Curable resin and method for producing same, curable resin composition, and cured product thereof

Abstract

The present invention provides: a curable resin having excellent low dielectric properties; a method for producing the curable resin; a curable resin composition; and a cured product of the curable resin composition.　The curable resin is represented by formula (1). In formula (1), each R1 is independently a C1-5 saturated hydrocarbon group. Each X is independently a structure represented by formula (a0). m is an integer of 0 to 4. n is an integer of 0 to 3, and the average nave of n satisfies 0.1 ≤ nave ≤ 3. In formula (a0), * represents the position of bonding to the 5-member ring of the indene structure of formula (1). Each R2 independently represents a C1-5 saturated hydrocarbon group. q represents an integer of 0 to 3. p is an integer of 0 to 5 when q is 0; p is an integer of 0 to 7 when q is 1; p is an integer of 0 to 9 when q is 2; and p is an integer of 0 to 11 when q is 3. j is an integer of 0 or 1.

Description

S硬化性樹脂およびその製造方法、硬化性樹脂組成物およびその硬化物

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

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

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

[0004] Against this backdrop, polymer materials with excellent low dielectric properties are being investigated. For example, Patent Document 1 proposes a thermosetting resin composition containing an imide compound having a maleimide group and a phenol aralkyl resin having an aliphatic unsaturated bond. However, on the other hand, since phenolic hydroxyl groups that do not participate in the reaction remain during the curing reaction, the electrical properties are not considered sufficient. Patent Document 2 discloses an allyl ether-modified biphenyl aralkyl novolac resin in which allyl groups are added along with phenolic hydroxyl groups. However, it has been shown that the allyl ether-modified biphenyl aralkyl novolac resin undergoes a Claisen rearrangement at 190°C, and at 200°C, which is a typical molding temperature for substrates, phenolic hydroxyl groups that do not contribute to the curing reaction are generated, so the electrical properties cannot be satisfied.

[0005] "Signal Loss Factors in High-Speed ​​Signal Transmission on Printed Circuit Boards," 29th Spring Conference of the Japan Society for Electronics Packaging, Session ID: 16P1-17, 2015.

[0006] Japanese Patent Publication No. 04-359911, International Publication No. 2016 / 002704, Japanese Patent No. 7454553

[0007] This invention has been made in view of the above circumstances, and aims to provide a curable resin having excellent low dielectric properties, a method for producing the same, a curable resin composition, and a cured product thereof.

[0008] The present invention relates to a curable resin represented by the following formula (1).

[0009]

[0010] In formula (1), R １ Each of these independently represents a saturated hydrocarbon group having 1 to 5 carbon atoms. Each of these independently represents a structure expressed by the following formula (a0). m is an integer from 0 to 4. n is an integer from 0 to 3, and n is the average value of n. ａｖｅ is 0.1 ≤ n ａｖｅ The value is ≤ 3.

[0011]

[0012] In formula (a0), * represents the bonding position to the 5-membered ring of the inden structure of formula (1). R ２ each independently represents a saturated hydrocarbon group having 1 to 5 carbon atoms. q represents an integer of 0 to 3. p when q is 0 is an integer of 0 to 5, p when q is 1 is an integer of 0 to 7, p when q is 2 is 0 to 9, and p when q is 3 is 0 to 11. j is an integer of 0 or 1.

[0013] In the present invention, “(numerical value 1) to (numerical value 2)” indicates that the upper and lower limit values are included.

[0014] According to the present invention, it is possible to provide a curable resin having excellent low dielectric properties, a method for producing the same, a curable resin composition, and a cured product thereof.

[0015] The HP-LC chart of Synthesis Example 1 is shown. The GPC chart of Synthesis Example 1 is shown. The １ 1H-NMR chart is shown. The HP-LC chart of Synthesis Example 2 is shown. The GPC chart of Synthesis Example 2 is shown. The １ 1H-NMR chart is shown. The HP-LC chart of Synthesis Example 3 is shown. The GPC chart of Synthesis Example 3 is shown. The １ 1H-NMR chart is shown. The HP-LC chart of Synthesis Example 4 is shown. The GPC chart of Synthesis Example 4 is shown. The １ 1H-NMR chart is shown. The HP-LC chart of Comparative Synthesis Example 1 is shown. The GPC chart of Comparative Synthesis Example 1 is shown. The １ 1H-NMR chart is shown. The HP-LC chart of Comparative Synthesis Example 2 is shown. The １ 1H-NMR chart is shown.

[0016] Hereinafter, the embodiments according to the present invention (hereinafter also referred to as “the present embodiments”) will be described in more detail.

[0017] The curable resin of the present embodiment is represented by the following formula (1).

[0018]

[0019] In the above formula (1), R １Each of these independently represents a hydrocarbon group having 1 to 5 carbon atoms, preferably an alkyl group (saturated hydrocarbon group) having 1 to 5 carbon atoms, more preferably an alkyl group (saturated hydrocarbon group) having 1 to 3 carbon atoms, and particularly preferably a methyl group. When the number of carbon atoms is 5 or less, molecular vibration is less likely when exposed to high frequency, resulting in excellent electrical properties. m is an integer from 0 to 4. X has a structure represented by the following formula (a0). n is an integer from 0 to 3, and it is preferable that n is 2 or 3. The average value of n is n ａｖｅ is 0.1 ≤ n ａｖｅ ≤ 3, and 0.5 ≤ n ａｖｅ Preferably, ≤ 3, and 1.0 ≤ n ａｖｅ It is more preferable that ≤ 3, and 1.5 ≤ n ａｖｅ It is even more preferable that ≤ 3, and 2 ≤ n ａｖｅ It is particularly preferable that ≤ 3, and 2.5 ≤ n ａｖｅ It is most preferable that n=0 is ≤ 3. The curable resin of this embodiment is an aggregate of compounds n=0, n=1, n=2, and n=3.

[0020] The curable resin of this embodiment is a curable resin represented by formula (1) above, and is a curable resin containing molecules having both the structure represented by formula (a0) and the structure represented by formula (b) below. The molecule in the curable resin represented by formula (1) above, which has both the structure represented by formula (a0) and the structure represented by formula (b) below, is represented by formula (2) below.

[0021]

[0022] In the above equation (2), X １ The following equation (a0), X ２ The following equation (b), n １ is 1 or 2, n ２ is 1 or 2, n １ to n ２ The sum is 2 to 3. １Each of these independently represents a hydrocarbon group having 1 to 5 carbon atoms, preferably an alkyl group (saturated hydrocarbon group) having 1 to 5 carbon atoms, more preferably an alkyl group (saturated hydrocarbon group) having 1 to 3 carbon atoms, and particularly preferably a methyl group. When the number of carbon atoms is 5 or less, molecular vibration is less likely to occur when exposed to high frequency, resulting in excellent electrical properties. m is an integer from 0 to 4.

[0023] The curable resin of this embodiment may be an aggregate of a compound of formula (1) n=0, a compound in which X of formula (1) is only the structure represented by formula (a0) below, a compound in which X of formula (1) is only the structure represented by formula (b) below, and a compound in which X of formula (1) is a combination of the structure represented by formula (a0) below and the structure represented by formula (b) below. In this case, the value (α / β) obtained by dividing the number of structures represented by formula (a0) below (α) by the number of structures represented by formula (b) below (β) is preferably 0.03 to 5.0, more preferably 0.07 to 4.0, even more preferably 0.1 to 3.0, particularly preferably 0.25 to 2.0, and most preferably 0.3 to 1.0. If α / β is less than 0.03, the solution stability after dissolution in the solvent may deteriorate. If α / β is greater than 5.0, sufficient curability may not be obtained, and the heat resistance may decrease. When n is 2 or 3, the multiple X may be a combination of the structure represented by formula (a0) and the structure represented by formula (b). That is, at least one of the multiple X may be the structure represented by formula (a0), and at least one other may be the structure represented by formula (b). When the multiple X are a combination of the structure represented by formula (a0) and the structure represented by formula (b), the value (α / β) obtained by dividing the number of structures represented by formula (a0) (α) by the number of structures represented by formula (b) (β) is preferably 0.03 to 5.0, more preferably 0.07 to 4.0, even more preferably 0.1 to 3.0, particularly preferably 0.25 to 2.0, and most preferably 0.3 to 1.0. If α / β is less than 0.03, the solution stability after solvent dissolution may deteriorate. If α / β is greater than 5.0, sufficient curability may not be obtained, and the heat resistance may decrease. In the case of a curable resin composed solely of compounds where X has the structure represented by formula (b) below, the crosslinking points become overcrowded, and vinylbenzyl groups that cannot contribute to curing remain. Due to the dipole moment of these remaining vinylbenzyl groups, dielectric properties tend to deteriorate, especially in the high-frequency range of 10 GHz or higher.Furthermore, by introducing the structure represented by the following formula (a0), the crosslinking density can be controlled, which allows for stress relaxation in high-temperature regions such as during solder reflow (for example, a decrease in the elastic modulus when heated to 260°C). Therefore, when combined with glass cloth, it is advantageous for suppressing substrate warping. m is an integer from 0 to 4, preferably an integer from 0 to 2, more preferably an integer from 0 to 1, and particularly preferably 0. When m is 0, it is particularly preferable because it can suppress deterioration of dielectric properties and water absorption properties associated with the formation of polar groups due to the oxidation reaction of alkyl groups during high-temperature storage tests. The residual halogen contained in the curable resin is preferably 1 to 10,000 ppm, more preferably 1 to 3,000 ppm, and even more preferably 1 to 2,000 ppm. If the residual halogen concentration exceeds 10,000 ppm, the residual halogen atoms may detach during curing (for example, at temperatures above 175°C) or during high-temperature, high-humidity testing (e.g., 85°C, 85% humidity or 120°C, 100% humidity), potentially leading to corrosion of the copper wiring.

[0024] In this embodiment, the molecular weight of the curable resin is preferably 100 to 1500, more preferably 150 to 1000, and even more preferably 200 to 750, as determined by GPC (gel permeation chromatography) analysis using a differential refractive index detector. If the number average molecular weight is less than 100, there is a risk that the heat resistance may decrease due to residual raw materials, or that tackiness may occur during B-stage formation. If the number average molecular weight exceeds 1500, there is a risk that the viscosity of the curable resin will increase, impairing circuit embedding properties, or that solvent solubility will decrease. Furthermore, the weight average molecular weight is preferably 150 to 2000, more preferably 200 to 1500, and even more preferably 250 to 1000. If the weight average molecular weight is less than 150, there is a risk that the heat resistance may decrease due to residual raw materials, or that tackiness may occur during B-stage formation. If the weight-average molecular weight exceeds 2000, the viscosity of the curable resin may increase, potentially impairing its circuit embedding properties or reducing its solvent solubility.

