Compound, mixture, curable resin composition and cured product of them

Abstract

To provide a compound, a mixture, and a curable resin composition which have excellent low dielectric characteristics, and a cured product of them.SOLUTION: A compound is represented by formula (1). In the formula (1), R is a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, l and n are each independently an integer of 1 to 4, k is an integer of 0 to 4, an average value kave of k is 0<kave≤4, m is an integer of 1 to 30, and an average value mave of m is 1≤mave≤20.SELECTED DRAWING: None

Description

[Technical field]

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

[0002] In recent years, the required characteristics of laminates on which electric and electronic components are mounted have become more extensive and sophisticated due to the expansion of the fields in which they are used. Conventional semiconductor chips were mainly mounted on metal lead frames, but semiconductor chips with high processing power, such as central processing units (hereinafter referred to as CPUs), are increasingly being mounted on laminates made of polymer materials.

[0003] The fifth generation communication system "5G", whose development is currently accelerating, is expected to further increase capacity and speed of communication. In 5G, the frequency used will become higher, but to realize high-speed communication using high frequencies, it is important to reduce transmission loss, and further low dielectric properties will be required for the board material. The transmission loss that occurs on the printed circuit board is due to conductor loss and dielectric loss. As described in Non-Patent Document 1, the conductor loss is proportional to the square root of the relative dielectric constant and the dielectric loss tangent of the dielectric, so it can be said that improving the dielectric loss tangent, which has a higher contribution rate than the relative dielectric constant, is effective in reducing transmission loss. Low-dielectric materials include thermoplastic materials such as PTFE (polytetrafluoroethylene) and LCP (liquid crystal polymer), but they are poor in moldability compared to thermosetting resins. In light of this, the development of thermosetting resins with excellent low dielectric properties is desired.

[0004] In light of this background, polymeric materials with excellent low dielectric properties have been studied. For example, Patent Document 1 proposes a composition containing a maleimide resin and a propenyl group-containing phenolic resin. However, on the other hand, since phenolic hydroxyl groups that do not participate in the curing reaction remain during the curing reaction, the electrical properties are not sufficient. Patent Document 2 discloses an allyl ether resin in which hydroxyl groups are substituted with allyl groups. However, it has been shown that Claisen rearrangement occurs 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 the electrical properties are not satisfactory. [Prior art documents] [Non-patent literature]

[0005] [Non-Patent Document 1] Signal loss factors in high-speed signal transmission on printed circuit boards (Mitsui Mining & Smelting Co., Ltd.) 29th Japan Institute of Electronics Packaging Spring Conference 16P1-17 [Patent documents]

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

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

[0008] That is, the present invention relates to the following [1] to [7]. Note that in this application, "(Numerical value 1) to (Numerical value 2)" indicates that the upper and lower limits are included. [1] A compound represented by the following formula (1):

[0009] [ka]

[0010] (In the above formula (1), each of the multiple R's independently represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. Each of the multiple 1's and n's independently represents an integer of 1 to 4. Each of the multiple k's independently represents an integer of 0 to 4, and the average value of k's is k ave is 0 <k ave Each of the multiple m's is independently an integer of 1 to 30, and the average value of m's is m ave is 1≦m ave ≦20. [2] A compound obtained by reacting a compound represented by the following formula (A) with a compound represented by the following formula (B).

[0011] [ka]

[0012] (In the above formula (A), each of the multiple R's independently represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. Each of the multiple n's independently represents an integer of 1 to 4. Each of the multiple k's independently represents a real number of 0 to 4, and the average value of k's is k ave is 0 <k ave ≦4. Each of the multiple m's is independently a real number from 1 to 30, and the average value of m's is m ave is 1≦m ave ≦20.

[0013] [ka]

[0014] (In the above formula (B), each of the multiple R's independently represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. Each of the multiple 1's independently represents an integer of 1 to 4. X represents a halogen atom.) [3] A mixture consisting of a compound represented by the following formula (1-1) and a compound represented by the following formula (1-2):

[0015] [ka]

[0016] (In the above formula (1-1), each of the multiple R's independently represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. Each of the multiple 1's and n's independently represents an integer of 1 to 4. Each of the multiple k's independently represents an integer of 0 to 4, and at least one of the two k's in formula (1-1) is an integer of 1 or more. Each of the multiple m's independently represents an integer of 1 to 30, and the average value of m's is ave is 1≦m ave ≦20.

[0017] [ka]

[0018] (In the above formula (1-2), each of the multiple R's independently represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. Each of the multiple 1's independently represents an integer of 1 to 4.) [4] A curable resin composition comprising the compound according to the above item [1] or [2], or the mixture according to the above item [3]. [5] A cured product obtained by curing the compound described in the preceding item [1] or [2], or the mixture described in the preceding item [3]. [6] A cured product obtained by curing the curable resin composition described in the above item [4]. [7] A method for producing the compound represented by the formula (1), which is obtained by reacting the compound represented by the formula (A) with the compound represented by the formula (B) in the presence of a basic catalyst in an aprotic polar solvent. Effect of the Invention

[0019] According to the present invention, it is possible to provide a compound, a mixture, a curable resin composition, and a cured product thereof, all of which have excellent low dielectric properties. [Brief description of the drawings]

[0020] [Figure 1] 1 shows a GPC chart at the end of the polybenzyl alcoholization reaction in Example 1. [Diagram 2] 2 shows a GPC chart of the reaction product of fluorene and polybenzyl alcohol in Example 1 at the end of the reaction. [Diagram 3] 2 shows a GPC chart of the reaction product of fluorene, polybenzyl alcohol, and chloromethylstyrene in Example 1 at the end of the reaction. [Figure 4] 1 shows a 1H-NMR chart of compound (F1) of Example 1. [Diagram 5] 1 shows an HP-LC chart of the compound (F2) of Comparative Synthesis Example 1. [Figure 6] 1H-NMR chart of compound (F2) of Comparative Synthesis Example 1 is shown. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0021] Hereinafter, an embodiment according to the present invention (hereinafter also referred to as "the present embodiment") will be described in further detail.

[0022] The compound of the present embodiment is represented by the following formula (1).

[0023] [ka]

[0024] In the above formula (1), each of the multiple R's independently represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, preferably a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, and more preferably a hydrogen atom. When the carbon number is 5 or less, the molecular vibration is unlikely to occur when exposed to high frequency waves, resulting in excellent electrical properties. In addition, when the R's are hydrogen atoms, deterioration of the dielectric properties and water absorption properties associated with the generation of polar groups resulting from the oxidation reaction of the alkyl groups during high temperature storage tests can be suppressed. Each of the multiple 1's and n's independently represents an integer of 1 to 4, and preferably 1. Each of the multiple k's independently represents an integer of 0 to 4, and the average value k ave is 0 <k ave ≦4, preferably 0 <k ave Each of the multiple m's is independently an integer from 1 to 30, and the average value of m's is m ave is 1≦m ave ≦20, preferably 2≦m ave ≦15, and more preferably 2≦m ave <= 12.

[0025] m in the above formula (1) ave can be calculated from the number average molecular weight by GPC of a polybenzyl alcohol compound represented by formula (P) described below, which is an intermediate in the synthesis of a compound represented by formula (A) described below, or can be calculated from the results of NMR analysis of the compound represented by formula (1) above.

[0026] The method for producing the compound represented by the formula (1) is not particularly limited, but the compound can be obtained by reacting a compound represented by the following formula (A) with a compound represented by the following formula (B).

[0027] [ka]

[0028] In the above formula (A), R, m, n, and k have the same meanings as in the above formula (1).

[0029] [ka]

[0030] In the above formula (B), R and 1 have the same meanings as in the above formula (1). X represents a halogen atom, and from the viewpoints of reactivity and suppression of waste generation, it is preferably a bromine atom or a chlorine atom, and more preferably a chlorine atom.

[0031] The softening point of the compound represented by formula (A) is preferably 180°C or lower, more preferably 150°C or lower. If the softening point is 180°C or lower, the viscosity when induced into the compound represented by formula (1) is low. This makes it easier to ensure fluidity, does not impregnate glass cloth or carbon fiber, and facilitates B-stage formation such as prepreg formation. If the viscosity is reduced by increasing the dilution solvent, there is a possibility that the resin will not sufficiently adhere to the fibrous material in the impregnation process.

[0032] In the case of synthesizing the compound represented by formula (1), when the number of moles of the compound represented by formula (A) is α and the number of moles of the compound represented by formula (B) is β, β / α is preferably 1.8 to 2.1, more preferably 1.8 to 2.0 mol, and particularly preferably 1.8 to 1.95. If β / α is less than 1.8, the compound represented by formula (A) remains unreacted, and the toughness of the cured film may decrease, and the dielectric properties may deteriorate. This is because the unreacted compound represented by formula (A) does not have a structure that can be crosslinked, and the methylene structure at the 9th position of the fluorene structure of the compound represented by formula (A) reacts with oxygen to generate a ketone, which increases the polarity. If β / α is greater than 2.1, the halogen element of the compound represented by formula (B) that has not been completely removed by purification may be eliminated during curing (for example, at a temperature of 175° C. or higher) or during a high-temperature, high-humidity test (85° C., 85% humidity, 120° C., 100% humidity, etc.), which may lead to corrosion of the copper wiring. The amount of residual halogen contained in the compound represented by formula (1) is preferably 1 to 10,000 ppm, more preferably 1 to 3,000 ppm, and even more preferably 1 to 2,000 ppm.

