Curable resin, curable resin composition, and cured product thereof

Abstract

To provide a curable resin having excellent dielectric properties, a curable resin composition, and cured products thereof.SOLUTION: The present invention provides a curable resin which is represented by formula (1). In formula (1), a plurality of R1 each independently represent a residue resulting from removing one hydrogen atom from a C9-based petroleum resin. A plurality of R2 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an amino group, or a hydroxy group. s and t are each independently a real number of 0 to 3, and the total of s and t that bind to the same aromatic ring is a real number of 0 to 3.SELECTED DRAWING: Figure 4

Description

[Technical field]

[0001] The present invention relates to a curable resin, a curable resin composition, and a cured product thereof, which are suitably used for electric and electronic parts such as semiconductor encapsulants, printed wiring boards, and build-up laminates.

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

[0003] The fifth generation communication system "5G", currently under development, is expected to achieve even greater capacity and faster communication speeds. Since the attenuation rate of signals flowing through the dielectric material that constitutes the printed wiring board is proportional to the dielectric tangent (tan δ), the need for low dielectric materials is increasing. In addition, since the attenuation of signals directly generates heat and causes a rise in temperature, a dielectric tangent of 0.005 or less is required for printed wiring boards (Non-Patent Documents 1 and 2). However, when epoxy resins are used as curing agents with phenols or amines, due to their reaction mechanism, hydroxyl groups are generated during the curing reaction, which tends to deteriorate the water absorption and electrical properties.

[0004] In view of this situation, maleimide resins and polyphenylene ethers have been studied in recent years as printed wiring board materials in the high frequency range. Maleimide resins themselves have the characteristic of being highly heat resistant due to their high crosslink density, but on the other hand, they have the problem of being prone to water absorption, which can easily deteriorate their properties (Patent Document 1). In addition, Patent Document 2 discloses a polyphenylene ether oligomer having specific vinyl groups at both ends, but it is difficult to say that its dielectric properties are sufficient. Patent Document 3 discloses a phenolic resin modified with a petroleum resin, but further improvement in the dielectric properties is required. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 04-178358 [Patent Document 2] WO 2005 / 73264 [Patent Document 3] JP 2020-111712 A [Non-patent literature]

[0006] [Non-Patent Document 1] 2021 Electronics Packaging New Materials Handbook [Non-Patent Document 2] Proceedings of the Microelectronics Symposium (Vol. 20, 2010, pp. 239-242) Summary of the Invention [Problem to be solved by the invention]

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

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

[14] . Note that in the present invention, "(Numerical value 1) to (Numerical value 2)" indicates that the upper and lower limits are included. [1] A curable resin represented by the following formula (1):

[0009] [ka]

[0010] (In formula (1), A represents any one of the following formulae (1-a) to (1-d). Each of the multiple X's independently represents any one of the following formulae (1-e) to (1-g). Each of the multiple R1's independently represents a residue obtained by removing one hydrogen atom from a C9 petroleum resin. Each of the multiple R2's independently represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an amino group, or a hydroxy group. Each of the multiple s's and t's independently represents an integer of 0 to 3. integer The sum of s and t bonded to the same aromatic ring is 0 to 3. integer The average value of s is s ave is 0 ave ≦3, and the average value of t ave t ave ≦2. n is the number of repetitions, and the average value of n ave 0.1≦n ave ≦5.)

[0011] [ka]

[0012] (In formulas (1-a) to (1-d), each of the multiple R3s independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. The wavy line represents a bonding site to the aromatic ring in formula (1).)

[0013] [ka]

[0014] (In formulas (1-e) to (1-g), the wavy lines represent the bonding sites to the oxygen atom in formula (1).) [2] A curable resin obtained by reacting a phenolic resin (P3) containing a C9 petroleum resin (P2) having a phenolic hydroxyl group with any of the compounds represented by the following formulas (4-a) to (4-d), and a compound represented by the following formulas (2-a) to (2-c).

[0015] ​ [ka]

[0016] (In formulae (4-a) to (4-d), each of the multiple R3's independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. Each of the multiple Y's independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, or an alkoxy group having 1 to 6 carbon atoms.)

[0017] [ka]

[0018] (In formulas (2-a) to (2-c), a plurality of Y's each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, or an alkoxy group having 1 to 6 carbon atoms.) [3] A curable resin obtained by reacting a phenolic resin obtained by reacting a polyhydric hydroxyl resin represented by the following formula (3) with a C9-based petroleum resin (P1) having a double bond, with a compound represented by any one of the following formulas (2-a) to (2-c).

[0019] [ka]

[0020] In formula (3), A represents any one of the following formulae (1-a) to (1-d). Each of the multiple R2's independently represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an amino group, or a hydroxy group. Each of the multiple t's independently represents an integer of 0 to 3. integer The average value of t is t ave t ave ≦2. n is the number of repetitions, and the average value of n ave 0.1≦n ave ≦5.)

[0021] [ka]

[0022] (In formulas (1-a) to (1-d), each of the multiple R3s independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. The wavy line represents a bonding site to the aromatic ring in formula (3).)

[0023] [ka]

[0024] (In formulas (2-a) to (2-c), a plurality of Y's each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, or an alkoxy group having 1 to 6 carbon atoms.) [4] A curable resin composition comprising the curable resin according to any one of the preceding items [1] to [3]. [5] The curable resin composition according to the above item [4], further comprising a polyphenylene ether resin. [6] The curable resin composition according to the above item [4] or [5], further comprising a maleimide resin. [7] The curable resin composition according to any one of the above items [4] to [6], further comprising a polyolefin resin or a polystyrene resin. [8] The curable resin composition according to any one of the above items [4] to [7], further comprising an inorganic filler. [9] The curable resin composition according to any one of the above items [4] to [8], further comprising a curing accelerator.

[10] The curable resin composition according to any one of items [4] to [9], further comprising a polymerization initiator.

[11] A cured product of the curable resin composition according to any one of items [4] to

[10] above.

[12] A prepreg obtained by using the curable resin composition according to any one of items [4] to

[10] above.

[13] A laminate obtained by curing the curable resin composition according to any one of the above items [4] to

[10] .

[14] A semiconductor substrate comprising the laminate according to item

[13] above. Effect of the Invention

[0025] According to the present invention, it is possible to provide a curable resin, a curable resin composition, and a cured product thereof, an insulating layer, a printed wiring board, and a semiconductor device, all of which have excellent low dielectric properties. [Brief description of the drawings]

[0026] [Figure 1] 1 shows a GPC chart of Synthesis Example 1. [Diagram 2] 1H-NMR chart of Synthesis Example 1 is shown. [Diagram 3] 1 shows a GPC chart of Example 1. [Figure 4] 1 shows a 1H-NMR chart of Example 1. [Diagram 5] 1 shows a GPC chart of Example 2. [Figure 6] 1H-NMR chart of Example 2 is shown. [Figure 7] 3 shows an IR chart of Example 2. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0027] The curable resin of the present embodiment is represented by the following formula (1).

[0028] [ka]

[0029] In formula (1), A represents any one of the following formulae (1-a) to (1-d). Each of the multiple X's independently represents any one of the following formulae (1-e) to (1-g). Each of the multiple R1's independently represents a residue obtained by removing one hydrogen atom from a C9 petroleum resin. Each of the multiple R2's independently represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an amino group, or a hydroxy group. Each of the multiple s's and t's independently represents an integer of 0 to 3. integer The sum of s and t bonded to the same aromatic ring is 0 to 3. integer The average value of s is s ave is 0 ave ≦3, and the average value of t ave t ave ≦2. n is the number of repetitions, and the average value of n ave 0.1≦n ave <=5.

[0030] [ka]

[0031] In formulas (1-a) to (1-d), each of the multiple R3s independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. The wavy line represents a bonding site to the aromatic ring in formula (1).

[0032] [ka]

[0033] In formulas (1-e) to (1-g), the wavy lines represent the bonding sites to the oxygen atom in formula (1).

[0034] The C9 petroleum resin refers to a resin obtained by polymerizing a C9 fraction (vinyl toluene, indene, α-methyl styrene, dicyclopentadiene, etc.) obtained by thermal decomposition of petroleum naphtha.

[0035] ​Industrially available C9-based petroleum resins include C9-based petroleum resins manufactured by Maruzen Petrochemical Co., Ltd., T-REZ RD-104, T-REZ PR802, Neopolymer L-90, Neopolymer 120, Neopolymer 130, Neopolymer 140, Neopolymer 150, Neopolymer 160, Neopolymer 170S, Neopolymer M-1, Neopolymer S, Neopolymer S100, Neopolymer 120S, Neopolymer 130S, Neopolymer 120P, Neopolymer E-100, Neopolymer E-130, Neoresin EP-140, Tosyoshasei Petrotack 60, Petrotack 70, Petrotack 90, Petrotack 90V, Petrotack 90HS, Petrotack 100V, Petcol LX, Petcol 120, Petcol 130, Petcol 140, and NEVILLE, manufactured by JXTG Nippon Oil & Energy Corporation. Examples of such resins include, but are not limited to, NP-10, NP-25, NEVPENE9545, NEVEX045, NEVCHEM100, NEVCHEM110, NEVCHEM120, NEVCHEM130, NEVCHEM140, NEVCHEM150, NEVCHEM200, NEVCHEM220, NEVCHEM240, NEVCHEM250, NEVCHEM300, NEVCHEM320, NEVCHEM340, NEVPENE9500, NEVPENE9510, NEVPENE9510-N, and NEVPENE9511 manufactured by CHEMICAL Corporation. C9-based petroleum resins can improve long-term dielectric properties because the water absorption rate is reduced due to the influence of low-polarity alkyl groups in the skeleton.

[0036] The number average molecular weight of the curable resin represented by the above formula (1) of this embodiment can be determined by gel permeation chromatography (GPC, detector: RI), and is preferably 300 to 10,000, more preferably 500 to 5,000, and particularly preferably 750 to 3,000.

[0037] The average value of n in the formula (1) ave The value was determined by gel permeation chromatography (GPC, detector: RI) or 1It can be determined by measuring 1H-NMR. n is preferably 0 ≦ n ≦ 20, more preferably 0 < n < 10. The average value n of n ave is 0.1 ≦ n ave ≦ 5, preferably 0.5 ≦ n ave ≦ 5, more preferably 1 ≦ n ave ≦ 3. When n ave is greater than 5, the solubility and fluidity in the solvent are poor, and molding becomes difficult. When n ave is less than 0.1, the crosslinking density of the cured product is low, so sufficient heat resistance cannot be exhibited.

