Compound, curable resin composition, and cured product thereof

Abstract

The present invention provides a compound having excellent low dielectric properties, a curable resin composition, and a cured product thereof.　Provided is a compound represented by formula (1). (In formula (1), X represents a C1-20 hydrocarbon group, and A represents a hydrocarbon group represented by formula (a) or formula (b). When multiple A are present, multiple A may be the same or different, and formulas (a) and (b) may be randomly combined. m represents an integer of 0-20, k represents an integer of 1-3, and the average value (m+k)ave of m+k is 0<(m+k)ave≤10. n is the average number of repetitions and is 1≤n≤20. R1 represents a C1-5 hydrocarbon group. l is an integer of 0-2.) (In formulas (a) and (b), * represents a bonding position to a benzene ring in formula (1) or to a benzene ring in formulas (a) and (b). The multiple R2 each independently represent a C1-5 hydrocarbon group . The multiple p are each independently an integer of 0-4.)

Description

Compound, curable resin composition and cured product thereof

[0001] The present invention relates to a compound having a specific structure, a curable resin composition, and a cured product thereof, which are 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.

[0002] In recent years, the required characteristics of laminates for mounting electrical and electronic components have become more widespread and sophisticated due to the expansion of their application fields. 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), currently undergoing accelerated development, is expected to further increase capacity and speed. 5G will use increasingly higher frequencies. Reducing transmission loss is crucial to achieving high-speed communication using high frequencies, necessitating even lower dielectric properties in circuit board materials. Transmission loss on printed circuit boards is due to conductor loss and dielectric loss. As noted in Non-Patent Document 1, conductor loss is proportional to the square root of the dielectric constant and the dielectric loss tangent of the dielectric. Therefore, improving the dielectric loss tangent, which contributes more to transmission loss than the dielectric constant, is an effective way to reduce transmission loss. Low-dielectric materials include synthetic rubber materials such as SBR (styrene butadiene rubber) and polybutadiene, but they have issues such as low reactivity and high tackiness during prepreg production. Given this, the development of thermosetting resins with excellent low dielectric properties is desirable.

[0004] In light of this background, polymeric materials with excellent low dielectric properties have been investigated. For example, Patent Document 1 proposes a composition containing a maleimide resin and a propenyl group-containing phenolic resin. However, the electrical properties are not sufficient because phenolic hydroxyl groups that are not involved in the curing reaction remain.

[0005] Japanese Patent Application Publication No. 04-359911

[0006] "Signal Loss Factors in High-Speed ​​Signal Transmission on Printed Circuit Boards," 29th Spring Conference of the Japan Institute of Electronics Packaging, Session ID: 16P1-17, 2015

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

[0008] That is, the present invention relates to the following [1] to

[10] . In the present invention, "(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]

[0010] In the above formula (1), X represents a hydrocarbon group having 1 to 20 carbon atoms, and A represents a hydrocarbon group represented by the following formula (a) or (b). When there are multiple As, the multiple As may be the same or different, and formula (a) and formula (b) may be bonded randomly. m represents an integer of 0 to 20, k represents an integer of 1 to 3, and the average value of m+k (m+k) ａｖｅ is 0 < (m + k) ａｖｅ ≦10. n is the average number of repetitions, and 1≦n≦20. R １ represents a hydrocarbon group having 1 to 5 carbon atoms, and l is an integer of 0 to 2.

[0011]

[0012] (In the above formulas (a) and (b), * represents the benzene ring in formula (1) or the bonding position to the benzene ring in formulas (a) and (b). Multiple R2s each independently represent a hydrocarbon group having 1 to 5 carbon atoms. Multiple p's each independently represent an integer of 0 to 4.) [2] The compound according to the above item [1], wherein in formula (1), n ​​is 1.1≦n≦20. [3] The compound according to the above item [1] or [2], wherein in formula (1), X is any one or more of (c) to (k) described in the following formula (2):

[0013]

[0014] (* indicates a bonding position.) [4] The compound according to the above item [3], wherein X in formula (2) is represented by (d) or (f). [5] The compound according to any one of the above items [1] to [4], which is derived from a compound represented by the following formula (3):

[0015]

[0016] In the above formula (3), X represents a hydrocarbon group having 1 to 20 carbon atoms, and A represents a hydrocarbon group represented by the following formula (a) or (b). When there are multiple As, the multiple As may be the same or different, and formula (a) and formula (b) may be bonded randomly. m represents an integer of 0 to 20, k represents an integer of 1 to 3, and the average value of m+k (m+k) ａｖｅ is 0 < (m + k) ａｖｅ ≦10. n is the average number of repetitions, and 1≦n≦20. R １ represents a hydrocarbon group having 1 to 5 carbon atoms; l is an integer of 0 to 2; and Y represents a halogen atom.

[0017]

[0018] (In the above formulas (a) and (b), * represents a benzene ring in formula (3) or a bonding position to the benzene ring in formulas (a) and (b). Multiple R2s each independently represent a hydrocarbon group having 1 to 5 carbon atoms. Multiple p's each independently represent an integer of 0 to 4.) [6] A curable resin composition containing the compound according to any one of the preceding items [1] to [5]. [7] The curable resin composition according to the preceding item [6], further containing at least one selected from the group consisting of a curing accelerator, a polymerization initiator, an epoxy resin, an active ester compound, a phenolic resin, a polyphenylene ether compound, an amine resin, a compound having an ethylenically unsaturated bond, an isocyanate resin, a polyamide resin, a maleimide compound, a cyanate ester resin, a polyimide resin, polybutadiene and modified products thereof, polystyrene and modified products thereof, polyethylene and modified products thereof, and a benzoxazine compound. [8] A cured product obtained by curing the compound according to any one of the preceding items [1] to [5]. [9] A cured product obtained by curing the curable resin composition according to the above item [6] or [7].

[10] A compound represented by the following formula (3):

[0019]

[0020] In the above formula (3), X represents a hydrocarbon group having 1 to 20 carbon atoms, and A represents a hydrocarbon group represented by the following formula (a) or (b). When there are multiple As, the multiple As may be the same or different, and formula (a) and formula (b) may be bonded randomly. m represents an integer of 0 to 20, k represents an integer of 1 to 3, and the average value of m+k (m+k) ａｖｅ is 0 < (m + k) ａｖｅ ≦10. n is the average number of repetitions, and 1≦n≦20. R １ represents a hydrocarbon group having 1 to 5 carbon atoms; l is an integer of 0 to 2; and Y represents a halogen atom.

[0021]

[0022] (In the above formulas (a) and (b), * represents the benzene ring in formula (3) or the bonding position to the benzene ring in formulas (a) and (b). Multiple R2s each independently represent a hydrocarbon group having 1 to 5 carbon atoms. Multiple p's each independently represent an integer of 0 to 4.)

[0023] According to the present invention, it is possible to provide a compound and a curable resin composition having excellent low dielectric properties.

[0024] The GPC chart of Synthesis Example 1 is shown. １ The H-NMR chart of Synthesis Example 2 is shown. The GPC chart of Synthesis Example 2 is shown. １ The H-NMR chart of Synthesis Example 3 is shown. The GPC chart of Synthesis Example 3 is shown. １ The H-NMR chart of Synthesis Example 4 is shown. The GPC chart of Synthesis Example 4 is shown. １ The H-NMR chart is shown below.

[0025] Hereinafter, an embodiment of the present invention (hereinafter also referred to as "the present embodiment") will be described in further detail.

[0026] The compound of this embodiment is represented by the following formula (1).

[0027]

[0028] In the above formula (1), X represents a hydrocarbon group having 1 to 20 carbon atoms, and A represents a hydrocarbon group represented by the following formula (a) or (b). When there are multiple As, the multiple As may be the same or different, and formulas (a) and (b) may be bonded randomly. m represents an integer of 0 to 10, k represents an integer of 1 to 3, and the average value of m+k (m+k) ａｖｅ is 1 < (m + k) ａｖｅ (m+k)≦10. ａｖｅ may be calculated from the results of GPC analysis or from the results of NMR analysis. Alternatively, the values ​​of the raw materials may be taken into consideration. From the viewpoint of adhesiveness and heat resistance, 0<(m+k) ａｖｅ ≦7.0, and preferably 1<(m+k) ａｖｅn is the average number of repeats, and is 1≦n≦20, preferably 1.1≦n≦20, more preferably 1.1≦n≦10, and particularly preferably 1.1≦n≦5. １ represents a hydrocarbon group having 1 to 5 carbon atoms, preferably a hydrocarbon group having 1 to 3 carbon atoms, and more preferably a methyl group. The value of n can be calculated from the weight average molecular weight (Mw) of the olefin compound determined by gel permeation chromatography (GPC). 1 is an integer of 0 to 2.

[0029]

[0030] In the above formulas (a) and (b), * represents the bonding position to the benzene ring in formula (1) or the benzene ring in formulas (a) and (b). ２ are each independently a hydrocarbon group having 1 to 5 carbon atoms, preferably a hydrocarbon group having 1 to 3 carbon atoms, and more preferably a methyl group. 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. Furthermore, when the carbon number is a hydrogen atom, deterioration of the dielectric properties and water absorption properties associated with the generation of polar groups resulting from the oxidation reaction of the alkyl group during high-temperature storage tests can be suppressed. Multiple p's each independently represent an integer from 0 to 4, and are preferably 0.

[0031] The weight average molecular weight of the compound represented by formula (1) determined by gel permeation chromatography (GPC) is preferably 200 or more and less than 5000, more preferably 300 or more and less than 3000, and particularly preferably 400 or more and less than 2000. The number average molecular weight is preferably 200 or more and less than 5000, more preferably 250 or more and less than 2000, and particularly preferably 300 or more and less than 1000. When the weight average molecular weight and number average molecular weight are less than 5000, purification by water washing becomes easy, and when they are 200 or more, the target compound does not volatilize in the solvent distillation step.

[0032] In the above formula (1), X is preferably one or more of (c) to (k) described in the following formula (2), and particularly preferably (d) or (f).

[0033]

[0034] (* indicates the bond position.)