[0033] The reaction between the compound represented by formula (A) and the compound represented by formula (B) will be described in detail. The compound represented by formula (1) is obtained by reacting the compound represented by formula (A) and the compound represented by formula (B) in an aprotic polar solvent in the presence of a basic catalyst. Examples of the aprotic polar solvent include dimethylsulfone, dimethylsulfoxide, dimethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, and N-methylpyrrolidone, and two or more of them may be used in combination. In addition, a non-water-soluble solvent may be used in combination as necessary. Examples of the non-water-soluble solvent include, but are not limited to, aromatic solvents such as toluene and xylene, aliphatic solvents such as cyclohexane and n-hexane, ethers such as diethyl ether and diisopropyl ether, ester solvents such as ethyl acetate and butyl acetate, and ketone solvents such as methyl isobutyl ketone and cyclopentanone, and two or more of them may be used in combination. The catalyst is not particularly limited, and examples thereof include basic catalysts such as sodium hydroxide, potassium hydroxide, and potassium carbonate. The order of adding the compound represented by formula (A), the compound represented by formula (B), and the base can be changed as necessary, but a method of adding the compound represented by formula (A), an aprotic polar solvent, and a base, sufficiently ionizing the compound represented by formula (A), and then adding the compound represented by formula (B) is preferred. When the reaction is performed without using an aprotic polar solvent, the reaction rate drops significantly. When an aprotic polar solvent is not used, the reaction is generally performed using an interphase transfer catalyst. In this case, the raw material is dissolved in a non-aqueous solvent such as toluene, and the compound represented by formula (A) and the compound represented by formula (B) are reacted in the presence of a base 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, making it difficult to achieve low dielectric properties (low dielectric constant and low dielectric loss tangent), and the remaining interphase transfer catalyst may cause problems such as ion migration when a substrate material using the compound represented by formula (1) is subjected to a long-term wet heat reliability test or the like.The reaction temperature is preferably 0 to 120°C, more preferably 0 to 100°C, and even more preferably 0 to 80°C. If the temperature is higher than the upper limit, the compound represented by the formula (1) may self-polymerize and gel. If the temperature is lower than the lower limit, the reaction may not proceed sufficiently. As a post-treatment after the reaction, neutralization may be performed with an arbitrary acid compound. If necessary, an alcohol compound, water, or the like may be added to the reaction solution to recover the target product as crystals. The obtained reaction solution or crystals may be re-dissolved in an arbitrary solvent to carry out an extraction step. 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 or toluene may be used in combination. After extraction, the organic layer is washed with water until the wastewater becomes neutral, and the target compound can be obtained by distilling off the solvent using an evaporator or the like.

[0034] The compound represented by the formula (A) can be obtained by reacting fluorene with a compound represented by the following formula (P).

[0035] [ka]

[0036] In the above formula (P), R, m, and n have the same meanings as in the above formula (1).

[0037] The number average molecular weight of the polybenzyl alcohol compound represented by the formula (P) is preferably 100 to 5000, more preferably 200 to 2500, and even more preferably 200 to 1500. The weight average molecular weight is preferably 100 to 7500, more preferably 200 to 4000, and even more preferably 200 to 2000. If the number average molecular weight or weight average molecular weight is less than 100, there is a risk that sufficient effects of low dielectric properties and low water absorption cannot be obtained. If the number average molecular weight is greater than 5000 or the weight average molecular weight is greater than 7500, there is a risk that the heat resistance is significantly reduced, and in addition, there is a risk that the solvent solubility is reduced, such as the compound represented by the formula (A) not being completely dissolved in a solvent when the compound represented by the formula (A) is reacted with the compound represented by the formula (B).

[0038] The polybenzyl alcohol compound represented by the formula (P) is derived by self-polymerizing the compound represented by the following formula (C) with an acid catalyst in the presence or absence of a solvent. As the catalyst, 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 ion exchange resins can be used. These may be used alone or in combination of two or more. The amount of catalyst used is preferably 0.1 to 40% by weight, preferably 0.1 to 20% by weight, based on the total weight of the compound represented by the following formula (C) used. If the amount of catalyst used is too large, the viscosity of the reaction solution may be too high, making stirring difficult, and if the amount is too small, the reaction may proceed slowly. The reaction may be carried out using an organic solvent such as hexane, cyclohexane, octane, toluene, or xylene, as necessary, or may be carried out without a solvent. For example, an acidic catalyst is added to a mixed solution of a compound represented by the following formula (C) and a solvent (or no solvent), and then the reaction is carried out for 0.5 to 20 hours at 0 to 180° C., preferably 10 to 170° C. The resulting reaction solution may be directly used for the reaction with fluorene, or the compound represented by the formula (P) may be taken out as a synthetic intermediate by distilling off the solvent after neutralization and washing with water.

[0039] [ka]

[0040] In the above formula (C), R and l have the same meanings as in the above formula (1). Y represents a hydroxyl group or a halogen atom, and from the viewpoints of reactivity and suppression of waste generation, it is preferably a hydroxyl group, a bromine atom, or a chlorine atom, and more preferably a hydroxyl group or a chlorine atom.

[0041] In obtaining the compound represented by formula (A), when fluorene and the compound represented by formula (P) are reacted, it is preferable to react 0.001 to 4 mol of the compound represented by formula (P) with 1 mol of fluorene, more preferably 0.002 to 3 mol, even more preferably 0.003 to 2 mol, and most preferably 0.003 to 1 mol. If it is less than 0.001 mol, there is a concern that the storage stability after dissolving in the solvent may deteriorate, such as crystals being precipitated when left for a long time after dissolving in the solvent, and if it exceeds 4 mol, there is a risk that the heat resistance may be significantly reduced, or the compound represented by formula (P) may become excessive and remain, which may impair the low dielectric properties.

[0042] When reacting fluorene with the compound represented by the formula (P), as necessary, hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, Lewis acids such as aluminum chloride and zinc chloride, activated clay, acidic clay, white carbon, zeolite, solid acids such as silica alumina, acidic ion exchange resins, etc. can be used as a catalyst. These may be used alone or in combination of two or more. The amount of catalyst used is preferably 0.1 to 40% by weight, preferably 0.1 to 20% by weight, based on the total weight of the fluorene and the compound represented by the formula (P) used. If the amount of catalyst used is too large, the viscosity of the reaction solution may be too high, making stirring difficult, and if the amount is too small, the reaction may proceed slowly. The reaction may be carried out using an organic solvent such as hexane, cyclohexane, octane, toluene, or xylene, as necessary, or may be carried out without a solvent. For example, after adding an acid catalyst to a mixed solution of fluorene, a compound represented by the formula (P), and a solvent (or no solvent), if the catalyst contains water, the water is removed from the system by azeotropy or the like. Then, the reaction is carried out at 40 to 180°C, preferably 50 to 170°C, for 0.5 to 20 hours. After the reaction is completed, the acid catalyst may be neutralized with an alkaline aqueous solution, but it is also possible to proceed to the water washing step without neutralizing it. In the water washing step, a water-insoluble organic solvent is added to the oil layer and water washing is repeated until the wastewater becomes neutral.

[0043] In addition, the compound represented by formula (A) obtained by the above reaction may be continuously derived into the compound represented by formula (1) by adding a neutralizing agent such as an alkali and an aprotic polar solvent to the solution after the reaction, and then adding a base catalyst and the compound represented by formula (B).

[0044] The compound represented by the formula (1) may be a mixture of compounds in which k in formula (1) is 1 or more and compounds in which k is 0. In this case, the compound may be expressed as a mixture of a compound represented by the following formula (1-1) and a compound represented by the following formula (1-2).

[0045] [ka]

[0046] In the above formula (1-1), each of the multiple R's independently represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, preferably a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, and more preferably a hydrogen atom. Each of the multiple 1's and n's independently represents an integer of 1 to 4, and preferably 1. Each of the multiple k's independently represents an integer of 0 to 4, and at least one of the two k's in formula (1-1) is an integer of 1 or more. The average value of k's is k ave is 0.5≦k ave ≦4, preferably 0.5≦k ave Each of the multiple m's is independently an integer from 1 to 30, and the average value of m's is m ave is 1≦m ave ≦20, preferably 2≦m ave ≦15, and more preferably 2≦m ave <= 12.

[0047] [ka]

[0048] In the above formula (1-2), each of the multiple R's independently represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, preferably a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, and more preferably a hydrogen atom. Each of the multiple 1's independently represents an integer of 1 to 4, and preferably 1.

[0049] In the mixture, the weight ratio of the compound represented by formula (1-1) to the compound represented by formula (1-2) is preferably 1:200 to 200:1, more preferably 1:100 to 100:1, even more preferably 1:99 to 1:1, and most preferably 1:99 to 10:90.

[0050] The compound represented by the formula (1) can be cured by itself by heating or the like, but performance can also be improved by adding various materials to form a curable resin composition.

[0051] [Cure accelerator] The curable resin composition of the present embodiment can also have improved curability by adding a curing accelerator. As the curing accelerator, an anionic curing accelerator that accelerates the curing reaction by generating anions upon irradiation with ultraviolet light or visible light or heating, or a cationic curing accelerator that accelerates the curing reaction by generating cations upon irradiation with ultraviolet light or visible light or heating, is preferred.

[0052] Examples of anionic curing accelerators include imidazoles such as 2-methylimidazole, 2-ethylimidazole, and 2-ethyl-4-methylimidazole, trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6,-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo(5,4,0)-undecene, with 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)-undecene being preferred. Other examples include phosphines such as triphenylphosphine, quaternary ammonium salts such as tetrabutylammonium salts, triisopropylmethylammonium salts, trimethyldecanylammonium salts, cetyltrimethylammonium salts, and hexadecyltrimethylammonium hydroxide, but are not limited thereto. These may be used alone or in combination.

