co., Ltd.), etc. Examples of polybutadiene include B-1000, B-2000, B-3000 (all manufactured by Nippon Soda Co., Ltd.), etc. The weight average molecular weight of polybutadiene and styrene-butadiene rubber is preferably 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 volatile content is high, making it difficult to adjust the solid content during prepreg preparation. Above the upper limit of the above range, the compatibility with other curable resins deteriorates. Generally, in the case of compounds containing heteroatoms such as oxygen and nitrogen like bismaleimide and polymaleimide, it is difficult to ensure compatibility with low-polarity compounds such as compounds mainly composed of hydrocarbons or compounds consisting only of hydrocarbons due to their polarity. On the other hand, due to the fact that the compound of this embodiment does not have a skeleton design in which heteroatoms such as oxygen and nitrogen are actively introduced, it also has excellent compatibility with materials having low polarity and low dielectric properties and compounds composed only of hydrocarbons.

[0108] [Polystyrene and its modified products] Polystyrene and its modified products are compounds having a structure derived from polystyrene in the molecule. Examples of polystyrene and its modified products include, but are not limited to, polystyrene, styrene-2-isopropenyl-2-oxazoline copolymer (both Epocros RPS-1005 and RP-61 are 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 block copolymer: Septon 8004, Septon 8006, Septon 8007L, all manufactured by Kuraray Co., Ltd.), SEEPS-OH (compound having a hydroxyl group at the terminal of a styrene-ethylene / ethylene·propylene-styrene block copolymer: Septon HG252 manufactured by Kuraray Co., Ltd.), SIS (styrene-isoprene-styrene block copolymer: Septon 5125, Septon 5127, both manufactured by Kuraray Co., Ltd.), hydrogenated SIS (hydrogenated styrene-isoprene-styrene block copolymer: Hybrar 7125F, Hybrar 7311F, both manufactured by Kuraray Co., Ltd.), SIBS (styrene-isobutylene-styrene block copolymer: SIBSTAR073T, SIBSTAR102T, SIBSTAR103T (all manufactured by Kaneka Corporation), Septon V9827 (manufactured by Kuraray Co., Ltd.)). These may be used alone or in combination. Polystyrene and its modified products preferably have no unsaturated bonds because they have higher heat resistance and are less prone 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. However, if it is too large, the compatibility with the low molecular weight component having a weight average molecular weight of about 50 to 1,000 and the oligomer component having a weight average molecular weight of about 1,000 to 5,000, in addition to the polyphenylene ether compound, deteriorates, making it difficult to ensure mixing and solvent stability. Therefore, it is preferably about 10,000 to 300,000.

[0109] [Polyethylene and its modified products] Polyethylene and its modified products are compounds having polyethylene or a structure derived from polyethylene 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 (such as EBT:K-8370EM, K-9330M manufactured by Mitsui Chemicals, Inc.), ethylene-propylene-vinyl norbornene copolymers (such as VNB-EPT:PX-006M, PX-008M, PX-009M manufactured by Mitsui Chemicals, Inc.), ethylene-vinyl alcohol copolymers, ethylene-vinyl acetate copolymers, etc. From the viewpoint of improving heat resistance, it is preferable to use an ethylene-propylene-ethylidene norbornene copolymer or an ethylene-propylene-vinyl norbornene copolymer containing a crosslinkable structure. These may be used alone or in combination. The weight average molecular weight of polyethylene and its modified products is not particularly limited as long as it is 10,000 or more, but if it is too large, in addition to the polyphenylene ether compound, the compatibility with a low molecular weight component having a weight average molecular weight of about 50 to 1,000 and an oligomer component having 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 compound] As the benzoxazine compound, any compound obtained by reacting a compound having a phenolic hydroxyl group, a compound having an amino group, and a compound having an aldehyde group may be used. The compound having a phenolic hydroxyl group is not particularly limited. For example, the aforementioned phenolic resins, phenols (which may have substituents such as alkenyl groups and alkyl groups), and bisphenols can be used. The compound having an amino group is not particularly limited. For example, the aforementioned amine resins, diamines, and anilines (which may have substituents such as alkenyl groups and alkyl groups) can be used. As the aldehyde compound, for example, the aforementioned aldehydes can be used, but formaldehyde is preferably used. As for the benzoxazine compound, commercially available products can be used, such as benzoxazine P-d, F-a, ALP-d (all manufactured by Shikoku Kasei Co., Ltd.), JBZ-BA100N, JBZ-FA100N, JBZ-DP100N, JBZ-OP100N, JBZ-OP100D, JBZ-OP100I (all manufactured by JFE Chemical Corporation), and BTBz (manufactured by Nippon Materials Technology Co., Ltd.).