[0035] The compound represented by formula (1) can be produced by any method, including dehydrohalogenation of a compound represented by formula (3) in a solvent in the presence of a basic catalyst. Examples of solvents that can be used include, but are not limited to, water-insoluble solvents such as 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. These solvents are not limited to these, and two or more of these solvents may be used in combination. Furthermore, aprotic polar solvents can also be used in combination with the water-insoluble solvents. Examples include dimethyl sulfone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, and N-methylpyrrolidone, and two or more of these solvents may be used in combination. When using an aprotic polar solvent, it is preferable to use one with a boiling point higher than that of the water-insoluble solvent used in combination. The catalyst is not particularly limited, but examples include basic catalysts such as sodium hydroxide, potassium hydroxide, and potassium carbonate. Because it is difficult to completely proceed with the dehydrohalogenation reaction, a large excess of aprotic polar solvent relative to the substrate may be used, or the dehydrohalogenation reaction may be repeated two or more times. For example, the dehydrohalogenation reaction of the compound represented by formula (1) may be carried out in an organic solvent in the presence of a base catalyst, and the resulting solution may be washed with water and then returned to the reaction vessel, where the base catalyst is added and the reaction is carried out again. This can increase the progress of the dehydrohalogenation reaction. In other words, it is possible to reduce the amount of residual halogen contained in the target compound. The amount of residual halogen is preferably 1 to 10,000 ppm, more preferably 1 to 1,000 ppm, and even more preferably 1 to 750 ppm. If the amount of residual halogen contained in the compound represented by formula (1) is high, molecular vibrations may occur when exposed to high frequency waves, adversely affecting electrical properties, particularly the dielectric loss tangent.Furthermore, if the amount of residual halogen is high, the risk of problems such as metal corrosion and ion migration increases in environmental tests such as HAST (High Accelerated Stress Test). Therefore, the above halogen content is preferable. The reaction temperature is preferably 0 to 120°C, more preferably 0 to 100°C, and even more preferably 0 to 80°C. At temperatures above the upper limit, self-polymerization of the compound of this embodiment may proceed, resulting in gelation. At temperatures below the lower limit, the reaction may not proceed sufficiently. Post-reaction treatment may involve neutralization with an optional 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 resulting reaction solution or crystals may also be redissolved in an optional solvent and subjected to an extraction step. For the extraction step, aromatic hydrocarbon solvents such as toluene and xylene may be used alone, or non-aromatic hydrocarbons such as cyclohexane and methylcyclohexane may be used in combination. After extraction, the organic layer is washed with water until the wastewater becomes neutral, and the target compound is obtained by distilling off the solvent using an evaporator or the like.

[0036]

[0037] In the above formula (3), Y represents a halogen atom, and from the viewpoints of reactivity and the stability of the raw materials, a bromine atom or a chlorine atom is preferred, with a bromine atom being particularly preferred. １ The definitions of k, m, l, and n, and the preferred ranges thereof are the same as those in formula (1) above.

[0038]

[0039] In the above formulas (a) and (b), * represents the bonding position to the benzene ring in formula (3) or the benzene ring in formulas (a) and (b). ２each independently represents a hydrocarbon group having 1 to 5 carbon atoms, preferably a hydrocarbon group having 1 to 3 carbon atoms, and more preferably a methyl group. 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. Furthermore, when the carbon number is a hydrogen atom, deterioration of the dielectric properties and water absorption properties associated with the generation of polar groups resulting from the oxidation reaction of the alkyl group during high-temperature storage tests can be suppressed. Multiple p's each independently represent an integer of 0 to 4, preferably 0. The molar ratio of formula (a) to formula (b) is preferably 1:2 to 1:5, and more preferably 1:2 to 1:4.

[0040] The method for producing the compound represented by formula (3) above is not particularly limited, but for example, when Y is a bromo atom, a compound having a 2-bromoethylbenzene structure may be self-polymerized in the presence of an acid catalyst such as hydrochloric acid or activated clay, followed by reaction with a bis-halogenated methyl arene compound, or a compound having a 2-bromoethylbenzene structure may be self-polymerized in the presence of an acid catalyst such as hydrochloric acid or activated clay, followed by reaction with a bis-hydroxymethyl arene compound. Alternatively, a compound having a 2-bromoethylbenzene structure may be reacted with a bis-halogenated methyl arene compound in the presence of an acid catalyst such as hydrochloric acid or activated clay, followed by reaction of the reaction product with a compound having a 2-bromoethylbenzene structure, or a compound having a 2-bromoethylbenzene structure may be reacted with a bis-hydroxymethyl arene compound in the presence of an acid catalyst such as hydrochloric acid or activated clay, followed by reaction of the reaction product with a compound having a 2-bromoethylbenzene structure. When hydrochloric acid is used as a catalyst, the reaction mixture is neutralized with an alkali metal such as sodium hydroxide or potassium hydroxide, extracted with an aromatic hydrocarbon solvent such as toluene or xylene, washed with water until the wastewater becomes neutral, and the solvent is distilled off using an evaporator or the like, thereby obtaining a target compound having at least two 2-bromoethylbenzene structures in the molecule.

[0041] Examples of compounds having a 2-bromoethylbenzene structure include, but are not limited to, 2-bromoethylbenzene, 1-(2-bromoethyl)-2-methylbenzene, 1-(2-bromoethyl)-3-methylbenzene, 1-(2-bromoethyl)-4-methylbenzene, 1-(2-bromoethyl)-2,3-dimethylbenzene, 1-(2-bromoethyl)-2,4-dimethylbenzene, 1-(2-bromoethyl)-2,5-dimethylbenzene, and 1-(2-bromoethyl)-2,6-dimethylbenzene. Since a larger number of carbon atoms improves solvent solubility but reduces heat resistance, the compound is preferably unsubstituted or substituted with an alkyl group having 1 to 3 carbon atoms, more preferably unsubstituted or substituted with an alkyl group having 1 to 2 carbon atoms, and most preferably unsubstituted or substituted with a methyl group.

[0042] Examples of the bishalogenated methylaryl compounds include o-xylylene difluoride, m-xylylene difluoride, p-xylylene difluoride, o-xylylene dichloride, m-xylylene dichloride, p-xylylene dichloride, o-xylylene dibromide, m-xylylene dibromide, p-xylylene dibromide, o-xylylene diiodide, m-xylylene diiodide, p-xylylene diiodide, 4,4'-bisfluoromethylenebiphenyl, 4,4'-bischloromethylenebiphenyl, 4,4'-bisbromomethylenebiphenyl, 4,4'-bisio Examples of halogen compounds include 2,4-bisfluoromethylenebiphenyl, 2,4-bischloromethylenebiphenyl, 2,4-bisbromomethylenebiphenyl, 2,4-bisiodomethylenebiphenyl, 2,2'-bisfluoromethylenebiphenyl, 2,2'-bischloromethylenebiphenyl, 2,2'-bisbromomethylenebiphenyl, and 2,2'-bisiodomethylenebiphenyl. From the viewpoint of the reactivity of raw materials during synthesis, chloride compounds, bromide compounds, and iodide compounds are preferred, and chloride compounds and bromide compounds are more preferred. Furthermore, other optional halogen compounds include cyanuric fluoride, cyanuric chloride, cyanuric bromide, and cyanuric iodide, but are not limited thereto.

[0043] Examples of bishydroxymethylaryl compounds include, but are not limited to, o-benzenedimethanol, m-benzenedimethanol, p-benzenedimethanol, 4,4'-bishydroxymethylbiphenyl, 2,4-bishydroxymethylbiphenyl, 2,2'-bishydroxymethylbiphenyl, α,α,α',α'-tetramethyl-1,4-benzenedimethanol, α,α,α',α'-tetramethyl-1,3-benzenedimethanol, and α,α,α',α'-tetramethyl-1,2-benzenedimethanol. These compounds may be used alone or in combination. The amount of these compounds used is preferably 0.01 to 0.8 wt %, more preferably 0.05 to 0.6 wt %, per 1 wt % of the compound having a 2-bromoethylbenzene structure.

[0044] When synthesizing the compound represented by formula (3), catalysts such as hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, p-toluenesulfonic acid, and methanesulfonic acid can be used as needed. These catalysts include Lewis acids such as aluminum chloride and zinc chloride, activated clay, acid clay, white carbon, zeolite, and silica alumina, and acidic ion exchange resins. These catalysts can be used alone or in combination. The amount of catalyst used is preferably 0.1 to 50 wt %, preferably 1 to 40 wt %, based on the total weight of the compound represented by formula (3) used. If the amount of catalyst used is too high, the viscosity of the reaction solution may become too high, making stirring difficult. If the amount of catalyst used is too low, the reaction may proceed slowly. The reaction may be carried out using an organic solvent such as hexane, cyclohexane, octane, toluene, or xylene, as needed, or may be carried out without a solvent. For example, an acidic catalyst is added to a mixed solution of a compound having a 2-bromoethylbenzene structure, a bis(halogenated methylarylene) compound, and a solvent (or no solvent), and if the catalyst contains water, the water is removed from the system by azeotropy or the like. The reaction is then carried out at 80 to 220°C, preferably 100 to 200°C, for 0.5 to 20 hours. After the reaction is complete, the acidic catalyst may be neutralized with an aqueous alkali solution, but the process can proceed to the water-washing step without neutralization. In the water-washing step, a water-insoluble organic solvent is added to the oil layer and the water-washing is repeated until the wastewater becomes neutral.

[0045] Furthermore, the compound represented by formula (3) obtained by the above reaction may be continuously derived into the compound represented by formula (1) by adding an aromatic hydrocarbon solvent such as toluene or xylene, a non-aromatic hydrocarbon solvent such as cyclohexane or methylcyclohexane, a neutralizing agent such as an alkali, and then adding an aprotic solvent and a base catalyst to the solution after the reaction.

[0046] 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.

[0047] [Curing Accelerator] The curability of the curable resin composition of the present embodiment can be improved by adding a curing accelerator. As the curing accelerator, an anionic curing accelerator that accelerates the curing reaction by generating anions upon irradiation with ultraviolet light or visible light or heating, or a cationic curing accelerator that accelerates the curing reaction by generating cations upon irradiation with ultraviolet light or visible light or heating, is preferred.