[0038] In the above formula (1), the average value of s can be calculated from the charging ratio of the polyhydric hydroxy resin represented by the following formula (3) and the C9 petroleum resin (P1) having a double bond, or the charging ratio of the C9 petroleum resin (P2) having a phenolic hydroxyl group in the phenolic resin (P3). s is preferably 0 < s ≦ 3. The average value s of s ave is 0 < s ave ≦ 3, preferably 0.1 ≦ s ave ≦ 2, more preferably 0.3 ≦ s ave ≦ 1.5, particularly preferably. t is preferably 0 ≦ t ≦ 2. The average value t of t ave is 0 ≦ t ave ≦ 2, preferably 0 ≦ t ave ≦ 1.5, more preferably 0 ≦ t ave ≦ 1, particularly preferably. However, the sum of s and t bonded to the same aromatic ring is 0 to 3 integer . When s ave is 0, the properties such as dielectric properties remain unimproved. When it is more than 3, the functional group density becomes too low and the curability tends to decrease. Also, when t ave is more than 2, the functional group density becomes low and the curability tends to decrease.

[0039] The curable resin represented by formula (1) is derived from a phenol resin represented by formula (2) below. Specifically, the curable resin represented by formula (1) above can be obtained by reacting the phenol resin represented by formula (2) above with a compound represented by any one of formulas (2-a), (2-b), and (2-c) below.

[0040] [ka]

[0041] (In formula (2), R1, R2, n, s, and t have the same meanings as in formula (1).)

[0042] [ka]

[0043] (In the formulas (2-a) to (2-c), Y represents any one of a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a hydroxy group, and an alkoxy group having 1 to 6 carbon atoms.)

[0044] The method for producing the curable resin represented by the formula (1) is not particularly limited, but for example, a method is generally used in which a phenolic resin represented by the formula (2), any one of the compounds represented by the formulas (2-a) to (2-c), a basic catalyst, and a solvent are all charged into a reaction vessel and dehydrohalogenated at a predetermined temperature, or a polyhydric hydroxyl resin and a catalyst are charged, and while maintaining the temperature at a predetermined level, any one of the compounds represented by the formulas (2-a) to (2-c) is added dropwise to cause the reaction. In this case, the drop time is usually 1 to 10 hours.

[0045] Examples of the solvent used in the production of the curable resin represented by the formula (1) include, but are not limited to, non-water-soluble solvents such as aromatic solvents such as toluene and xylene, aliphatic solvents such as cyclohexane and n-hexane, ethers such as diethyl ether, diisopropyl ether, and 4-methyltetrahydropyran, ester solvents such as ethyl acetate and butyl acetate, and ketone solvents such as methyl isobutyl ketone and cyclopentanone. Two or more of these may be used in combination. In addition to the non-water-soluble solvent, a non-protic polar solvent may also be used in combination. Examples include dimethyl sulfone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, and N-methylpyrrolidone, and two or more of these may be used in combination. When using an aprotic polar solvent, it is preferable to use one with a higher boiling point than the non-water-soluble solvent to be used in combination.

[0046] The catalyst used in the production of the curable resin represented by the formula (1) is not particularly limited, and examples thereof include basic catalysts such as sodium hydroxide, potassium hydroxide, and potassium carbonate. Since it is difficult to completely proceed with the dehydrohalogenation reaction, the aprotic polar solvent may be used in large excess relative to the substrate, and the dehydrohalogenation reaction may be repeated two or more times. For example, the dehydrohalogenation reaction of the curable resin represented by the 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, and the base catalyst may be added to cause the reaction again. In this way, the progress of the dehydrohalogenation reaction can be increased. That is, it is possible to reduce the amount of residual halogen contained in the target compound. If a solvent is used after the reaction, the catalyst component may be removed as necessary, and the solvent may then be distilled off to obtain the resin used in this embodiment.

[0047] The curable resin represented by the formula (1) can also be purified by a known method. The purification method is not particularly limited, but examples include separation and washing with water, and reprecipitation using a poor solvent. By adding a purification step, phenolic hydroxyl groups derived from the raw materials and alcoholic hydroxyl groups purified during the reaction can be removed, improving the dielectric properties.

[0048] Next, a method for producing the phenolic resin represented by the formula (2) will be described. The method for producing the phenolic resin represented by the formula (2) is not particularly limited, but an example of the method is a method obtained by subjecting a polyhydric hydroxyl resin represented by the following formula (3) to an addition reaction with a C9-based petroleum resin (P1) having a double bond. Another method is a method obtained by reacting a phenolic resin (P3) containing a C9-based petroleum resin (P2) having a phenolic hydroxyl group with any of the compounds represented by the following formulas (4-a) to (4-d).

[0049] [ka]

[0050] (In formula (3), A, R2, n, and t have the same meanings as in formula (1).)

[0051] [ka]

[0052] (In formulae (4-a) to (4-d), R3 has the same meaning as in formulae (1-a) to (1-d). Y has the same meaning as in formula (2-a).)

[0053] The polyhydric hydroxyl resin represented by the formula (3) is a compound having a phenolic hydroxyl group in the molecule. Examples of phenolic resins include, but are not limited to, reaction products of phenols and aldehydes, reaction products of phenols and diene compounds, reaction products of phenols and ketones, reaction products of phenols and substituted biphenyls, reaction products of phenols and substituted phenyls, and reaction products of bisphenols and aldehydes. These may be used alone or in combination.

[0054] [Polymer containing a C9 petroleum resin structure with double bonds (P1)] The polymer (P1) containing a C9 petroleum resin structure having a double bond can be obtained by cationic polymerization of at least one of the compounds represented by the following formulas (5-a) to (5-c) in the presence of an acid catalyst.

[0055] [ka]

[0056] The number average molecular weight of the C9 petroleum resin (P1) having a double bond is preferably from 200 to 10,000, more preferably from 300 to 5,000, and even more preferably from 500 to 3,000.

[0057] [C9 petroleum resin with phenolic hydroxyl groups (P2)] The C9 petroleum resin (P2) having a phenolic hydroxyl group is not particularly limited, but can be obtained by reacting the C9 petroleum resin (P1) having a double bond with a polyhydric hydroxy compound. Specific examples of the C9 petroleum resin (P2) having a phenolic hydroxyl group include Neopolymer E-100 and Neopolymer E-130 manufactured by JXTG Nippon Oil & Energy Corporation. The number average molecular weight of the C9 petroleum resin (P2) having a phenolic hydroxyl group is usually 200 to 5,000, preferably 300 to 3,000, and more preferably 500 to 1,000.

[0058] [Phenol resin (P3) containing C9 petroleum resin (P2) with phenolic hydroxyl groups] The phenolic resin (P3) containing a C9 petroleum resin (P2) having a phenolic hydroxyl group is a phenolic resin containing a C9 petroleum resin (P2) having a phenolic hydroxyl group as an essential component, and may further contain other phenols. Other phenols that can be combined are not particularly limited as long as they are compounds having a phenolic hydroxyl group, and examples thereof include monofunctional phenol compounds such as phenol, alkyl-substituted phenols, aromatic-substituted phenols, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, and dihydroxynaphthalene, bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, bisphenol I, etc.), and polycondensates of these phenol compounds with various aldehydes (formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.).

[0059] In the production of the phenolic resin represented by the formula (2), a solvent can be used in the presence of an acidic or basic catalyst as necessary. Examples of the solvent to 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, diisopropyl ether, and 4-methyltetrahydropyran, ester solvents such as ethyl acetate and butyl acetate, and ketone solvents such as methyl isobutyl ketone and cyclopentanone. Two or more of these may be used in combination. In addition to the water-insoluble solvent, an aprotic polar solvent can also be used in combination. Examples include dimethyl sulfone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, and N-methylpyrrolidone, and two or more of these may be used in combination. When an aprotic polar solvent is used, it is preferable to use one having a higher boiling point than the water-insoluble solvent to be used in combination.

[0060] The catalyst used in the production of the phenolic resin represented by the formula (2) is not particularly limited, and examples thereof include known acid catalysts such as mineral acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; organic acids such as oxalic acid, methanesulfonic acid, toluenesulfonic acid, and acetic acid; heteropolyacids such as tungstic acid, activated clay, inorganic acids, stannic chloride, zinc chloride, and ferric chloride, and other acidic organic and inorganic acid salts; and alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide; alkali metal alkoxides such as sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, and potassium-tert-butoxide; and alkaline earth metal alkoxides such as magnesium methoxide and magnesium ethoxide. Amine-based catalysts can also be used, and examples thereof include triethylamine, ethanolamine, pyridine, piperidine, and morpholine. In particular, when an amine-based catalyst is used, it can also be used as a solvent. These catalysts may be used alone or in combination of two or more. The amount of the catalyst used is usually 0.001 to 10 times by mole, preferably 0.01 to 2 times by mole, relative to the polyhydric hydroxyl resin represented by the formula (3) or the polymer (P2) containing a C9 petroleum resin structure having a phenolic hydroxyl group. When the catalyst is used as a solvent, it is preferable to add about 10 to 200% by mass relative to the polyhydric hydroxyl resin represented by the formula (3) or the polymer (P2) containing a C9 petroleum resin structure having a phenolic hydroxyl group.

[0061] The curable resin of the present embodiment can also be used as a curable resin composition. The composition is not limited, but examples include epoxy resins, active ester compounds, maleimide compounds, inorganic fillers, curing accelerators, polymerization initiators, polymerization inhibitors, flame retardants, light stabilizers, binder resins, additives, phenolic resins, polyphenylene ether compounds, amine resins, compounds containing ethylenically unsaturated bonds, isocyanate resins, polyamide resins, polyimide resins, cyanate ester resins, polybutadiene and modified products thereof, polystyrene and modified products thereof, and the like. These may be used alone or in combination. Of these compounds, it is preferable to contain polyphenylene ether compounds, maleimide compounds, compounds having ethylenically unsaturated bonds, cyanate ester resins, polybutadiene and modified products thereof, and polystyrene and modified products thereof, in view of the balance of heat resistance, adhesion, and dielectric properties. By containing these compounds, the brittleness of the cured product can be improved and adhesion to metals can be improved, and cracks in the package during reliability tests such as solder reflow and thermal cycles can be suppressed. The amount of the compound 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 curable resin composition, unless otherwise specified. 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 being within the above range, the effect of each compound added can be added while taking advantage of the effect of the low dielectric properties of the curable resin composition of this embodiment. As for these components, the following exemplified ones can be used.