[0025]

[0026] In formula (a0), * represents the bonding position of the indene structure in formula (1) to the five-membered ring. ２ Each of these independently represents an alkyl group (saturated hydrocarbon group) having 1 to 5 carbon atoms, preferably an alkyl group (saturated hydrocarbon group) having 1 to 3 carbon atoms, and particularly preferably a methyl group. When the number of carbon atoms is 5 or less, molecular vibration is less likely when exposed to high frequency, resulting in excellent electrical properties. q represents the number of repetitions and is an integer from 0 to 3, preferably an integer from 0 to 2. When q is 4 or more, the molecular weight is large and the viscosity of the resin alone increases, which may impair the impregnation properties into fibers such as glass cloth. In formula (a0), a structure with q = 0 means that it contains a benzene structure, a structure with q = 1 means that it contains a naphthalene structure, a structure with q = 2 means that it contains an anthracene structure, and a structure with q = 3 means that it contains a naphthacene structure. Also, in formula (a0), R ２ p may be substituted at any position on the aromatic ring as long as it is a substitutable position. When q is 0, p is an integer from 0 to 5; when q is 1, p is an integer from 0 to 7; when q is 2, p is from 0 to 9; and when q is 3, p is from 0 to 11. It is more preferable that p is an integer from 0 to 3, and even more preferable that it is an integer from 0 to 1. j is an integer of 0 or 1.

[0027] The above formula (a0) is preferably represented by the following formula (a).

[0028] In formula (a) above, * represents the bonding position of the indene structure to the five-membered ring in formula (1). ２ p, q, and j are the same as in equation (a0) above.

[0029] The above formula (a) is preferably represented by the following formula (a1) or (a2).

[0030]

[0031] In formulas (a1) and (a2), * represents the bonding position of the indene structure in formula (1) to the five-membered ring. ２This is the same as formula (a) above. p is an integer from 0 to 5, preferably from 0 to 3, and more preferably from 0 to 1. In formula (a1), p is preferably 0, and in formula (a2), p is particularly preferably 1.

[0032] In the curable resin of this embodiment, when formula (a0) in formula (1) is represented by the structure of formula (a1), the number average molecular weight of the curable resin is preferably 100 to 1500, more preferably 150 to 1000, and even more preferably 200 to 500, as determined by GPC (gel permeation chromatography) analysis using a differential refractive index detector. If the number average molecular weight is less than 100, there is a risk that the heat resistance will decrease due to residual raw materials, etc., or that tackiness will occur during B-stage formation. If the number average molecular weight exceeds 1500, there is a risk that the viscosity of the curable resin will increase, impairing circuit embedding properties, or that solvent solubility will decrease. Furthermore, as for the weight average molecular weight, it is preferably 150 to 2000, more preferably 200 to 1000, and even more preferably 250 to 500, as determined by GPC (gel permeation chromatography) analysis using a differential refractive index detector. If the weight-average molecular weight is less than 150, there is a risk that the heat resistance may decrease due to residual raw materials, etc., or that tackiness may occur during B-stage formation. If the weight-average molecular weight exceeds 2000, there is a risk that the circuit embedding ability may be impaired or that solvent solubility may decrease due to an increase in the viscosity of the curable resin. In the curable resin of this embodiment, when formula (a0) in formula (1) is represented by formula (a2), the number-average molecular weight of the curable resin is preferably 100 to 1500, more preferably 150 to 1000, and even more preferably 200 to 750, as determined by analysis results using a differential refractive index detector in GPC (gel permeation chromatography) analysis. If the number-average molecular weight is less than 150, there is a risk that the heat resistance may decrease due to residual raw materials, etc., or that tackiness may occur during B-stage formation. If the number-average molecular weight exceeds 750, there is a risk that the circuit embedding ability may be impaired or that solvent solubility may decrease due to an increase in the viscosity of the curable resin. Furthermore, the weight-average molecular weight is preferably 150 to 2000, preferably 200 to 1500, and more preferably 250 to 1000, as determined by GPC (gel permeation chromatography) analysis using a differential refractive index detector.If the weight-average molecular weight is less than 200, there is a risk that heat resistance may decrease due to residual raw materials, or that tackiness may develop during B-stage formation. If the weight-average molecular weight exceeds 2000, there is a risk that circuit embedding ability may be impaired due to an increase in the viscosity of the curable resin, or that solvent solubility may decrease.

[0033] The above formula (a) is preferably represented by the following formula (a3).

[0034]

[0035] In formula (a3), * represents the bonding position of the indene structure in formula (1) to the five-membered ring. ２, p, and q are the same as in formula (a0) above. Furthermore, it is particularly preferable that p be 0. q represents the number of repetitions and is an integer from 1 to 3, preferably an integer from 1 to 2, and particularly preferable that it be 1. By setting q within the above range, a highly curable resin with a low coefficient of thermal expansion (low CTE) can be obtained. If q is 4 or more, the molecular weight is large and the viscosity of the resin alone increases, which may impair the impregnation properties into fibers such as glass cloth. If q is between 1 and 3, the stacking effect of the structure represented by (a3) ​​is exhibited, and the coefficient of thermal expansion can be further reduced. In the curable resin of this embodiment, when formula (a0) in formula (1) is the structure represented by formula (a3), the number average molecular weight of the curable resin is preferably 100 to 1500, more preferably 200 to 1000, and even more preferably 300 to 750, as determined by GPC (gel permeation chromatography) analysis using a differential refractive index detector. If the number average molecular weight is less than 200, there is a risk that the heat resistance may decrease due to residual raw materials, etc., or that tackiness may occur during B-stage formation. If the number average molecular weight exceeds 750, there is a risk that the viscosity of the curable resin may increase, impairing circuit embedding properties, or that solvent solubility may decrease. Furthermore, the weight average molecular weight is preferably 200 to 2000, more preferably 200 to 1500, and even more preferably 250 to 1000, as determined by GPC (gel permeation chromatography) analysis using a differential refractive index detector. If the weight-average molecular weight is less than 200, there is a risk that heat resistance may decrease due to residual raw materials, or that tackiness may develop during B-stage formation. If the weight-average molecular weight exceeds 2000, there is a risk that circuit embedding ability may be impaired due to an increase in the viscosity of the curable resin, or that solvent solubility may decrease.

[0036]

[0037] In formula (b) above, * represents the bonding position of the indene structure to the five-membered ring in formula (1) above. ３Each of these independently represents a hydrocarbon group having 1 to 5 carbon atoms, preferably an alkyl group (saturated hydrocarbon group) having 1 to 5 carbon atoms, more preferably an alkyl group (saturated hydrocarbon group) having 1 to 3 carbon atoms, and particularly preferably a methyl group. When the number of carbon atoms is 5 or less, molecular vibration is less likely to occur when exposed to high frequency, resulting in excellent electrical properties. l is an integer from 0 to 4, preferably 0. When l is 0, it is particularly preferable because it can suppress the deterioration of dielectric properties and water absorption properties associated with the formation of polar groups due to the oxidation reaction of alkyl groups during high-temperature storage tests.

[0038] The method for producing the curable resin of this embodiment is not particularly limited, but it can be obtained by reacting a compound represented by the following formula (A0) with a compound represented by the following formula (C), or by reacting a compound represented by the following formula (A0) with a compound represented by the following formula (B) with a compound represented by the following formula (C).

[0039]

[0040] In the above formula (A0), R ２ The same as in formula (a0) above, and the values ​​and preferred ranges of p, q, and j are the same as in formula (a0) above. Y represents a halogen atom, and is preferably a bromine atom or a chlorine atom from the viewpoint of reactivity and waste generation suppression, and more preferably a bromine atom.

[0041] The above formula (A0) is preferably represented by the following formula (A). In the above formula (A), R ２ p, q, and j are the same as in formula (A0) above. Y represents a halogen atom, and is preferably a bromine atom or a chlorine atom from the viewpoint of reactivity and waste generation suppression.

[0042] The above formula (A) is preferably the following formula (A1) or (A2).

[0043]

[0044] In the above formulas (A1) and (A2), R ２And Y are the same as in formula (A) above. The value and preferred range of p in formula (A1) are the same as in formula (a1) above. The value and preferred range of p in formula (A2) are the same as in formula (a2) above.

[0045] The above formula (A) is preferably the following formula (A3).

[0046]

[0047] In the above formula (A3), R ２ q and Y are the same as in formula (A) above. The value of p and the preferred range in formula (A3) above are the same as in formula (a3) ​​above.

[0048]

[0049] In the above formula (B), R ３ ,l is the same as in formula (b) above. Y represents a halogen atom, and is preferably a bromine atom or a chlorine atom, and more preferably a chlorine atom, from the viewpoint of reactivity and suppression of waste generation. As the halomethylstyrene represented by formula (B) above, any one or more of o-halomethylstyrene, m-halomethylstyrene, and p-halomethylstyrene may be used, regardless of the substitution position of the vinyl group. From the viewpoint of obtaining the effect of improving curability and reducing CTE, it is preferable to use m- and p-halomethylstyrene.

[0050]

[0051] In the above formula (C), R １ ,m is the same as in equation (1) above.

[0052] When synthesizing the curable resin of this embodiment, when M1 is the total number of moles of the compounds represented by formulas (A0) and (B), and M2 is the number of moles of the compound represented by formula (C), it is preferable that M1 / M2 be between 1.0 and 3.1, more preferably between 1.5 and 3.0, and particularly preferably between 1.8 and 2.95. If M1 / M2 is less than 1.0, the compound represented by formula (C) remains unreacted, so sufficient curability cannot be achieved, and the toughness of the cured film may decrease. If M1 / M2 is greater than 3.15, halogen atoms of the compounds represented by formulas (A0) and (B) that could not be completely removed by purification may desorb during curing (for example, at temperatures of 175°C or higher) or during high-temperature and high-humidity testing (85°C, 85% humidity or 120°C, 100% humidity, etc.), potentially leading to corrosion of copper wiring. The amount of residual halogen contained in the reaction product containing the curable resin of this embodiment is preferably 1 to 10,000 ppm, more preferably 1 to 3,000 ppm, and even more preferably 1 to 2,000 ppm. Here, "residual halogen" originates from unreacted raw material compounds and impurities contained in the raw material compounds, which are contained in the reaction product obtained by reacting the compounds represented by formulas (A0) and (B) above with the compound represented by formula (C) above to obtain the curable resin of this embodiment.