[0048] Examples of anionic curing accelerators include imidazoles such as 2-methylimidazole, 2-ethylimidazole, and 2-ethyl-4-methylimidazole; trialkylamines such as triethylamine and tributylamine; 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo(5,4,0)-undecene, with 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)-undecene being preferred. Other examples include phosphines such as triphenylphosphine; and quaternary ammonium salts such as tetrabutylammonium salt, triisopropylmethylammonium salt, trimethyldecanylammonium salt, cetyltrimethylammonium salt, and hexadecyltrimethylammonium hydroxide, but are not limited thereto. These may be used alone or in combination.

[0049] Examples of cationic curing accelerators include quaternary phosphonium salts such as triphenylbenzylphosphonium salt, triphenylethylphosphonium salt, and tetrabutylphosphonium salt (the counter ion of the quaternary salt may be a halogen, an organic acid ion, a hydroxide ion, or the like, and is not particularly specified, but an organic acid ion or a hydroxide ion is particularly preferred), and transition metal compounds (transition metal salts) such as tin octylate, zinc carboxylate (zinc 2-ethylhexanoate, zinc stearate, zinc behenate, zinc myristate), and zinc phosphate ester (zinc octylphosphate, zinc stearylphosphate), but are not limited thereto. These may be used alone or in combination.

[0050] The curing accelerator is used in an amount of 0.01 to 5.0 parts by mass based on 100 parts by mass of the curable resin composition, as needed.

[0051] [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, as well as inorganic fillers obtained by shaping these into a spherical or crushed form, but are not limited thereto. These fillers may be used alone or in combination.

[0052] When a curable resin composition for semiconductor encapsulation is obtained, the amount of inorganic filler used is preferably 80 to 92 parts by mass, and more preferably 83 to 90 parts by mass, per 100 parts by mass of the curable resin composition. When a curable resin composition for interlayer insulating layer formation, or a substrate material such as a copper-clad laminate, prepreg, or RCC is obtained, the amount of inorganic filler used is preferably 5 to 80 parts by mass, and more preferably 10 to 60 parts by mass, per 100 parts by mass of the curable resin composition.

[0053] [Polymerization Initiator] The curability of the curable resin composition of this embodiment can be improved by adding a polymerization initiator. The polymerization initiator is a compound capable of polymerizing an olefin functional group such as an ethylenically unsaturated bond, and examples thereof include an olefin metathesis polymerization initiator, an anionic polymerization initiator, a cationic polymerization initiator, and a radical polymerization initiator. Among these, it is preferable to use a radical polymerization initiator that has curability and appropriate stability. The radical polymerization initiator is a compound that generates radicals upon irradiation with ultraviolet light or visible light or heating, thereby initiating a chain polymerization reaction. Usable radical polymerization initiators include organic peroxides, azo compounds, and benzopinacols. Organic peroxides are preferred because they are effective in controlling the curing temperature, suppress outgassing, and minimize the impact of decomposition products on electrical properties.

[0054] Examples of the organic peroxides include ketone peroxides such as methyl ethyl ketone peroxide and acetylacetone peroxide, diacyl peroxides such as benzoyl peroxide, dialkyl peroxides such as dicumyl peroxide and 1,3-bis-(t-butylperoxyisopropyl)-benzene, peroxyketals such as t-butyl peroxybenzoate and 1,1-di-t-butylperoxycyclohexane, α-cumylperoxyneodecanoate, t-butylperoxyneodecanoate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, t-butylperoxymethyl ... Examples of the peroxycarbonate include, but are not limited to, alkyl peresters such as di-2-ethylhexyl peroxydicarbonate, t-amylperoxy-3,5,5-trimethylhexanoate, t-butylperoxy-3,5,5-trimethylhexanoate, and t-amylperoxybenzoate, peroxycarbonates such as di-2-ethylhexyl peroxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, t-butylperoxyisopropyl carbonate, and 1,6-bis(t-butylperoxycarbonyloxy)hexane, t-butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxyoctoate, and lauroyl peroxide. These peroxycarbonates may be used alone or in combination. Among the above organic peroxides, ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, alkyl peresters, peroxycarbonates, etc. are preferred, with dialkyl peroxides being more preferred.

[0055] Examples of the azo compounds include, but are not limited to, azobisisobutyronitrile, 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2,4-dimethylvaleronitrile), etc. These compounds may be used alone or in combination.

[0056] The amount of polymerization initiator added is preferably 0.01 to 5 parts by mass, and particularly preferably 0.01 to 3 parts by mass, relative to 100 parts by mass of the curable resin composition. If the amount of polymerization initiator used is less than 0.01 part by mass, there is a risk that the molecular weight will not be sufficiently elongated during the polymerization reaction, and if it is more than 5 parts by mass, there is a risk that the dielectric properties such as the dielectric constant and the dielectric loss tangent will be impaired.

[0057] [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. Controlling the reaction initiation temperature makes it easier to ensure fluidity, does not impair impregnation into glass cloth or the like, and facilitates B-staging, such as prepreg formation. If the polymerization reaction proceeds too much during prepreg formation, problems such as difficulty in lamination in the lamination step are likely to occur.

[0058] The polymerization inhibitor may be added during or after the synthesis of the compound of this embodiment. The amount of the polymerization inhibitor used is 0.008 to 1 part by mass, preferably 0.01 to 0.5 parts by mass, per 100 parts by mass of the compound of this embodiment.

[0059] Examples of the polymerization inhibitor include phenol-based, sulfur-based, phosphorus-based, hindered amine-based, nitroso-based, and nitroxyl radical-based. One type of polymerization inhibitor may be used alone, or multiple types may be used in combination. Among these, in this embodiment, phenol-based, hindered amine-based, nitroso-based, and nitroxyl radical-based inhibitors are preferred.

[0060] Examples of the phenolic polymerization inhibitor include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, stearyl-β-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, 2,4-bis[(octylthio)methyl]-o ...butylated hydroxyanisole, butylated hydroxyanisole, butylated hydroxyanisole, butylated hydroxyanisole, butylated hydroxyanisole, butylated hydroxyanisole, butylated hydroxyanisole, butylated hydroxyanisole, butylated hydroxyanisole, butylated hydroxyanisole, butylated hydroxyanisole, butylated hydroxyanisole, butylated hydroxyanisole, butylated hydroxyanisole, butylated hydroxyanisole, butylated hydroxyanisole, butylated hydroxyanisole, butylated hydroxyanisole, butylated hydroxyani Monophenols such as resol, 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol), 4,4'-thiobis(3-methyl-6-t-butylphenol), 4,4'-butylidenebis(3-methyl-6-t-butylphenol), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, 3,9-bis[1,1-dimethyl-2-{β-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}ethyl]2,4,8,10-tetraoxaspiro[5,5]undecane, bis(3,5-di-t-butyl bisphenols such as calcium ethyl-4-hydroxybenzylsulfonate, 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, tetrakis-[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methane, bis[3,3'-bis-(4'-hydroxy-3'-t-butylphenyl)butyric acid]glycol ester, tris-(3,Examples of the phenolic compound include, but are not limited to, polymeric phenols such as 1,3,5-tris(3',5'-di-t-butyl-4'-hydroxybenzyl)-isocyanurate, 1,3,5-tris(3',5'-di-t-butyl-4'-hydroxybenzyl)-S-triazine-2,4,6-(1H,3H,5H)trione, and tocopherol.

[0061] 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.

[0062] Examples of the phosphorus-based polymerization inhibitor include triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, tris(nonylphenyl) phosphite, diisodecyl pentaerythritol phosphite, tris(2,4-di-t-butylphenyl) phosphite, cyclic neopentane tetrayl bis(octadecyl) phosphite, cyclic neopentane tetrayl bis(2,4-di-t-butylphenyl) phosphite, cyclic neopentane tetrayl bis(2,4-di-t-butyl-4-methylphenyl) phosphite, bis[2- phosphites such as t-butyl-6-methyl-4-{2-(octadecyloxycarbonyl)ethyl}phenyl]hydrogen phosphite, and oxaphosphaphenanthrene oxides such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(3,5-di-t-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, but are not limited to these.

[0063] Examples of the hindered amine polymerization inhibitor include ADK STAB LA-40MP, ADK STAB LA-40Si, ADK STAB LA-402AF, ADK STAB LA-87, ADK STAB LA-82, ADK STAB LA-81, ADK STAB LA-77Y, ADK STAB LA-77G, ADK STAB LA-72, ADK STAB LA-68, ADK STAB LA-63P, ADK STAB LA-57, ADK 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, but are not limited thereto.

[0064] Examples of the nitroso-based polymerization inhibitor include, but are not limited to, p-nitrosophenol, N-nitrosodiphenylamine, and the ammonium salt of N-nitrosophenylhydroxyamine (cupferron). Of these, the ammonium salt of N-nitrosophenylhydroxyamine (cupferron) is preferred.

[0065] Examples of the nitroxyl radical polymerization inhibitor include di-tert-butyl nitroxide, 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-amino-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-acetoxy-2,2,6,6-tetramethylpiperidine-1-oxyl, and 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl, but are not limited to these.

[0066] [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.

[0067] The phosphorus-based flame retardant may be a reactive type or an additive type. Specific examples include phosphate esters such as trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylylene phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylylene phosphate, 1,3-phenylenebis(dixylylene phosphate), 1,4-phenylenebis(dixylylene phosphate), and 4,4'-biphenyl(dixylylene 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 an epoxy resin with the active hydrogen of the above-mentioned phosphanes; and red phosphorus. These may be used alone or in combination. Of the above-listed substances, phosphate esters, phosphanes, and phosphorus-containing epoxy compounds are preferred, with 1,3-phenylenebis(dixylilenyl phosphate), 1,4-phenylenebis(dixylilenyl phosphate), 4,4'-biphenyl(dixylilenyl phosphate), and phosphorus-containing epoxy compounds being particularly preferred.

[0068] The content of the flame retardant is preferably in the range of 0.1 to 0.6 parts by mass per 100 parts by mass of the curable resin composition. If the content is less than 0.1 part by mass, the flame retardancy may be insufficient, and if the content is more than 0.6 part by mass, the moisture absorption and dielectric properties of the cured product may be adversely affected.