[0053] Examples of cationic curing accelerators include quaternary phosphonium salts such as triphenylbenzylphosphonium salt, triphenylethylphosphonium salt, and tetrabutylphosphonium salt (counter ions of quaternary salts are halogen, organic acid ions, hydroxide ions, etc., and are not particularly specified, but organic acid ions and hydroxide ions are particularly preferred), transition metal compounds (transition metal salts) such as tin octylate, zinc carboxylate (zinc 2-ethylhexanoate, zinc stearate, zinc behenate, zinc myristate), and zinc phosphate (zinc octyl phosphate, zinc stearyl phosphate), but are not limited thereto. These may be used alone or in combination.

[0054] The curing accelerator is used in an amount of 0.01 to 5.0 parts by weight based on 100 parts by weight of the curable resin composition, as required.

[0055] [Inorganic filler] The curable resin composition of the present embodiment may contain an inorganic filler. Examples of inorganic fillers 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, and glass powder, and inorganic fillers obtained by making these into a spherical or crushed shape, but are not limited thereto. In addition, these may be used alone or in combination.

[0056] When the curable resin composition for semiconductor encapsulation is obtained, the inorganic filler is used in an amount of preferably 80 to 92 parts by weight, more preferably 83 to 90 parts by weight, based on 100 parts by weight of the curable resin composition. When the curable resin composition for interlayer insulating layer forming material, copper-clad laminate, prepreg, RCC, or other substrate material is obtained, the inorganic filler is used in an amount of preferably 5 to 80 parts by weight, more preferably 10 to 60 parts by weight, based on 100 parts by weight of the curable resin composition.

[0057] [Polymerization initiator] The curable resin composition of the present embodiment can also improve the curability by adding a polymerization initiator. The polymerization initiator is a compound capable of polymerizing an olefin functional group such as an ethylenically unsaturated bond, and examples of such a polymerization initiator include an olefin metathesis polymerization initiator, an anionic polymerization initiator, a cationic polymerization initiator, and a radical polymerization initiator. Among these, it is preferable to use a radical polymerization initiator having curability and moderate stability. The radical polymerization initiator is a compound that generates radicals by irradiation with ultraviolet light or visible light or by heating, and initiates a chain polymerization reaction. Examples of radical polymerization initiators that can be used include organic peroxides, azo compounds, and benzopinacoles, and it is preferable to use an organic peroxide because it has little effect on curing temperature control, outgassing suppression, and electrical properties of decomposition products.

[0058] Examples of the organic peroxides include ketone peroxides such as methyl ethyl ketone peroxide and acetylacetone peroxide, diacyl peroxides such as benzoyl peroxide, dialkyl peroxides such as dicumyl peroxide and 1,3-bis-(t-butylperoxyisopropyl)-benzene, peroxyketals such as t-butyl peroxybenzoate and 1,1-di-t-butylperoxycyclohexane, α-cumyl peroxyneodecanoate, t-butyl peroxyneodecanoate, t-butyl peroxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-amyl peroxy-2-ethylhex ...amyl peroxy-2-ethylhexanoate, t-butyl peroxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-amyl peroxy-2-ethylhexanoate, t-butyl peroxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-amyl peroxy-2-ethylhexanoate, t-butyl peroxypivalate, 1,1, Examples of the peroxycarbonates include, but are not limited to, alkyl peresters such as t-amyl 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, t-butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxyoctoate, and lauroyl peroxide. These may be used alone or in combination. Among the above organic peroxides, ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, alkyl peresters, percarbonates, etc. are preferred, and dialkyl peroxides are more preferred.

[0059] Examples of the azo-based compound 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.

[0060] The amount of the polymerization initiator added is preferably 0.01 to 5 parts by weight, particularly preferably 0.01 to 3 parts by weight, relative to 100 parts by weight of the curable resin composition. If the amount of the polymerization initiator used is less than 0.01 part by weight, the molecular weight may not be sufficiently extended during the polymerization reaction, and if it is more than 5 parts by weight, the dielectric properties such as the dielectric constant and dielectric loss tangent may be impaired.

[0061] [Polymerization inhibitor] The curable resin composition of the present embodiment may contain a polymerization inhibitor. By containing a polymerization inhibitor, storage stability is improved and the reaction initiation temperature can be controlled. By controlling the reaction initiation temperature, it becomes easy to ensure fluidity, impregnation into glass cloth and the like is not impaired, and B-stage such as prepreg formation is facilitated. If the polymerization reaction proceeds too much during prepreg formation, problems such as difficulty in lamination during the lamination process are likely to occur.

[0062] The polymerization inhibitor may be added when or after the compound represented by the formula (1) is synthesized. The amount of the polymerization inhibitor used is 0.008 to 1 part by weight, preferably 0.01 to 0.5 parts by weight, based on 100 parts by weight of the compound represented by the formula (1).

[0063] Examples of the polymerization inhibitor include phenol-based, sulfur-based, phosphorus-based, hindered amine-based, nitroso-based, and nitroxyl radical-based. The polymerization inhibitor may be used alone or in combination. Among these, in the present embodiment, the phenol-based, hindered amine-based, nitroso-based, and nitroxyl radical-based are preferred.

[0064] Examples of the phenol-based polymerization inhibitor include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, stearyl-β-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, 2,4-bis[(octylthio)methyl]-o ... Monophenols such as resol, 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol), 4,4'-thiobis(3-methyl-6-t-butylphenol), 4,4'-butylidenebis(3-methyl-6-t-butylphenol), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] , N,N'-Hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, 3,9-bis[1,1-dimethyl-2-{β-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}ethyl]2,4,8,10-tetraoxaspiro[5,5]undecane, bis(3,5-di-t-butyl Bisphenols such as calcium ethyl-4-hydroxybenzylsulfonate, 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, tetrakis-[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methane, bis[3,3'-bis-(4'-hydroxy-3'-t-butylphenyl)butyric acid]glycol ester, tris-(3,5-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 and other polymeric phenols are included, but are not limited to these.

[0065] Examples of the sulfur-based polymerization inhibitor include, but are not limited to, dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, and distearyl-3,3'-thiodipropionate.

[0066] Examples of the phosphorus-based polymerization inhibitor include triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, tris(nonylphenyl) phosphite, diisodecyl pentaerythritol phosphite, tris(2,4-di-t-butylphenyl) phosphite, cyclic neopentane tetrayl bis(octadecyl) phosphite, cyclic neopentane tetrayl bi(2,4-di-t-butylphenyl) phosphite, cyclic neopentane tetrayl bi(2,4-di-t-butyl-4-methylphenyl) phosphite, bis[2-t 10-(3,5-di-t-butyl-4-hydroxybenzyl)-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, and other oxaphosphaphenanthrene oxides, but are not limited to these.

[0067] Examples of the hindered amine polymerization inhibitor include, but are not limited to, Adeka STAB LA-40MP, Adeka STAB LA-40Si, Adeka STAB LA-402AF, Adeka STAB LA-87, Deka STAB LA-82, Deka STAB LA-81, Adeka STAB LA-77Y, Adeka STAB LA-77G, Adeka STAB LA-72, Adeka STAB LA-68, Adeka STAB LA-63P, Adeka STAB LA-57, Adeka STAB LA-52, Chimassorb 2020FDL, Chimassorb 944FDL, Chimassorb 944LD, Tinuvin 622SF, Tinuvin PA144, Tinuvin 765, Tinuvin 770DF, Tinuvin XT55FB, Tinuvin 111FDL, Tinuvin 783FDL, Tinuvin 791FB, and the like.

[0068] Examples of the nitroso-based 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 preferred.

[0069] Examples of the nitroxyl radical polymerization inhibitor include di-tert-butyl nitroxide, 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-amino-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-acetoxy-2,2,6,6-tetramethylpiperidine-1-oxyl, and 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl, but are not limited thereto.

[0070] [Flame retardant] The curable resin composition of the present embodiment may contain a flame retardant. Examples of the flame retardant include halogen-based flame retardants, inorganic flame retardants (antimony compounds, metal hydroxides, nitrogen compounds, boron compounds, etc.), and phosphorus-based flame retardants. From the viewpoint of achieving halogen-free flame retardancy, phosphorus-based flame retardants are preferred. The phosphorus-based flame retardant may be of reactive type or additive type. Specific examples include phosphoric acid esters such as trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylyleneyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylyleneyl phosphate, 1,3-phenylene bis(dixylyleneyl phosphate), 1,4-phenylene bis(dixylyleneyl phosphate), and 4,4'-biphenyl(dixylyleneyl phosphate), phosphanes such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 10(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, phosphorus-containing epoxy compounds obtained by reacting epoxy resins with active hydrogen of the phosphanes, red phosphorus, etc., but are not limited thereto. Also, these may be used alone or in combination. Of the above-listed substances, phosphates, phosphanes, or phosphorus-containing epoxy compounds are preferred, with 1,3-phenylenebis(dixylilenyl phosphate), 1,4-phenylenebis(dixylilenyl phosphate), 4,4'-biphenyl(dixylilenyl phosphate) or phosphorus-containing epoxy compounds being particularly preferred. The content of the flame retardant is preferably in the range of 0.1 to 0.6 parts by weight based on 100 parts by weight of the curable resin composition. If the content is less than 0.1 part by weight, the flame retardancy may be insufficient, and if the content is more than 0.6 parts by weight, the moisture absorption and dielectric properties of the cured product may be adversely affected.