[0053] The curable resin of this embodiment is obtained by reacting a compound represented by formula (A0) with a compound represented by formula (C), or a compound represented by formula (A0), a compound represented by formula (B), and a compound represented by formula (C) in an aprotic polar solvent in the presence of a basic catalyst. Examples of aprotic polar solvents include dimethyl sulfone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, and N-methylpyrrolidone, and two or more may be used in combination. In addition, a water-insoluble solvent may be used in combination as needed. Examples of water-insoluble solvents include aromatic solvents such as toluene and xylene, aliphatic solvents such as cyclohexane and n-hexane, ethers such as diethyl ether and diisopropyl ether, ester solvents such as ethyl acetate and butyl acetate, and ketone solvents such as methyl isobutyl ketone and cyclopentanone, but are not limited to these, and two or more may be used in combination. The basic catalyst is not particularly limited, but examples include basic catalysts such as sodium hydroxide, potassium hydroxide, and potassium carbonate. The order in which the compounds represented by formulas (A0), (B), and (C) and the basic catalyst are added can be changed as needed, but it is preferable to add the compounds represented by formulas (A0), (B), and (C) and the aprotic polar solvent first, and then add the basic catalyst. If the reaction is carried out without using an aprotic polar solvent, the reaction rate will decrease significantly. When an aprotic polar solvent is not used, the reaction is generally carried out using a phase transfer catalyst. In this case, the compounds represented by formulas (A0), (B), and (C), which are the starting materials, are dissolved in a water-insoluble solvent such as toluene, and the compounds represented by formulas (A0) and (B) are reacted with the compound represented by formula (C) in the presence of a basic catalyst such as an aqueous sodium hydroxide solution and a phase transfer catalyst such as tetrabutylammonium bromide. In this case, it is difficult to completely remove the interphase transfer catalyst such as tetrabutylammonium bromide, making it difficult to achieve low dielectric properties (low dielectric constant and low dielectric loss tangent). Furthermore, residual interphase transfer catalysts may cause problems such as ion migration when the substrate material using the curable resin of this embodiment is subjected to long-term moist heat reliability tests.The reaction temperature is preferably 0 to 120°C, more preferably 0 to 100°C, and even more preferably 0 to 80°C. Above the upper limit, the curable resin of this embodiment may undergo self-polymerization and gelation. Below the lower limit, the reaction may not proceed sufficiently. As a post-reaction treatment, neutralization may be performed with any acid compound. Alternatively, if necessary, an alcohol compound or water may be added to the reaction solution to recover the target product as crystals of the curable resin of this embodiment. The obtained reaction solution or crystals may also be redissolved in any solvent and an extraction step may be performed. For the extraction step, an aromatic hydrocarbon solvent such as toluene or xylene may be used alone, or a non-aromatic hydrocarbon such as cyclohexane or n-hexane may be used in combination. After extraction, the organic layer is washed with water until the wastewater is neutral, and the solvent is removed using an evaporator or the like to obtain the curable resin of this embodiment.

[0054] The curable resin of this embodiment can be cured on its own by heating or other means, but its performance can also be improved by adding various materials to form a curable resin composition.

[0055] [Curing Accelerator] The curable resin composition of this embodiment can also have its curability improved by adding a curing accelerator. Preferred curing accelerators are anionic curing accelerators that promote the curing reaction by generating anions upon irradiation with ultraviolet light or visible light or by heating, or cationic curing accelerators that promote the curing reaction by generating cations upon irradiation with ultraviolet light or visible light or by heating.

[0056] 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, tetrabutylammonium salt, triisopropylmethylammonium salt, trimethyldecanylammonium salt, cetyltrimethylammonium salt, and quaternary ammonium salts such as hexadecyltrimethylammonium hydroxide, but are not limited to these. These may be used individually or in combination.

[0057] Examples of cationic curing accelerators include, but are not limited to, quaternary phosphonium salts such as triphenylbenzylphosphonium salt, triphenylethylphosphonium salt, and tetrabutylphosphonium salt, as well as transition metal compounds (transition metal salts) such as tin octoate, zinc carboxylates (e.g., zinc 2-ethylhexanoate, zinc stearate, zinc behenate, zinc myristate), and zinc phosphate esters (zinc octyl phosphate, zinc stearyl phosphate). The counterions of the quaternary phosphonium salts are not particularly specified, but organic acid ions and hydroxide ions are especially preferred. These may be used individually or in combination.

[0058] The amount of curing accelerator used is 0.01 to 5.0 parts by mass per 100 parts by mass of the curable resin composition, as needed.

[0059] [Inorganic Fillers] The curable resin composition of this embodiment may contain inorganic fillers. Examples of inorganic fillers include, but are not limited to, powders such as fused silica, crystalline silica, porous silica, alumina, zircon, calcium silicate, calcium carbonate, quartz powder, silicon carbide, silicon nitride, boron nitride, zirconia, aluminum nitride, graphite, forsterite, steatite, spinel, mullite, titania, talc, clay, iron oxide, asbestos, and glass powder, or inorganic fillers made by shaping these into spheres or crushed forms. Furthermore, these may be used individually or in combination of multiple types.

[0060] When an inorganic filler is used in a curable resin composition for semiconductor encapsulation, the amount used is preferably 80 to 92 parts by mass, and more preferably 83 to 90 parts by mass, per 100 parts by mass of the curable resin composition. Furthermore, when obtaining a curable resin composition for interlayer insulating layer forming materials, copper-clad laminates and prepregs, and substrate materials such as RCC (Resin Coated Copper), the amount of the above-mentioned inorganic filler used is preferably 5 to 80 parts by mass, and more preferably 10 to 60 parts by mass, per 100 parts by mass of the curable resin composition.

[0061] [Polymerization Initiator] The curable resin composition of this embodiment can also have its curability improved by adding a polymerization initiator. A polymerization initiator is a compound capable of polymerizing olefin functional groups such as ethylenically unsaturated bonds, and examples include olefin metathesis polymerization initiators, anionic polymerization initiators, cationic polymerization initiators, and radical polymerization initiators. Among these, it is preferable to use a radical polymerization initiator that has curability and appropriate stability. A radical polymerization initiator is a compound that generates radicals by irradiation with ultraviolet light or visible light or by heating, and initiates a chain polymerization reaction. Examples of radical polymerization initiators that can be used include organic peroxides, azo compounds, and benzopinacols, and it is preferable to use organic peroxides because they have little effect on curing temperature control, outgassing suppression, and the electrical properties of decomposition products.

[0062] Examples of the above 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-tetramethylbutyl peroxy-2-ethylhexanoate, t-amyl peroxy-2-ethylhexanoate, and t-butyl peroxy Examples of alkyl peresters such as -oxy-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-butyl peroxycarbonyloxy)hexane; t-butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxyoctoate, and lauroyl peroxide are examples, but are not limited to these. Furthermore, these may be used individually or in combination. Among the above organic peroxides, ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, alkyl peresters, and peroxycarbonates are preferred, with dialkyl peroxides being more preferred.

[0063] Examples of the above-mentioned azo compounds include, but are not limited to, azobisisobutyronitrile, 4,4'-azobis(4-cyanovaleric acid), and 2,2'-azobis(2,4-dimethylvaleronitrile). Furthermore, these compounds may be used individually or in combination.

[0064] The amount of polymerization initiator added is preferably 0.01 to 5 parts by mass, and particularly preferably 0.01 to 3 parts by mass, per 100 parts by mass of the curable resin composition. If the amount of polymerization initiator used is less than 0.01 parts by mass, the molecular weight may not elongate sufficiently during the polymerization reaction, and if it is more than 5 parts by mass, dielectric properties such as dielectric constant and dielectric loss tangent may be impaired.

[0065] [Polymerization Inhibitor] The curable resin composition of this embodiment may contain a polymerization inhibitor. Including a polymerization inhibitor improves storage stability and allows control of the reaction initiation temperature. Controlling the reaction initiation temperature makes it easier to ensure fluidity, prevents impregnation into glass cloth and the like, and facilitates B-stage production such as prepreg formation. If the polymerization reaction proceeds too far during prepreg formation, problems such as difficulty in lamination during the lamination process are likely to occur.

[0066] The polymerization inhibitor may be added when synthesizing the curable resin of this embodiment, or after synthesis. The amount of polymerization inhibitor used is 0.008 to 1 part by mass, preferably 0.01 to 0.5 parts by mass, per 100 parts by mass of the curable resin of this embodiment.

[0067] Examples of polymerization inhibitors include phenol-based, sulfur-based, phosphorus-based, nitroso-based, and nitroxyl radical-based agents. Furthermore, one type of polymerization inhibitor may be used, or multiple types may be used in combination. Of these, phenol-based, nitroso-based, and nitroxyl radical-based agents are preferred in this embodiment.

[0068] Examples of the above phenolic polymerization inhibitors 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, and 2,4-bis[(octylthio)methyl]-o-c Monophenols such as resols, 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-hydroxyhydrocinnamamide), 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- Bisphenols such as calcium trimethyl-4-hydroxybenzylsulfonate ethyl, 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, tetrakis-[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methane, bis[3,3'-bis-(4'-hydroxy-3'-t-butylphenyl)butyric acid]glycol ester, tris-(3,Examples include, but are not limited to, high molecular weight phenols such as 5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-tris(3',5'-di-t-butyl-4'-hydroxybenzyl)-S-triazine-2,4,6-(1H,3H,5H)trione, and tocopherol.

[0069] Examples of sulfur-based polymerization inhibitors include, but are not limited to, dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, and distearyl-3,3'-thiodipropionate.

[0070] Examples of the phosphorus polymerization inhibitors mentioned above include triphenyl phosphite, diphenylisodecyl phosphite, phenyldiisodecyl phosphite, tris(nonylphenyl) phosphite, diisodecylpentaerythritol phosphite, tris(2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbis(octadecyl) phosphite, cyclic neopentanetetraylbis(2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbis(2,4-di-t-butyl-4-methylphenyl) phosphite, and bis[2- Examples include, but are not limited to, phosphites such as t-butyl-6-methyl-4-{2-(octadecyloxycarbonyl)ethyl}phenyl]hydrogen phosphite, oxaphosphaphenanthrene oxides such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(3,5-di-t-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.

[0071] Examples of the nitroso polymerization inhibitors mentioned above include, but are not limited to, p-nitrosophenol, N-nitrosodiphenylamine, and ammonium salts of N-nitroso-N-phenylhydroxyamine (cuperone). Of these, ammonium salts of N-nitroso-N-phenylhydroxyamine (cuperone) are preferred.

[0072] Examples of the above-mentioned nitroxyl radical polymerization inhibitors include, but are not limited to, di-tert-butylnitroxide, 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.

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

[0074] The phosphorus-based flame retardants mentioned above may be reactive or additive types. Specific examples include phosphorus esters such as trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixyllenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixyllenyl phosphate, 1,3-phenylenebis(dixyllenyl phosphate), 1,4-phenylenebis(dixyllenyl phosphate), and 4,4'-biphenyl(dixyllenyl 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 resin with the active hydrogen of the above phosphanes; and red phosphorus, but are not limited to these. Furthermore, these may be used individually or in combination of multiple types. Of the above example substances, phosphate esters, phosphans, or phosphorus-containing epoxy compounds are preferred, and 1,3-phenylenebis(dixyllenyl phosphate), 1,4-phenylenebis(dixyllenyl phosphate), 4,4'-biphenyl(dixyllenyl phosphate), or phosphorus-containing epoxy compounds are particularly preferred.

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

[0076] [Light stabilizer] The curable resin composition of this embodiment may also contain a light stabilizer. Suitable light stabilizers include hindered amine light stabilizers (HALS) and the like. 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-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine succinate, 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 Examples include, but are not limited to, 2,6,6-pentamethyl-4-piperidyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(1-octyroxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, 2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-n-butylmalonate bis(1,2,2,6,6-pentamethyl-4-piperidyl). Furthermore, these may be used individually or in combination.Specific examples of the above light stabilizers include, for example, AdekaStab (registered trademark) LA-40MP, AdekaStab LA-40Si, AdekaStab LA-402AF, AdekaStab LA-87, AdekaStab LA-82, AdekaStab LA-81, AdekaStab LA-77Y, AdekaStab LA-77G, AdekaStab LA-72, AdekaStab LA-68, AdekaStab LA-63P, AdekaStab LA-57, and AdekaStab LA-52 (all manufactured by ADEKA Corporation). Examples include, but are not limited to, Chimassorb® 2020FDL, Chimassorb 944FDL, Chimassorb 944LD, Tinuvin® 622SF, Tinuvin PA144, Tinuvin 765, Tinuvin 770DF, Tinuvin XT55FB, Tinuvin 111FDL, Tinuvin 783FDL, and Tinuvin 791FB (all manufactured by BASF). In addition, the above light stabilizers may be used as polymerization inhibitors.