[0069] [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 preferred. Examples of HALS include reaction products 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, reaction products of dimethyl succinate-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, and poly[{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidyl)imino}hexamethylene{(2,2,6,6-tetramethyl-4-piperidyl) Examples of suitable hydroxybenzyl compounds include, but are not limited to, bis(1,2,2,6,6-pentamethyl-4-piperidyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butyl malonate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, and bis(1,2,2,6,6-pentamethyl-4-piperidyl) 2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-n-butylmalonate. These compounds may be used alone or in combination.

[0070] The content of the light stabilizer is preferably in the range of 0.001 to 0.1 parts by mass relative to 100 parts by mass of the curable resin composition. If the content is less than 0.001 part by mass, the light stabilizing effect may be insufficient, and if the content is more than 0.1 part by mass, the moisture absorption and dielectric properties of the cured product may be adversely affected.

[0071] [Binder Resin] The curable resin composition of this embodiment may use a binder resin. Examples of binder resins include, but are not limited to, butyral-based resins, acetal-based resins, acrylic-based resins, epoxy-nylon-based resins, NBR-phenol-based resins, epoxy-NBR-based resins, and silicone-based resins. These may be used alone or in combination.

[0072] The blending 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 mass, and more preferably 0.05 to 20 parts by mass, per 100 parts by mass of the curable resin composition, as needed.

[0073] [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.

[0074] The amount of the additive to be added is preferably 1,000 parts by mass or less, more preferably 700 parts by mass or less, per 100 parts by mass of the curable resin composition.

[0075] The curable resin composition of this embodiment may further contain epoxy resins, active ester compounds, phenolic resins, polyphenylene ether compounds, amine resins, compounds having an ethylenically unsaturated bond, isocyanate resins, polyamide resins, maleimide compounds, cyanate ester resins, polyimide resins, polybutadiene and modified products thereof, polystyrene and modified products thereof, polyethylene and modified products thereof, etc., and these may be used alone or in combination. Among these compounds, polyphenylene ether compounds, compounds having an ethylenically unsaturated bond, cyanate ester resins, polybutadiene and modified products thereof, and polystyrene and modified products thereof are preferred in terms of the balance of heat resistance, adhesion, and dielectric properties. By containing these compounds, the brittleness of the cured product and adhesion to metals can be improved, and package cracking can be suppressed during reliability tests such as solder reflow and thermal cycling.

[0076] Unless otherwise specified, the amount of the above compounds used is preferably 10 times by mass or less, more preferably 5 times by mass or less, and particularly preferably 3 times by mass or less, relative to the compound of this embodiment. The preferred lower limit is 0.1 times by mass or more, more preferably 0.25 times by mass or more, and even more preferably 0.5 times by mass or more. By keeping the amount within the above range, the effects of each compound added can be enhanced while taking advantage of the low dielectric properties of the compound of this embodiment. The following examples of these components can be used.

[0077] [Epoxy Resin] Preferred examples of epoxy resins are shown below, but are not limited to these. The epoxy resin may be liquid or solid, and may be used alone or in combination.

[0078] Examples of liquid epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, phenol novolac type epoxy resins, alicyclic epoxy resins having an ester skeleton, cyclohexane type epoxy resins, cyclohexanedimethanol type epoxy resins, glycidyl amine type epoxy resins, and epoxy resins having a butadiene structure. Specific examples include "RE310S" and "RE410S" (all manufactured by Nippon Kayaku Co., Ltd., bisphenol A type epoxy resins), "RE303S", "RE304S", "RE403S", and "RE404S" (all manufactured by Nippon Kayaku Co., Ltd., bisphenol F type epoxy resins), "HP4032", "HP4032D", and "HP4032SS" (all manufactured by DIC Corporation, naphthalene type epoxy resins), "828US", "jER828EL", "825", and "828EL" (all manufactured by Mitsubishi Chemical Corporation, bisphenol A type epoxy resins), "jE807", and "1750" (all manufactured by Mitsubishi Chemical Corporation, bisphenol F type epoxy resins), and "jER152" (manufactured by Mitsubishi Chemical Corporation, phenolic 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). These may be used alone or in combination of two or more.

[0079] 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 Corporation, 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, biphenyl-type epoxy resin) Examples of epoxy resins that can be used include "YX-8800" (manufactured by Mitsubishi Chemical Corporation, anthracene-type epoxy resin), "PG-100" and "CG-500" (manufactured by Osaka Gas Chemicals Co., Ltd., fluorene-based epoxy resin), "YL-7760" (manufactured by Mitsubishi Chemical Corporation, bisphenol AF-type epoxy resin), "YL-7800" (manufactured by Mitsubishi Chemical Corporation, fluorene-type epoxy resin), "jER1010" (manufactured by Mitsubishi Chemical Corporation, solid bisphenol A-type epoxy resin), and "jER1031S" (manufactured by Mitsubishi Chemical Corporation, tetraphenylethane-type epoxy resin).These may be used alone or in combination of two or more.

[0080] [Active Ester Compound] An active ester compound refers to a compound containing at least one ester bond in its structure, and having an aliphatic chain, an aliphatic ring, or an aromatic ring bonded to both sides of the ester bond. Examples of active ester compounds include compounds having two or more highly reactive ester groups per molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds. These active ester compounds are obtained by a condensation reaction between at least one compound selected from a carboxylic acid compound, an acid chloride, and a thiocarboxylic acid compound and at least one compound selected from a hydroxy compound and a thiol compound. In particular, from the viewpoint of improving heat resistance, active ester compounds obtained from a carboxylic acid compound or an acid chloride and a hydroxy compound are preferred, and the hydroxy compound is preferably a phenol compound or a naphthol compound. Active ester compounds may be used alone or in combination of two or more types.

[0081] 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.

[0082] 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.

[0083] Examples of the phenol compound and naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalene, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzenetriol, dicyclopentadiene-type diphenol compounds, phenol novolak, and the phenolic resins described below. Here, the term "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.

[0084] Preferred specific examples of the active ester compound include active ester compounds containing a dicyclopentadiene-type diphenol structure, active ester compounds containing a naphthalene structure, active ester compounds containing an acetylated phenol novolac, active ester compounds containing a benzoylated phenol novolac, the compound described in Example 2 of WO 2020 / 095829, and the compounds disclosed in WO 2020 / 059625. Among these, active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene-type diphenol structure are more preferred. The dicyclopentadiene-type diphenol structure refers to a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

[0085] 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 "EXB9416-70BK" (manufactured by DIC Corporation) as a phenolic compound. Examples of active ester compounds containing acetylated volac include "DC808" (manufactured by Mitsubishi Chemical Corporation), active ester compounds containing benzoylated phenol novolac include "YLH1026," "YLH1030," and "YLH1048" (manufactured by Mitsubishi Chemical Corporation), an active ester curing agent that is an acetylated phenol novolac, "DC808" (manufactured by Mitsubishi Chemical Corporation), and an active ester curing agent containing a phosphorus atom, "EXB-9050L-62M" (manufactured by DIC Corporation).

[0086] Regarding the compounding ratio of the active ester compound and the epoxy resin, the ratio (α / β) of the active ester equivalent (α) to the epoxy equivalent (β) is preferably 0.5 to 1.5, more preferably 0.8 to 1.2, and even more preferably 0.90 to 1.10. If the ratio is outside the above range, excess epoxy groups or active ester groups may remain in the system, which may deteriorate the properties 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%).

[0087] [Phenol Resin] A phenol resin is a compound having two or more phenolic hydroxyl groups in the molecule. Examples of phenol resins include, but are not limited to, reaction products of phenols and aldehydes, reaction products of phenols and diene compounds, reaction products of phenols and ketones, reaction products of phenols and substituted biphenyls, reaction products of phenols and substituted phenyls, and reaction products of bisphenols and aldehydes. These may be used alone or in combination. Specific examples of the above raw materials are listed below, but are not limited to these. <Phenols> Phenol, alkyl-substituted phenol, aromatic-substituted phenol, hydroquinone, resorcinol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc. <Aldehydes> Formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, furfural, etc. <Diene compounds> Dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc. <Ketones> Acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, fluorenone, etc. <Substituted biphenyls> 4,4'-bis(chloromethyl)-1,1'-biphenyl, 4,4'-bis(methoxymethyl)-1,1'-biphenyl, 4,4'-bis(hydroxymethyl)-1,1'-biphenyl, etc. <Substituted phenyls> 1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene, 1,4-bis(hydroxymethyl)benzene, etc.

[0088] [Polyphenylene Ether Compound] 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 Corporation, a polyphenylene ether compound having a methacrylic group) and OPE-2St 1200 (manufactured by Mitsubishi Gas Chemical Company, a polyphenylene ether compound having a styrene structure). The number average molecular weight (Mn) of the polyphenylene ether compound is preferably 500 to 5,000, more preferably 2,000 to 5,000, and even more preferably 2,000 to 4,000. If the molecular weight is less than 500, the heat resistance of the cured product tends to be insufficient. Furthermore, if the molecular weight is greater than 5,000, the melt viscosity increases, and sufficient fluidity cannot be obtained, which tends to result in molding defects. Furthermore, the reactivity decreases, the curing reaction takes a long time, and the amount of unreacted polyphenylene ether not incorporated into the curing system increases, which lowers the glass transition temperature of the cured product and reduces the heat resistance of the cured product. If the number average molecular weight of the polyphenylene ether compound is 500 to 5,000, it is possible to exhibit excellent heat resistance and moldability while maintaining excellent dielectric properties. The number average molecular weight here can be measured specifically using gel permeation chromatography or the like.

[0089] 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 approximately 10,000 to 30,000. Furthermore, these compounds may be used as raw materials and reacted with a compound having an ethylenically unsaturated bond, such as methacrylic acid chloride, acrylic acid chloride, or chloromethylstyrene, to impart radical polymerizability. A polyphenylene ether compound obtained by a redistribution reaction may be obtained, for example, by heating a high-molecular-weight polyphenylene ether compound in a solvent such as toluene in the presence of a phenolic compound and a radical initiator to cause a redistribution reaction. Such polyphenylene ether compounds obtained by a redistribution reaction are preferred because they have hydroxyl groups derived from the phenolic compound at both ends of the molecular chain that contribute to curing, thereby maintaining even higher heat resistance. Furthermore, functional groups can be introduced at both ends of the molecular chain even after modification with a compound having an ethylenically unsaturated bond. Furthermore, polyphenylene ether compounds obtained by a polymerization reaction are preferred because they exhibit excellent fluidity.