[0111] The curable resin composition of this embodiment is obtained by preparing the above components in a predetermined ratio, pre-cured in the range of 130 to 180 °C for 30 to 500 seconds, and further post-cured at 150 to 200 °C for 2 to 15 hours, so that a sufficient curing reaction proceeds to obtain the cured product of this embodiment. Also, the components of the curable resin composition can be uniformly dispersed or dissolved in a solvent or the like, and after removing the solvent, it can be post-cured.

[0112] The method for preparing the curable resin composition of this embodiment is not particularly limited. It may be simply mixing the components uniformly or prepolymerizing them. For example, the mixture containing the compound of this embodiment is prepolymerized by heating in the presence or absence of a curing accelerator or a polymerization initiator and in the presence or absence of a solvent. Similarly, compounds such as amine compounds, compounds having an ethylenically unsaturated bond, maleimide compounds, cyanate ester compounds, polybutadiene and its modified products, polystyrene and its modified products, inorganic fillers, and other additives can be added and prepolymerized. The mixing or prepolymerization of each component is carried out using, for example, an extruder, a kneader, a roll, etc. in the absence of a solvent, and a reaction kettle equipped with a stirrer, etc. in the presence of a solvent.

[0113] As a method of uniformly mixing, it is mixed by kneading using a device such as a kneader, a roll, or a planetary mixer at a temperature within the range of 50 to 100°C to obtain a uniform resin composition. The obtained resin composition is pulverized and then molded into a cylindrical tablet shape using a molding machine such as a tablet machine, or into a granular powder or a powdery molded body, or these compositions are melted on a surface support and molded into a sheet shape with a thickness of 0.05 mm to 10 mm to obtain a curable resin composition molded body. The obtained molded body becomes a non-sticky molded body at 0 to 20°C, and even when stored at -25 to 0°C for one week or more, its fluidity and curability hardly decrease. The obtained molded body 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 is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. as needed to make a varnish, and impregnated into a base material such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc., and heat-dried to obtain a prepreg, which can be thermally press-molded to obtain a cured product of the curable resin composition of this embodiment. The solvent used at this time occupies 10 to 70% by weight, preferably 15 to 70% by weight, in the mixture of the curable resin composition of this embodiment and the solvent. Also, if it is a liquid composition, a cured product containing carbon fiber can be obtained as it is, for example, by the RTM method.

[0115] In addition, the curable resin composition of the present embodiment can also be used as a modifier for film-type compositions. Specifically, it can be used when improving 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 the present embodiment as a varnish onto a release film, removing the solvent under heating, and then performing B-staging. 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 the present embodiment can also be heated and melted to reduce its viscosity, and then impregnated into reinforcing fibers such as glass fibers, carbon fibers, polyester fibers, polyamide fibers, and alumina fibers to obtain a prepreg. Specific examples thereof include, for example, 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, and further fibers of inorganic substances other than glass and organic fibers such as polyparaphenylene terephthalamide (Kevlar (registered trademark), manufactured by DuPont), wholly aromatic polyamide, polyester, polyparaphenylene benzoxazole, polyimide, and carbon fibers, but it is not particularly limited thereto. The shape of the base material is not particularly limited, and examples thereof include woven fabric, non-woven fabric, roving, and chopped strand mat. Also, as the weaving method of the woven fabric, plain weave, nanako weave, twill weave, etc. are known, and these known ones can be appropriately selected and used according to the intended use and performance. Further, those obtained by opening the woven fabric or glass woven fabric surface-treated with a silane coupling agent or the like are preferably used. The thickness of the base material is not particularly limited, but is preferably about 0.01 to 0.4 mm. Also, the prepreg can be obtained by impregnating the above varnish into the reinforcing fibers and heating and drying them.