[0062] [Epoxy resin] The curable resin composition of the present embodiment may contain an epoxy resin. Preferable examples of the epoxy resin to be contained are shown below, but are not limited thereto. These may be used alone or in combination.

[0063] Of the above-mentioned epoxy resins, examples of liquid epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, phenol novolac type epoxy resins, alicyclic epoxy resins having an ester skeleton, cyclohexane type epoxy resins, cyclohexane dimethanol type epoxy resins, glycidyl amine type epoxy resins, and epoxy resins having a butadiene structure. Of these, bisphenol A type epoxy resins are particularly preferred. Specific examples include "RE310S", "RE410S" (all manufactured by Nippon Kayaku Co., Ltd., bisphenol A type epoxy resin), "RE303S", "RE304S", "RE403S", "RE404S" (all manufactured by Nippon Kayaku Co., Ltd., bisphenol F type epoxy resin), "HP4032", "HP4032D", "HP4032SS" (all manufactured by DIC Corporation, naphthalene type epoxy resin), "828US", "jER828EL", "825", "828EL" (all manufactured by Mitsubishi Chemical Corporation, bisphenol A type epoxy resin), "jE807", "1750" (all manufactured by Mitsubishi Chemical Corporation, bisphenol F type epoxy resin), "jER152" (manufactured by Mitsubishi Chemical Corporation, phenol Novolac type epoxy resin), "630", "630LSD" (all manufactured by Mitsubishi Chemical Corporation, glycidylamine type epoxy resin), "ZX1059" (manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin), "EX-721" (manufactured by Nagase ChemteX Corporation, glycidyl ester type epoxy resin), "Celloxide 2021P" (manufactured by Daicel Corporation, alicyclic epoxy resin having an ester skeleton), "PB-3600" (manufactured by Daicel Corporation, epoxy resin having a butadiene structure), "ZX1658", "ZX1658GS" (all manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., liquid 1,4-glycidylcyclohexane type epoxy resin), etc. may be mentioned. These may be used alone or in combination of two or more.

[0064] Of the above-mentioned epoxy resins, preferred examples of solid epoxy resins include bixylenol-type epoxy resins, naphthalene-type epoxy resins, naphthalene-type tetrafunctional epoxy resins, cresol novolac-type epoxy resins, dicyclopentadiene-type epoxy resins, trisphenol-type epoxy resins, naphthol-type epoxy resins, biphenyl-type epoxy resins, naphthylene ether-type epoxy resins, anthracene-type epoxy resins, bisphenol A-type epoxy resins, bisphenol AF-type epoxy resins, and tetraphenylethane-type epoxy resins, and examples of such solid epoxy resins include naphthol-type epoxy resins, bisphenol AF-type epoxy resins, naphthalene-type epoxy resins, and biphenyl-type epoxy resins.Specific examples include "HP4032H" (manufactured by DIC Corporation, naphthalene type epoxy resin), "HP-4700", and "HP-4710" (all manufactured by DIC Corporation, naphthalene type tetrafunctional epoxy resin), "N-690" (manufactured by DIC Corporation, cresol novolac type epoxy resin), "N-695" (manufactured by DIC Corporation, cresol novolac type epoxy resin), "HP-7200" (manufactured by DIC Corporation, dicyclopentadiene type epoxy resin), "HP-7200", "HP-7200HH", and "HP-7200H" (all manufactured by DIC Corporation, dicyclopentadiene type epoxy resin). epoxy resin), "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP-6000" (all manufactured by DIC, naphthylene ether type epoxy resin), "EPPN-502H" (manufactured by Nippon Kayaku Co., Ltd., trisphenol type epoxy resin), "NC-7000L", "NC-7300" (all manufactured by Nippon Kayaku Co., Ltd., naphthol-cresol novolac type epoxy resin), "NC-3000H", "NC-3000", "NC-3000L", "NC-3100" (all manufactured by Nippon Kayaku Co., Ltd., biphenyl ether type epoxy resin). arylalkyl type epoxy resin), "XD-1000-2L", "XD-1000-L", "XD-1000-H", "XD-1000-H" (all manufactured by Nippon Kayaku Co., Ltd., dicyclopentadiene type epoxy resin), "ESN475V" (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., naphthol type epoxy resin), "ESN485" (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., naphthol novolac type epoxy resin), "YX-4000H", "YX-4000", "YL6121" (all manufactured by Mitsubishi Chemical Corporation, biphenyl type epoxy resin), "YX-4000HK" (manufactured by Mitsubishi Chemical Corporation, bixyl Examples of epoxy resins that can be used include "YX-8800" (manufactured by Mitsubishi Chemical Corporation, anthracene type epoxy resin), "PG-100", "CG-500" (manufactured by Osaka Gas Chemical Co., Ltd., fluorene type epoxy resin), "YL-7760" (manufactured by Mitsubishi Chemical Corporation, bisphenol AF type epoxy resin), "YL-7800" (manufactured by Mitsubishi Chemical Corporation, fluorene type epoxy resin), "jER1010" (manufactured by Mitsubishi Chemical Corporation, solid bisphenol A type epoxy resin), and "jER1031S" (manufactured by Mitsubishi Chemical Corporation, tetraphenylethane type epoxy resin).These may be used alone or in combination of two or more.

[0065] [Active ester compounds] The curable resin composition of the present embodiment may contain an active ester compound. The active ester compound refers to a compound that contains at least one ester bond in the structure and has an aliphatic chain, an aliphatic ring, or an aromatic ring bonded to both sides of the ester bond. For example, compounds having two or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, can be mentioned, and are obtained by a condensation reaction between at least one compound of a carboxylic acid compound, an acid chloride, or a thiocarboxylic acid compound and at least one compound of a hydroxy compound or a thiol compound. In particular, from the viewpoint of improving heat resistance, it is preferable to obtain it from a carboxylic acid compound or an acid chloride and a hydroxy compound, and the hydroxy compound is preferably a phenol compound or a naphthol compound. In addition, it is preferable that the active ester compound has a vinyl group. Examples of the active ester compound having a vinyl group include the compounds described in Example 2 of WO 2020 / 095829 and the compounds disclosed in WO 2020 / 059625. These may be used alone or in combination of two or more.

[0066] 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.

[0067] 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.

[0068] Examples of the phenol compounds and naphthol compounds include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene-type diphenol compounds, phenol novolac, and phenol resins described below. Here, the term "dicyclopentadiene-type diphenol compounds" refers to diphenol compounds obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.

[0069] Preferable specific examples of the active ester compound include an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and an active ester compound containing a benzoylated product of phenol novolac. Among them, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene-type diphenol structure are more preferable. The dicyclopentadiene-type diphenol structure refers to a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

[0070] Commercially available active ester compounds include, for example, "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "HPC-8000H-65TM", "EXB-8000L-65TM", and "EXB-8150-65T" (manufactured by DIC Corporation) as active ester compounds containing a dicyclopentadiene-type diphenol structure, "EXB9416-70BK" (manufactured by DIC Corporation) as an active ester compound containing a naphthalene structure, and "phenolnoxamine" (manufactured by DIC Corporation). Examples of active ester compounds containing acetylated phenol novolac include "DC808" (manufactured by Mitsubishi Chemical Corporation); active ester compounds containing benzoylated phenol novolac include "YLH1026," "YLH1030," and "YLH1048" (manufactured by Mitsubishi Chemical Corporation); "DC808" (manufactured by Mitsubishi Chemical Corporation) is an active ester curing agent which is an acetylated phenol novolac; and "EXB-9050L-62M" (manufactured by DIC Corporation) is an active ester curing agent containing a phosphorus atom.

[0071] [Maleimide compounds] The curable resin composition of the present embodiment may contain a maleimide compound. A maleimide compound is a compound having one or more maleimide groups in a molecule. Examples of the maleimide compound include 4,4'-diphenylmethane bismaleimide, polyphenylmethane maleimide, m-phenylene bismaleimide, 2,2'-bis[4-(4-maleimidophenoxy)phenyl]propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 4,4'-diphenylether bismaleimide, 4,4'-diphenylsulfone bismaleimide, 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene), Xylox type maleimide compound (anilix), and the like. Maleimide, manufactured by Mitsui Chemicals Fine Co., Ltd.), biphenylaralkyl-type maleimide compound (solidified by distilling off the solvent under reduced pressure from a resin solution containing the maleimide compound (M2) described in Example 4 of JP 2009-001783 A), bisaminocumylbenzene-type maleimide (maleimide compound described in WO 2020 / 054601 A), maleimide compounds having an indane structure described in Japanese Patent No. 6629692 or WO 2020 / 217679, MATERIAL STAGE Vol. 18, No. 12 2019 ``~Continued Epoxy Resin CAS Number Story~ Hardener CAS Number Memorandum No. 31 Bismaleimide (1)'' and MATERIAL STAGE Vol. 19, No. 2 2019 ``~Continued Epoxy Resin CAS Number Story~ Hardener CAS Number Memorandum No. 32 Bismaleimide (2) and the like can be used, but are not limited thereto. These can be used alone or in combination.

[0072] The amount of the maleimide compound added 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 curable resin of this embodiment. The lower limit is preferably 0.01 times by mass or more, and more preferably 0.1 times by mass or more. Within the above range, the effects of low dielectric properties and low water absorption of the curable resin of this embodiment can be utilized.

[0073] [Phenol resin] A phenolic resin is a compound having two or more phenolic hydroxyl groups in a molecule. Examples of phenolic resins include, but are not limited to, reaction products of phenols and aldehydes, reaction products of phenols and diene compounds, reaction products of phenols and ketones, reaction products of phenols and substituted biphenyls, reaction products of phenols and substituted phenyls, and reaction products of bisphenols and aldehydes. These may be used alone or in combination. Specific examples of the above-mentioned raw materials are given below, but the raw materials are not limited thereto. <Phenols> Phenol, alkyl-substituted phenol, aromatic-substituted phenol, hydroquinone, resorcin, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc. <Aldehydes> Formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, furfural, and the like. <Diene compounds> Dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, and the like. <Ketones> Acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, fluorenone, etc. <Substituted biphenyls> 4,4'-bis(chloromethyl)-1,1'-biphenyl, 4,4'-bis(methoxymethyl)-1,1'-biphenyl, 4,4'-bis(hydroxymethyl)-1,1'-biphenyl and the like. <Substituted phenyls> 1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene, 1,4-bis(hydroxymethyl)benzene and the like.