[0090] In the case of polyphenylene ether compounds obtained by polymerization, the molecular weight of the polyphenylene ether compound can be adjusted by adjusting the polymerization conditions, etc. In the case of polyphenylene ether compounds obtained by redistribution, the molecular weight of the resulting polyphenylene ether compound can be adjusted by adjusting the conditions, etc. of the redistribution reaction. More specifically, adjusting the amount of the phenolic compound used in the redistribution reaction can be considered. That is, the greater the amount of the phenolic compound, the lower the molecular weight of the resulting polyphenylene ether compound. In this case, poly(2,6-dimethyl-1,4-phenylene ether) or the like can be used as the high-molecular-weight polyphenylene ether compound that undergoes the redistribution reaction. Furthermore, the phenolic compound used in the redistribution reaction is not particularly limited, but preferred are, for example, polyfunctional phenolic compounds having two or more phenolic hydroxyl groups per molecule, such as bisphenol A, phenol novolac, and cresol novolac. These compounds may be used alone or in combination of two or more.

[0091] The content of the polyphenylene ether compound is not particularly limited, but is preferably 5 to 1,000 parts by mass, and more preferably 10 to 750 parts by mass, relative to 100 parts by mass of the curable resin composition. A content of the polyphenylene ether compound within the above range is preferable in that it not only has excellent heat resistance and the like, but also allows a cured product to be obtained that fully exhibits the excellent dielectric properties of the polyphenylene ether compound.

[0092] [Amine Resin] An amine resin is a compound having two or more amino groups in the molecule. Examples of the amine resin include diaminodiphenylmethane, diaminodiphenylsulfone, isophoronediamine, naphthalenediamine, aniline novolak (a reaction product of aniline and formalin), N-methylaniline novolak (a reaction product of N-methylaniline and formalin), orthoethylaniline novolak (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 suitable aniline resins include, but are not limited to, aniline resins disclosed in Japanese Patent No. 6,429,862, reaction products of aniline and substituted biphenyls (such as 4,4'-bis(chloromethyl)-1,1'-biphenyl and 4,4'-bis(methoxymethyl)-1,1'-biphenyl), reaction products of aniline and substituted phenyls (such as 1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene and 1,4-bis(hydroxymethyl)benzene), 4,4'-(1,3-phenylenediisopropylidene)bisaniline, 4,4'-(1,4-phenylenediisopropylidene)bisaniline, reaction products of aniline and diisopropenylbenzene, and dimer diamine. These may be used alone or in combination.

[0093] [Compound containing an ethylenically unsaturated bond] The compound containing an ethylenically unsaturated bond is a compound having one or more ethylenically unsaturated bonds in the molecule that can be polymerized by heat or light, regardless of whether a polymerization initiator is used. Examples of compounds containing an ethylenically unsaturated bond include, but are not limited to, reaction products of the above-mentioned phenolic resins with ethylenically unsaturated bond-containing halogen-based compounds (chloromethylstyrene, allyl chloride, methallyl chloride, acrylic acid chloride, methacrylic acid chloride, etc.), reaction products of ethylenically unsaturated bond-containing phenols (2-allylphenol, 2-propenylphenol, 4-allylphenol, 4-propenylphenol, eugenol, isoeugenol, etc.) with halogen-based compounds (1,4-bis(chloromethyl)benzene, 4,4'-bis(chloromethyl)biphenyl, 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-dibromobenzophenone, cyanuric chloride, etc.), reaction products of epoxy resins or alcohols with (meth)acrylic acids (acrylic acid, methacrylic acid, etc.), and acid-modified products thereof. These compounds may be used alone or in combination.

[0094] [Isocyanate Resin] An isocyanate resin is a compound having two or more isocyanate groups in the molecule. Examples of the isocyanate resin include aromatic diisocyanates such as p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 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 compounds of isocyanate monomers or isocyanate compounds 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 to these. These may be used alone or in combination.

[0095] [Polyamide Resin] Examples of polyamide resins include a reaction product of one or more of diamines, diisocyanates, and oxazolines with dicarboxylic acids, a reaction product of diamines with acid chlorides, and ring-opening polymerization products of lactam compounds. These may be used alone or in combination. Specific examples of the above-mentioned raw materials are listed below, but are not limited thereto.<Diamines> Ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decanediamine, undecanediamine, dodecanediamine, tridecanediamine, tetradecanediamine, pentadecanediamine, hexadecanediamine, heptadecanediamine, octadecanediamine, nonadecanediamine, eicosanediamine, 2-methyl-1,5-diaminopentane, 2-methyl diamino-1,8-diaminooctane, dimer diamine, cyclohexanediamine, bis-(4-aminocyclohexyl)methane, bis(3-methyl-4-aminocyclohexyl)methane, xylylenediamine, norbornanediamine, isophoronediamine, bisaminomethyltricyclodecane, phenylenediamine, diethyltoluenediamine, naphthalenediamine, diaminodiphenylmethane, bis(4-amino-3,5-dimethylphenyl)methane, bis(4-amino-3,5-diethylphenyl)methane , 4,4'-methylenebis-o-toluidine, 4,4'-methylenebis-o-ethylaniline, 4,4'-methylenebis-2-ethyl-6-methylaniline, 4,4'-methylenebis-2,6-diisopropylaniline, 4,4-ethylenedianiline, 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.<Diisocyanates> 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 acids> 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-sodiumsulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, cyclohexanedicarboxylic acid, biphenyldicarboxylic acid, naphthalenedicarboxylic acid, benzophenonedicarboxylic acid, furandicarboxylic acid, 4,4'-dicarboxydiphenyl ether, 4,4'-dicarboxydiphenyl sulfide, and the like. <Acid chlorides> 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, azelayl chloride, 2,5-furandicarbonyl dichloride, phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, trimesic acid chloride, bis(4-chlorocarbonylphenyl) ether, 4,4'-diphenyldicarbonyl chloride, 4,4'-azodibenzoyl dichloride, etc. <Lactams> ε-caprolactam, ω-undecanelactam, ω-laurolactam, etc.

[0096] [Polyimide Resin] Examples of polyimide resins include, but are not limited to, reaction products of the above diamines with the tetracarboxylic dianhydrides exemplified below. These may be used alone or in combination. <Tetracarboxylic Dianhydrides> 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-cyclohexene-1,2dicarboxylic anhydride, pyromellitic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4 '-diphenylsulfonetetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, methylene-4,4'-diphthalic dianhydride, 1,1-ethylidene-4,4'-diphthalic dianhydride, 2,2'-propylidene-4,4'-diphthalic dianhydride, 1,2-ethylene-4,4'-diphthalic dianhydride, 1,3-trimethylene-4,4'-diphthalic dianhydride, 1,4-tetramethylene-4,4'-diphthalic dianhydride, 1,5-pentamethylene-4,4'- Diphthalic dianhydride, 4,4'-oxydiphthalic dianhydride, thio-4,4'-diphthalic dianhydride, sulfonyl-4,4'-diphthalic 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- dicarboxyphenoxy)phenyl]benzene dianhydride, bis[3-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride, bis[4-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride, 2,2-bis[3-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, bis(3,4-dicarboxyphenoxy)dimethylsilane dianhydride, 1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldisiloxane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3,4,9,10-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, 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) 4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,1-ethylidene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 2,2-propylidene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, oxy-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, thio-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, sulfonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride hydrates, rel-[1S,5R,6R]-3-oxabicyclo[3,2,1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, ethylene glycol-bis-(3,4-dicarboxylic anhydride phenyl) ether, 4,4'-biphenylbis(trimellitic acid monoester acid anhydride), 9,9'-bis(3,4-dicarboxyphenyl)fluorene dianhydride, etc.

[0097] [Maleimide Compound] The curable resin composition of this embodiment may contain a maleimide compound. A maleimide compound is a compound having one or more maleimide groups in the molecule. Examples of 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), and Xyloc-type maleimide compounds (anilix maleimide, manufactured by Mitsui Chemicals Fine Co., Ltd.), biphenylaralkyl-type maleimide compounds (solidified by distilling off the solvent under reduced pressure from a resin solution containing the maleimide compound (M2) described in Example 4 of JP 2009-001783 A), bisaminocumylbenzene-type maleimide (maleimide compounds described in WO 2020 / 054601 A), maleimide compounds having an indane structure described in Japanese Patent No. 6629692 or WO 2020 / 217679, MATERIAL STAGE Vol. 18, No. 12 2019 "Continued Epoxy Resin CAS Number Story - Curing Agent CAS Number Memorandum No. 31 Bismaleimide (1)" and MATERIAL STAGE Vol. 19, No. 12 2019 Examples of suitable compounds include, but are not limited to, the maleimide compounds described in "Epoxy Resin CAS Number Story Continued - Hardener CAS Number Memorandum No. 32, Bismaleimide (2)" published in February 2019. These compounds may be used alone or in combination.

[0098] [Cyanate Ester Resin] Cyanate ester resins are cyanate ester compounds obtained by reacting a phenolic resin with a cyanogen halide. Specific examples include dicyanatobenzene, tricyanatobenzene, dicyanatonaphthalene, dicyanatobiphenyl, 2,2'-bis(4-cyanatophenyl)propane, bis(4-cyanatophenyl)methane, bis(3,5-dimethyl-4-cyanatophenyl)methane, 2,2'-bis(3,5-dimethyl-4-cyanatophenyl)propane, 2,2'-bis(4-cyanatophenyl)ethane, 2,2'-bis(4-cyanatophenyl)hexafluoropropane, bis(4-cyanatophenyl)sulfone, bis(4-cyanatophenyl)thioether, phenol novolac cyanate, and phenol-dicyclopentadiene co-condensates in which the hydroxyl groups have been converted to cyanate groups, but are not limited thereto. These compounds may be used alone or in combination. Furthermore, the cyanate ester compounds whose synthesis methods are described in JP-A-2005-264154 are particularly preferred as cyanate ester compounds because they have low moisture absorption, excellent flame retardancy, and excellent dielectric properties. The cyanate ester resin may contain a catalyst such as zinc naphthenate, cobalt naphthenate, copper naphthenate, lead naphthenate, zinc octoate, tin octoate, lead acetylacetonate, or dibutyltin maleate, in order to trimerize the cyanate group to form a sym-triazine ring, as necessary.