[0071] [Light stabilizer] The curable resin composition of the present embodiment may contain a light stabilizer. As the light stabilizer, a hindered amine light stabilizer, particularly HALS, etc., is preferable. 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 malonate bis(1,2,2,6,6-pentamethyl-4-piperidyl) and the like, but are not limited thereto. These may be used alone or in combination.

[0072] The content of the light stabilizer is preferably in the range of 0.001 to 0.1 parts by weight based on 100 parts by weight of the curable resin composition. If the content is less than 0.001 part by weight, the light stabilizing effect may be insufficient, and if the content is more than 0.1 part by weight, the moisture absorption and dielectric properties of the cured product may be adversely affected.

[0073] [Binder resin] The curable resin composition of the present 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, and silicone resins. These may be used alone or in combination.

[0074] The amount of the binder resin is preferably within a range that does not impair the flame retardancy and heat resistance of the cured product, and is preferably 0.05 to 50 parts by weight, and more preferably 0.05 to 20 parts by weight, per 100 parts by weight of the curable resin composition, as needed.

[0075] [Additives] The curable resin composition of the present embodiment may contain additives, such as modified acrylonitrile copolymers, polyethylene, fluororesins, silicone gels, silicone oils, surface treatment agents for fillers such as silane coupling agents, release agents, and colorants such as carbon black, phthalocyanine blue, and phthalocyanine green.

[0076] The amount of the additive is preferably 1,000 parts by weight or less, and more preferably 700 parts by weight or less, based on 100 parts by weight of the curable resin composition.

[0077] The curable resin composition of the present embodiment may further contain 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 modified products thereof, polystyrene and modified products thereof, polyethylene and modified products thereof, etc., which may be used alone or in combination. Of these compounds, it is preferable to contain polyphenylene ether compounds, compounds having ethylenically unsaturated bonds, cyanate ester resins, polybutadiene and modified products thereof, and polystyrene and modified products thereof, from the perspective of the balance of heat resistance, adhesion, and dielectric properties. By containing these compounds, the brittleness of the cured product and adhesion to metals can be improved, and cracks in the package during solder reflow and during reliability tests such as thermal cycles can be suppressed. The total amount of these compounds used is preferably 10 times by weight or less, more preferably 5 times by weight or less, and particularly preferably 3 times by weight or less, relative to the compound represented by formula (1), unless otherwise specified. The lower limit is preferably 0.1 times by weight or more, more preferably 0.25 times by weight or more, and even more preferably 0.5 times by weight or more. By being within the above range, the effect of each compound added can be added while taking advantage of the effect of the low dielectric property of the compound represented by the formula (1). As these components, the following examples can be used.

[0078] [Epoxy resin] Preferred examples of the epoxy resin are shown below, but the epoxy resin is not limited thereto. The epoxy resin may be liquid or solid, and may be used alone or in combination.

[0079] Examples of liquid epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, phenol novolac type epoxy resins, alicyclic epoxy resins having an ester skeleton, cyclohexane type epoxy resins, cyclohexane dimethanol type epoxy resins, glycidyl amine type epoxy resins, and epoxy resins having a butadiene structure. Specific examples include "RE310S", "RE410S" (all manufactured by Nippon Kayaku Co., Ltd., bisphenol A type epoxy resin), "RE303S", "RE304S", "RE403S", "RE404S" (all manufactured by Nippon Kayaku Co., Ltd., bisphenol F type epoxy resin), "HP4032", "HP4032D", "HP4032SS" (all manufactured by DIC Corporation, naphthalene type epoxy resin), "828US", "jER828EL", "825", "828EL" (all manufactured by Mitsubishi Chemical Corporation, bisphenol A type epoxy resin), "jE807", "1750" (all manufactured by Mitsubishi Chemical Corporation, bisphenol F type epoxy resin), "jER152" (manufactured by Mitsubishi Chemical Corporation, phenol Novolac type epoxy resin), "630", "630LSD" (all manufactured by Mitsubishi Chemical Corporation, glycidylamine type epoxy resin), "ZX1059" (manufactured by Nippon Steel & Sumitomo Metal 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), "Celloxide 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" (all manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., liquid 1,4-glycidylcyclohexane type epoxy resin), etc. may be mentioned. These may be used alone or in combination of two or more.

[0080] Preferred examples of solid epoxy resins include bixylenol type epoxy resins, naphthalene type epoxy resins, naphthalene type tetrafunctional epoxy resins, cresol novolac type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol type epoxy resins, naphthol type epoxy resins, biphenyl type epoxy resins, naphthylene ether type epoxy resins, anthracene type epoxy resins, bisphenol A type epoxy resins, bisphenol AF type epoxy resins, and tetraphenylethane type epoxy resins, and examples of such solid epoxy resins include naphthol type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, and biphenyl type epoxy resins.Specific examples include "HP4032H" (manufactured by DIC Corporation, naphthalene type epoxy resin), "HP-4700", and "HP-4710" (all manufactured by DIC Corporation, naphthalene type tetrafunctional epoxy resin), "N-690" (manufactured by DIC Corporation, cresol novolac type epoxy resin), "N-695" (manufactured by DIC Corporation, cresol novolac type epoxy resin), "HP-7200" (manufactured by DIC Corporation, dicyclopentadiene type epoxy resin), "HP-7200", "HP-7200HH", and "HP-7200H" (all manufactured by DIC Corporation, dicyclopentadiene type epoxy resin). 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., trisphenol type epoxy resin), "NC-7000L", "NC-7300" (all manufactured by Nippon Kayaku Co., Ltd., naphthol-cresol novolac type epoxy resin), "NC-3000H", "NC-3000", "NC-3000L", "NC-3100" (all manufactured by Nippon Kayaku Co., Ltd., biphenyl ether type epoxy resin). arylalkyl 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 novolac type epoxy resin), "YX-4000H", "YX-4000", "YL6121" (all manufactured by Mitsubishi Chemical Corporation, biphenyl type epoxy resin), "YX-4000HK" (manufactured by Mitsubishi Chemical Corporation, bixyl Examples of epoxy resins that can be used include "YX-8800" (manufactured by Mitsubishi Chemical Corporation, anthracene type epoxy resin), "PG-100", "CG-500" (manufactured by Osaka Gas Chemical Co., Ltd., fluorene type 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), and "jER1031S" (manufactured by Mitsubishi Chemical Corporation, tetraphenylethane type epoxy resin).These may be used alone or in combination of two or more.

[0081] [Active ester compounds] The active ester compound refers to a compound that contains at least one ester bond in the structure and has 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 in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, and are obtained by a condensation reaction between at least one compound of a carboxylic acid compound, an acid chloride, or a thiocarboxylic acid compound and at least one compound of a hydroxy compound or a thiol compound. In particular, from the viewpoint of improving heat resistance, it is preferable to obtain it from a carboxylic acid compound or an acid chloride and a hydroxy compound, and the hydroxy compound is preferably a phenol compound or a naphthol compound. The active ester compound may be used alone or in combination of two or more types.

[0082] Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.

[0083] Examples of the acid chloride include acetyl chloride, acrylic acid chloride, methacrylic acid chloride, malonyl chloride, succinic acid dichloride, diglycolyl chloride, glutaric acid dichloride, suberic acid dichloride, sebacic acid dichloride, adipic acid dichloride, dodecandioyl dichloride, azelaic acid chloride, 2,5-furandicarbonyl dichloride, phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, trimesic acid chloride, bis(4-chlorocarbonylphenyl) ether, 4,4'-diphenyldicarbonyl chloride, and 4,4'-azodibenzoyl dichloride.

[0084] Examples of the phenol compounds and naphthol compounds include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene-type diphenol compounds, phenol novolac, and phenol resins described below. Here, the term "dicyclopentadiene-type diphenol compounds" refers to diphenol compounds obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.

[0085] Preferred specific examples of the active ester compound include an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, an active ester compound containing a benzoylated product of phenol novolac, a compound described in Example 2 of International Publication No. 2020 / 095829, and a compound disclosed in International Publication No. 2020 / 059625. Among them, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene-type diphenol structure are more preferred. The dicyclopentadiene-type diphenol structure refers to a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

[0086] Commercially available active ester compounds include, for example, "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "HPC-8000H-65TM", "EXB-8000L-65TM", and "EXB-8150-65T" (manufactured by DIC Corporation) as active ester compounds containing a dicyclopentadiene-type diphenol structure, "EXB9416-70BK" (manufactured by DIC Corporation) as an active ester compound containing a naphthalene structure, and "phenolnoxamine" (manufactured by DIC Corporation). Examples of active ester compounds containing acetylated phenol novolac include "DC808" (manufactured by Mitsubishi Chemical Corporation); active ester compounds containing benzoylated phenol novolac include "YLH1026," "YLH1030," and "YLH1048" (manufactured by Mitsubishi Chemical Corporation); "DC808" (manufactured by Mitsubishi Chemical Corporation) is an active ester curing agent which is an acetylated phenol novolac; and "EXB-9050L-62M" (manufactured by DIC Corporation) is an active ester curing agent containing a phosphorus atom.

[0087] Regarding the compounding ratio of the active ester compound and the epoxy resin, the ratio (α / β) of the active ester equivalent (α) to the epoxy equivalent (β) is preferably 0.5 to 1.5, more preferably 0.8 to 1.2, and even more preferably 0.90 to 1.10. If it is out of the above range, there is a risk that excess epoxy groups or active ester groups will remain in the system, and the characteristics may deteriorate in a high-temperature storage test (e.g., 150°C, 1000 hours) or a long-term reliability test under high-temperature and high-humidity conditions (e.g., temperature: 85°C, humidity: 85%).