[0077] The amount of light stabilizer is preferably in the range of 0.001 to 0.1 parts by mass per 100 parts by mass of the curable resin composition. If the amount is less than 0.001 parts by mass, it may be insufficient to exhibit the light stabilization effect, and if it is more than 0.1 parts by mass, it may adversely affect the hygroscopicity and dielectric properties of the cured product.

[0078] [Binder Resin] The curable resin composition of this embodiment may also use a binder resin. Examples of binder resins include butyral resins, acetal resins, acrylic resins, epoxy-nylon resins, NBR (Nitrile Butadiene Rubber)-phenol resins, epoxy-NBR resins, silicone resins, etc., but are not limited to these. Furthermore, these may be used individually or in combination of multiple types.

[0079] The amount of binder resin added is preferably within a range that does not impair the flame retardancy and heat resistance of the cured product, and is preferably 0.05 to 50 parts by mass per 100 parts by mass of the curable resin composition, and more preferably 0.05 to 20 parts by mass as needed.

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

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

[0082] The curable resin composition of this embodiment may further contain epoxy resins, active ester compounds, phenolic resins, polyphenylene ether compounds, amine resins, compounds having ethylenically unsaturated bonds, isocyanate resins, polyamide resins, maleimide compounds, cyanate ester resins, polyimide resins, polybutadiene and its modified counterparts, polystyrene and its modified counterparts, polyethylene and its modified counterparts, benzoxazine compounds, etc., and these may be used individually or in combination of multiple compounds. Among these compounds, it is preferable to include polyphenylene ether compounds, compounds having ethylenically unsaturated bonds, cyanate ester resins, polybutadiene and its modified counterparts, polystyrene and its modified counterparts, in order to balance heat resistance, adhesion, and dielectric properties. By including these compounds, the brittleness of the cured product can be improved and adhesion to metal can be enhanced, and cracks in the package can be suppressed during reliability tests such as solder reflow and thermal cycling. Unless otherwise specified, the total amount of the above compounds used is preferably 10 times or less by mass, more preferably 5 times or less by mass, and particularly preferably 3 times or less by mass, relative to the curable resin of this embodiment. Furthermore, the preferred lower limit is 0.1 times the mass or more, more preferably 0.25 times the mass or more, and even more preferably 0.5 times the mass or more. By being within the above range, the effect of each added compound can be added while taking advantage of the low dielectric properties of the curable resin of this embodiment. The following examples of components can be used.

[0083] [Epoxy Resin] The following are examples of preferred epoxy resins, but are not limited to these. The epoxy resin may be liquid or solid, and may be used alone or in combination of multiple types.

[0084] Examples of liquid epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, glycidylamine type epoxy resin, and epoxy resin having a butadiene structure. Specific examples include "RE310S", "RE410S" (both manufactured by Nippon Kayaku Co., Ltd., bisphenol A type epoxy resin), "RE303S", "RE304S", "RE403S", "RE404S" (all manufactured by Nippon Kayaku Co., Ltd., bisphenol F type epoxy resin), "HP-4032", "HP-4032D", "HP-4032SS" (all manufactured by DIC Corporation, naphthalene type epoxy resin), "jER(registered trademark)828US", "jER828EL", "jER825", "jER828EL" (all manufactured by Mitsubishi Chemical Corporation, bisphenol A type epoxy resin), "jER807", "jER1750" (both manufactured by Mitsubishi Chemical Corporation, bisphenol F type epoxy resin), "jER152" (manufactured by Mitsubishi Chemical Corporation, Examples include phenol novolac type epoxy resin, "jER630", "jER630LSD" (both 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), "Celoxide (registered trademark) 2021P" (manufactured by Daicel Corporation, alicyclic epoxy resin with an ester skeleton), "PB-3600" (manufactured by Daicel Corporation, epoxy resin with a butadiene structure), "ZX1658", "ZX1658GS" (both manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., liquid 1,4-glycidylcyclohexane type epoxy resin). These may be used individually or in combination of two or more types.

[0085] Preferred solid epoxy resins include, for example, bixylenol-type epoxy resin, naphthalene-type epoxy resin, naphthalene-type tetrafunctional epoxy resin, cresol novolac-type epoxy resin, dicyclopentadiene-type epoxy resin, trisphenol-type epoxy resin, naphthol-type epoxy resin, biphenyl-type epoxy resin, naphthylene ether-type epoxy resin, anthracene-type epoxy resin, bisphenol A-type epoxy resin, bisphenol AF-type epoxy resin, and tetraphenylethane-type epoxy resin.Specific examples include "HP4032H" (manufactured by DIC Corporation, naphthalene-type epoxy resin), "HP-4700", "HP-4710" (both manufactured by DIC Corporation, naphthalene-type tetrafunctional epoxy resin), "N-690" (manufactured by DIC Corporation, cresol novolac-type epoxy resin), "N-695" (manufactured by DIC Corporation, cresol novolac-type epoxy resin), "HP-7200", "HP-7200HH", "HP-7200H" (both manufactured by DIC Corporation, dicyclopentadiene-type epoxy resin), "EXA-7311", "EXA-7311- "G3", "EXA-7311-G4", "EXA-7311-G4S", "HP-6000" (all manufactured by DIC Corporation, naphthylene ether type epoxy resin), "EPPN-502H" (manufactured by Nippon Kayaku Co., Ltd., trisphenol type epoxy resin), "NC-7000L", "NC-7300" (both 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 aralkyl type epoxy resin) "XD-1000-2L", "XD-1000-L", "XD-1000-H" (all manufactured by Nippon Kayaku Co., Ltd., dicyclopentadiene type epoxy resin), "ESN475V" (manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., naphthol type epoxy resin), "ESN485" (manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., naphthol novolac type epoxy resin), "YX-4000H", "YX-4000", "YL6121" (all manufactured by Mitsubishi Chemical Corporation, biphenyl type epoxy resin), "YX-4000HK" (manufactured by Mitsubishi Chemical Corporation, bixylenol type epoxy resin), Examples 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 individually or in combination of two or more types.

[0086] [Active Ester Compounds] Active ester compounds are compounds that contain at least one ester bond in their structure, and on both sides of the ester bond, aliphatic chains, aliphatic rings, or aromatic rings are bonded. Examples of active ester compounds include compounds having two or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds. They 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 that they be obtained from a carboxylic acid compound or an acid chloride and a hydroxy compound, and phenol compounds or naphthol compounds are preferred as the hydroxy compound. Active ester compounds may be used alone or in combination of two or more.

[0087] Examples of the carboxylic acid compounds mentioned above include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.

[0088] Examples of the above-mentioned acid chlorides include acetyl chloride, acrylate chloride, methacrylate chloride, malonyl chloride, succinate dichloride, diglycolyl chloride, glutarate dichloride, suberate dichloride, sebacate dichloride, adipic acid dichloride, dodecanediol dichloride, azera oil chloride, 2,5-franzicarbonyl dichloride, phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, trimesic acid chloride, bis(4-chlorocarbonylphenyl) ether, 4,4'-diphenyldicarbonyl chloride, and 4,4'-azodibenzoyl dichloride.

[0089] Examples of the above-mentioned phenol compounds and naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene-type diphenol compounds, phenol novolac, and phenol resins described later. Here, "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by the condensation of two molecules of phenol with one molecule of dicyclopentadiene.

[0090] Preferred examples of active ester compounds include active ester compounds containing a dicyclopentadiene-type diphenol structure, active ester compounds containing a naphthalene structure, active ester compounds containing an acetylated phenol novolac, active ester compounds containing a benzoylated phenol novolac, the compound described in Example 2 of International Publication No. 2020 / 095829, and the compounds disclosed in International Publication No. 2020 / 059625. Among these, active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene-type diphenol structure are more preferred. The dicyclopentadiene-type diphenol structure represents a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

[0091] Examples of 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; "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing an acetylated phenol novolac; "YLH1026," "YLH1030," and "YLH1048" (manufactured by Mitsubishi Chemical Corporation) as active ester compounds containing a benzoylated phenol novolac; and "EXB-9050L-62M" (manufactured by DIC Corporation) as a phosphorus atom-containing active ester curing agent.

[0092] Regarding the blending ratio of the active ester compound and epoxy resin, the ratio of the active ester equivalent (E1) to the epoxy equivalent (E2) (E1 / E2) is preferably 0.5 to 1.5, more preferably 0.8 to 1.2, and even more preferably 0.0 to 1.1. If it falls outside the above range, there is a risk that excess epoxy groups or active ester groups will remain in the system, which may lead to deterioration of properties in high-temperature storage tests (e.g., 150°C, 1000 hours) or long-term reliability tests under high-temperature and high-humidity conditions (e.g., temperature: 85°C, humidity: 85%).

[0093] [Phenol Resins] Phenolic resins are compounds having two or more phenolic hydroxyl groups in their molecules. Examples of phenolic resins include, but are not limited to, reaction products of phenols and aldehydes, reaction products of phenols and diene compounds, reaction products of phenols and ketones, reaction products of phenols and substituted biphenyls, reaction products of phenols and substituted phenyls, reaction products of bisphenols and aldehydes, etc. Furthermore, these may be used individually or in combination of multiple types. Specific examples of the above raw materials are given below, but are not limited to these. <Phenols> Phenol, alkyl-substituted phenol, aromatic-substituted phenol, hydroquinone, resorcinol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc. <Aldehydes> Formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, furfural, etc. <Diene Compounds> Dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc. <Ketones> Acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, fluorenone, etc. <Substitutive biphenyls> 4,4'-bis(chloromethyl)-1,1'-biphenyl, 4,4'-bis(methoxymethyl)-1,1'-biphenyl, 4,4'-bis(hydroxymethyl)-1,1'-biphenyl, etc. <Substitutive phenyls> 1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene, 1,4-bis(hydroxymethyl)benzene, etc.

[0094] [Polyphenylene Ether Compounds] From the viewpoint of heat resistance and electrical properties, polyphenylene ether compounds are preferably polyphenylene ether compounds having ethylenically unsaturated bonds, and more preferably polyphenylene ether compounds having acrylic groups, methacrylic groups, or styrene structures. Commercially available products include SA-9000 (manufactured by SABIC, a polyphenylene ether compound having methacrylic groups) and OPE-2St 1200 (manufactured by Mitsubishi Gas Chemical Co., Ltd., a polyphenylene ether compound having a styrene structure). The number average molecular weight (Mn) of the polyphenylene ether compound is preferably 500 to 5000, more preferably 2000 to 5000, and even more preferably 2000 to 4000. If the number average molecular weight is less than 500, the heat resistance of the cured product tends not to be sufficient. Also, if the number average molecular weight is greater than 5000, the melt viscosity becomes high, and sufficient fluidity cannot be obtained, which tends to lead to molding defects. Furthermore, reduced reactivity leads to a longer curing time, an increase in unreacted material not incorporated into the curing system, a decrease in the glass transition temperature of the cured product, and a tendency for the heat resistance of the cured product to decrease. If the number-average molecular weight of the polyphenylene ether compound is between 500 and 5000, it is possible to exhibit excellent heat resistance and moldability while maintaining excellent dielectric properties. Specifically, the number-average molecular weight can be measured using methods such as gel permeation chromatography.