[0099] The catalyst is preferably used in an amount of 0.0001 to 0.10 parts by mass, and more preferably 0.00015 to 0.0015 parts by mass, per 100 parts by mass of the cyanate ester resin and the curable resin composition.

[0100] [Polybutadiene and Modified Products Thereof] Polybutadiene and modified products thereof are compounds having polybutadiene or 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, and styrene-butadiene rubber. These may be used alone or in combination. Of these, polybutadiene or styrene-butadiene rubber is preferred from the viewpoint of dielectric properties. Examples of styrene-butadiene rubber (SBR) include RICON-100, RICON-181, and RICON-184 (all manufactured by Cray Valley Chemical Industries, Ltd.) and 1,2-SBS (manufactured by Nippon Soda Co., Ltd.). Examples of polybutadienes include B-1000, B-2000, and B-3000 (all manufactured by Nippon Soda Co., Ltd.). The molecular weight of polybutadiene and styrene-butadiene rubber is preferably a weight-average molecular weight of 500 to 10,000, more preferably 750 to 7,500, and even more preferably 1,000 to 5,000. Below the lower limit of the above range, the amount of volatilization is high, making it difficult to adjust the solids content during prepreg production. Above the upper limit of the above range, compatibility with other curable resins deteriorates. In general, in the case of compounds containing heteroatoms such as oxygen and nitrogen, such as bismaleimides and polymaleimides, their polarity makes it difficult to ensure compatibility with low-polarity compounds, such as compounds composed mainly of hydrocarbons or compounds composed only of hydrocarbons. On the other hand, the compound of the present embodiment does not have a skeleton design in which heteroatoms such as oxygen and nitrogen are actively introduced, and therefore has excellent compatibility with materials having low polarity and low dielectric properties and compounds composed only of hydrocarbons.

[0101] [Polystyrene and Modified Polystyrene] Polystyrene and modified polystyrene 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 copolymer). Examples of suitable block copolymers include SEPTON 8004, SEPTON 8006, and SEPTON 8007L, all manufactured by Kuraray Co., Ltd.), SEEPS-OH (a styrene-ethylene / ethylene propylene-styrene block copolymer having a hydroxyl group at its terminal: SEPTON HG252, manufactured by Kuraray Co., Ltd.), SIS (styrene-isoprene-styrene block copolymer: SEPTON 5125 and SEPTON 5127, both manufactured by Kuraray Co., Ltd.), hydrogenated SIS (hydrogenated styrene-isoprene-styrene block copolymer: HYBRAR 7125F and HYBRAR 7311F, both manufactured by Kuraray Co., Ltd.), and SIBS (styrene-isobutylene-styrene block copolymer: SIBSTAR073T, SIBSTAR102T, and SIBSTAR103T (all manufactured by Kaneka Corporation), and SEPTON V9827 (manufactured by Kuraray Co., Ltd.)), but are not limited thereto. These may be used alone or in combination. Polystyrene and modified products thereof are preferably free of unsaturated bonds, since they have higher heat resistance and are less susceptible to oxidative degradation.Furthermore, there are no particular restrictions on the weight-average molecular weight of polystyrene and modified products thereof as long as it is 10,000 or more. However, if it is too large, compatibility with not only the polyphenylene ether compound 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.

[0102] [Polyethylene and Modified Polyethylenes] Polyethylene and modified polyethylenes are compounds having polyethylene or a polyethylene-derived structure in the molecule. Examples of polyethylene and modified polyethylenes include, but are not limited to, ethylene-propylene copolymers, ethylene-styrene copolymers, ethylene-propylene-ethylidene norbornene copolymers (EBT: K-8370EM, K-9330M, etc., manufactured by Mitsui Chemicals, Inc.), ethylene-propylene-vinyl norbornene copolymers (VNB-EPT: PX-006M, PX-008M, PX-009M, etc., manufactured by Mitsui Chemicals, Inc.), ethylene-vinyl alcohol copolymers, and ethylene-vinyl acetate copolymers. From the viewpoint of improving heat resistance, it is preferable to use ethylene-propylene-ethylidene norbornene copolymers or ethylene-propylene-vinyl norbornene copolymers containing a crosslinkable structure. These may be used alone or in combination. There are no particular restrictions on the weight-average molecular weight of polyethylene and modified polyethylenes thereof as long as it is 10,000 or more. However, if it is too large, compatibility with not only the polyphenylene ether compound 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.

[0103] [Benzoxazine Compound] Any benzoxazine compound may be used as long as it is a compound obtained by reacting a compound having a phenolic hydroxyl group, a compound having an amino group, or a compound having an aldehyde group. The compound having a phenolic hydroxyl group is not particularly limited, but for example, the above-mentioned phenolic resin, phenols (which may have a substituent such as an alkenyl group or an alkyl group), and bisphenols can be used. The compound having an amino group is not particularly limited, but the above-mentioned amine resin, diamine, and anilines (which may have a substituent such as an alkenyl group or an alkyl group) can be used. The aldehyde compound may be, for example, the above-mentioned aldehydes, but formaldehyde is preferably used. Commercially available benzoxazine compounds may be used, such as benzoxazine P-d, Fa, and ALP-d (all manufactured by Shikoku Chemical Industry Co., Ltd.), JBZ-BA100N, JBZ-FA100N, JBZ-DP100N, JBZ-OP100N, JBZ-OP100D, and JBZ-OP100I (all manufactured by JFE Chemical Corporation), and BTBz (manufactured by Japan Materials Technology Co., Ltd.). The curable resin composition of this embodiment can be obtained by preparing the above components in a predetermined ratio, pre-curing at 130 to 180°C for 30 to 500 seconds, and then post-curing at 150 to 200°C for 2 to 15 hours, thereby allowing the curing reaction to proceed sufficiently and obtaining a cured product of this embodiment. Alternatively, the components of the curable resin composition can be uniformly dispersed or dissolved in a solvent or the like, and then cured after removing the solvent.

[0104] The method for preparing the curable resin composition of this embodiment is not particularly limited, and the components may be simply mixed uniformly, or may be prepolymerized. For example, a mixture containing the compound of this embodiment is heated in the presence or absence of a curing accelerator or a polymerization initiator, and in the presence or absence of a solvent, to form a prepolymer. Similarly, compounds such as amine compounds, compounds having ethylenically unsaturated bonds, maleimide compounds, cyanate ester compounds, polybutadiene and its modified products, polystyrene and its modified products, inorganic fillers, and other additives may be added to form a prepolymer. The components may be mixed or prepolymerized using, for example, an extruder, kneader, or rolls in the absence of a solvent, or a reaction kettle equipped with a stirrer in the presence of a solvent.

[0105] The uniform mixing method involves kneading the components using a device such as a kneader, roll, or planetary mixer at a temperature within the range of 50 to 100°C to obtain a uniform resin composition. The resulting resin composition can be pulverized and then molded into cylindrical tablets using a molding machine such as a tablet machine, or into a granular powder or powder-like molded body. Alternatively, these compositions can be melted on a surface support and molded into a sheet with a thickness of 0.05 mm to 10 mm to obtain a molded curable resin composition. The resulting molded body is non-sticky at 0 to 20°C, and exhibits little loss of fluidity or curability even when stored at -25 to 0°C for one week or more. The resulting molded body can be molded into a cured product using a transfer molding machine or compression molding machine.

[0106] The curable resin composition of this embodiment can also be made into a varnish-like composition (hereinafter simply referred to as varnish) by adding an organic solvent. The curable resin composition of this embodiment can be dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, or N-methylpyrrolidone, as needed, to form a varnish. This varnish is then impregnated into a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, or paper, and heated and dried to obtain a prepreg. This prepreg can then be hot-press molded to form a cured product of the curable resin composition of this embodiment. The solvent used in this case accounts for 10 to 70 wt %, preferably 15 to 70 wt %, of the mixture of the curable resin composition of this embodiment and the solvent. Furthermore, if the composition is in liquid form, a curable resin composition containing carbon fiber can also be obtained as is, for example, by the RTM method.

[0107] The curable resin composition of this embodiment can also be used as a modifier for film-type compositions. Specifically, it can be used to improve flexibility and the like in the B-stage. Such a film-type resin composition can be obtained as a sheet-like adhesive by applying the curable resin composition of this embodiment as a varnish onto a release film, removing the solvent under heating, and then performing B-staging. This sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like.

[0108] The curable resin composition of this embodiment can also be used to obtain a prepreg by heating and melting it to reduce its viscosity and impregnating it into reinforcing fibers such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, and alumina fiber. Specific examples include glass fibers such as E-glass cloth, D-glass cloth, S-glass cloth, Q-glass cloth, spherical glass cloth, NE-glass cloth, and T-glass cloth; inorganic fibers other than glass; and organic fibers such as polyparaphenylene terephthalamide (Kevlar®, manufactured by DuPont), wholly aromatic polyamide, polyester, polyparaphenylene benzoxazole, polyimide, and carbon fiber, but are not limited thereto. The shape of the substrate is not particularly limited, but examples include woven fabric, nonwoven fabric, roving, and chopped strand mat. Known weaving methods for woven fabrics include plain weave, saddle-weave, and twill weave, and these known methods can be appropriately selected and used depending on the intended application and performance. Also preferred are woven fabrics that have been opened or glass woven fabrics that have been surface-treated with a silane coupling agent or the like. The thickness of the substrate is not particularly limited, but is preferably about 0.01 to 0.4 mm. Also, a prepreg can be obtained by impregnating reinforcing fibers with the varnish and drying the impregnated fibers by heating.