[0074] [Polyphenylene ether compounds] From the viewpoint of heat resistance and electrical properties, the polyphenylene ether compound is preferably a polyphenylene ether compound having an ethylenically unsaturated bond, and more preferably a polyphenylene ether compound having an acrylic group, a methacrylic group, or a styrene structure. Commercially available products include SA-9000 (manufactured by SABIC, a polyphenylene ether compound having a methacrylic group) and OPE-2St 1200 (manufactured by Mitsubishi Gas Chemical, a polyphenylene ether compound having a styrene structure). The number average molecular weight (Mn) of the polyphenylene ether compound is preferably 500 to 5000, more preferably 2000 to 5000, and more preferably 2000 to 4000. If the molecular weight is less than 500, the heat resistance of the cured product tends to be insufficient. If the molecular weight is more than 5000, the melt viscosity increases and sufficient fluidity cannot be obtained, which tends to lead to molding defects. In addition, the reactivity decreases, the curing reaction takes a long time, and the amount of unreacted material that is not incorporated into the curing system increases, which decreases the glass transition temperature of the cured product and tends to decrease the heat resistance of the cured product. If the number average molecular weight of the polyphenylene ether compound is 500 to 5000, it is possible to exhibit excellent heat resistance, moldability, etc. while maintaining excellent dielectric properties. The number average molecular weight here can be specifically measured using gel permeation chromatography, etc.

[0075] The polyphenylene ether compound may be one obtained by a polymerization reaction, or one obtained by a redistribution reaction of a high molecular weight polyphenylene ether compound having a number average molecular weight of about 10,000 to 30,000. In addition, these may be used as raw materials and reacted with a compound having an ethylenically unsaturated bond, such as methacryl chloride, acrylic chloride, or chloromethylstyrene, to impart radical polymerizability. The polyphenylene ether compound obtained by the redistribution reaction is obtained, for example, by heating a high molecular weight polyphenylene ether compound in a solvent such as toluene in the presence of a phenolic compound and a radical initiator to cause a redistribution reaction. The polyphenylene ether compound obtained by the redistribution reaction in this way has hydroxyl groups derived from a phenolic compound that contributes to curing at both ends of the molecular chain, and is therefore preferable in that it can maintain even higher heat resistance, and that functional groups can be introduced at both ends of the molecular chain even after modification with a compound having an ethylenically unsaturated bond. In addition, the polyphenylene ether compound obtained by the polymerization reaction is preferable in that it exhibits excellent fluidity.

[0076] The molecular weight of the polyphenylene ether compound can be adjusted by adjusting the polymerization conditions, etc., in the case of a polyphenylene ether compound obtained by a polymerization reaction. In addition, in the case of a polyphenylene ether compound obtained by a redistribution reaction, the molecular weight of the obtained polyphenylene ether compound can be adjusted by adjusting the conditions of the redistribution reaction, etc. More specifically, it is possible to adjust the amount of the phenolic compound used in the redistribution reaction. That is, the greater the amount of the phenolic compound, the lower the molecular weight of the obtained polyphenylene ether compound. In this case, poly(2,6-dimethyl-1,4-phenylene ether) and the like can be used as the high molecular weight polyphenylene ether compound that undergoes the redistribution reaction. In addition, the phenolic compound used in the redistribution reaction is not particularly limited, but for example, a multifunctional phenolic compound having two or more phenolic hydroxyl groups in the molecule, such as bisphenol A, phenol novolac, cresol novolac, etc., is preferably used. These may be used alone or in combination of two or more.

[0077] The content of the polyphenylene ether compound is not particularly limited, but is preferably 5 to 1000 parts by mass, and more preferably 10 to 750 parts by mass, when the total mass of the curable resin composition is 100 parts by mass. When the content of the polyphenylene ether compound is in the above range, it is preferable in that a cured product is obtained that is not only excellent in heat resistance, etc., but also fully exhibits the excellent dielectric properties of the polyphenylene ether compound.

[0078] [Amine resin] Amine resins are compounds having two or more amino groups in the molecule. Examples of amine resins include diaminodiphenylmethane, diaminodiphenylsulfone, isophoronediamine, naphthalenediamine, aniline novolac (a reaction product of aniline and formalin), N-methylaniline novolac (a reaction product of N-methylaniline and formalin), orthoethylaniline novolac (a reaction product of orthoethylaniline and formalin), a reaction product of 2-methylaniline and formalin, a reaction product of 2,6-diisopropylaniline and formalin, a reaction product of 2,6-diethylaniline and formalin, a reaction product of 2-ethyl-6-ethylaniline and formalin, a reaction product of 2,6-dimethylaniline and formalin, and a reaction product obtained by reacting aniline and xylylene chloride. Examples of the aniline resin include, but are not limited to, the aniline resin disclosed in Japanese Patent No. 6429862, a reaction product of aniline and a substituted biphenyl (4,4'-bis(chloromethyl)-1,1'-biphenyl, 4,4'-bis(methoxymethyl)-1,1'-biphenyl, etc.), a reaction product of aniline and a substituted phenyl (1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene, 1,4-bis(hydroxymethyl)benzene, etc.), 4,4'-(1,3-phenylenediisopropylidene)bisaniline, 4,4'-(1,4-phenylenediisopropylidene)bisaniline, a reaction product of aniline and diisopropenylbenzene, dimer diamine, etc. Furthermore, these may be used alone or in combination.

[0079] [Compounds containing ethylenically unsaturated bonds] A compound containing an ethylenically unsaturated bond is a compound that has one or more ethylenically unsaturated bonds in the molecule that can be polymerized by heat or light, regardless of whether a polymerization initiator is used or not. Examples of compounds containing ethylenically unsaturated bonds include, but are not limited to, reaction products of the above-mentioned phenol resins and halogen-based compounds containing ethylenically unsaturated bonds (chloromethylstyrene, allyl chloride, methallyl chloride, acrylic acid chloride, methacrylic acid chloride, etc.), reaction products of phenols containing ethylenically unsaturated bonds (2-allylphenol, 2-propenylphenol, 4-allylphenol, 4-propenylphenol, eugenol, isoeugenol, etc.) and halogen-based compounds (1,4-bis(chloromethyl)benzene, 4,4'-bis(chloromethyl)biphenyl, 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-dibromobenzophenone, cyanuric chloride, etc.), reaction products of epoxy resins or alcohols and (meth)acrylic acids (acrylic acid, methacrylic acid, etc.), and acid-modified products thereof. In addition, these may be used alone or in combination.

[0080] [Isocyanate resin] An isocyanate resin is a compound that has two or more isocyanate groups in its molecule. Examples of the isocyanate resin include aromatic diisocyanates such as p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and naphthalene diisocyanate; aliphatic or alicyclic diisocyanates such as isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, norbornene diisocyanate, and lysine diisocyanate; polyisocyanates such as one or more biuret forms of isocyanate monomers or isocyanate forms obtained by trimerizing the above diisocyanate compounds; and polyisocyanates obtained by a urethanization reaction between the above isocyanate compounds and polyol compounds, but are not limited thereto. These may be used alone or in combination.

[0081] [Polyamide resin] Examples of polyamide resins include reaction products of one or more of diamines, diisocyanates, and oxazolines with dicarboxylic acids, reaction products of diamines with acid chlorides, and ring-opening polymers of lactam compounds. These may be used alone or in combination. Specific examples of the above-mentioned raw materials are given below, but the raw materials are not limited thereto. <Diamine> Ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decanediamine, undecanediamine, dodecanediamine, tridecanediamine, tetradecanediamine, pentadecanediamine, hexadecanediamine, heptadecanediamine, octadecanediamine, nonadecanediamine, eicosanediamine, 2-methyl-1,5-diaminopentane, 2-methyl 1,8-diaminooctane, dimer diamine, cyclohexane diamine, bis-(4-aminocyclohexyl)methane, bis(3-methyl-4-aminocyclohexyl)methane, xylylene diamine, norbornane diamine, isophorone diamine, bisaminomethyltricyclodecane, phenylenediamine, diethyltoluenediamine, naphthalenediamine, diaminodiphenylmethane, bis(4-amino-3,5-dimethylphenyl)methane, bis(4-amino-3,5-diethylphenyl)methane , 4,4'-methylenebis-o-toluidine, 4,4'-methylenebis-o-ethylaniline, 4,4'-methylenebis-2-ethyl-6-methylaniline, 4,4'-methylenebis-2,6-diisopropylaniline, 4,4-ethylenedianiline, diaminodiphenyl sulfone, diaminodiphenyl ether, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 4,4-bis(4-aminophenoxy)biphenyl, 2,2-bis[4-(4-amino 4,4'-(1,3-phenylenediisopropylidene)bisaniline, 4,4'-(1,4-phenylenediisopropylidene)bisaniline, 9,9-bis(4-aminophenyl)fluorene, 2,7-diaminofluorene, aminobenzylamine, diaminobenzophenone, and the like. <Diisocyanate> Benzene diisocyanate, toluene diisocyanate, 1,3-bis(isocyanatomethyl)benzene, 1,3-bis(isocyanatomethyl)cyclohexane, bis(4-isocyanatophenyl)methane, isophorone diisocyanate, 1,3-bis(2-isocyanato-2-propyl)benzene, 2,2-bis(4-isocyanatophenyl)hexafluoropropane, dicyclohexylmethane-4,4'-diisocyanate, and the like. <Dicarboxylic acid> Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, 5-hydroxyisophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, cyclohexanedicarboxylic acid, biphenyldicarboxylic acid, naphthalenedicarboxylic acid, benzophenonedicarboxylic acid, furandicarboxylic acid, 4,4'-dicarboxydiphenyl ether, 4,4'-dicarboxydiphenyl sulfide, etc. <Acid chloride> Acetyl chloride, acrylic acid chloride, methacrylic acid chloride, malonyl chloride, succinic acid dichloride, diglycolyl chloride, glutaric acid dichloride, suberic acid dichloride, sebacic acid dichloride, adipic acid dichloride, dodecandioyl dichloride, azelaic acid chloride, 2,5-furandicarbonyl dichloride, phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, trimesic acid chloride, bis(4-chlorocarbonylphenyl) ether, 4,4'-diphenyldicarbonyl chloride, 4,4'-azodibenzoyl dichloride, and the like. <Lactam> ε-caprolactam, ω-undecanelactam, ω-laurolactam, and the like.