[0088] [Phenol resin] A phenolic resin is a compound having two or more phenolic hydroxyl groups in a molecule. Examples of phenolic resins include, but are not limited to, reaction products of phenols and aldehydes, reaction products of phenols and diene compounds, reaction products of phenols and ketones, reaction products of phenols and substituted biphenyls, reaction products of phenols and substituted phenyls, and reaction products of bisphenols and aldehydes. These may be used alone or in combination. Specific examples of the above-mentioned raw materials are given below, but the raw materials are not limited thereto. <Phenols> Phenol, alkyl-substituted phenol, aromatic-substituted phenol, hydroquinone, resorcin, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc. <Aldehydes> Formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, furfural, and the like. <Diene compounds> Dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, and the like. <Ketones> Acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, fluorenone, etc. <Substituted biphenyls> 4,4'-bis(chloromethyl)-1,1'-biphenyl, 4,4'-bis(methoxymethyl)-1,1'-biphenyl, 4,4'-bis(hydroxymethyl)-1,1'-biphenyl and the like. <Substituted phenyls> 1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene, 1,4-bis(hydroxymethyl)benzene and the like.

[0089] [Polyphenylene ether compounds] From the viewpoint of heat resistance and electrical properties, the polyphenylene ether compound is preferably a polyphenylene ether compound having an ethylenically unsaturated bond, and more preferably a polyphenylene ether compound having an acrylic group, a methacrylic group, or a styrene structure. Commercially available products include SA-9000 (manufactured by SABIC, a polyphenylene ether compound having a methacrylic group) and OPE-2St 1200 (manufactured by Mitsubishi Gas Chemical, 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 more preferably 2000 to 4000. If the molecular weight is less than 500, the heat resistance of the cured product tends to be insufficient. If the molecular weight is more than 5000, the melt viscosity increases and sufficient fluidity cannot be obtained, which tends to lead to molding defects. In addition, the reactivity decreases, the curing reaction takes a long time, and the amount of unreacted material that is not incorporated into the curing system increases, which decreases the glass transition temperature of the cured product and tends to decrease the heat resistance of the cured product. If the number average molecular weight of the polyphenylene ether compound is 500 to 5000, it is possible to exhibit excellent heat resistance, moldability, etc. while maintaining excellent dielectric properties. The number average molecular weight here can be specifically measured using gel permeation chromatography, etc.

[0090] The polyphenylene ether compound may be one obtained by a polymerization reaction, or one obtained by a redistribution reaction of a high molecular weight polyphenylene ether compound having a number average molecular weight of about 10,000 to 30,000. In addition, these may be used as raw materials and reacted with a compound having an ethylenically unsaturated bond, such as methacryl chloride, acrylic chloride, or chloromethylstyrene, to impart radical polymerizability. 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 phenolic compound and a radical initiator to cause a redistribution reaction. The polyphenylene ether compound obtained by the redistribution reaction in this way has hydroxyl groups derived from a phenolic compound that contributes to curing at both ends of the molecular chain, and is therefore preferable in that it can maintain even higher heat resistance, and that functional groups can be introduced at both ends of the molecular chain even after modification with a compound having an ethylenically unsaturated bond. In addition, the polyphenylene ether compound obtained by the polymerization reaction is preferable in that it exhibits excellent fluidity.

[0091] The molecular weight of the polyphenylene ether compound can be adjusted by adjusting the polymerization conditions, etc., in the case of a polyphenylene ether compound obtained by a polymerization reaction. In addition, in the case of a polyphenylene ether compound obtained by a redistribution reaction, the molecular weight of the obtained polyphenylene ether compound can be adjusted by adjusting the conditions of the redistribution reaction, etc. More specifically, it is possible to adjust the amount of the phenolic compound used in the redistribution reaction. That is, the greater the amount of the phenolic compound, the lower the molecular weight of the obtained polyphenylene ether compound. In this case, poly(2,6-dimethyl-1,4-phenylene ether) and the like can be used as the high molecular weight polyphenylene ether compound that undergoes the redistribution reaction. In addition, the phenolic compound used in the redistribution reaction is not particularly limited, but for example, a multifunctional phenolic compound having two or more phenolic hydroxyl groups in the molecule, such as bisphenol A, phenol novolac, cresol novolac, etc., is preferably used. These may be used alone or in combination of two or more.

[0092] The content of the polyphenylene ether compound is not particularly limited, but is preferably 5 to 1000 parts by weight, more preferably 10 to 750 parts by weight, relative to 100 parts by weight of the curable resin composition. The content of the polyphenylene ether compound in the above range is preferable in that a cured product is obtained that is not only excellent in heat resistance, but also fully exhibits the excellent dielectric properties of the polyphenylene ether compound.

[0093] [Amine resin] Amine resins are compounds having two or more amino groups in the molecule. Examples of amine resins include diaminodiphenylmethane, diaminodiphenylsulfone, isophoronediamine, naphthalenediamine, aniline novolac (a reaction product of aniline and formalin), N-methylaniline novolac (a reaction product of N-methylaniline and formalin), orthoethylaniline novolac (a reaction product of orthoethylaniline and formalin), a reaction product of 2-methylaniline and formalin, a reaction product of 2,6-diisopropylaniline and formalin, a reaction product of 2,6-diethylaniline and formalin, a reaction product of 2-ethyl-6-ethylaniline and formalin, a reaction product of 2,6-dimethylaniline and formalin, and a reaction product obtained by reacting aniline and xylylene chloride. Examples of the aniline resin include, but are not limited to, the aniline resin disclosed in Japanese Patent No. 6429862, a reaction product of aniline and a substituted biphenyl (4,4'-bis(chloromethyl)-1,1'-biphenyl, 4,4'-bis(methoxymethyl)-1,1'-biphenyl, etc.), a reaction product of aniline and a substituted phenyl (1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene, 1,4-bis(hydroxymethyl)benzene, etc.), 4,4'-(1,3-phenylenediisopropylidene)bisaniline, 4,4'-(1,4-phenylenediisopropylidene)bisaniline, a reaction product of aniline and diisopropenylbenzene, dimer diamine, etc. Furthermore, these may be used alone or in combination.

[0094] [Compounds containing ethylenically unsaturated bonds] A compound containing an ethylenically unsaturated bond is a compound that has one or more ethylenically unsaturated bonds in the molecule that can be polymerized by heat or light, regardless of whether a polymerization initiator is used or not. Examples of compounds containing ethylenically unsaturated bonds include, but are not limited to, reaction products of the above-mentioned phenol resins and halogen-based compounds containing ethylenically unsaturated bonds (chloromethylstyrene, allyl chloride, methallyl chloride, acrylic acid chloride, methacrylic acid chloride, etc.), reaction products of phenols containing ethylenically unsaturated bonds (2-allylphenol, 2-propenylphenol, 4-allylphenol, 4-propenylphenol, eugenol, isoeugenol, etc.) and halogen-based compounds (1,4-bis(chloromethyl)benzene, 4,4'-bis(chloromethyl)biphenyl, 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-dibromobenzophenone, cyanuric chloride, etc.), reaction products of epoxy resins or alcohols and (meth)acrylic acids (acrylic acid, methacrylic acid, etc.), and acid-modified products thereof. In addition, these may be used alone or in combination.

[0095] [Isocyanate resin] An isocyanate resin is a compound that has two or more isocyanate groups in its molecule. Examples of the isocyanate resin include aromatic diisocyanates such as p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and naphthalene diisocyanate; aliphatic or alicyclic diisocyanates such as isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, norbornene diisocyanate, and lysine diisocyanate; polyisocyanates such as one or more biuret forms of isocyanate monomers or isocyanate forms obtained by trimerizing the above diisocyanate compounds; and polyisocyanates obtained by a urethanization reaction between the above isocyanate compounds and polyol compounds, but are not limited thereto. These may be used alone or in combination.

[0096] [Polyamide resin] Examples of polyamide resins include reaction products of one or more of diamines, diisocyanates, and oxazolines with dicarboxylic acids, reaction products of diamines with acid chlorides, and ring-opening polymers of lactam compounds. These may be used alone or in combination. Specific examples of the above-mentioned raw materials are given below, but the raw materials 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, cyclohexane diamine, bis-(4-aminocyclohexyl)methane, bis(3-methyl-4-aminocyclohexyl)methane, xylylene diamine, norbornane diamine, isophorone diamine, 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, diaminodiphenyl sulfone, diaminodiphenyl ether, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 4,4-bis(4-aminophenoxy)biphenyl, 2,2-bis[4-(4-amino 4,4'-(1,3-phenylenediisopropylidene)bisaniline, 4,4'-(1,4-phenylenediisopropylidene)bisaniline, 9,9-bis(4-aminophenyl)fluorene, 2,7-diaminofluorene, aminobenzylamine, diaminobenzophenone, and the like. <Diisocyanate> Benzene diisocyanate, toluene diisocyanate, 1,3-bis(isocyanatomethyl)benzene, 1,3-bis(isocyanatomethyl)cyclohexane, bis(4-isocyanatophenyl)methane, isophorone diisocyanate, 1,3-bis(2-isocyanato-2-propyl)benzene, 2,2-bis(4-isocyanatophenyl)hexafluoropropane, dicyclohexylmethane-4,4'-diisocyanate, and the like. <Dicarboxylic acid> Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, 5-hydroxyisophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, cyclohexanedicarboxylic acid, biphenyldicarboxylic acid, naphthalenedicarboxylic acid, benzophenonedicarboxylic acid, furandicarboxylic acid, 4,4'-dicarboxydiphenyl ether, 4,4'-dicarboxydiphenyl sulfide, etc. <Acid chloride> Acetyl chloride, acrylic acid chloride, methacrylic acid chloride, malonyl chloride, succinic acid dichloride, diglycolyl chloride, glutaric acid dichloride, suberic acid dichloride, sebacic acid dichloride, adipic acid dichloride, dodecandioyl dichloride, azelaic acid chloride, 2,5-furandicarbonyl dichloride, phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, trimesic acid chloride, bis(4-chlorocarbonylphenyl) ether, 4,4'-diphenyldicarbonyl chloride, 4,4'-azodibenzoyl dichloride, and the like. <Lactam> ε-caprolactam, ω-undecanelactam, ω-laurolactam, and the like.