[0109] A laminate can also be manufactured using the prepreg. The laminate is not particularly limited as long as it comprises one or more prepregs, and may also have any other layers. The method for manufacturing the laminate can be any generally known method, and is not particularly limited. For example, when molding a metal foil-clad laminate, a multi-stage press, a multi-stage vacuum press, a continuous molding machine, an autoclave molding machine, or the like can be used. The prepregs are laminated together and then heated and pressure molded to obtain a laminate. The heating temperature is not particularly limited, but is preferably 65 to 300°C, and more preferably 120 to 270°C. The pressure applied is also not particularly limited, but if the pressure is too high, it becomes difficult to adjust the solid content of the resin in the laminate, resulting in unstable quality. If the pressure is too low, air bubbles will form and adhesion between the laminate layers will be poor. Therefore, a pressure of 2.0 to 5.0 MPa is preferred, and 2.5 to 4.0 MPa is more preferred. The laminate of this embodiment, having a layer made of metal foil, can be suitably used as a metal foil-clad laminate, as described below. The prepreg is cut into a desired shape and laminated with copper foil or the like as needed. The laminate is then heated and cured while applying pressure to the laminate 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.

[0110] The curable resin composition of this embodiment can also be made into a resin sheet. A method for obtaining a resin sheet from the curable resin composition of this embodiment includes, for example, applying the curable resin composition to a support film (support), drying the composition, and forming a resin composition layer on the support film. When the curable resin composition of this embodiment is used for a resin sheet, it is essential that the film softens under the lamination temperature conditions (70°C to 140°C) in the vacuum lamination method and exhibits fluidity (resin flow) that allows resin filling of via holes or through holes present in the circuit board simultaneously with lamination of the circuit board. It is preferable to blend the above components so as to exhibit such properties. The resulting resin sheet or circuit board (such as a copper-clad laminate) requires a uniform appearance in order to exhibit consistent performance at any location without causing a phenomenon in which locally different characteristic values ​​are exhibited due to phase separation or the like.

[0111] Here, the diameter of the through-holes in the circuit board is 0.1 to 0.5 mm, and the depth is 0.1 to 1.2 mm, and it is preferable to make it possible to fill the resin within this range. When laminating both sides of the circuit board, it is desirable to fill about half of the through-holes.

[0112] A specific method for producing the above-mentioned resin sheet includes preparing a resin composition varnished by blending an organic solvent therewith, 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).

[0113] The organic solvent used here preferably includes, for example, ketones such as acetone, methyl ethyl ketone, and cyclohexanone; acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; dimethylformamide, dimethylacetamide, and N-methylpyrrolidone; and it is preferable to use the organic solvent in such a proportion that the nonvolatile content of the organic solvent is 30 to 60% by mass of the total.

[0114] The thickness of the resin composition layer (X) formed must be equal to or greater than the thickness of the conductor layer of the circuit board to which the resin composition layer (X) is laminated. Since the thickness of the conductor layer of the circuit board is in the range of 5 to 70 μm, the thickness of the resin composition layer (X) is preferably 10 to 100 μm. The resin composition layer (X) in this embodiment may be protected with a protective film described below. Protection with a protective film can prevent the adhesion of dust and scratches to the surface of the resin composition layer (X).

[0115] Examples of the support film and protective film include 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 protective film may be subjected to a mud treatment, corona treatment, or release treatment. The thickness of the support film is not particularly limited, but is generally in the range of 10 to 150 μm, preferably 25 to 50 μm. The thickness of the protective film is preferably 1 to 40 μm.

[0116] The support film (Y) is peeled off after laminating the resin composition layer (X) onto a circuit board, or after forming an insulating layer by heat-curing the resin composition layer (X). If the support film (Y) is peeled off after the resin composition layer (X) constituting the resin sheet has been heat-cured, adhesion of dust and the like during the curing process can be prevented. When peeling off after curing the resin composition layer (X), the support film (Y) is previously subjected to a release treatment.

[0117] A multilayer printed circuit board can be produced from the resin sheet obtained as described above. For example, when the resin composition layer (X) is protected by a protective film, the protective film is peeled off, and then the resin composition layer (X) is laminated onto one or both sides of the circuit board so as to be in direct contact with the circuit board, for example, by a vacuum lamination method. The lamination method may be a batch method or a continuous method using a roll. If necessary, the resin sheet and the circuit board may be heated (preheated) before lamination. The lamination conditions are preferably a pressure bonding temperature (lamination temperature) of 70 to 140°C and a pressure bonding pressure of 1 to 11 kgf / cm. ２ (9.8 x 10 ４ ~107.9 x 10 ４ N / m ２ ), and lamination is preferably carried out under reduced air pressure of 20 mmHg (26.7 hPa) or less.

[0118] The curable resin composition of the present embodiment can be used to manufacture semiconductor devices, such as dual in-line packages (DIPs), quad flat packages (QFPs), ball grid arrays (BGAs), chip size packages (CSPs), small outline packages (SOPs), thin small outline packages (TSOPs), and thin quad flat packages (TQFPs).

[0119] The curable resin composition and its cured product according to this embodiment can be used in a wide range of fields. Specifically, they can be used in various applications such as molding materials, adhesives, composite materials, and paints. The cured product of the curable resin composition according to this 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, and laminates (printed wiring boards, BGA substrates, build-up substrates, etc.), lightweight, high-strength structural composite materials such as carbon fiber reinforced plastics and glass fiber reinforced plastics, 3D printing, and the like.

[0120] The present invention will now be described in more detail with reference to examples. Unless otherwise specified, all parts are by mass. However, the present invention is not limited to these examples.

[0121] The various analytical methods used in the examples are described below. <Number average molecular weight (Mn), weight average molecular weight (Mw)> Calculated in terms of polystyrene using a polystyrene standard solution. GPC: DGU-20A3R, LC-20AD, SIL-20AHT, RID-20A, SPD-20A, CTO-20A, CBM-20A (all manufactured by Shimadzu Corporation) Column: Shodex KF-603, KF-602x2, KF-601x2) Coupled eluent: tetrahydrofuran Flow rate: 0.5 ml / min Column temperature: 40°C Detection: RI (differential refractometer)

[0122] [Synthesis Example 1] While purging nitrogen into a flask equipped with a thermometer, a condenser, and a stirrer, 253.6 parts of 2-bromoethylbenzene (manufactured by Tokyo Chemical Industry Co., Ltd.) and 25.4 parts of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were added and reacted at 170 ° C. for 5 hours. Thereafter, the internal temperature was cooled to 80 ° C., and 43.8 parts of α,α'-dichloro-p-xylene (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, followed by a reaction at 100 ° C. for 2 hours and then at 130 ° C. for 4 hours. Thereafter, the internal temperature was cooled to 60 ° C., extracted with 220.0 parts of toluene, neutralized by adding 34.8 parts of a 30% aqueous sodium hydroxide solution, and the organic layer was washed five times with 100 parts of water. By placing the mixture under heating and reduced pressure to recover the toluene, 192.4 parts of an olefin resin precursor (b-1) was obtained as a liquid resin (Mn 528, MW: 737). The GPC chart of the obtained compound is shown in FIG. 1. (m + k) in the following formula (b-1) calculated from the area percentage of each peak ａｖｅ The obtained compound １ The H-NMR data (deuterated chloroform) is shown in FIG. １A signal for ethylene bridge hydrogen derived from formula (b-2) below was observed at 2.80-3.00 ppm in the H-NMR chart, and a signal for methine hydrogen derived from formula (b-3) below was observed at 4.00-4.30 ppm. The integral value of the peak derived from the hydrogen of the ethylene bridge was 11.6, and the integral value of the peak derived from the methine hydrogen was 1.0. The ratio of (b-2) to (b-3) in X in formula (b-1) below calculated from these was 1:2.9. Furthermore, a signal for bromoethyl hydrogen derived from formula (b-1) below was observed at 3.00-3.70 ppm, and a signal for methylene bridge hydrogen was observed at 3.80-4.10 ppm. The integral value of the peak derived from the hydrogen of the bromoethyl group was 15.7, and the integral value of the peak derived from the hydrogen of the methylene bridge was 8.7. The value of n in formula (b-1) below calculated from these was 1.2.

[0123]

[0124] In the above formula (b-1), A represents a hydrocarbon group represented by the following formula (b-2) or (b-3).

[0125]

[0126] In the above formulas (b-2) and (b-3), * represents the bonding position to the benzene ring in formula (b-1) or the benzene ring in formulas (b-2) and (b-3).

[0127] Synthesis Example 2 While purging with nitrogen into a flask equipped with a thermometer, a condenser, and a stirrer, 80.0 parts of (b-1) obtained in Synthesis Example 1, 100 parts of toluene, 300 parts of dimethyl sulfoxide, 0.04 parts of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (free radical), and 27.7 parts of 48% aqueous sodium hydroxide solution were added, and the reaction was continued at 40°C for 7 hours. 26 parts of water was added, and the aqueous layer was extracted. 280 parts of toluene was added, and the organic layer was repeatedly washed with 26 parts of water until the wastewater became neutral. The mixture was concentrated under reduced pressure using an evaporator, and 49 parts of an olefin resin represented by the following formula (b-4) was obtained (Mn: 431, Mw: 789). The GPC chart of the obtained compound is shown in Figure 3. １ The H-NMR data (deuterated chloroform) is shown in FIG. １A signal for ethylene bridge hydrogen derived from the following formula (b-5) was observed at 2.60-3.20 ppm in the H-NMR chart, and a signal for methine hydrogen derived from the following formula (b-6) was observed at 4.10-4.30 ppm. The integral value of the peak derived from the hydrogen of the ethylene bridge was 12.7, and the integral value of the peak derived from the methine hydrogen was 1.0. The ratio of (b-5) to (b-6) in A in the following formula (b-4) calculated from these was 1:3.2. Furthermore, a signal for terminal hydrogen of the vinyl group derived from the following formula (b-4) was observed at 5.00-6.00 ppm, and a signal for methylene bridge hydrogen was observed at 3.60-4.10 ppm. The integral value of the peak derived from the terminal hydrogen of the vinyl group was 7.9, and the integral value of the peak derived from the hydrogen of the methylene bridge was 9.1. The value of n in the following formula (b-4) calculated from these was 1.2.