[0082] [Polyimide resin] Examples of polyimide resins include, but are not limited to, reaction products of the diamines and the tetracarboxylic dianhydrides shown below. These may be used alone or in combination. <Tetracarboxylic acid dianhydride> 4,4'-(Hexafluoroisopropylidene)diphthalic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-cyclohexene-1,2 dicarboxylic anhydride, pyromellitic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 2,2',3, 3'-Biphenyltetracarboxylic dianhydride, methylene-4,4'-diphthalic dianhydride, 1,1-ethylidene-4,4'-diphthalic dianhydride, 2,2'-propylidene-4,4'-diphthalic dianhydride, 1,2-ethylene-4,4'-diphthalic dianhydride, 1,3-trimethylene-4,4'-diphthalic dianhydride, 1,4-tetramethylene-4,4'-diphthalic dianhydride, 1,5-pentamethylene-4,4'-diphthalic dianhydride, 4,4'-oxydiphthalic dianhydride, thio-4,4'-diphthalic dianhydride, sulfonyl-4,4'-diphthalic acid Dianhydride, 1,3-bis(3,4-dicarboxyphenyl)benzene dianhydride, 1,3-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 1,3-bis[2-(3,4-dicarboxyphenyl)-2-propyl]benzene dianhydride, 1,4-bis[2-(3,4-dicarboxyphenyl)-2-propyl]benzene dianhydride, bis[3-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride, bis[4-(3,4-dicarboxyphenoxy)phenyl]methane 2,2-bis[3-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, bis(3,4-dicarboxyphenoxy)dimethylsilane dianhydride, 1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldisiloxane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3,4,9,10-Perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, ethylenetetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride tetracarboxylic dianhydride, 3,3',4,4'-bicyclohexyltetracarboxylic dianhydride, carbonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic) dianhydride, methylene-4,4'-bis(cyclohexane-1,2-dicarboxylic) dianhydride, 1,2-ethylene-4,4'-bis(cyclohexane-1,2-dicarboxylic) dianhydride, 1,1-ethylidene-4,4'-bis(cyclohexane-1,2-dicarboxylic) dianhydride, 2,2-propylidene -4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, oxy-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, thio-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, sulfonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, rel-[1S,5R,6R]-3-oxabicyclo[3,2 ,1]Octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, ethylene glycol-bis-(3,4-dicarboxylic anhydride phenyl) ether, 4,4'-biphenyl bis(trimellitic acid monoester acid anhydride), 9,9'-bis(3,4-dicarboxyphenyl)fluorene dianhydride, etc.,

[0083] [Cyanate ester resin] Cyanate ester resins are compounds obtained by reacting phenolic resins with cyanogen halides, and specific examples include dicyanatobenzene, tricyanatobenzene, dicyanatonaphthalene, dicyanatobiphenyl, 2,2'-bis(4-cyanatophenyl)propane, bis(4-cyanatophenyl)methane, bis(3,5-dimethyl-4-cyanatophenyl)methane, 2,2'-bis(3,5-dimethyl-4-cyanatophenyl)propane, 2,2'-bis(4-cyanatophenyl)ethane, 2,2'-bis(4-cyanatophenyl)hexafluoropropane, bis(4-cyanatophenyl)sulfone, bis(4-cyanatophenyl)thioether, phenol novolac cyanate, and phenol-dicyclopentadiene co-condensates in which the hydroxyl groups have been converted to cyanate groups, but are not limited thereto. These may be used alone or in combination. Furthermore, the cyanate ester compound, the synthesis method of which is described in JP-A-2005-264154, is particularly preferred as the cyanate ester compound because it has low moisture absorption, excellent flame retardancy, and excellent dielectric properties. The cyanate ester resins can optionally contain a catalyst, such as zinc naphthenate, cobalt naphthenate, copper naphthenate, lead naphthenate, zinc octoate, tin octoate, lead acetylacetonate, or dibutyltin maleate, to trimerize the cyanate groups to form sym-triazine rings.

[0084] 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 total of the curable resin composition containing the cyanate ester resin and the curable resin of this embodiment.

[0085] [Polybutadiene and its modified products] The polybutadiene and its modified products are polybutadiene or compounds having a structure derived from polybutadiene in the molecule. The unsaturated bonds in the polybutadiene-derived structure may be partially or entirely converted to single bonds by hydrogenation. Examples of polybutadiene and modified products thereof include, but are not limited to, polybutadiene, hydroxyl-terminated polybutadiene, (meth)acrylate-terminated polybutadiene, carboxylic acid-terminated polybutadiene, amine-terminated polybutadiene, styrene-butadiene rubber, and the like. These may be used alone or in combination. Among these, polybutadiene or styrene-butadiene rubber is preferred from the viewpoint of dielectric properties. Examples of styrene-butadiene rubber (SBR) include RICON-100, RICON-181, RICON-184 (all manufactured by Cray Valley), 1,2-SBS (manufactured by Nippon Soda Co., Ltd.), and examples of polybutadiene include B-1000, B-2000, B-3000 (all manufactured by Nippon Soda Co., Ltd.). The molecular weight of polybutadiene and styrene-butadiene rubber is preferably a weight average molecular weight of 500 to 10,000, more preferably 750 to 7,500, and even more preferably 1,000 to 5,000. Below the lower limit of the above range, the amount of volatilization is large, making it difficult to adjust the solid content during preparation of the prepreg, whereas above the upper limit of the above range, compatibility with other curable resins is deteriorated.

[0086] [Polystyrene and its modified products] Polystyrene and modified products thereof are polystyrene or compounds having a structure derived from polystyrene in the molecule. Examples of polystyrene and modified products thereof include polystyrene, styrene-2-isopropenyl-2-oxazoline copolymers (Epocross RPS-1005, RP-61, both manufactured by Nippon Shokubai Co., Ltd.), SEP (styrene-ethylene-propylene copolymer: Septon 1020, manufactured by Kuraray Co., Ltd.), SEPS (styrene-ethylene-propylene-styrene copolymer: Septon 2002, Septon 2004F, Septon 2005, Septon 2006, Septon 2063, Septon 2104, all manufactured by Kuraray Co., Ltd.), SEEPS (styrene-ethylene / ethylene-propylene-styrene block copolymer: Septon 4003, Septon 4044, Septon 4055, Septon 4077, Septon 4099, all manufactured by Kuraray Co., Ltd.), SEBS (styrene-ethylene-butylene-styrene block copolymer: Septon 4003, Septon 4044, Septon 4055, Septon 4077, Septon 4099, all manufactured by Kuraray Co., Ltd.), Examples of the block copolymer include Septon 8004, Septon 8006, and Septon 8007L (all manufactured by Kuraray Co., Ltd.), SEEPS-OH (a compound having a hydroxyl group at the end of a styrene-ethylene / ethylene-propylene-styrene block copolymer: Septon HG252 manufactured by Kuraray Co., Ltd.), SIS (styrene-isoprene-styrene block copolymer: Septon 5125 and Septon 5127 manufactured by Kuraray Co., Ltd.), hydrogenated SIS (hydrogenated styrene-isoprene-styrene block copolymer: Hybler 7125F and Hybler 7311F manufactured by Kuraray Co., Ltd.), SIBS (styrene-isobutylene-styrene block copolymer: SIBSTAR073T, SIBSTAR102T, and SIBSTAR103T (all manufactured by Kaneka Co., Ltd.), and Septon V9827 (manufactured by Kuraray Co., Ltd.)), but are not limited thereto. These may be used alone or in combination. Polystyrene and its modified products are preferably those that do not have unsaturated bonds, since they have higher heat resistance and are less susceptible to oxidation deterioration. The weight-average molecular weight of polystyrene and its modified products is not particularly limited as long as it is 10,000 or more, but if it is too large, the compatibility with not only polyphenylene ether compounds, but also low molecular weight components with weight-average molecular weights of about 50 to 1,000 and oligomer components with weight-average molecular weights of about 1,000 to 5,000 deteriorates, making it difficult to ensure mixing and solvent stability, so it is preferably about 10,000 to 300,000.

[0087] [Inorganic filler] The curable resin composition of the present embodiment may contain an inorganic filler. Examples of inorganic fillers include powders such as fused silica, crystalline silica, porous silica, alumina, zircon, calcium silicate, calcium carbonate, quartz powder, silicon carbide, silicon nitride, boron nitride, zirconia, aluminum nitride, graphite, forsterite, steatite, spinel, mullite, titania, talc, clay, iron oxide asbestos, and glass powder, and inorganic fillers obtained by making these into a spherical or crushed shape, but are not limited thereto. In addition, these may be used alone or in combination.

[0088] When a curable resin composition for semiconductor encapsulation is obtained, the amount of the inorganic filler used is preferably 80 to 92 parts by mass, more preferably 83 to 90 parts by mass, based on 100 parts by mass of the curable resin composition. When a curable resin composition for interlayer insulating layer forming material, copper-clad laminate, prepreg, RCC, or other substrate material is obtained, the amount of the inorganic filler used is preferably 5 to 80 parts by mass, more preferably 10 to 60 parts by mass, based on 100 parts by mass of the curable resin composition.

[0089] [Cure accelerator] The curable resin composition of the present embodiment can also have improved curability by adding a curing accelerator. As the curing accelerator, an anionic curing accelerator that accelerates the curing reaction by generating anions upon heating, or a cationic curing accelerator that accelerates the curing reaction by generating cations upon heating, is preferred.

[0090] Examples of anionic curing accelerators include imidazoles such as 2-methylimidazole, 2-ethylimidazole, and 2-ethyl-4-methylimidazole, trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6,-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo(5,4,0)-undecene, with 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)-undecene being preferred. Other examples include phosphines such as triphenylphosphine, quaternary ammonium salts such as tetrabutylammonium salts, triisopropylmethylammonium salts, trimethyldecanylammonium salts, cetyltrimethylammonium salts, and hexadecyltrimethylammonium hydroxide, but are not limited thereto. These may be used alone or in combination.

[0091] Examples of cationic curing accelerators include quaternary phosphonium salts such as triphenylbenzylphosphonium salt, triphenylethylphosphonium salt, and tetrabutylphosphonium salt (counter ions of quaternary salts are halogen, organic acid ions, hydroxide ions, etc., and are not particularly specified, but organic acid ions and hydroxide ions are particularly preferred), transition metal compounds (transition metal salts) such as tin octylate, zinc carboxylate (zinc 2-ethylhexanoate, zinc stearate, zinc behenate, zinc myristate), and zinc phosphate (zinc octyl phosphate, zinc stearyl phosphate), but are not limited thereto. These may be used alone or in combination.

[0092] 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 of the present embodiment, as necessary.