[0095] The polyphenylene ether compound may be obtained by polymerization or by redistributing a high molecular weight polyphenylene ether compound with a number average molecular weight of about 10,000 to 30,000. Alternatively, these can be used as raw materials and reacted with compounds having ethylenically unsaturated bonds, such as methacrylate chloride, acrylate chloride, and chloromethylstyrene, to impart radical polymerizability. The polyphenylene ether compound obtained by redistribution is, for example, obtained 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 redistribute it. Polyphenylene ether compounds obtained by this redistribution reaction are preferable because they have hydroxyl groups derived from phenolic compounds that contribute to curing at both ends of the molecular chain, thus maintaining even higher heat resistance, and because functional groups can be introduced to both ends of the molecular chain even after modification with a compound having ethylenically unsaturated bonds. Furthermore, polyphenylene ether compounds obtained by polymerization are preferable because they exhibit excellent fluidity.

[0096] The molecular weight of polyphenylene ether compounds can be adjusted by adjusting polymerization conditions, etc., in the case of polyphenylene ether compounds obtained by polymerization reactions. In the case of polyphenylene ether compounds obtained by redistribution reactions, the molecular weight of the resulting polyphenylene ether compound can be adjusted by adjusting the conditions of the redistribution reaction, etc. More specifically, this can be done by adjusting the amount of phenolic compound used in the redistribution reaction. That is, the higher the amount of phenolic compound used, the lower the molecular weight of the resulting polyphenylene ether compound. In this case, poly(2,6-dimethyl-1,4-phenylene ether) can be used as the high molecular weight polyphenylene ether compound that undergoes the redistribution reaction. Furthermore, the phenolic compound used in the above redistribution reaction is not particularly limited, but polyfunctional phenolic compounds having two or more phenolic hydroxyl groups in the molecule, such as bisphenol A, phenol novolac, and cresol novolac, are preferably used. These may be used individually or in combination of two or more.

[0097] 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, per 100 parts by mass of the curable resin composition. When the content of the polyphenylene ether compound is within the above range, it is preferable not only to obtain a cured product that is excellent in heat resistance and the like, but also in that the excellent dielectric properties of the polyphenylene ether compound are fully exhibited.

[0098] [Amine Resins] Amine resins are compounds having two or more amino groups in their molecule. Examples of amine resins include diaminodiphenylmethane, diaminodiphenylsulfone, isophoronediamine, naphthalenediamine, aniline novolac (reaction product of aniline and formalin), N-methylaniline novolac (reaction product of N-methylaniline and formalin), orthoethylaniline novolac (reaction product of orthoethylaniline and formalin), reaction product of 2-methylaniline and formalin, reaction product of 2,6-diisopropylaniline and formalin, reaction product of 2,6-diethylaniline and formalin, reaction product of 2-ethyl-6-ethylaniline and formalin, reaction product of 2,6-dimethylaniline and formalin, and those obtained by the reaction of aniline with xylylene chloride. Examples of aniline resins include, but are not limited to, aniline and substituted biphenyls (such as 4,4'-bis(chloromethyl)-1,1'-biphenyl and 4,4'-bis(methoxymethyl)-1,1'-biphenyl) as described in Japanese Patent Publication No. 6429862, aniline and substituted phenyls (such as 1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene and 1,4-bis(hydroxymethyl)benzene), 4,4'-(1,3-phenylenediisopropylidene)bisaniline, 4,4'-(1,4-phenylenediisopropylidene)bisaniline, aniline and diisopropenylbenzene, and dimer amines. Furthermore, these may be used individually or in combination.

[0099] [Compounds containing ethylenically unsaturated bonds] Compounds containing ethylenically unsaturated bonds are compounds that have one or more ethylenically unsaturated bonds in their molecule, which 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 the reaction product of the phenol resin and halogenated compounds containing ethylenically unsaturated bonds (chloromethylstyrene, allyl chloride, methallyl chloride, acrylate chloride, methacrylate chloride, etc.), and phenols containing ethylenically unsaturated bonds (2-allylphenol, 2-propenylphenol, 4-allylphenol, 4-propenylphenol, eugenol, isoeugenol, etc.) and halogenated compounds (1,4-bis(chloromethyl)benzene, 4,4'-bis( Reaction products of chloromethyl)biphenyl, 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-dibromobenzophenone, cyanuryl chloride, etc.; reaction products of epoxy resins or alcohols with (meth)acrylic acids (acrylic acid, methacrylic acid, etc.) and acid-modified products thereof; poly(arylene ether) polymers (HC-G0037, HC-G0024, HC-G0030, HC-G0038, all manufactured by JSR Corporation. These may contain monomer units containing pyridazine, pyrimidine, or pyrazine groups.) Reaction products of fluorenes or indenes with halogen compounds containing ethylenically unsaturated bonds (chloromethylstyrene, allyl chloride, methyl chloride, acrylate chloride, methacrylate chloride, etc.), compounds described in Japanese Patent No. 6951829, copolymers containing divinylbenzene as a constituent unit (ODV-XET(X3), ODV-XET(X4), ODV-XET(X5), all manufactured by Nippon Steel Chemical & Material Co., Ltd.), styrene, vinyltoluene, ethyl vinylbenzene Examples include, but are not limited to, benzene, vinylnaphthalene, vinylbiphenyl, vinylfluorene, divinylbenzene, divinylnaphthalene, divinylbiphenyl, divinylfluorene, BVPM (bis(vinylphenyl)methane), BVPE (bis(vinylphenyl)ethane), BVPH (bis(vinylphenyl)hexane), trivinylcyclohexane, and thermosetting cycloolefin copolymers (Mitsui Chemicals: GigaFreak, Zeon Corporation: TU-01A). These can be used individually or in combination.

[0100] [Isocyanate resin] An isocyanate resin is a compound that has two or more isocyanate groups in its molecule. Examples of isocyanate resins include, but are not limited to, aromatic diisocyanates such as p-phenylenediisocyanate, m-phenylenediisocyanate, p-xylenediisocyanate, m-xylenediisocyanate, 2,4-tollylenediisocyanate, 2,6-tollylenediisocyanate, 4,4'-diphenylmethanediisocyanate, and naphthalenediisocyanate; aliphatic or alicyclic diisocyanates such as isophorone diisocyanate, hexamethylenediisocyanate, 4,4'-dicyclohexylmethanediisocyanate, hydrogenated xylenediisocyanate, norbornene diisocyanate, and lysine diisocyanate; polyisocyanates such as one or more isocyanate monomers or isocyanate compounds obtained by trimerizing the above diisocyanate compounds; and polyisocyanates obtained by urethane reaction between the above isocyanate compounds and polyol compounds. Furthermore, these can be used individually or in combination.

[0101] [Polyamide Resins] Examples of polyamide resins include reaction products of one or more of diamines, diisocyanates, or oxazolines with dicarboxylic acids, reaction products of diamines and acid chlorides, and ring-opening polymers of lactam compounds. These may be used individually or in combination of multiple types. Specific examples of the above raw materials are given below, but the material is not limited to these.<Diamines> Ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decanediamine, undecanediamine, dodecanediamine, tridecanediamine, tetradecanediamine, pentadecanediamine, hexadecanediamine, heptadecanediamine, octadecanediamine, nonadecanediamine, eicosanediamine, 2-methyl-1,5-diaminopentane, 2-methyl 1,8-diaminooctane, dimeramine, cyclohexanediamine, bis-(4-aminocyclohexyl)methane, bis(3-methyl-4-aminocyclohexyl)methane, xylylenediamine, norbornanediamine, isophoronediamine, bisaminomethyltricyclodecane, phenylenediamine, diethyltoluenediamine, naphthalenediamine, diaminodiphenylmethane, bis(4-amino-3,5-dimethylphenyl)methane, bis(4-amino-3,5-diethylphenyl)methane 4,4'-methylenebis-o-toluidine, 4,4'-methylenebis-o-ethylaniline, 4,4'-methylenebis-2-ethyl-6-methylaniline, 4,4'-methylenebis-2,6-diisopropylaniline, 4,4-ethylenedianiline, diaminodiphenylsulfone, 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 [phenoxy)phenyl]propane, bis[4-(4-aminophenoxy)phenyl]sulfone, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-(1,3-phenylenediisopropylidene)bisaniline, 4,4'-(1,4-phenylenediisopropylidene)bisaniline, 9,9-bis(4-aminophenyl)fluorene, 2,7-diaminofluorene, aminobenzylamine, diaminobenzophenone, etc.<Diisocyanates> Benzene diisocyanate, toluene diisocyanate, 1,3-bis(isocyanatomethyl)benzene, 1,3-bis(isocyanatomethyl)cyclohexane, bis(4-isocyanatophenyl)methane, isophorone diisocyanate, 1,3-bis(2-isocyanato-2-propyl)benzene, 2,2-bis(4-isocyanatophenyl)hexafluoropropane, dicyclohexylmethane-4,4'-diisocyanate, etc. <Dicarboxylic acids> Oxalic acid, malonic acid, succicic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, undecanediic acid, dodecanediic 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, francicarboxylic acid, 4,4'-dicarboxydiphenyl ether, 4,4'-dicarboxydiphenyl sulfide, etc. <Acid Chlorides> Acetyl chloride, acrylate chloride, methacrylate chloride, malonyl chloride, succinate dichloride, diglycolyl chloride, glutarate dichloride, suberate dichloride, sebacate dichloride, adipic acid dichloride, dodecane dioyl chloride, azera oil chloride, 2,5-franzicarbonyl dichloride, phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, trimesinate chloride, bis(4-chlorocarbonylphenyl) ether, 4,4'-diphenyl dicarbonyl chloride, 4,4'-azodibenzoyl dichloride, etc. <Lactams> ε-caprolactam, ω-undecane lactam, ω-laurolactam, etc.

[0102] [Polyimide Resin] Examples of polyimide resins include, but are not limited to, the reaction products of the above-mentioned diamine and the tetracarboxylic dianhydrides exemplified below. Furthermore, these may be used individually or in combination of multiple types. <Tetracarboxylic Dianhydrides> 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 '-diphenylsulfontetracarboxylic acid dianhydride, 2,2',3,3'-biphenyltetracarboxylic acid dianhydride, methylene-4,4'-diphthalic acid dianhydride, 1,1-ethylidene-4,4'-diphthalic acid dianhydride, 2,2'-propyridene-4,4'-diphthalic acid dianhydride, 1,2-ethylene-4,4'-diphthalic acid dianhydride, 1,3-trimethylene-4,4'-diphthalic acid dianhydride, 1,4-tetramethylene-4,4'-diphthalic acid dianhydride, 1,5-pentamethylene-4,4'- Diphthalic acid dianhydride, 4,4'-oxydiphthalic acid dianhydride, thio-4,4'-diphthalic acid 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 dianhydride, 2,2-bis[3-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, bis(3,4-dicarboxyphenoxy)dimethylsilane dianhydride, 1,3-bis(3,4-Dicarboxyphenyl)-1,1,3,3-tetramethyldisiloxane dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, 2,3,6,7-anthracenetetracarboxylic acid dianhydride, 1,2,7,8-phenanthrenetetracarboxylic acid dianhydride, ethylenetetracarboxylic acid dianhydride, 1,2,3,4-butanetetracarboxylic acid dianhydride, 1, 2,3,4-cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, 3,3',4,4'-bicyclohexyltetracarboxylic dianhydride, carbonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, methylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,2-ethylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride (Bonic acid) dianhydride, 1,1-ethylidene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 2,2-propyridene-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]octo-7-ene-2,3,5,6-tetracarboxylic acid dianhydride Water compounds, rel-[1S,5R,6R]-3-oxabicyclo[3,2,1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride, ethylene glycol-bis-(3,4-dicarboxylic acid anhydride phenyl) ether, 4,4'-biphenylbis(trimellitic acid monoester anhydride), 9,9'-bis(3,4-dicarboxyphenyl)fluorene dianhydride, etc.