[0128] In the above formula (b-4), A represents a hydrocarbon group represented by the following formula (b-5) or (b-6).

[0129]

[0130] In the above formulas (b-5) and (b-6), * represents the bonding position to the benzene ring of formula (b-4) or the benzene ring of formulas (b-5) and (b-6).

[0131] [Synthesis Example 3] A flask equipped with a thermometer, a condenser, and a stirrer was purged with nitrogen, and 152.3 parts of 2-bromoethylbenzene (manufactured by Tokyo Chemical Industry Co., Ltd.) and 15.2 parts of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were added and reacted at 170 ° C. for 5 hours. The internal temperature was then cooled to 80 ° C., and 37.7 parts of 4,4'-bis(chloromethyl)biphenyl (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was reacted at 80 ° C. for 3 hours, at 100 ° C. for 8 hours, and at 130 ° C. for 4 hours. The internal temperature was then cooled to 60 ° C., extracted with 440.0 parts of toluene, neutralized by adding 20.9 parts of a 30% aqueous sodium hydroxide solution, and the organic layer was washed five times with 50 parts of water. The mixture was heated under reduced pressure to recover the toluene, and 121.3 parts of an olefin resin precursor (b-7) was obtained as a liquid resin (Mn: 181, MW: 3496). The GPC chart of the obtained compound is shown in Figure 5. The (m + k) of the following formula (b-7) calculated from the area percentage of each peak ａｖｅ The obtained compound １ The H-NMR data (deuterated chloroform) is shown in FIG. １ A signal for ethylene bridge hydrogen derived from the following formula (b-8) was observed at 3.00-3.60 ppm in the H-NMR chart, and a signal for methine hydrogen derived from the following formula (b-9) was observed at 4.00-4.30 ppm. The integral value of the peak derived from the hydrogen of the ethylene bridge was 5.9, and the integral value of the peak derived from the methine hydrogen was 1.0. The ratio of (b-8) to (b-9) in A in the following formula (b-7) calculated from these values ​​was 1:1.5. Furthermore, a signal for bromoethyl hydrogen derived from the following formula (b-7) was observed at 3.00-3.70 ppm, and a signal for methylene bridge hydrogen was observed at 3.80-4.10 ppm. The integral value of the peak derived from the hydrogen of the bromoethyl group was 9.3, and the integral value of the peak derived from the hydrogen of the methylene bridge was 3.2. The value of n in the following formula (b-7) calculated from these values ​​was 1.5.

[0132]

[0133] In the above formula (b-7), A represents a hydrocarbon group represented by the following formula (b-8) or (b-9).

[0134]

[0135] In the above formulas (b-8) and (b-9), * represents the bonding position to the benzene ring in formula (b-7) or the benzene ring in formulas (b-8) and (b-9).

[0136] Synthesis Example 4 While purging with nitrogen into a flask equipped with a thermometer, a condenser, and a stirrer, 50.0 parts of (b-1) obtained in Synthesis Example 1, 87.5 parts of toluene, 162.5 parts of dimethyl sulfoxide, 0.03 parts of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (free radical), and 19.0 parts of 48% aqueous sodium hydroxide solution were added, and the reaction was continued at 40°C for 7 hours. 26 parts of water was added, and the aqueous layer was extracted. After that, 175 parts of toluene was added, and the organic layer was repeatedly washed with 17 parts of water until the wastewater became neutral. The mixture was concentrated under reduced pressure using an evaporator, and 26 parts of an olefin resin represented by the following formula (b-10) was obtained (Mn: 544, Mw: 4438). The GPC chart of the obtained compound is shown in Figure 7. １ The H-NMR data (deuterated chloroform) is shown in FIG. １ A signal for ethylene bridge hydrogen derived from the following formula (b-11) was observed at 2.30-3.00 ppm in the H-NMR chart, and a signal for methine hydrogen derived from the following formula (b-12) was observed at 4.10-4.30 ppm. The integral value of the peak derived from the hydrogen of the ethylene bridge was 5.5, and the integral value of the peak derived from the methine hydrogen was 1.0. The ratio of (b-11) to (b-12) in A in the following formula (b-10) calculated from these was 1:1.4. Furthermore, a signal for terminal hydrogen of the vinyl group derived from the following formula (b-10) was observed at 5.00-6.80 ppm, and a signal for methylene bridge hydrogen was observed at 3.80-4.10 ppm. The integral value of the peak derived from terminal hydrogen of the vinyl group was 1.9, and the integral value of the peak derived from hydrogen of the methylene bridge was 3.0. The value of n in the following formula (b-10) calculated from these was 1.6.

[0137] In the above formula (b-10), A represents a hydrocarbon group represented by the following formula (b-11) or (b-12).

[0138]

[0139] In the above formulae (b-11) and (b-12), * represents the bonding position to the benzene ring of formula (b-10) or the benzene ring of formulae (b-11) and (b-12).

[0140] [Examples 1 and 2, Comparative Example 1] Compound (b-4) obtained in Synthesis Example 2, compound (b-10) obtained in Synthesis Example 4, and OPE-2St (a polyphenylene ether compound manufactured by Mitsubishi Gas Chemical Company, Inc.) were used in the amounts shown in Table 1, and vacuum press-molded while sandwiched between mirror-finish copper foils (T4X: manufactured by Fukuda Metal Copper Foil Co., Ltd.), followed by curing at 220°C for 2 hours. At this time, a piece of cushion paper with a thickness of 250 μm, cut out in the center to a size of 150 mm length and width, was used as a spacer. For evaluation, test pieces were cut to the desired size using a laser cutter as necessary, and evaluation was performed.

[0141] <Dielectric loss tangent test> A 10 GHz cavity resonator manufactured by AET Corporation was used to perform the test at 25°C using a cavity resonator perturbation method. The test was performed on a sample with a width of 1.7 mm, a length of 100 mm, and a thickness of 0.3 mm. The evaluation results are shown in Table 1.

[0142]

[0143] From the results in Table 1, it was confirmed that the compounds of the present invention have excellent low dielectric properties.

[0144] The compound of the present invention is suitably used in electric and electronic parts such as semiconductor encapsulants, printed wiring boards, and build-up laminates.

Claims

1. A compound represented by the following formula (1): 【Chemistry 1】 (In the above formula (1), X represents a hydrocarbon group having 1 to 20 carbon atoms, A represents a hydrocarbon group represented by the following formula (a) or the following formula (b), and one molecule contains at least one hydrocarbon group represented by the following formula (a) or the following formula (b). When there are multiple As, the multiple As may be the same or different, and formula (a) and formula (b) may be bonded randomly. m represents an integer of 0 to 20, k represents an integer of 1 to 3, and the average value of m+k (m+k) ａｖｅ is 0 < (m + k) ａｖｅ ≦10. n is the average number of repetitions, and 1≦n≦20. R １ represents a hydrocarbon group having 1 to 5 carbon atoms, and l is an integer of 0 to 2. 【Chemistry 2】 (In the above formulas (a) and (b), * represents the bonding position to the benzene ring in formula (1) or the benzene ring in formulas (a) and (b). ２ each independently represents a hydrocarbon group having 1 to 5 carbon atoms; and multiple p's each independently represent an integer of 0 to 4.

2. The compound according to claim 1, wherein n satisfies the formula (1) and satisfies the formula (1) above.

3. The compound according to claim 1, wherein X in the formula (1) is any one or more of (c) to (k) in the following formula (2): 【Transformation 3】 (* indicates the bond position.)

4. The compound according to claim 3, wherein X in formula (2) is represented by (d) or (f).

5. The compound according to claim 1, which is derived from a compound represented by the following formula (3): 【Chemistry 4】 In the above formula (3), X represents a hydrocarbon group having 1 to 20 carbon atoms, and A represents a hydrocarbon group represented by the following formula (a) or (b). When there are multiple As, the multiple As may be the same or different, and formula (a) and formula (b) may be bonded randomly. m represents an integer of 0 to 20, k represents an integer of 1 to 3, and the average value of m+k (m+k) ａｖｅ is 0 < (m + k) ａｖｅ ≦10. n is the average number of repetitions, and 1≦n≦20. R １ represents a hydrocarbon group having 1 to 5 carbon atoms; l is an integer of 0 to 2; and Y represents a halogen atom. 【Transformation 5】 (In the above formulas (a) and (b), * represents the bonding position to the benzene ring in formula (3) or the benzene ring in formulas (a) and (b). ２ each independently represents a hydrocarbon group having 1 to 5 carbon atoms; and multiple p's each independently represent an integer of 0 to 4.

6. A curable resin composition comprising the compound according to claim 1 .

7. The curable resin composition according to claim 6, further comprising at least one selected from the group consisting of a curing accelerator, a polymerization initiator, an epoxy resin, an active ester compound, a phenolic resin, a polyphenylene ether compound, an amine resin, a compound having an ethylenically unsaturated bond, an isocyanate resin, a polyamide resin, a maleimide compound, a cyanate ester resin, a polyimide resin, polybutadiene and modified products thereof, polystyrene and modified products thereof, polyethylene and modified products thereof, and a benzoxazine compound.

8. A cured product obtained by curing the compound according to claim 1 .

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

10. A compound represented by the following formula (3): 【Transformation 6】 In the above formula (3), X represents a hydrocarbon group having 1 to 20 carbon atoms, and A represents a hydrocarbon group represented by the following formula (a) or (b). When there are multiple As, the multiple As may be the same or different, and formula (a) and formula (b) may be bonded randomly. m represents an integer of 0 to 20, k represents an integer of 1 to 3, and the average value of m+k (m+k) ａｖｅ is 0 < (m + k) ａｖｅ ≦10. n is the average number of repetitions, and 1≦n≦20. R １ represents a hydrocarbon group having 1 to 5 carbon atoms; l is an integer of 0 to 2; and Y represents a halogen atom. 【Transformation 7】 (In the above formulas (a) and (b), * represents the bonding position to the benzene ring in formula (3) or the benzene ring in formulas (a) and (b). ２ each independently represents a hydrocarbon group having 1 to 5 carbon atoms; and multiple p's each independently represent an integer of 0 to 4.

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