[0117] In addition, 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 it may have any other layers. As a method for manufacturing the laminate, generally known methods can be appropriately applied and are not particularly limited. For example, when forming a metal foil-clad laminate, a multi-stage press, a multi-stage vacuum press, a continuous forming machine, an autoclave forming machine, etc. can be used. By laminating the prepregs together and performing heat and pressure forming, a laminate can be obtained. At this time, the heating temperature is not particularly limited, but a temperature of 65 to 300 °C is preferable, and 120 to 270 °C is more preferable. Also, the pressure applied is not particularly limited, but if the pressure is too high, it is difficult to adjust the solid content of the resin in the laminate and the quality is unstable. On the other hand, if the pressure is too low, the air bubbles and the adhesion between the layers will deteriorate. Therefore, 2.0 to 5.0 MPa is preferable, and 2.5 to 4.0 MPa is more preferable. The laminate of this embodiment can be suitably used as a metal foil-clad laminate described later by including a layer made of a metal foil. The above prepreg is cut into a desired shape, and if necessary, laminated with a copper foil or the like. Then, while applying pressure to the laminate by a press forming method, an autoclave forming method, a sheet winding forming method, etc., the curable resin composition is heat-cured to obtain a laminate for electric and electronic applications (printed wiring board) or a carbon fiber reinforcing material.

[0118] The curable resin composition of this embodiment can also be made into a resin sheet. As a method for obtaining a resin sheet from the curable resin composition of this embodiment, for example, there is a method of applying the curable resin composition on a support film (support), drying it, and forming a resin composition layer on the support film. When the curable resin composition of this embodiment is used for a resin sheet, the film softens under the temperature conditions (70°C to 140°C) of lamination in the vacuum lamination method, and at the same time as the lamination of the circuit board, it is important that it exhibits fluidity (resin flow) that enables resin filling in via holes or through holes existing in the circuit board. It is preferable to blend the above components so as to exhibit such characteristics. In addition, in the obtained resin sheet and circuit board (copper-clad laminate, etc.), in order not to cause a phenomenon such as locally different characteristic values due to phase separation, etc., and to exhibit a certain performance at any site, appearance uniformity is required.

[0119] Here, the diameter of the through hole of the circuit board is 0.1 to 0.5 mm, and the depth is 0.1 to 1.2 mm. It is preferable to enable resin filling within this range. When laminating both sides of the circuit board, it is desirable that the through hole be filled about half.

[0120] As a specific method for manufacturing the above resin sheet, after preparing a resin composition varnished by blending an organic solvent, the varnished resin composition is applied to the surface of a support film (Y), and the organic solvent is dried by further heating or blowing hot air, etc. to form a resin composition layer (X).

[0121] Examples of the organic solvent used herein include 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, N-methylpyrrolidone, etc. It is preferable to use them, and it is also preferable to use the organic solvent at a ratio such that the non-volatile content is 30 to 60% by mass of the whole.

[0122] In addition, the thickness of the resin composition layer (X) to be formed needs to be equal to or greater than the thickness of the conductor layer of the circuit board on 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) preferably has a thickness of 10 to 100 μm. In addition, the resin composition layer (X) in the present embodiment may be protected by a protective film described later. By protecting with a protective film, it is possible to prevent the adhesion of dust and the like and scratches on the surface of the resin composition layer (X).

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

[0124] The above support film (Y) is peeled off after laminating the resin composition layer (X) on the circuit board or after forming an insulating layer by heat-curing the resin composition layer (X). If the support film (Y) is peeled off after the resin composition layer (X) constituting the resin sheet is heat-cured, it is possible to prevent the adhesion of dust and the like in the curing process. When the support film (Y) is peeled off after the curing of the resin composition layer (X), the support film (Y) is previously subjected to a release treatment.

[0125] In addition, a multilayer printed circuit board can be manufactured using the resin sheet obtained as described above. For example, when the resin composition layer (X) is protected by a protective film, after peeling off the protective film, the resin composition layer (X) is laminated on 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 type or a continuous type using a roll. Also, if necessary, the resin sheet and the circuit board may be heated (preheated) as necessary before lamination. The lamination conditions preferably have a crimping temperature (lamination temperature) of 70 to 140°C, a crimping pressure of 1 to 11 kgf / cm 2 (9.8×10 4 ~107.9×10 4 N / m 2 ), and it is preferable to laminate under a reduced pressure with an air pressure of 20 mmHg (26.7 hPa) or less.