[0093] [Polymerization initiator] The curable resin composition of the present embodiment can also improve the curability by adding a polymerization initiator. The polymerization initiator is a compound capable of polymerizing an olefin functional group such as an ethylenically unsaturated bond, and examples of the polymerization initiator include an olefin metathesis polymerization initiator, an anionic polymerization initiator, a cationic polymerization initiator, and a radical polymerization initiator. Among these, it is preferable to use a radical polymerization initiator having curability and moderate stability. The radical polymerization initiator is a compound that generates radicals by heating and starts a chain polymerization reaction. Examples of radical polymerization initiators that can be used include organic peroxides, azo compounds, and benzopinacoles, and it is preferable to use an organic peroxide because it has little effect on curing temperature control, outgassing suppression, and electrical properties of decomposition products.

[0094] Examples of the organic peroxides include ketone peroxides such as methyl ethyl ketone peroxide and acetylacetone peroxide, diacyl peroxides such as benzoyl peroxide, dialkyl peroxides such as dicumyl peroxide and 1,3-bis-(t-butylperoxyisopropyl)-benzene, peroxyketals such as t-butyl peroxybenzoate and 1,1-di-t-butylperoxycyclohexane, α-cumyl peroxyneodecanoate, t-butyl peroxyneodecanoate, t-butyl peroxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-amyl peroxy-2-ethylhex ...amyl peroxy-2-ethylhexanoate, t-butyl peroxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-amyl peroxy-2-ethylhexanoate, t-butyl peroxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-amyl peroxy-2-ethylhexanoate, t-butyl peroxypivalate, 1,1, Examples of the peroxycarbonates include, but are not limited to, alkyl peresters such as t-amyl peroxy-2-ethylhexanoate, t-amyl peroxy-3,5,5-trimethylhexanoate, t-butyl peroxy-3,5,5-trimethylhexanoate, and t-amyl peroxybenzoate, peroxycarbonates such as di-2-ethylhexyl peroxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, t-butyl peroxyisopropyl carbonate, and 1,6-bis(t-butylperoxycarbonyloxy)hexane, t-butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxyoctoate, and lauroyl peroxide. These may be used alone or in combination. Among the above organic peroxides, ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, alkyl peresters, peroxycarbonates, etc. are preferred, with dialkyl peroxides being more preferred.

[0095] Examples of the azo-based compound include, but are not limited to, azobisisobutyronitrile, 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2,4-dimethylvaleronitrile), etc. These may be used alone or in combination.

[0096] The amount of the 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 the polymerization initiator used is less than 0.01 part by mass, the molecular weight may not be sufficiently extended during the polymerization reaction, and if it is more than 5 parts by mass, the dielectric properties such as the dielectric constant and dielectric loss tangent may be impaired.

[0097] [Polymerization inhibitor] The curable resin composition of the present embodiment may contain a polymerization inhibitor. By containing a polymerization inhibitor, storage stability is improved and the reaction initiation temperature can be controlled. By controlling the reaction initiation temperature, it becomes easy to ensure fluidity, impregnation into glass cloth and the like is not impaired, and B-stage such as prepreg formation is facilitated. If the polymerization reaction proceeds too much during prepreg formation, problems such as difficulty in lamination during the lamination process are likely to occur.

[0098] The polymerization inhibitor may be added when or after the curable resin of the present embodiment is synthesized. The amount of the polymerization inhibitor used is 0.008 to 1 part by mass, preferably 0.01 to 0.5 parts by mass, based on 100 parts by mass of the curable resin of the present embodiment.

[0099] Examples of the polymerization inhibitor include phenol-based, sulfur-based, phosphorus-based, hindered amine-based, nitroso-based, and nitroxyl radical-based. The polymerization inhibitor may be used alone or in combination. Among these, in the present embodiment, the phenol-based, hindered amine-based, nitroso-based, and nitroxyl radical-based are preferred.

[0100] Examples of the phenol-based polymerization inhibitor include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, stearyl-β-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, 2,4-bis[(octylthio)methyl]-o ... resol, etc. monophenols, 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol), 4,4'-thiobis(3-methyl-6-t-butylphenol), 4,4'-butylidenebis(3-methyl-6-t-butylphenol), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] , N,N'-Hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, 3,9-bis[1,1-dimethyl-2-{β-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}ethyl]2,4,8,10-tetraoxaspiro[5,5]undecane, bis(3,5-di-t-butyl Bisphenols such as calcium ethyl-4-hydroxybenzylsulfonate, 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, tetrakis-[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methane, bis[3,3'-bis-(4'-hydroxy-3'-t-butylphenyl)butyric acid]glycol ester, tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-tris(3',5'-di-t-butyl-4'-hydroxybenzyl)-S-triazine-2,4,6-(1H,3H,5H)trione, tocopherol and other polymeric phenols are included, but are not limited to these.

[0101] 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.

[0102] Examples of the phosphorus-based polymerization inhibitor include triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, tris(nonylphenyl) phosphite, diisodecyl pentaerythritol phosphite, tris(2,4-di-t-butylphenyl) phosphite, cyclic neopentane tetrayl bis(octadecyl) phosphite, cyclic neopentane tetrayl bi(2,4-di-t-butylphenyl) phosphite, cyclic neopentane tetrayl bi(2,4-di-t-butyl-4-methylphenyl) phosphite, bis[2-t 10-(3,5-di-t-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(3,5-di-t-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and other oxaphosphaphenanthrene oxides, but are not limited to these.

[0103] Examples of the hindered amine polymerization inhibitor include, but are not limited to, Adeka STAB LA-40MP, Adeka STAB LA-40Si, Adeka STAB LA-402AF, Adeka STAB LA-87, Deka STAB LA-82, Deka STAB LA-81, Adeka STAB LA-77Y, Adeka STAB LA-77G, Adeka STAB LA-72, Adeka STAB LA-68, Adeka STAB LA-63P, Adeka STAB LA-57, Adeka STAB LA-52, Chimassorb 2020FDL, Chimassorb 944FDL, Chimassorb 944LD, Tinuvin 622SF, Tinuvin PA144, Tinuvin 765, Tinuvin 770DF, Tinuvin XT55FB, Tinuvin 111FDL, Tinuvin 783FDL, Tinuvin 791FB, and the like.

[0104] Examples of the nitroso-based polymerization inhibitor include, but are not limited to, p-nitrosophenol, N-nitrosodiphenylamine, ammonium salt of N-nitrosophenylhydroxyamine, (cupferron), etc. Among these, the ammonium salt of N-nitrosophenylhydroxyamine (cupferron) is preferred.

[0105] Examples of the nitroxyl radical polymerization inhibitor include di-tert-butyl nitroxide, 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-amino-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-acetoxy-2,2,6,6-tetramethylpiperidine-1-oxyl, and 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl, but are not limited thereto.

[0106] [Flame retardant] The curable resin composition of the present embodiment may contain a flame retardant. Examples of the flame retardant include halogen-based flame retardants, inorganic flame retardants (antimony compounds, metal hydroxides, nitrogen compounds, boron compounds, etc.), and phosphorus-based flame retardants. From the viewpoint of achieving halogen-free flame retardancy, phosphorus-based flame retardants are preferred. The phosphorus-based flame retardant may be of reactive type or additive type. Specific examples include phosphoric acid esters such as trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylenyl phosphate, 1,3-phenylene bis(dixylenyl phosphate), 1,4-phenylene bis(dixylenyl phosphate), and 4,4'-biphenyl(dixylenyl phosphate), phosphanes such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 10(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, phosphorus-containing epoxy compounds obtained by reacting epoxy resins with active hydrogen of the phosphanes, red phosphorus, etc., but are not limited thereto. Also, these may be used alone or in combination. Of the above-listed substances, phosphates, phosphanes, or phosphorus-containing epoxy compounds are preferred, with 1,3-phenylenebis(dixylenyl phosphate), 1,4-phenylenebis(dixylenyl phosphate), 4,4'-biphenyl(dixylenyl phosphate) or phosphorus-containing epoxy compounds being particularly preferred.

[0107] The content of the flame retardant is preferably in the range of 0.1 to 0.6 parts by mass, assuming that the total of non-volatile matters in the curable resin composition excluding inorganic fillers is 100 parts by mass. 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.

[0108] [Light stabilizer] The curable resin composition of the present embodiment may contain a light stabilizer. As the light stabilizer, a hindered amine light stabilizer, particularly HALS, etc., is preferable. Examples of HALS include the reaction product of dibutylamine·1,3,5-triazine·N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine and N-(2,2,6,6-tetramethyl-4-piperidyl)butylamine, the reaction product of dimethyl succinate-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, poly[{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidyl)imino}hexamethylene{(2,2,6,6-tetramethyl-4-piperidyl)imino}], bis(1,2 ,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl] butyl malonate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, 2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-n-butyl malonate bis(1,2,2,6,6-pentamethyl-4-piperidyl) and the like, but are not limited thereto. These may be used alone or in combination.

[0109] The content of the light stabilizer is preferably in the range of 0.001 to 10 parts by mass, assuming that the total of non-volatile contents excluding inorganic fillers in the curable resin composition is 100 parts by mass. If the content is less than 0.001 part by mass, it may be insufficient to exhibit a light stabilizing effect, and if the content is more than 10 parts by mass, it may have an adverse effect on the hygroscopicity and dielectric properties of the cured product.

[0110] [Binder resin] The curable resin composition of the present embodiment may use a binder resin. Examples of the binder resin include, but are not limited to, butyral resins, acetal resins, acrylic resins, epoxy-nylon resins, NBR-phenol resins, epoxy-NBR resins, and silicone resins. These may be used alone or in combination.

[0111] The amount of the binder resin is preferably within a range that does not impair the flame retardancy and heat resistance of the cured product, and is preferably 0.05 to 50 parts by mass, and more preferably 0.05 to 20 parts by mass, relative to 100 parts by mass of the total curable resin composition.

[0112] [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.

[0113] The amount of the additives to be added is preferably 1,000 parts by mass or less, and more preferably 700 parts by mass or less, based on 100 parts by mass of the curable resin composition.

[0114] The curable resin composition of the present embodiment is obtained by preparing the above-mentioned components in a predetermined ratio, and the curing reaction proceeds sufficiently by curing for 1 to 15 hours at 150 to 250° C., and the cured product of the present embodiment is obtained. Alternatively, the components of the curable resin composition may be uniformly dispersed or dissolved in a solvent or the like, and the solvent may be removed before curing.