[0097] [Polyimide resin] Examples of polyimide resins include, but are not limited to, reaction products of the diamines and the tetracarboxylic dianhydrides shown below. These may be used alone or in combination. <Tetracarboxylic acid dianhydride> 4,4'-(Hexafluoroisopropylidene)diphthalic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-cyclohexene-1,2 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 acid Dianhydride, 1,3-bis(3,4-dicarboxyphenyl)benzene dianhydride, 1,3-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 1,3-bis[2-(3,4-dicarboxyphenyl)-2-propyl]benzene dianhydride, 1,4-bis[2-(3,4-dicarboxyphenyl)-2-propyl]benzene dianhydride, bis[3-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride, bis[4-(3,4-dicarboxyphenoxy)phenyl]methane 2,2-bis[3-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, bis(3,4-dicarboxyphenoxy)dimethylsilane dianhydride, 1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldisiloxane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3,4,9,10-Perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, ethylenetetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride tetracarboxylic dianhydride, 3,3',4,4'-bicyclohexyltetracarboxylic dianhydride, carbonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic) dianhydride, methylene-4,4'-bis(cyclohexane-1,2-dicarboxylic) dianhydride, 1,2-ethylene-4,4'-bis(cyclohexane-1,2-dicarboxylic) dianhydride, 1,1-ethylidene-4,4'-bis(cyclohexane-1,2-dicarboxylic) dianhydride, 2,2-propylidene -4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, oxy-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, thio-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, sulfonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, rel-[1S,5R,6R]-3-oxabicyclo[3,2 ,1]Octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, ethylene glycol-bis-(3,4-dicarboxylic anhydride phenyl) ether, 4,4'-biphenyl bis(trimellitic acid monoester acid anhydride), 9,9'-bis(3,4-dicarboxyphenyl)fluorene dianhydride, etc.,

[0098] [Maleimide compounds] The curable resin composition of the present embodiment may contain a maleimide compound. A maleimide compound is a compound having one or more maleimide groups in a molecule. Examples of the maleimide compound include 4,4'-diphenylmethane bismaleimide, polyphenylmethane maleimide, m-phenylene bismaleimide, 2,2'-bis[4-(4-maleimidophenoxy)phenyl]propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 4,4'-diphenylether bismaleimide, 4,4'-diphenylsulfone bismaleimide, 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene), Xylox type maleimide compound (anilix), and the like. Maleimide, manufactured by Mitsui Chemicals Fine Co., Ltd.), biphenylaralkyl-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 2009-001783 A), bisaminocumylbenzene-type maleimide (maleimide compound described in WO 2020 / 054601 A), maleimide compounds having an indane structure described in Japanese Patent No. 6629692 or WO 2020 / 217679, MATERIAL STAGE Vol. 18, No. 12 2019 ``~Continued Epoxy Resin CAS Number Story~ Hardener CAS Number Memorandum No. 31 Bismaleimide (1)'' and MATERIAL STAGE Vol. 19, No. 2 2019 ``~Continued Epoxy Resin CAS Number Story~ Hardener CAS Number Memorandum No. 32 Bismaleimide (2) and the like can be used, but are not limited thereto. These can be used alone or in combination.

[0099] [Cyanate ester resin] Cyanate ester resins are cyanate ester compounds obtained by reacting phenolic resins with cyanogen halides, and specific examples include dicyanatobenzene, tricyanatobenzene, dicyanatonaphthalene, dicyanatobiphenyl, 2,2'-bis(4-cyanatophenyl)propane, bis(4-cyanatophenyl)methane, bis(3,5-dimethyl-4-cyanatophenyl)methane, 2,2'-bis(3,5-dimethyl-4-cyanatophenyl)propane, 2,2'-bis(4-cyanatophenyl)ethane, 2,2'-bis(4-cyanatophenyl)hexafluoropropane, bis(4-cyanatophenyl)sulfone, bis(4-cyanatophenyl)thioether, phenol novolac cyanate, and phenol-dicyclopentadiene co-condensates in which the hydroxyl groups have been converted to cyanate groups, but are not limited thereto. These may be used alone or in combination. Furthermore, the cyanate ester compound, the synthesis method of which is described in JP-A-2005-264154, is particularly preferred as the cyanate ester compound because it has low moisture absorption, excellent flame retardancy, and excellent dielectric properties. The cyanate ester resins can optionally contain a catalyst, such as zinc naphthenate, cobalt naphthenate, copper naphthenate, lead naphthenate, zinc octoate, tin octoate, lead acetylacetonate, or dibutyltin maleate, to trimerize the cyanate groups to form sym-triazine rings.

[0100] The catalyst is preferably used in an amount of 0.0001 to 0.10 parts by weight, and more preferably 0.00015 to 0.0015 parts by weight, based on 100 parts by weight of the cyanate ester resin and the curable resin composition.

[0101] [Polybutadiene and its modified products] The polybutadiene and its modified products are polybutadiene or compounds having a structure derived from polybutadiene in the molecule. The unsaturated bonds in the polybutadiene-derived structure may be partially or entirely converted to single bonds by hydrogenation. Examples of polybutadiene and modified products thereof include, but are not limited to, polybutadiene, hydroxyl-terminated polybutadiene, (meth)acrylate-terminated polybutadiene, carboxylic acid-terminated polybutadiene, amine-terminated polybutadiene, styrene-butadiene rubber, and the like. These may be used alone or in combination. Among these, polybutadiene or styrene-butadiene rubber is preferred from the viewpoint of dielectric properties. Examples of styrene-butadiene rubber (SBR) include RICON-100, RICON-181, RICON-184 (all manufactured by Cray Valley), 1,2-SBS (manufactured by Nippon Soda Co., Ltd.), and examples of polybutadiene include B-1000, B-2000, B-3000 (all manufactured by Nippon Soda Co., Ltd.). The molecular weight of polybutadiene and styrene-butadiene rubber is preferably a weight average molecular weight of 500 to 10,000, more preferably 750 to 7,500, and even more preferably 1,000 to 5,000. Below the lower limit of the above range, the amount of volatilization is large, making it difficult to adjust the solid content during prepreg preparation, and above the upper limit of the above range, the compatibility with other curable resins is deteriorated. In general, in the case of compounds containing heteroatoms such as oxygen and nitrogen, such as bismaleimide and polymaleimide, it is difficult to ensure compatibility with low-polarity compounds such as compounds mainly composed of hydrocarbons or compounds composed only of hydrocarbons due to their polarity. On the other hand, the compound represented by the above formula (1) is excellent in compatibility with materials having low polarity and low dielectric properties and compounds composed only of hydrocarbons, due to the fact that the compound itself does not have a skeleton design in which heteroatoms such as oxygen and nitrogen are actively introduced.

[0102] [Polystyrene and its modified products] Polystyrene and modified products thereof are polystyrene or compounds having a structure derived from polystyrene in the molecule. Examples of polystyrene and modified products thereof include polystyrene, styrene-2-isopropenyl-2-oxazoline copolymers (Epocross RPS-1005, RP-61, both manufactured by Nippon Shokubai Co., Ltd.), SEP (styrene-ethylene-propylene copolymer: Septon 1020, manufactured by Kuraray Co., Ltd.), SEPS (styrene-ethylene-propylene-styrene copolymer: Septon 2002, Septon 2004F, Septon 2005, Septon 2006, Septon 2063, Septon 2104, all manufactured by Kuraray Co., Ltd.), SEEPS (styrene-ethylene / ethylene-propylene-styrene block copolymer: Septon 4003, Septon 4044, Septon 4055, Septon 4077, Septon 4099, all manufactured by Kuraray Co., Ltd.), SEBS (styrene-ethylene-butylene-styrene block copolymer: Septon 4003, Septon 4044, Septon 4055, Septon 4077, Septon 4099, all manufactured by Kuraray Co., Ltd.), Examples of the block copolymer include Septon 8004, Septon 8006, and Septon 8007L (all manufactured by Kuraray Co., Ltd.), SEEPS-OH (a compound having a hydroxyl group at the end of a styrene-ethylene / ethylene-propylene-styrene block copolymer: Septon HG252 manufactured by Kuraray Co., Ltd.), SIS (styrene-isoprene-styrene block copolymer: Septon 5125 and Septon 5127 manufactured by Kuraray Co., Ltd.), hydrogenated SIS (hydrogenated styrene-isoprene-styrene block copolymer: Hybler 7125F and Hybler 7311F manufactured by Kuraray Co., Ltd.), SIBS (styrene-isobutylene-styrene block copolymer: SIBSTAR073T, SIBSTAR102T, and SIBSTAR103T (all manufactured by Kaneka Co., Ltd.), and Septon V9827 (manufactured by Kuraray Co., Ltd.)), but are not limited thereto. These may be used alone or in combination. Polystyrene and its modified products are preferably those that do not have unsaturated bonds, since they have higher heat resistance and are less susceptible to oxidation deterioration. The weight-average molecular weight of polystyrene and its modified products is not particularly limited as long as it is 10,000 or more, but if it is too large, the compatibility with not only polyphenylene ether compounds, but also low molecular weight components with weight-average molecular weights of about 50 to 1,000 and oligomer components with weight-average molecular weights of about 1,000 to 5,000 deteriorates, making it difficult to ensure mixing and solvent stability, so it is preferably about 10,000 to 300,000.