[0126] Also, a semiconductor device can be manufactured using the curable resin composition of the present embodiment. Examples of the semiconductor device include DIP (Dual In-line Package), QFP (Quad Flat Package), BGA (Ball Grid Array), CSP (Chip Size Package), SOP (Small Outline Package), TSOP (Thin Small Outline Package), TQFP (Thin Quad Flat Package), and the like.

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

Examples

[0128] Next, the present invention will be described more specifically with reference to examples. Hereinafter, unless otherwise specified, "parts" are parts by mass. Note that the present 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), On-line 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 Refractometer (RID-20A, manufactured by Shimadzu Corporation)

[0130] [Example 1] While purging nitrogen into a flask equipped with a thermometer, a condenser, a stirrer, and a Dean-Stark tube, 16.6 parts of fluorene, 8.3 parts of xylene formaldehyde resin (Nicanol (registered trademark) LL, manufactured by Fudo Co., Ltd.), 16.6 parts of methylcyclohexane, and 1.2 parts of p-toluenesulfonic acid were added. The temperature was raised to 100 °C, and the reaction was carried out for 2 hours while removing the generated water out of the system using the Dean-Stark tube by azeotropic dehydration. Subsequently, the internal temperature was cooled to 80 °C, and 0.3 part of sodium hydroxide was added. Then, methylcyclohexane was recovered until the internal temperature reached 140 °C. After cooling to 80 °C, 100 parts of dimethyl sulfoxide and 12 parts of sodium hydroxide were added, and the mixture was stirred at 60 °C for 30 minutes. Then, while maintaining the internal temperature at 65 °C or lower, 29.0 parts of CMS-14 (manufactured by AGC Seimi Chemical Co., a 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 5 times with 100 parts of water. The obtained organic layer was concentrated to obtain 17.6 parts of the compound (F1) represented by the following formula (f-1). The HP-LC chart of the obtained compound (F1) is shown in Figure 1. Also, the 1 1H-NMR data (deuterated chloroform) of the obtained compound is shown in Figure 2. 1Signals derived from the terminal hydrogens of vinyl groups (two hydrogens per vinyl group) were observed at 4.90 - 5.56 ppm in the 1H-NMR chart, signals derived from methylene bonds in the repeating unit of n were observed at 3.76 - 4.26 ppm, signals derived from methylene bonds in the repeating unit of q were observed at 3.40 - 3.76, and signals derived from the methylene structure of R2 were 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 total integral value of the peaks derived from each hydrogen of the methylene bond site in the repeating unit of q was 0.56, and the integral value of the peaks derived from each hydrogen of the methylene bond site in the repeating unit of n was 2.10. The average value k of k in the following formula (f-1) calculated from this ave 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 the compound (F1) was 447, and the weight average molecular weight Mw was 619.

[0131] [Chemical formula]

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

[0133] [Chemical formula]

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

[0135] [Comparative Synthesis Example 1] While purging 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 part of hydroquinone, and 64 parts of a 50 wt% aqueous sodium hydroxide solution were added to a flask equipped with a thermometer, a cooling tube, and a stirrer, and the internal temperature was raised to 60°C. Then, 71.2 parts of CMS-P (a mixture of 4-chloromethylstyrene and 3-chloromethylstyrene manufactured by AGC Seimi Chemical Co., Ltd., 4-chloromethylstyrene:3-chloromethylstyrene = 1:1 (molar ratio), purity 95.59 wt%) were added dropwise over 1 hour, and the reaction was carried out at 60°C for 9 hours. The mixture was neutralized with 41.6 parts of a 35 wt% aqueous hydrochloric acid solution, and the organic layer was washed 3 times with 100 parts of water. Recrystallization was carried out with toluene and methanol to obtain 35.6 parts of the compound (F2) represented by the following formula (f-2). The HP-LC chart of the obtained compound (F2) is shown in Figure 4, 1 The 1H-NMR data (deuterated chloroform) are shown in Figure 5.

[0136] [Chemical formula]

[0137] [Example 2, Comparative Examples 1 and 2] Using the respective compounds (F1, F2) obtained in Example 1 and Comparative Synthesis Example 1, and ОPE-2St (a polyphenylene ether compound manufactured by Mitsubishi Gas Chemical Company) in the amounts shown in Table 1, vacuum press molding was carried out while sandwiching with a mirror-finished copper foil (T4X: manufactured by Fukuda Metal Foil Co., Ltd.), and curing was carried out at 220°C for 2 hours. At this time, a cushion paper with a thickness of 250 μm and a central portion cut out to 150 mm in length and width was used as a spacer. For the evaluation, test pieces were cut out to the desired size using a laser cutter as necessary, and the evaluation was carried out.