[0103] [Maleimide Compounds] The curable resin composition of this embodiment may contain maleimide compounds. Maleimide compounds are compounds having one or more maleimide groups in their molecule. Examples of maleimide compounds include 4,4'-diphenylmethanebismaleimide, polyphenylmethanemaleimide, m-phenylenebismaleimide, 2,2'-bis[4-(4-maleimoidphenoxy)phenyl]propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 4,4'-diphenyletherbismaleimide, 4,4'-diphenylsulfonebismaleimide, 1,3-bis(3-maleimoidphenoxy)benzene, 1,3-bis(4-maleimoidphenoxy) (Noxy)benzene), Zyloc-type maleimide compounds (anilix maleimide, manufactured by Mitsui Chemicals Fine Co., Ltd.), biphenylaralkyl-type maleimide compounds (solidified by solvent distillation under reduced pressure of a resin solution containing the maleimide compound (M2) described in Example 4 of Japanese Patent Publication No. 2009-001783), bisaminocumylbenzene-type maleimide (maleimide compound described in International Publication No. 2020 / 054601), maleimide compounds having an indan structure described in Japanese Patent No. 6629692 or International Publication No. 2020 / 217679, MATERIAL STAGE Vol. 18, No. 12 2019 "Continued Epoxy Resin CAS Number Story - Curing Agent CAS Number Memo No. 31 Bismaleimide (1)" and MATERIAL STAGE Vol. 19, No. 2. Maleimide compounds, etc., as described in "Continued Story of Epoxy Resin CAS Numbers - Memorandum on CAS Numbers for Hardeners, Part 32: Bismaleimide (2)" (2019), are examples, but are not limited to these. Furthermore, these may be used individually or in combination of multiple types.

[0104] [Cyanate Ester Resins] Cyanate ester resins are cyanate ester compounds obtained by reacting phenol resins with cyanide halides. Specific examples include, but are not limited to, dicyanatebenzene, tricyanatebenzene, dicyanatenaphthalene, dicyanatebiphenyl, 2,2'-bis(4-cyanatephenyl)propane, bis(4-cyanatephenyl)methane, bis(3,5-dimethyl-4-cyanatephenyl)methane, 2,2'-bis(3,5-dimethyl-4-cyanatephenyl)propane, 2,2'-bis(4-cyanatephenyl)ethane, 2,2'-bis(4-cyanatephenyl)hexafluoropropane, bis(4-cyanatephenyl)sulfone, bis(4-cyanatephenyl)thioether, phenol novolac cyanate, and phenol-dicyclopentadiene cocondensates in which the hydroxyl groups have been converted to cyanate groups. Furthermore, these may be used individually or in combination of multiple types. In addition, the cyanate ester compound whose synthesis method is described in Japanese Patent Publication No. 2005-264154 is particularly preferred as a cyanate ester compound because it has excellent low hygroscopicity, flame retardancy, and dielectric properties. The cyanate ester resin may also contain catalysts such as zinc naphthenate, cobalt naphthenate, copper naphthenate, lead naphthenate, zinc octoate, tin octoate, lead acetylacetonate, or dibutyltin maleate in order to trimerize the cyanate group and form a sym-triazine ring as needed.

[0105] It is preferable to use 0.0001 to 0.10 parts by mass, preferably 0.00015 to 0.0015 parts by mass, of the catalyst per 100 parts by mass of the cyanate ester resin and the curable resin composition.

[0106] [Polybutadiene and its modified products] Polybutadiene and its modified products are compounds that have polybutadiene or a structure derived from polybutadiene within their molecule. The structure derived from polybutadiene may have some or all of its unsaturated bonds converted to single bonds by hydrogenation. Examples of polybutadiene and its modified products include, but are not limited to, polybutadiene, hydroxyl-terminated polybutadiene, terminally (meth)acrylated polybutadiene, carboxylic acid-terminated polybutadiene, amine-terminated polybutadiene, and styrene-butadiene rubber. Furthermore, these may be used individually or in combination. Of these, polybutadiene or styrene-butadiene rubber is preferred from the viewpoint of dielectric properties. Examples of styrene-butadiene rubber (SBR) include RICON-100, RICON-181, RICON-184 (all manufactured by Clay Valley Corporation), and 1,2-SBS (manufactured by Nippon Soda Co., Ltd.). Examples of polybutadiene include B-1000, B-2000, and B-3000 (all manufactured by Nippon Soda Co., Ltd.). The weight-average molecular weight of polybutadiene and styrene-butadiene rubber is preferably 500 to 10000, more preferably 750 to 7500, and even more preferably 1000 to 5000. Below the lower limit of the above range, the volatility is high, making it difficult to adjust the solid content during prepreg preparation, and above the upper limit of the above range, the compatibility with other curable resins deteriorates. In general, in the case of compounds containing heteroatoms such as oxygen and nitrogen, such as bismaleimide and polymaleimide, it is difficult to ensure compatibility with low-polarity compounds such as compounds mainly composed of hydrocarbons or compounds consisting only of hydrocarbons, due to their polarity. On the other hand, because the compounds of this embodiment do not have a framework design that actively incorporates heteroatoms such as oxygen and nitrogen, they exhibit excellent compatibility with materials that have low polarity and low dielectric properties, as well as with compounds composed solely of hydrocarbons.

[0107] [Polystyrene and its modified products] Polystyrene and its modified products are polystyrene or compounds that have a structure derived from polystyrene within their molecules. Examples of polystyrene and its modified products include polystyrene, styrene-2-isopropenyl-2-oxazoline copolymer (Epocross RPS-1005, RP-61, both manufactured by Nippon Shokubai Co., Ltd.), SEP (styrene-ethylene-propylene copolymer: Septon® 1020, manufactured by Kuraray Co., Ltd.), SEPS (styrene-ethylene-propylene-styrene copolymer: Septon 2002, Septon 2004F, Septon 2005, Septon 2006, Septon 2063, Septon 2104, all manufactured by Kuraray Co., Ltd.), SEEPS (styrene-ethylene / ethylene-propylene-styrene block copolymer: Septon 4003, Septon 4044, Septon 4055, Septon 4077, Septon 4099) All manufactured by Kuraray Co., Ltd.), SEBS (styrene-ethylene-butylene-styrene block copolymer: Septon 8004, Septon 8006, Septon 8007L, all manufactured by Kuraray Co., Ltd.), SEEPS-OH (compound having hydroxyl groups at the ends of styrene-ethylene / ethylene-propylene-styrene block copolymer: Septon HG252, manufactured by Kuraray Co., Ltd.), SIS (styrene-isoprene-styrene block copolymer: Septon 5125, Septon 5127, all manufactured by Kuraray Co., Ltd.), Hydrogenated SIS (hydrogenated styrene-isoprene-styrene block copolymer: Hybrar® 7125F, Hybrar 7311F) Examples include, but are not limited to, polystyrene-isobutylene-styrene block copolymers (SIBS: SIBSTAR® 073T, SIBSTAR 102T, SIBSTAR 103T (all manufactured by Kaneka Corporation), Septon V9827 (manufactured by Kuraray Co., Ltd.)), etc. Furthermore, these may be used individually or in combination. Polystyrene and its modified products are preferable to have those without unsaturated bonds because they have higher heat resistance and are less susceptible to oxidative degradation.Furthermore, while there are no particular restrictions on the weight-average molecular weight of polystyrene and its modified products as long as it is 10,000 or more, if it is too high, the compatibility with polyphenylene ether compounds, as well as low molecular weight components with a weight-average molecular weight of about 50 to 1,000 and oligomer components with a weight-average molecular weight of about 1,000 to 5,000 deteriorates, making it difficult to ensure mixing and solvent stability. Therefore, it is preferable that the weight-average molecular weight be around 10,000 to 300,000.

[0108] [Polyethylene and Modified Products thereof] Polyethylene and modified products thereof refer to polyethylene or compounds having a structure derived from polyethylene within their molecules. Examples of polyethylene and modified products thereof include, but are not limited to, ethylene-propylene copolymers, ethylene-styrene copolymers, ethylene-propylene-ethylidene norbornene copolymers (Mitsui Chemicals, Ltd. EBT: K-8370EM, K-9330M, etc.), ethylene-propylene-vinyl norbornene copolymers (Mitsui Chemicals, Ltd. VNB-EPT: PX-006M, PX-008M, PX-009M, etc.), ethylene-vinyl alcohol copolymers, and ethylene-vinyl acetate copolymers. From the viewpoint of improving heat resistance, it is preferable to use ethylene-propylene-ethylidene norbornene copolymers and ethylene-propylene-vinyl norbornene copolymers that contain a crosslinkable structure. Furthermore, these may be used individually or in combination of multiple types. While there are no particular restrictions on the weight-average molecular weight of polyethylene and its modified products as long as it is 10,000 or more, if it is too high, the compatibility with polyphenylene ether compounds, as well as low molecular weight components with a weight-average molecular weight of about 50 to 1,000 and oligomer components with a weight-average molecular weight of about 1,000 to 5,000 deteriorates, making it difficult to ensure mixing and solvent stability. Therefore, it is preferable that the molecular weight be around 10,000 to 300,000.

[0109] [Benzoxazine Compounds] Any benzoxazine compound may be used as a compound obtained by reacting a compound having a phenolic hydroxyl group, a compound having an amino group, or a compound having an aldehyde group. The compound having a phenolic hydroxyl group is not particularly limited, but for example, the aforementioned phenolic resins, phenols (which may have substituents such as alkenyl groups or alkyl groups), and bisphenols can be used. The compound having an amino group is not particularly limited, but for example, the aforementioned amine resins, diamines, and anilines (which may have substituents such as alkenyl groups or alkyl groups) can be used. As for the aldehyde compound, for example, the aforementioned aldehydes can be used, but formaldehyde is preferred. Commercially available benzoxazine compounds may be used, including benzoxazine P-d, F-a, ALP-d (all manufactured by Shikoku Chemicals Co., Ltd.), JBZ-BA100N, JBZ-FA100N, JBZ-DP100N, JBZ-OP100N, JBZ-OP100D, JBZ-OP100I (all manufactured by JFE Chemical Corporation), and BTBz (manufactured by Nippon Materials Technology Co., Ltd.).

[0110] The curable resin composition of this embodiment is obtained by preparing the above components in predetermined proportions, pre-curing at 130 to 180°C for 30 to 500 seconds, and then post-curing at 150 to 200°C for 2 to 15 hours to allow the curing reaction to proceed sufficiently and obtain the cured product of this embodiment. Alternatively, the components of the curable resin composition can be uniformly dispersed or dissolved in a solvent, and then cured after removing the solvent.