[0115] The method for preparing the curable resin composition of the present embodiment is not particularly limited, but each component may be mixed uniformly or may be prepolymerized. For example, a mixture containing the components represented by the formula (1) is heated in the presence or absence of a curing accelerator or a polymerization initiator, and in the presence or absence of a solvent to form a prepolymer. Similarly, an amine compound, a compound having an ethylenically unsaturated bond, a maleimide compound, a cyanate ester compound, polybutadiene and its modified products, polystyrene and its modified products, inorganic fillers, and other additives may be added to form a prepolymer. For mixing or prepolymerization of each component, for example, an extruder, a kneader, a roll, or the like is used in the absence of a solvent, and a reaction kettle with a stirrer is used in the presence of a solvent. By prepolymerization, the tackiness after B-stage and the storage stability in the varnish can be improved.

[0116] As a method of uniformly mixing, the mixture is kneaded at a temperature in the range of 50 to 100°C using a device such as a kneader, roll, or planetary mixer to obtain a uniform resin composition. The obtained resin composition is crushed and then molded into a cylindrical tablet shape using a molding machine such as a tablet machine, or into a granular powder or powder molded body, or these compositions can be melted on a surface support and molded into a sheet with a thickness of 0.05 mm to 10 mm to obtain a molded curable resin composition. The obtained molded body is a non-sticky molded body at 0 to 20°C, and even if stored at -25 to 0°C for one week or more, the flowability and curability are hardly reduced. The obtained molded article can be molded into a cured product using a transfer molding machine or a compression molding machine.

[0117] The curable resin composition of the present embodiment can be made into a varnish-like composition (hereinafter, simply referred to as varnish) by adding an organic solvent. The curable resin composition of the present embodiment can be dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, or N-methylpyrrolidone as necessary to obtain a varnish, which can be impregnated into a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, or paper, and dried by heating to obtain a prepreg. The prepreg can be hot-press molded to obtain a cured product of the curable resin composition of the present embodiment. The solvent used in this case is in an amount of 10 to 70% by weight, preferably 15 to 70% by weight, in the mixture of the curable resin composition of the present embodiment and the solvent. In addition, if the composition is in a liquid state, a cured product of the curable resin containing carbon fiber can be obtained as it is, for example, by the RTM method.

[0118] The curable resin composition of the present embodiment can also be used as a modifier for a film-type composition. Specifically, it can be used to improve flexibility in the B-stage. Such a film-type resin composition is obtained as a sheet-like adhesive by applying the curable resin composition of the present embodiment as the curable resin composition varnish onto a release film, removing the solvent under heating, and then performing B-stage formation. This sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like.

[0119] The curable resin composition of the present embodiment can be heated and melted to reduce the viscosity, and impregnated into reinforcing fibers such as glass fibers, carbon fibers, polyester fibers, polyamide fibers, and alumina fibers to obtain a prepreg. Specific examples thereof include glass fibers such as E glass cloth, D glass cloth, S glass cloth, Q glass cloth, spherical glass cloth, NE glass cloth, and T glass cloth, inorganic fibers other than glass, and organic fibers such as polyparaphenylene terephthalamide (Kevlar (registered trademark), manufactured by DuPont), wholly aromatic polyamide, polyester, polyparaphenylene benzoxazole, polyimide, and carbon fibers, but are not particularly limited thereto. The shape of the substrate is not particularly limited, but examples thereof include woven fabric, nonwoven fabric, roving, chopped strand mat, and the like. In addition, as the weaving method of the woven fabric, plain weave, saddle weave, twill weave, and the like are known, and these known weaves can be appropriately selected and used depending on the intended use and performance. In addition, woven fabrics that have been subjected to fiber opening treatment and glass woven fabrics that have been surface-treated with a silane coupling agent or the like are preferably used. The thickness of the substrate is not particularly limited, but is preferably about 0.01 to 0.4 mm. A prepreg can also be obtained by impregnating reinforcing fibers with the varnish and drying the fibers by heating.

[0120] The prepreg can also be used to manufacture a laminate. The laminate is not particularly limited as long as it has one or more prepregs, and may have any other layers. The method for manufacturing the laminate can be appropriately applied by a generally known method, and is not particularly limited. For example, a multi-stage press machine, a multi-stage vacuum press machine, a continuous molding machine, an autoclave molding machine, etc. can be used when molding a metal foil-clad laminate, and the prepregs are laminated together and heated and pressurized to obtain a laminate. At this time, the heating temperature is not particularly limited, but is preferably 65 to 300 ° C, and more preferably 120 to 270 ° C. In addition, the pressure to be applied is not particularly limited, but if the pressure is too high, it is difficult to adjust the solid content of the resin in the laminate, and the quality is not stable, and if the pressure is too low, air bubbles and adhesion between the laminates are deteriorated, so that the pressure is preferably 2.0 to 5.0 MPa, and more preferably 2.5 to 4.0 MPa. The laminate of this embodiment can be suitably used as a metal foil-clad laminate described later by providing a layer made of metal foil. The prepreg is cut into a desired shape and laminated with copper foil or the like if necessary. The laminate is then heated and cured while applying pressure thereto by press molding, autoclave molding, sheet winding molding, or the like, to obtain an electrical and electronic laminate (printed wiring board) or a carbon fiber reinforced material.

[0121] The curable resin composition of this embodiment can also be made into a resin sheet. As a method for obtaining a resin sheet from the curable resin composition of this embodiment, for example, a method of applying the curable resin composition onto a support film (support), drying it, and forming a resin composition layer on the support film can be mentioned. When the curable resin composition of this embodiment is used for a resin sheet, it is essential that the film softens under the temperature conditions (70°C to 140°C) for lamination in the vacuum lamination method, and exhibits a fluidity (resin flow) that allows resin filling in via holes or through holes present in the circuit board at the same time as laminating the circuit board, and it is preferable to mix each of the above components so as to express such characteristics. In addition, in the obtained resin sheet or circuit board (copper-clad laminate, etc.), a phenomenon that locally different characteristic values ​​are exhibited due to phase separation or the like does not occur, and a certain performance is expressed at any part, so that a uniform appearance is required.

[0122] Here, the through-holes in the circuit board have a diameter of 0.1 to 0.5 mm and a depth of 0.1 to 1.2 mm, and it is preferable that the resin be filled within this range. When laminating both sides of the circuit board, it is preferable that about half of the through-holes are filled.

[0123] A specific method for producing the resin sheet includes preparing a resin composition varnished by blending an organic solvent, applying the varnished resin composition to the surface of a support film (Y), and then drying the organic solvent by heating or blowing hot air or the like to form a resin composition layer (X).

[0124] The organic solvent used here preferably includes, for example, ketones such as acetone, methyl ethyl ketone, cyclohexanone, etc., acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, etc., carbitols such as cellosolve, butyl carbitol, etc., aromatic hydrocarbons such as toluene, xylene, etc., dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc., and it is preferable to use the organic solvent in a proportion such that the nonvolatile content is 30 to 60 mass%.

[0125] The thickness of the resin composition layer (X) formed must be equal to or greater than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is in the range of 5 to 70 μm, the thickness of the resin composition layer (X) is preferably 10 to 100 μm. The resin composition layer (X) in this embodiment may be protected with a protective film described below. By protecting the resin composition layer with a protective film, adhesion of dirt and the like to the surface of the resin composition layer and scratches can be prevented.

[0126] The support film and the protective film may be made of polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate, polycarbonate, polyimide, and even release paper and metal foils such as copper foil and aluminum foil. The support film and the protective film may be subjected to a release treatment in addition to a mud treatment and a corona treatment. The thickness of the support film is not particularly limited, but is in the range of 10 to 150 μm, and preferably 25 to 50 μm. The thickness of the protective film is preferably 1 to 40 μm.

[0127] The support film (Y) is peeled off after laminating it onto a circuit board or after forming an insulating layer by heat curing. If the support film (Y) is peeled off after the resin composition layer constituting the resin sheet is heat cured, adhesion of dust and the like during the curing process can be prevented. When peeling off after curing, the support film is previously subjected to a release treatment.

[0128] A multilayer printed circuit board can be manufactured from the resin sheet obtained as described above. For example, when the resin composition layer (X) is protected by a protective film, the film is peeled off, and then the resin composition layer (X) is laminated on one or both sides of the circuit board so as to be in direct contact with the circuit board, for example, by a vacuum lamination method. The lamination method may be a batch method or a continuous method using a roll. If necessary, the resin sheet and the circuit board may be heated (preheated) before lamination. The lamination conditions are preferably a pressure bonding temperature (lamination temperature) of 70 to 140°C and a pressure bonding pressure of 1 to 11 kgf / cm. 2 (9.8×10 4 ~107.9×10 4 N / m 2 ), and lamination is preferably performed under reduced air pressure of 20 mmHg (26.7 hPa) or less.

[0129] The curable resin composition of the present embodiment can be used to manufacture a semiconductor device, such as a DIP (dual in-line package), a QFP (quad flat package), a BGA (ball grid array), a CSP (chip size package), a SOP (small outline package), a TSOP (thin small outline package), or a TQFP (thin quad flat package).

[0130] The curable resin composition of the present embodiment and its cured product can be used in a wide range of fields. Specifically, it can be used in various applications such as molding materials, adhesives, composite materials, and paints. The cured product of the curable resin composition described in the present embodiment exhibits excellent heat resistance and dielectric properties, and is therefore suitable for use in electrical and electronic components such as encapsulants for semiconductor elements, encapsulants for liquid crystal display elements, encapsulants for organic EL elements, laminates (printed wiring boards, BGA substrates, build-up substrates, etc.), composite materials for lightweight and high-strength structural materials such as carbon fiber reinforced plastics and glass fiber reinforced plastics, 3D printing, etc. EXAMPLES

[0131] The present invention will now be described in more detail with reference to examples. Unless otherwise specified, all parts are by weight. However, the present invention is not limited to these examples.

[0132] Various analytical methods used in the examples are described below.