[0138] [Dielectric constant test · Dielectric tangent test] Using a 10 GHz cavity resonator manufactured by AET Co., Ltd., a test was carried out at 25°C by the cavity resonator perturbation method. The sample size was 1.7 mm in width × 100 mm in length, and the thickness was 0.3 mm for the test. 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 (a biphenyl aralkyl type epoxy resin manufactured by Nippon Kayaku Co., Ltd.), 0.5 part of MDEA: 4,4'-methylenebis(2-ethyl-6-methylaniline) (an amine compound manufactured by Tokyo Chemical Industry Co., Ltd.), 1 part of DICY: dicyandiamide (an amide compound manufactured by Tokyo Chemical Industry Co., Ltd.), 0.5 part of KAYAHARD MCD (an acid anhydride compound manufactured by Nippon Kayaku Co., Ltd.), 0.5 part of KAYAHARD GPH-65 (a biphenyl aralkyl type phenol resin manufactured by Nippon Kayaku Co., Ltd.), 0.5 part of Unifier W-575 (an active ester resin manufactured by Unitika Ltd.), 0.5 part of G4-142MHR (a carboxylic acid compound manufactured by Nippon Kayaku Co., Ltd.), 2.5 parts of MIR-3000-70MT (a maleimide compound manufactured by Nippon Kayaku Co., Ltd.), 2.5 parts of MIZ-001 (a maleimide compound manufactured by Nippon Kayaku Co., Ltd.), 0.5 part of phenyl maleimide (a maleimide compound manufactured by Tokyo Chemical Industry Co., Ltd.), 0.5 part of SYTESTER TA (a bisphenol A type cyanate resin manufactured by Mitsubishi Gas Chemical Company, Inc.), 60 parts of OPE-2st 2200 (a polyphenylene ether compound manufactured by Mitsubishi Gas Chemical Company, Inc.), 3 parts of STR-2000 (a compound having an ethylenically unsaturated bond manufactured by Nippon Kayaku Co., Ltd.), 1 part of KAYARAD R-684 (a compound having an ethylenically unsaturated bond manufactured by Nippon Kayaku Co., Ltd.), 0.5 part of acenaphthylene (a compound having an ethylenically unsaturated bond manufactured by Tokyo Chemical Industry Co., Ltd.), 1 part of the polyimide compound obtained by the method described in WO2023 / 013224A1, 1 part of TAIC: triallyl isocyanurate (an allyl compound manufactured by Mitsubishi Chemical Corporation), 1 part of Septon 2104 (a polystyrene-modified product manufactured by Kuraray Co., Ltd.), 1 part of P-d type benzoxazine (a benzoxazine compound manufactured by Shikoku Chemicals Corporation), 0.5 part of 2E4MZ: 2-ethyl-4-methylimidazole (a curing accelerator manufactured by Shikoku Chemicals Corporation), 0.5 part of TPP: triphenylphosphine (a curing accelerator manufactured by Hokko Chemical Industry Co., Ltd.), 0.1 part of Octop Zn (a curing accelerator manufactured by Hope Pharmaceutical Co., Ltd.), 0.1 part of Sun Aide SI-B5 (a curing accelerator manufactured by Sanshin Chemical Industry Co., Ltd.), 1 part of DCP: dicumyl peroxide (a polymerization initiator manufactured by Kayaku Nucreon Co., Ltd.), 99.2 parts of toluene and 49 parts of tetrahydrofuran as solvents.It was blended at a ratio of 6 parts and cured by heating at 110 °C for 10 minutes and then at 220 °C for 1 hour under a nitrogen atmosphere to obtain a cured product.