[0111] The method for preparing the curable resin composition of this embodiment is not particularly limited, but may be done by simply uniformly mixing each component or by prepolymerization. For example, prepolymerization can be performed by heating a mixture containing the curable resin of this embodiment in the presence or absence of a curing accelerator and polymerization initiator, in the presence or absence of a solvent. Similarly, prepolymerization may be performed by adding compounds such as amine compounds, compounds having ethylenically unsaturated bonds, maleimide compounds, cyanate ester compounds, polybutadiene and its modified products, polystyrene and its modified products, inorganic fillers, and other additives. Mixing or prepolymerization of each component can be performed using, for example, an extruder, kneader, or roll in the absence of a solvent, and a reaction vessel with a stirring device can be used in the presence of a solvent.

[0112] For uniform mixing, the resin composition is kneaded using equipment such as a kneader, roll, or planetary mixer at a temperature in the range of 50 to 100°C. After pulverization, the resulting resin composition can be molded into cylindrical tablets using a molding machine such as a tablet machine, or into granular powder or powdery molded bodies. Alternatively, these compositions can be melted on a surface support and molded into sheets with a thickness of 0.05 mm to 10 mm to produce curable resin composition molded bodies. The resulting molded bodies are non-sticky at 0 to 20°C and maintain their fluidity and curability with almost no decrease even after storage at -25 to 0°C for more than a week. The resulting molded bodies can be molded into cured products using a transfer molding machine or a compression molding machine.

[0113] The curable resin composition of this embodiment can also be converted into a varnish-like composition (hereinafter simply referred to as varnish) by adding an organic solvent. The curable resin composition of this embodiment can be dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, or N-methylpyrrolidone as needed to form a varnish, which can then be impregnated into a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, or paper, and heated and dried to obtain a prepreg. The resulting prepreg can then be hot-press molded to obtain a cured product of the curable resin composition of this embodiment. In this case, the solvent used should account for 10 to 70% by weight, preferably 15 to 70% by weight, of the mixture of the curable resin composition of this embodiment and the solvent. If the composition is liquid, a cured product of the curable resin containing carbon fibers can also be obtained directly, for example, by the RTM method.

[0114] Furthermore, the curable resin composition of this embodiment can also be used as a modifier for film-type compositions. Specifically, it can be used to improve flexibility and other properties in the B-stage. Such a film-type resin composition can be obtained as a sheet-like adhesive by applying the curable resin composition of this embodiment as a varnish onto a release film, removing the solvent under heating, and then performing the B-stage process. This sheet-like adhesive can be used as an interlayer insulating layer in multilayer substrates and the like.

[0115] The curable resin composition of this embodiment can also be heated and melted to reduce viscosity and impregnate reinforcing fibers such as glass fibers, carbon fibers, polyester fibers, polyamide fibers, and alumina fibers to obtain a prepreg. Specific examples include, but are not limited to, 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, as well as inorganic fibers other than glass, and organic fibers such as poly(p-phenylene terephthalamide) (Kevlar®, manufactured by DuPont), fully aromatic polyamide, polyester, poly(p-phenylene benzoxazole), polyimide, and carbon fibers. The shape of the substrate is not particularly limited, but examples include woven fabrics, nonwoven fabrics, rovings, and chopped strand mats. As for the weaving method of the woven fabric, plain weave, twill weave, etc., are known, and these can be appropriately selected and used depending on the intended application and performance. Furthermore, glass woven fabrics that have been opened or surface-treated with silane coupling agents are preferably used. The thickness of the base material is not particularly limited, but is preferably about 0.01 to 0.4 mm. Alternatively, a prepreg can be obtained by impregnating reinforcing fibers with the above varnish and then heating and drying them.

[0116] Furthermore, laminates can also be manufactured using the above-mentioned prepregs. The laminate is not particularly limited as long as it comprises one or more prepregs, and may have any other layers. The method for manufacturing the laminate is not particularly limited and can be any generally known method as appropriate. For example, when forming a metal foil laminate, a multi-stage press, a multi-stage vacuum press, a continuous molding machine, an autoclave molding machine, etc., can be used, and a laminate can be obtained by laminating the above-mentioned prepregs together and then heating and pressing them. At this time, the heating temperature is not particularly limited, but 65 to 300°C is preferred, and 120 to 270°C is more preferred. The pressurizing pressure is not particularly limited, but if the pressurizing 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 pressurizing pressure is too low it becomes difficult to form air bubbles and the adhesion between layers is poor, so 2.0 to 5.0 MPa is preferred, and 2.5 to 4.0 MPa is more preferred. The laminate of this embodiment can be suitably used as a metal foil laminate described later by comprising a layer made of metal foil. By cutting the above prepreg into the desired shape, laminating it with copper foil or other materials as needed, and then applying pressure to the laminate using methods such as press molding, autoclave molding, or sheet winding molding while heating and curing a curable resin composition, electrical and electronic laminates (printed wiring boards) and carbon fiber reinforced materials can be obtained.

[0117] The curable resin composition of this embodiment can also be made into a resin sheet. One method for obtaining a resin sheet from the curable resin composition of this embodiment is to apply the curable resin composition onto a support film (support), and then dry it to form a resin composition layer on the support film. When using the curable resin composition of this embodiment to make a resin sheet, it is important that the film softens at the lamination temperature conditions (70°C to 140°C) in the vacuum lamination method and exhibits fluidity (resin flow) that allows for simultaneous lamination of the circuit board and resin filling of via holes or through holes present in the circuit board. It is preferable to blend the above components in such a way as to exhibit such characteristics. Furthermore, in order to ensure that the resulting resin sheet and circuit board (copper-clad laminate, etc.) exhibit consistent performance in any desired area, and to prevent phenomena such as locally different characteristic values ​​caused by phase separation, uniformity of appearance is required.

[0118] Here, the diameter of the through-holes in the circuit board is 0.1 to 0.5 mm, and the depth is 0.1 to 1.2 mm. It is preferable to be able to fill the holes with resin within this range. When laminating both sides of the circuit board, it is desirable that the through-holes be filled to about half their extent.

[0119] A specific method for manufacturing the above-mentioned resin sheet is to prepare a varnished resin composition by incorporating an organic solvent, apply the varnished resin composition to the surface of a support film, and then dry the organic solvent by heating or blowing hot air to form a resin composition layer.

[0120] The organic solvents used here preferably include ketones such as acetone, methyl ethyl ketone, and cyclohexanone; acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. It is also preferable to use the organic solvent in a proportion such that the non-volatile content is 30 to 60% by mass of the total.

[0121] Furthermore, the thickness of the formed resin composition layer must be greater than or equal to the thickness of the conductive layer of the circuit board to which the resin composition layer is laminated. Since the thickness of the conductive layer of the circuit board is in the range of 5 to 70 μm, it is preferable that the thickness of the resin composition layer be 10 to 100 μm. In addition, the resin composition layer in this embodiment may be protected by a protective film, which will be described later. By protecting it with a protective film, it is possible to prevent dirt and other debris from adhering to the surface of the resin composition layer and to prevent scratches.

[0122] The above-mentioned support film and protective film can be made of polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate, polycarbonate, polyimide, and also release paper, copper foil, aluminum foil, and other metal foils. The support film and protective film may be treated with a mat treatment, corona treatment, or release treatment. The thickness of the support film is not particularly limited, but is 10 to 150 μm, preferably in the range of 25 to 50 μm. The thickness of the protective film is preferably 1 to 40 μm.

[0123] The support film described above is peeled off after the resin composition layer is laminated to the circuit board, or after an insulating layer is formed by heat curing the resin composition layer. If the support film is peeled off after the resin composition layer constituting the resin sheet has heat cured, it is possible to prevent the adhesion of dust and other debris during the curing process. When the support film is peeled off after the resin composition layer has cured, the support film is treated with a release agent beforehand.

[0124] Furthermore, a multilayer printed circuit board can be manufactured from the resin sheet obtained as described above. For example, if the resin composition layer is protected by a protective film, the protective film is peeled off from the resin composition layer, and then the resin composition layer is laminated to one or both sides of the circuit board so that it is in direct contact with the circuit board, for example, by a vacuum lamination method. The lamination method may be batch type or continuous type using a roll. Also, if necessary, the resin sheet and circuit board may be heated (preheated) before lamination. Preferably, the lamination conditions are a pressure temperature (lamination temperature) of 70 to 140°C and a pressure of 1 to 11 kgf / cm². ２ (9.8 x 10 ４ ~107.9 x 10 ４ N / m ２ It is preferable to use this method, and it is preferable to laminate under reduced pressure of 20 mmHg (26.7 hPa) or less.

[0125] Furthermore, semiconductor devices can be manufactured using the curable resin composition of this embodiment. Examples of semiconductor devices include DIP (Dual In-Line Package), QFP (Quad Flat Package), BGA (Ball Grid Array), CSP (Chip Size Package), SOP (Small Outline Package), TSOP (Thin Small Outline Package), and TQFP (Thin Quad Flat Package).

[0126] The curable resin composition and its cured product according to this embodiment 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. Because the cured product of the curable resin composition described in this embodiment exhibits excellent heat resistance and dielectric properties, it is suitably used in electrical and electronic components such as encapsulants for semiconductor devices, encapsulants for liquid crystal display devices, encapsulants for organic EL devices, laminates (printed wiring boards, BGA (ball grid array) substrates, build-up substrates, etc.), composite materials for lightweight, high-strength structural materials such as carbon fiber reinforced plastics and glass fiber reinforced plastics, and 3D printing.

[0127] Next, the present invention will be described in more detail with reference to examples. Hereinafter, unless otherwise specified, parts refer to parts by mass. However, the present invention is not limited to these examples.

[0128] The various analytical methods used in the examples are described below. <GPC (Gel Permeation Chromatography) Analysis> Apparatus: Online degassing unit (DGU-20A), liquid delivery unit (LC-20AD), autosampler (SIL-20A), photodiode array detector (SPD-M40), column oven (CTO-20A), system controller (CBM-20A), all manufactured by Shimadzu Corporation Column: SHODEX GPC KF-601 (2), KF-602, KF-602.5, KF-603 Flow rate: 1.5 ml / min. Column temperature: 40℃ Solvent used: THF (tetrahydrofuran) Detector: Differential refractive detector (RID-20A, manufactured by Shimadzu Corporation)

[0129] <High-Performance Liquid Chromatography (HP-LC)> HP-LC: Liquid delivery unit (LC-20AB), online degasser (DGU-20A3), autosampler (SIL-20A), column oven (CTO-20A), system controller (CBM-20A), absorbance detector (SPD-M20A) (all manufactured by Shimadzu Corporation) Column: ODS-2 (manufactured by GL Sciences Co., Ltd.) Eluent: Tetrahydrofuran:Water = 3:1 (no gradient) Flow rate: 0.5 ml / min. Column temperature: 40°C Detection: PDA (Photodiode Array Detector)

[0130] < １ H-NMR measurement > • JEOL-400 (manufactured by JEOL: uses 400MHz NMR) • Number of integrated samples: 8 • Solvent: Deuterated chloroform

[0131] [Synthesis Example 1] In a flask equipped with a thermometer, condenser, and stirrer, 11.6 parts indene, 28.2 parts CMS-P (AGC Seimi Chemical Co., Ltd., mixture of 4-chloromethylstyrene and 3-chloromethylstyrene, 4-chloromethylstyrene:3-chloromethylstyrene = 1:1 (mol ratio), purity 95.59% by weight), 18.5 parts (2-bromoethyl)benzene, 80 parts dimethyl sulfoxide, and 40 parts toluene were added while purging with nitrogen. Then, 18 parts sodium hydroxide was added and the mixture was reacted at 20°C for 16 hours. 110 parts toluene was added and the organic layer was washed five times with 100 parts water. The resulting organic layer was concentrated to obtain 39 parts of curable resin (I1). In formula (1), m = 0 and the average value of n calculated from the charging ratio (n ａｖｅ ) = 2.77, in equation (a0), p = 0, q = 0, j = 1, in equation (b), l = 0, and the value α / β = 0.566 obtained by dividing the number of structures represented by equation (a0) (α) by the content of structures represented by equation (b) calculated from the input ratio. The HP-LC chart of the obtained curable resin (I1) is shown in Figure 1, and the GPC chart is shown in Figure 2. １ The 1H-NMR chart (deuterated chloroform) is shown in Figure 3. The number-average molecular weight (Mn) of the curable resin (I1) determined by GPC analysis was 344, and the weight-average molecular weight (Mw) was 351. １ A signal originating from terminal hydrogens of the vinyl group (two hydrogens per vinyl group) was observed in the 5.10–5.80 ppm range of the H-NMR chart.