[0103] [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 ethylene-propylene copolymers, ethylene-styrene copolymers, ethylene-propylene-ethylidenenorbornene copolymers (EBT: K-8370EM, K-9330M, etc., manufactured by Mitsui Chemicals), ethylene-propylene-vinylnorbornene copolymers (VNB-EPT: PX-006M, PX-008M, PX-009M, etc., manufactured by Mitsui Chemicals), ethylene-vinyl alcohol copolymers, ethylene-vinyl acetate copolymers, etc., but are not limited thereto. From the viewpoint of improving heat resistance, it is preferable to use ethylene-propylene-ethylidenenorbornene copolymers and ethylene-propylene-vinylnorbornene copolymers containing a crosslinkable structure. In addition, these may be used alone or in combination. There are no particular limitations on the weight-average molecular weight of polyethylene and modified products thereof as long as it is 10,000 or more. However, if it is too large, compatibility with not only polyphenylene ether compounds but also low molecular weight components having a weight-average molecular weight of about 50 to 1,000 and oligomer components 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.

[0104] The curable resin composition of the present embodiment is obtained by preparing the above-mentioned components in a predetermined ratio, pre-curing at 130 to 180° C. for 30 to 500 seconds, and further post-curing at 150 to 200° C. for 2 to 15 hours, whereby a sufficient curing reaction proceeds to obtain a cured product of the present embodiment. Alternatively, the components of the curable resin composition may be uniformly dispersed or dissolved in a solvent or the like, and cured after removing the solvent.

[0105] The method for preparing the curable resin composition of the present embodiment is not particularly limited, but each component may be mixed uniformly or may be prepolymerized. For example, a mixture containing the compound represented by formula (1) is heated in the presence or absence of a curing accelerator or a polymerization initiator, and in the presence or absence of a solvent to form a prepolymer. Similarly, an amine compound, a compound having an ethylenically unsaturated bond, a maleimide compound, a cyanate ester compound, polybutadiene and its modified products, polystyrene and its modified products, inorganic fillers, and other additives may be added to form a prepolymer. The mixing or prepolymerization of each component is carried out using, for example, an extruder, a kneader, or a roll in the absence of a solvent, and a reaction kettle with a stirrer in the presence of a solvent.

[0106] As a method of uniformly mixing, the mixture is kneaded at a temperature in the range of 50 to 100°C using a device such as a kneader, roll, or planetary mixer to obtain a uniform resin composition. The obtained resin composition is crushed and then molded into a cylindrical tablet shape using a molding machine such as a tablet machine, or into a granular powder or powder molded body, or these compositions can be melted on a surface support and molded into a sheet with a thickness of 0.05 mm to 10 mm to obtain a molded curable resin composition. The obtained molded body is a non-sticky molded body at 0 to 20°C, and even if stored at -25 to 0°C for one week or more, the flowability and curability are hardly reduced. The obtained molded article can be molded into a cured product using a transfer molding machine or a compression molding machine.

[0107] The curable resin composition of the present embodiment can be made into a varnish-like composition (hereinafter, simply referred to as varnish) by adding an organic solvent. The curable resin composition of the present embodiment can be dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, or N-methylpyrrolidone as necessary to obtain a varnish, which can be impregnated into a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, or paper, and dried by heating to obtain a prepreg. The prepreg can be hot-press molded to obtain a cured product of the curable resin composition of the present embodiment. The solvent used in this case is in an amount of 10 to 70% by weight, preferably 15 to 70% by weight, in the mixture of the curable resin composition of the present embodiment and the solvent. In addition, if the composition is in a liquid state, a cured product of the curable resin containing carbon fiber can be obtained as it is, for example, by the RTM method.

[0108] The curable composition of the present embodiment can also be used as a modifier for a film-type composition. Specifically, it can be used to improve flexibility in the B-stage. Such a film-type resin composition is obtained as a sheet-like adhesive by applying the curable resin composition of the present embodiment as the curable resin composition varnish onto a release film, removing the solvent under heating, and then performing B-stage formation. This sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like.

[0109] The curable resin composition of the present embodiment can be heated and melted to reduce the viscosity, and impregnated into reinforcement fibers such as glass fibers, carbon fibers, polyester fibers, polyamide fibers, and alumina fibers to obtain a prepreg. Specific examples thereof include glass fibers such as E glass cloth, D glass cloth, S glass cloth, Q glass cloth, spherical glass cloth, NE glass cloth, and T glass cloth, inorganic fibers other than glass, and organic fibers such as polyparaphenylene terephthalamide (Kevlar (registered trademark), manufactured by DuPont), wholly aromatic polyamide, polyester, polyparaphenylene benzoxazole, polyimide, and carbon fibers, but are not particularly limited thereto. The shape of the substrate is not particularly limited, but examples thereof include woven fabric, nonwoven fabric, roving, chopped strand mat, and the like. In addition, as the weaving method of the woven fabric, plain weave, saddle weave, twill weave, and the like are known, and these known weaves can be appropriately selected and used depending on the intended use and performance. In addition, woven fabrics that have been subjected to fiber opening treatment and glass woven fabrics that have been surface-treated with a silane coupling agent or the like are preferably used. The thickness of the substrate is not particularly limited, but is preferably about 0.01 to 0.4 mm. A prepreg can also be obtained by impregnating reinforcing fibers with the varnish and drying the fibers by heating.

[0110] The prepreg can also be used to manufacture a laminate. The laminate is not particularly limited as long as it has one or more prepregs, and may have any other layers. The method for manufacturing the laminate can be appropriately applied by a generally known method, and is not particularly limited. For example, a multi-stage press machine, a multi-stage vacuum press machine, a continuous molding machine, an autoclave molding machine, etc. can be used when molding a metal foil-clad laminate, and the prepregs are laminated together and heated and pressurized to obtain a laminate. At this time, the heating temperature is not particularly limited, but is preferably 65 to 300 ° C, and more preferably 120 to 270 ° C. In addition, the pressure to be applied is not particularly limited, but if the pressure is too high, it is difficult to adjust the solid content of the resin in the laminate, and the quality is not stable, and if the pressure is too low, air bubbles and adhesion between the laminates are deteriorated, so that the pressure is preferably 2.0 to 5.0 MPa, and more preferably 2.5 to 4.0 MPa. The laminate of this embodiment can be suitably used as a metal foil-clad laminate described later by providing a layer made of metal foil. The prepreg is cut into a desired shape and laminated with copper foil or the like if necessary. The laminate is then heated and cured while applying pressure thereto by press molding, autoclave molding, sheet winding molding, or the like, to obtain an electrical and electronic laminate (printed wiring board) or a carbon fiber reinforced material.

[0111] 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, a method of applying the curable resin composition onto a support film (support), drying it, and forming a resin composition layer on the support film can be mentioned. When the curable resin composition of this embodiment is used for a resin sheet, it is essential that the film softens under the temperature conditions (70°C to 140°C) for lamination in the vacuum lamination method, and exhibits a fluidity (resin flow) that allows resin filling in via holes or through holes present in the circuit board at the same time as laminating the circuit board, and it is preferable to mix each of the above components so as to express such characteristics. In addition, in the obtained resin sheet or circuit board (copper-clad laminate, etc.), a phenomenon that locally different characteristic values ​​are exhibited due to phase separation or the like does not occur, and a certain performance is expressed at any part, so that a uniform appearance is required.

[0112] Here, the through-holes in the circuit board have a diameter of 0.1 to 0.5 mm and a depth of 0.1 to 1.2 mm, and it is preferable that the resin be filled within this range. When laminating both sides of the circuit board, it is preferable that about half of the through-holes are filled.

[0113] A specific method for producing the resin sheet includes preparing a resin composition varnished by blending an organic solvent, applying the varnished resin composition to the surface of a support film (Y), and then drying the organic solvent by heating or blowing hot air or the like to form a resin composition layer (X).

[0114] The organic solvent used here preferably includes, for example, ketones such as acetone, methyl ethyl ketone, cyclohexanone, etc., acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, etc., carbitols such as cellosolve, butyl carbitol, etc., aromatic hydrocarbons such as toluene, xylene, etc., dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc., and it is preferable to use the organic solvent in a proportion such that the nonvolatile content is 30 to 60% by weight.

[0115] The thickness of the resin composition layer (X) formed must be equal to or greater than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is in the range of 5 to 70 μm, the thickness of the resin composition layer (X) is preferably 10 to 100 μm. The resin composition layer (X) in this embodiment may be protected with a protective film described below. By protecting the resin composition layer with a protective film, adhesion of dirt and the like to the surface of the resin composition layer and scratches can be prevented.

[0116] The support film and the protective film may be made of polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate, polycarbonate, polyimide, and even release paper and metal foils such as copper foil and aluminum foil. The support film and the protective film may be subjected to a release treatment in addition to a mud treatment and a corona treatment. The thickness of the support film is not particularly limited, but is in the range of 10 to 150 μm, and preferably 25 to 50 μm. The thickness of the protective film is preferably 1 to 40 μm.

[0117] The support film (Y) is peeled off after laminating it onto a circuit board or after forming an insulating layer by heat curing. If the support film (Y) is peeled off after the resin composition layer constituting the resin sheet is heat cured, adhesion of dust and the like during the curing process can be prevented. When peeling off after curing, the support film is previously subjected to a release treatment.