[0133] Hydroxyl equivalent It is measured by the following method, and the unit is g / eq. The phenolic resin is reacted with an excess of acetic anhydride and the amount of free acetic acid is measured by titration with a 0.5N ethanolic KOH solution using a potentiometer. Reagents: acetic anhydride, triphenylphosphine, pyridine Solvent: Tetrahydrofuran, propylene glycol monomethyl ether Automatic titration device: COM-1600 manufactured by Hiranuma Co., Ltd. Burette: Hiranuma Corporation B-2000

[0134] · 1 H-NMR analysis Equipment: JNM-ECS400 Accumulation count: 16 Relaxation time: 5 seconds Solvent: CDCl3 Measurement temperature: room temperature

[0135] ·IR analysis Equipment: FTIR-8400 (Shimadzu Corporation) Frequency: 400-4000cm -1

[0136] ·GPC (gel permeation chromatography) analysis Columns: SHODEX GPC KF-601 (2 columns), KF-602, KF-602.5, KF-603 Flow rate: 1.5ml / min. Column temperature: 40℃ Solvent used: THF (tetrahydrofuran) Detector: RI (Differential Refraction Detector)

[0137] [Synthesis Example 1] In a flask equipped with a thermometer, a condenser, a stirrer, and a Dean-Stark, 109.3 parts of Neopolymer E-100 (manufactured by JXTG Energy Corporation, hydroxyl equivalent: 729 g / eq), 270.0 parts of toluene, and 3.9 parts of methanesulfonic acid (manufactured by Junsei Chemical Co., Ltd.) were charged, and the mixture was stirred at 80 ° C. while bubbling nitrogen to dissolve. Next, using a dropping funnel, 6.4 parts of 35% aqueous formalin solution (manufactured by Junsei Chemical Co., Ltd.) was dropped over 30 minutes, and the mixture was reacted at 80 ° C. for 3 hours, and then at 120 ° C. for 4 hours while distilling off water. The mixture was cooled to room temperature and neutralized with 5.4 parts of 30% sodium hydroxide. The wastewater was repeatedly washed with water until it became neutral, and the toluene and low molecular weight volatile components were distilled off under heating and reduced pressure to synthesize the phenolic resin (PH-1) represented by the above formula (2). The hydroxyl equivalent of PH-1 was 712 g / eq, the number average molecular weight was 893, and the weight average molecular weight was 1,291. The GPC chart is shown in Figure 1. 1 The H-NMR chart is shown in Figure 2.

[0138] [Example 1] In a flask equipped with a thermometer, a cooling tube, a stirrer, and a Dean-Stark tube, 23.4 parts of PH-1 obtained in Synthesis Example 1, 5.5 parts of 30% aqueous sodium hydroxide solution, and 68.5 parts of dimethyl sulfoxide (manufactured by Toray Fine Chemical Co., Ltd.) were charged, and the mixture was stirred at 120°C while bubbling nitrogen, and dissolved, and the water in the system was distilled off. Then, the mixture was cooled to 50°C, and 22.8 parts of toluene (manufactured by Junsei Chemical Co., Ltd.) was added and homogenized. 6.0 parts of 4-(chloromethyl)styrene (manufactured by Seimi Chemical Co., Ltd., CMS-14) was added dropwise over 30 minutes using a dropping funnel, and the mixture was reacted at 50°C for 3 hours. After the reaction was completed, 100.0 parts of toluene (manufactured by Junsei Chemical Co., Ltd.) was added, and washing with water was repeated, and it was confirmed that the wastewater became neutral. After toluene was distilled off under heating and reduced pressure, the resin was redissolved in 10 parts of toluene (manufactured by Junsei Chemical Co., Ltd.) and reprecipitated by dropping into 500 parts of methanol (manufactured by Junsei Chemical Co., Ltd.) to remove low molecular weight impurities. The GPC chart of the obtained resin (S-1) is shown in Figure 3.1 The H-NMR chart is shown in Figure 4. The number average molecular weight was 1,254, the weight average molecular weight was 3,249, and proton peaks derived from the olefin represented by formula (1-e) were confirmed at 5.2-5.3 ppm, 5.7-5.8 ppm, and 6.6-6.8 ppm, respectively.

[0139] [Example 2] A flask equipped with a thermometer, a cooling tube, and a stirrer was equipped with an aspirator and a base trap. 21.4 parts of PH-1 obtained in Synthesis Example 1, 7.3 parts of triethylamine (Tokyo Chemical Industry Co., Ltd.), and 41.1 g of 4-methyltetrahydropyran (Kanto Chemical Industry Co., Ltd.) were charged in this flask, stirred, dissolved, and 4.7 parts of methacryloyl chloride (Tokyo Chemical Industry Co., Ltd.) were dropped at room temperature for 1 hour while the hydrogen chloride generated was collected in the base trap. Then, the mixture was heated to 40°C and reacted for 6 hours while the hydrogen chloride generated was collected in the base trap. 100 parts of methyl isobutyl ketone and 12 parts of a 30 wt% aqueous sodium hydroxide solution were dropped to make the reaction solution basic, and the organic layer was washed five times with 50 parts of water. After distilling off the solvent under heating and reduced pressure, 80 g of toluene was added, and the excess solvent was removed again under heating and reduced pressure to obtain a methacrylic resin (S-2). The GPC chart is shown in FIG. 1 The H-NMR chart is shown in FIG. 6, and the IR chart is shown in FIG. 7. The number average molecular weight was 1,053, and the weight average molecular weight was 2,112. Proton peaks derived from the olefin represented by formula (1-g) were confirmed at 5.8-5.9 ppm and 6.2-6.3 ppm, respectively. -1 The absorption is due to the carbonyl group in the methacrylate.

[0140] [Examples 3 to 5] The olefin resin S-1 obtained in Example 1, the olefin resin S-2 obtained in Example 2, SA-9000 (polyphenylene ether resin manufactured by SABIC), OPE-2St-1200 (polyphenylene ether resin manufactured by Mitsubishi Gas Chemical Co., Ltd.), and OPE-2St-2200 (polyphenylene ether resin manufactured by Mitsubishi Gas Chemical Co., Ltd.) were mixed in equal amounts according to the preparation table in Table 1 to prepare a toluene solution. In Examples 3 and 4, 1% by weight of DCP (dicumyl peroxide, manufactured by Nouryon Chemical Industries, Ltd.) was further added thereto, and the mixture was thinly cast into a polyimide film, and then pre-dried at 60°C under vacuum for about 10 minutes. The obtained dried body was ground in an agate mortar to remove the solvent by low-temperature history, and 0.5 g was placed on copper foil, and the mixture was molded in a vacuum heating press while sandwiched between the opposing copper foils, and cured under the conditions described in Table 1. In this case, a piece of cushion paper with a thickness of 250 μm and a size of 100 mm×50 mm cut out in the center was used as a spacer.

[0141] <Dielectric constant (Dk) test / Dielectric loss tangent (Df) test> The measurements were performed at a frequency of 10 GHz using an AET coaxial resonant type dielectric constant measuring device ADMS01OC1.

[0142] [Table 1]

[0143] [Examples 6 and 7] In order to confirm the long-term stability of the dielectric properties of the curable resin of the present invention, the test piece obtained in Example 5 was exposed to the accelerated conditions shown in Table 2, and then the dielectric properties were confirmed.

[0144] [Table 2]

[0145] As shown in Tables 1 and 2, the dielectric loss tangent of all of Examples 3 to 7 was 0.005 or less. This value satisfies the required characteristics of Non-Patent Documents 1 and 2. Patent Document 3 discloses the dielectric loss tangent of a resin composition containing a petroleum resin-modified phenolic resin, and even Example 6, which has the lowest dielectric loss tangent, is 0.006, confirming that Examples 3 to 7 of the present application have excellent low dielectric characteristics.

[0146] The curable resin and the curable resin composition of the present invention are suitably used for electric and electronic parts such as semiconductor encapsulants, printed wiring boards, and build-up laminates.

Claims

1. A curable resin represented by the following formula (1): 【Chemistry 1】 In formula (1), A represents any one of the following formulas (1-a), (1-c), and (1-d). Each of the multiple X's independently represents any one of the following formulas (1-e) to (1-g). １ Each independently represents a residue obtained by removing one hydrogen atom from a C9 petroleum resin. ２ each independently represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an amino group, or a hydroxy group. Each of the multiple s and t's is independently an integer of 0 to 3, and the sum of s and t's bonded to the same aromatic ring is an integer of 0 to 3. The average value of s's is s ａｖｅ is 0 < s ａｖｅ ≦3, and the average value of t ａｖｅ t ａｖｅ ≦2. n is the number of repetitions, and the average value of n ａｖｅ 0.1≦n ａｖｅ ≦5.) 【Chemistry 2】 (In formulas (1-a) to (1-d), there are multiple R ３ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. The wavy line represents a bonding site to the aromatic ring in formula (1). 【Chemistry 3】 (In formulas (1-e) to (1-g), the wavy lines represent the bonding sites to the oxygen atom in formula (1).)

2. A curable resin obtained by reacting a phenolic resin obtained by reacting a phenolic resin (P3) containing a C9 petroleum resin (P2) having a phenolic hydroxyl group with any of compounds represented by the following formulas (4-a), (4-c), and (4-d), and a compound represented by any of the following formulas (2-a) to (2-c). 【Chemistry 4】 (In formulas (4-a) to (4-d), there are multiple R ３ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms; and each of the multiple Y's independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, or an alkoxy group having 1 to 6 carbon atoms. 【Chemistry 5】 (In formulas (2-a) to (2-c), each of the multiple Y's independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, or an alkoxy group having 1 to 6 carbon atoms.)

3. A curable resin obtained by reacting a phenolic resin obtained by reacting a polyhydric hydroxyl resin represented by the following formula (3) with a C9-based petroleum resin (P1) having a double bond, with a compound represented by any one of the following formulas (2-a) to (2-c). 【Chemistry 6】 (In formula (3), A represents any one of the following formulas (1-a), (1-c), and (1-d). ２ Each independently represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an amino group, or a hydroxyl group. Each of the multiple t's is independently an integer of 0 to 3. The average value of t's is t ａｖｅ t ａｖｅ ≦2. n is the number of repetitions, and the average value of n ａｖｅ 0.1≦n ａｖｅ ≦5.) 【Chemistry 7】 (In formulas (1-a) to (1-d), there are multiple R ３ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. The wavy line represents a bonding site to the aromatic ring in formula (3). 【Chemistry 8】 (In formulas (2-a) to (2-c), each of the multiple Y's independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, or an alkoxy group having 1 to 6 carbon atoms.)

4. A curable resin composition comprising the curable resin according to claim 1 .

5. The curable resin composition according to claim 4, further comprising a polyphenylene ether resin.

6. The curable resin composition according to claim 4 , further comprising a maleimide resin.

7. The curable resin composition according to claim 4 , further comprising a polyolefin resin or a polystyrene resin.

8. The curable resin composition according to claim 4 , further comprising an inorganic filler.

9. The curable resin composition according to claim 4 , further comprising a curing accelerator.

10. The curable resin composition according to claim 4 , further comprising a polymerization initiator.

11. A cured product of the curable resin composition according to claim 4.

12. A prepreg obtained by using the curable resin composition according to claim 4.

13. A laminate obtained by curing the curable resin composition according to claim 4.

14. A semiconductor substrate comprising the laminate of claim 13.

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