[0142] [Reference Example 2] 5 parts of the compound (F1) obtained in Example 1, 50 parts of NC-3000 (manufactured by Nippon Kayaku Co., Ltd., biphenyl aralkyl type epoxy resin), 10 parts of MIZ-001 (manufactured by Nippon Kayaku Co., Ltd., maleimide compound), 5 parts of STR-2000 (manufactured by Nippon Kayaku Co., Ltd., compound having an ethylenically unsaturated bond), 45 parts of KAYARAD R-684 (manufactured by Nippon Kayaku Co., Ltd., compound having an ethylenically unsaturated bond), 1 part of Irgacure OXE-04 (manufactured by BASF, polymerization initiator), and 1 part of Irgacure 290 (manufactured by BASF, polymerization initiator) were blended, coated on a PET film to a film thickness of 100 μm, and a PET film was also attached to the surface not in contact with the film, and irradiated with ultraviolet rays of 3000 mJ / cm 2 to obtain a cured product. [Industrial Applicability]

[0143] The compound of the present invention is suitably used for electrical and electronic components such as semiconductor encapsulants, printed wiring boards, build-up laminated boards, and optical waveguide devices.

Claims

1. A compound represented by the following formula (1). 【Chemical 1】 In the above formula (1), multiple Rs １ and R ３ each independently represent a hydrocarbon group having 1 to 5 carbon atoms. Multiple Rs ２ each independently represent a hydrocarbon group represented by the following formula (a). Multiple ps each independently represent an integer of 0 to 4. q is the average value of the repetition number and 1 < q ≦ 20. Multiple ls each independently represent an integer of 0 to 4. Multiple ks each independently represent an integer of 0 to 3, and the average value k ａｖｅ of k is 0 < k ａｖｅ ≦ 3. n is the average value of the repetition number and represents a number from 0.05 to 20. [Chemical 2] In the above formula (a), * represents the bonding position to the fluorene structure of formula (1). When there are a plurality of Rs ４ each independently represents 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). [Chemical Formula 3] In the above formula (A), a plurality of R's ２ each independently represents a hydrocarbon group represented by the following formula (a). A plurality of R's ３ each independently represents a hydrocarbon group having 1 to 5 carbon atoms. A plurality of p's each independently represents an integer of 0 to 4. q is the average value of the repetition number and 1 < q ≦ 20. A plurality of k's 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 repetition number and represents a number of 0.05 to 20. 【Chemical 4】 In the above formula (a), * represents the bonding position to the fluorene structure of formula (A). When there are a plurality of Rs ４ each independently represents a hydrocarbon group having 1 to 5 carbon atoms. Each m independently represents an integer of 0 to 5. 【Chemical Formula 5】 In the above formula (B), a plurality of R's １ each 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 Claim 1 or Claim 2.

4. Furthermore, at least one 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. The curable resin composition according to Claim 3.

5. A cured product obtained by curing the compound according to Claim 1 or Claim 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. 【Chemical Formula 6】 In the above formula (A), a plurality of R's ２ each independently represent a hydrocarbon group represented by the following formula (a). A plurality of R's ３ each independently represent a hydrocarbon group having 1 to 5 carbon atoms. A plurality of p's each independently represent an integer of 0 to 4. q is the average value of the number of repetitions and 1 < q ≦ 20. A plurality of k's each independently represent 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 number of repetitions and represents a number from 0.05 to 20. 【Chemical Formula 7】 In the above formula (a), * represents the bonding position to the fluorene structure of formula (A). A plurality of Rs ４ 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. [Chemical Formula 8] In the above formula (B), a plurality of R's １ each independently represents a hydrocarbon group having 1 to 5 carbon atoms. l represents an integer of 0 to 4. X represents a halogen atom. 【Chemical Formula 9】 In the above formula (1), R existing in plural １ and R ３ each independently represents a hydrocarbon group having 1 to 5 carbon atoms. R existing in plural ２ each independently represents a hydrocarbon group represented by the following formula (a). Each of the plural p independently represents an integer of 0 to 4. q is the average value of the number of repetitions and 1 < q ≦ 20. Each of the plural l independently represents an integer of 0 to 4. Each of the plural k independently represents an integer of 0 to 3, and the average value k ａｖｅ of k is 0 < k ａｖｅ ≦ 3. n is the average value of the number of repetitions and represents a number of 0.05 to 20. 【Chemical Formula 10】 In the above formula (a), * represents the bonding position to the fluorene structure of formula (1). A plurality of R ４ each independently represents a hydrocarbon group having 1 to 5 carbon atoms. A plurality of R ２ In formula (a) representing m each independently represents an integer of 0 to 5.

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