[0118] A multilayer printed circuit board can be manufactured from the resin sheet obtained as described above. For example, when the resin composition layer (X) is protected by a protective film, the film is peeled off, and then 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 method or a continuous method using a roll. If necessary, the resin sheet and the circuit board may be heated (preheated) before lamination. The lamination conditions are preferably a pressure bonding temperature (lamination temperature) of 70 to 140°C and a pressure bonding pressure of 1 to 11 kgf / cm. 2 (9.8×10 4 ~107.9×10 4 N / m 2 ), and lamination is preferably performed under reduced air pressure of 20 mmHg (26.7 hPa) or less.

[0119] The curable resin composition of the present embodiment can be used to manufacture a semiconductor device, such as a DIP (dual in-line package), a QFP (quad flat package), a BGA (ball grid array), a CSP (chip size package), a SOP (small outline package), a TSOP (thin small outline package), or a TQFP (thin quad flat package).

[0120] The curable resin composition of the present embodiment and its cured product can be used in a wide range of fields. Specifically, it can be used in various applications such as molding materials, adhesives, composite materials, and paints. The cured product of the curable resin composition described in the present embodiment exhibits excellent heat resistance and dielectric properties, and is therefore 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, laminates (printed wiring boards, BGA substrates, build-up substrates, etc.), composite materials for lightweight and high-strength structural materials such as carbon fiber reinforced plastics and glass fiber reinforced plastics, 3D printing, etc. EXAMPLES

[0121] Next, the present invention will be described in more detail with reference to examples. Hereinafter, unless otherwise specified, "parts" are parts by weight. Note that the present embodiment is not limited to these examples.

[0122] The following describes various analysis methods used in the examples. <GPC (Gel Permeation Chromatography) Analysis> Column: SHODEX GPC KF-601 (two), KF-602, KF-602.5, KF-603 Flow rate: 1.5 ml / min. Column temperature: 40 °C Solvent used: THF (tetrahydrofuran) Detector: RI (differential refractive index detector) <High Performance Liquid Chromatography (HP-LC)> HP-LC: LC-20AB, DGU-20A3, SIL-20A, CTO-20A, CBM-20A, 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)

[0123] [Example 1] While purging with nitrogen, 43.3 parts of benzyl alcohol and 2.2 parts of methanesulfonic acid were added to a flask equipped with a thermometer, a condenser, a stirrer, and a Dean-Stark apparatus, and the temperature was raised to 130 °C. The reaction was carried out for 4 hours while removing the generated water out of the system using the Dean-Stark apparatus. The GPC chart at the completion of the polybenzyl alcoholization reaction is shown in FIG. 1. The number average molecular weight (Mn) calculated from the GPC (detector: RI) analysis was 972, and the weight average molecular weight (Mw) was 1571. The average value m of m in the following formula (a) calculated therefrom ave was 10.78. 16.6 parts of fluorene was added to this reaction solution, and the temperature was raised again to 130°C. The reaction was continued for 4 hours while removing the generated water from the system using a Dean-Stark detector. The GPC chart at the time of completion of the reaction is shown in Figure 2. The number average molecular weight of the polybenzyl alcohol obtained in the above reaction and the average value k calculated from the amount of raw materials charged were ave was 0.037. After that, after cooling to 80°C, 1.0 part of sodium hydroxide was added and stirred for 30 minutes. After cooling the internal temperature to 60°C, 100 parts of dimethyl sulfoxide (hereinafter also written as DMSO) and 12 parts of sodium hydroxide were added and stirred at 60°C for 30 minutes. Then, while keeping the internal temperature below 65°C, 29.0 parts of CMS-14 (AGC Seimi Chemical Co., Ltd., mixture of 4-chloromethylstyrene and 3-chloromethylstyrene, 4-chloromethylstyrene:3-chloromethylstyrene=95:5 (molar ratio), purity 96.87% by weight) was added dropwise over 2 hours and reacted at 65°C for 3 hours. GPC at the time of reaction completion is shown in Figure 3. The number average molecular weight (Mn) calculated from GPC (detector: RI) analysis was 625, and the weight average molecular weight (Mw) was 2242. Then, 200 parts of toluene was added, and the organic layer was washed four times with 100 parts of water. The obtained organic layer was concentrated to obtain 52.0 parts of compound (F1) represented by the following formula (a). 1 H-NMR data (deuterated chloroform) is shown in Figure 4. 1 In the H-NMR chart, signals derived from the terminal hydrogens of the vinyl groups (two hydrogens per vinyl group) were observed at 5.05-5.65 ppm, and signals derived from the methylene bonds of the benzyl groups modified with polybenzyl alcohol were observed at 3.60-4.20 ppm.

[0124] [ka]

[0125] [Comparative Synthesis Example 1] While purging with nitrogen into a flask equipped with a thermometer, a cooling tube, and a stirrer, 133 parts of methyl isobutyl ketone (hereinafter also referred to as MIBK), 33.3 parts of fluorene, 1.9 parts of tetrabutylammonium bromide, 0.49 parts of hydroquinone, and 64 parts of 50 wt% aqueous sodium hydroxide solution were added, and the internal temperature was raised to 60 ° C. Then, 71.2 parts of CMS-P (AGC Seimi Chemical Co., Ltd., mixture of 4-chloromethylstyrene and 3-chloromethylstyrene, 4-chloromethylstyrene: 3-chloromethylstyrene = 1: 1 (molar ratio), purity 95.59 wt%) was dropped over 1 hour, and the reaction was carried out at 60 ° C. for 9 hours. Neutralized with 41.6 parts of 35 wt% aqueous hydrochloric acid solution, and the organic layer was washed three times with 100 parts of water. Recrystallized with toluene and methanol to obtain 35.6 parts of compound (F2) represented by the following formula (b). The HP-LC chart of the obtained compound (F2) is shown in FIG. 1 H-NMR data (deuterated chloroform) is shown in Figure 6.

[0126] [ka]

[0127] [Example 2, Comparative Examples 1 and 2] The compounds (F1, F2) obtained in Example 1 and Comparative Synthesis Example 1, and OPE-2St (polyphenylene ether compound, manufactured by Mitsubishi Gas Chemical Co., Ltd.) were used in the amounts shown in Table 1, and were sandwiched between mirror-finished copper foils (T4X: manufactured by Fukuda Metal Copper Foil Co., Ltd.) and vacuum-press molded, then cured at 220°C for 2 hours. At this time, a spacer was used in which the center of a 250 μm-thick cushion paper was cut out to 150 mm length and width. For evaluation, a test piece was cut out to the desired size using a laser cutter as necessary, and evaluation was performed.

[0128] <Dielectric constant test / dielectric loss test> The test was performed at 25°C using a 10GHz cavity resonator manufactured by ATE Co., Ltd., using a cavity resonator perturbation method. The sample size was 1.7mm wide x 100mm long, and the thickness was 0.3mm. The evaluation results are shown in Table 1.

[0129] [Table 1]

[0130] From the results in Table 1, it was confirmed that the compounds of the present invention have excellent low dielectric properties. [Industrial Applicability]

[0131] The compound of the present invention is suitably used for electric and electronic parts such as semiconductor encapsulation materials, printed wiring boards, and build-up laminates.

Claims

1. A compound represented by the following formula (1): 【Chemistry 1】 (In the above formula (1), each of the multiple R's independently represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. Each of the multiple 1's and n's independently represents an integer of 1 to 4. Each of the multiple k's independently represents an integer of 0 to 4, and the average value of k is k ａｖｅ is 0 < k ａｖｅ Each of the multiple m's is independently an integer from 1 to 30, and the average value of m's is m ａｖｅ is 1≦m ａｖｅ ≦20.)

2. A compound obtained by reacting a compound represented by the following formula (A) with a compound represented by the following formula (B). 【Chemistry 2】 (In the above formula (A), each of the multiple R's independently represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. Each of the multiple n's independently represents an integer of 1 to 4. Each of the multiple k's independently represents a real number of 0 to 4, and the average value of k's is k ａｖｅ is 0 < k ａｖｅ Each of the multiple m's is independently a real number from 1 to 30, and the average value of m's is m ａｖｅ is 1≦m ａｖｅ ≦20.) 【Chemistry 3】 (In the above formula (B), each of the multiple R's independently represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. Each of the multiple 1's independently represents an integer of 1 to 4. X represents a halogen atom.)

3. A mixture consisting of a compound represented by the following formula (1-1) and a compound represented by the following formula (1-2): 【Chemistry 4】 (In the above formula (1-1), each of the multiple R's independently represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. Each of the multiple 1's and n's independently represents an integer of 1 to 4. Each of the multiple k's independently represents an integer of 0 to 4, and at least one of the two k's in formula (1-1) is an integer of 1 or more. Each of the multiple m's independently represents an integer of 1 to 30, and the average value of m's is m ａｖｅ is 1≦m ａｖｅ ≦20.) 【Chemistry 5】 (In the above formula (1-2), each of the multiple R's independently represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. Each of the multiple 1's independently represents an integer of 1 to 4.)

4. A curable resin composition comprising a compound according to claim 1 or 2, or a mixture according to claim 3.

5. A cured product obtained by curing the compound according to claim 1 or 2, or the mixture according to claim 3.

6. A cured product obtained by curing the curable resin composition according to claim 4.

7. A method for producing the compound represented by formula (1), which is obtained by reacting the compound represented by formula (A) with the compound represented by formula (B) in an aprotic polar solvent in the presence of a basic catalyst.

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