[0132] [Synthesis Example 2] In a flask equipped with a thermometer, condenser, and stirrer, 11.6 parts indene, 28.2 parts CMS-14 (AGC Seimi Chemical Co., Ltd., mixture of 4-chloromethylstyrene and 3-chloromethylstyrene, 4-chloromethylstyrene:3-chloromethylstyrene = 95:5 (mol ratio), purity 96.87% by weight), 14.1 parts α-chloro-p-xylene, 80 parts dimethyl sulfoxide, and 40 parts toluene were added while purging with nitrogen. Then, 18 parts sodium hydroxide was added and the mixture was reacted at 25°C for 12 hours. 110 parts toluene was added and the organic layer was washed five times with 100 parts water. The obtained organic layer was concentrated to obtain 40 parts of curable resin (I2). In formula (1), m = 0, and the average value of n calculated from the charging ratio (n ａｖｅ ) = 2.79, in equation (a0), p = 1, R ２ =methyl group, q=0, j=0, in formula (b), l=0, the number of structures represented by formula (a0) (α) calculated from the charging ratio is divided by the content of the structure represented by formula (b) (β), resulting in α / β = 0.557. The HP-LC chart of the obtained curable resin (I2) is shown in Figure 4, and the GPC chart is shown in Figure 5. Furthermore, the obtained curable resin １ The 1H-NMR chart (deuterated chloroform) is shown in Figure 6. The number-average molecular weight (Mn) of I2, determined by GPC analysis, was 331, and the weight-average molecular weight (Mw) was 344. １ A signal originating from terminal hydrogen atoms of the vinyl group (two hydrogen atoms per vinyl group) was observed in the 5.00–5.70 ppm range of the H-NMR chart.

[0133] [Synthesis Example 3] In a flask equipped with a thermometer, condenser, and stirrer, 11.6 parts indene, 28.2 parts CMS-P (AGC Seimi Chemical Co., Ltd., mixture of 4-chloromethylstyrene and 3-chloromethylstyrene, 4-chloromethylstyrene:3-chloromethylstyrene = 1:1 (mol ratio), purity 95.59% by weight), 17.6 parts 1-chloromethylnaphthalene, 80 parts dimethyl sulfoxide, and 40 parts toluene were added while purging with nitrogen. Then, 18 parts sodium hydroxide was added and the mixture was reacted at 25°C for 12 hours. 110 parts toluene was added and the organic layer was washed five times with 100 parts water. The obtained organic layer was concentrated to obtain 43 parts of curable resin (I3). In formula (1), m = 0, and the average value of n calculated from the charging ratio (n ａｖｅ ) = 2.76, in equation (a0), p = 0, q = 1, j = 0, in equation (b), l = 0, and the value α / β = 0.564 obtained by dividing the number of structures represented by equation (a0) (α) by the content of structures represented by equation (b) calculated from the charging ratio. The HP-LC chart of the obtained curable resin (I3) is shown in Figure 7, and the GPC chart is shown in Figure 8. Furthermore, the obtained curable resin １ The 1H-NMR chart (deuterated chloroform) is shown in Figure 9. The number-average molecular weight (Mn) of I3, determined by GPC analysis, was 350, and the weight-average molecular weight (Mw) was 432. １ A signal originating from terminal hydrogen atoms of the vinyl group (two hydrogen atoms per vinyl group) was observed at 5.00–6.00 ppm in the H-NMR chart.

[0134] [Synthesis Example 4] In a flask equipped with a thermometer, condenser, and stirrer, 11.6 parts indene, 28.2 parts CMS-14 (AGC Seimi Chemical Co., Ltd., mixture of 4-chloromethylstyrene and 3-chloromethylstyrene, 4-chloromethylstyrene:3-chloromethylstyrene = 95:5 (mol ratio), purity 96.87% by weight), 17.6 parts 1-chloromethylnaphthalene, 80 parts dimethyl sulfoxide, and 40 parts toluene were added while purging with nitrogen. Then, 18 parts sodium hydroxide was added and the mixture was reacted at 25°C for 12 hours. 110 parts toluene was added and the organic layer was washed five times with 100 parts water. The resulting organic layer was concentrated to obtain 43 parts of curable resin (I4). In formula (1), m = 0 and the average value of n calculated from the charging ratio (n ａｖｅ ) = 2.79, in equation (a0), p = 0, q = 1, j = 0, in equation (b), l = 0, and the value α / β = 0.557 obtained by dividing the number of structures represented by equation (a0) (α) by the content of structures represented by equation (b) calculated from the charging ratio. The HP-LC chart of the obtained curable resin (I4) is shown in Figure 10, and the GPC chart is shown in Figure 11. Furthermore, the obtained curable resin １ The 1H-NMR chart (deuterated chloroform) is shown in Figure 12. The number-average molecular weight (Mn) of I4, determined by GPC analysis, was 338, and the weight-average molecular weight (Mw) was 363. １ A signal originating from terminal hydrogen atoms of the vinyl group (two hydrogen atoms per vinyl group) was observed at 5.00–6.00 ppm in the H-NMR chart.

[0135] [Comparative Synthesis Example 1] In a flask equipped with a thermometer, condenser, and stirrer, 11.6 parts indene, 43.5 parts CMS-P (AGC Seimi Chemical Co., Ltd., mixture of 4-chloromethylstyrene and 3-chloromethylstyrene, 4-chloromethylstyrene:3-chloromethylstyrene = 1:1 (mol ratio), purity 95.59% by weight), 80 parts dimethyl sulfoxide, and 40 parts toluene were added while purging with nitrogen. Then, 18 parts sodium hydroxide was added and the mixture was reacted at 25°C for 14 hours. 110 parts toluene was added and the organic layer was washed five times with 100 parts water. The resulting organic layer was concentrated to obtain 40 parts of curable resin (C1). In curable resin (C1), in formula (1), X is the structure represented by formula (b), m = 0, and the average value of n calculated from the charging ratio (n ａｖｅ ) = 2.72, in equation (b), l = 0, and α / β = 0 calculated from the input ratio. The HP-LC chart of the obtained curable resin (C1) is shown in Figure 13, and the GPC chart is shown in Figure 14. １ Figure 15 shows the 1H-NMR chart (deuterated chloroform). The number-average molecular weight (Mn) of C1, determined by GPC analysis, was 304, and the weight-average molecular weight (Mw) was 351. １ A signal originating from terminal hydrogen atoms of the vinyl group (two hydrogen atoms per vinyl group) was observed at 5.00–6.00 ppm in the H-NMR chart.

[0136] [Comparative Synthesis Example 2] In a flask equipped with a thermometer, condenser, and stirrer, 133 parts of methyl isobutyl ketone, 33.3 parts of fluorene, 1.9 parts of tetrabutylammonium bromide, 0.49 parts of hydroquinone, and 64 parts of 50 wt% sodium hydroxide aqueous solution were added while purging with nitrogen, and the internal temperature was raised to 60°C. Then, 71.2 parts of CMS-P (AGC Seimi Chemical Co., Ltd., a mixture of 4-chloromethylstyrene and 3-chloromethylstyrene, 4-chloromethylstyrene:3-chloromethylstyrene = 1:1 (mol ratio), purity 95.59 wt%) were added dropwise over 1 hour, and the mixture was reacted at 60°C for 9 hours. The mixture was neutralized with 41.6 parts of 35 wt% hydrochloric acid aqueous solution, and the organic layer was washed three times with 100 parts of water. Recrystallization with toluene and methanol was performed to obtain 35.6 parts of a curable resin (F2) represented by the following formula (f-2). The HP-LC chart of the obtained curable resin (F2) is shown in Figure 16. １ The 1H-NMR data (deuterated chloroform) is shown in Figure 17.

[0137]

[0138] [Examples 1-4, Comparative Examples 1-3] The curable resins (C1, F2) obtained in Synthesis Examples 1-4 (I1-I4) and Comparative Synthesis Examples 1 and 2, and OPE-2St (Mitsubishi Gas Chemical Co., Ltd., polyphenylene ether compound) were used in the amounts shown in Tables 1-3, and vacuum-press molded while sandwiched between mirror-finish copper foil (T4X: Fukuda Metal Copper Foil Co., Ltd.), and cured at 220°C for 2 hours. At this time, a 250 μm thick cushion paper with a 150 mm x 150 mm cutout in the center was used as a spacer, and a 0.1 mm thick test piece was obtained. For evaluation, the test piece was cut to the desired size using a laser cutter as needed, and the evaluation was carried out.

[0139] <Dielectric Constant Test and Dielectric Loss Tangent Test> Tests were conducted using a 10 GHz cavity resonator manufactured by AET Co., Ltd. at 25°C using the cavity resonator perturbation method. The sample size was 1.7 mm wide x 100 mm long with a thickness of 0.1 mm. The evaluation results are shown in Tables 1 and 2.

[0140]

[0141]

[0142] The results in Tables 1 and 2 confirm that the curable resin of the present invention has excellent low dielectric loss tangent.

[0143] <Coefficient of Linear Expansion (CTE)> Manufacturer: TA Instrument Equipment: TMAQ400 (manufactured by TA Instrument Co., Ltd.) Measurement mode: Tensile heating rate: 2°C / min. Measurement temperature range: 25°C to 330°C After performing the first run at the heating rate and measurement temperature range described above, the sample was cooled to 25°C. Subsequently, the measurement results in the range of 60°C to 90°C during the second run at the same heating rate and measurement temperature range were defined as the coefficient of linear expansion.

[0144]

[0145] The results in Table 3 confirm that the curable resin of the present invention exhibits excellent low dielectric loss tangent and low linear expansion characteristics.

[0146] <Curing Test> [Reference Example 1] Five parts of the curable resin (I2) obtained in Synthesis Example 2, 20 parts of NC-3000 (manufactured by Nippon Kayaku Co., Ltd., biphenyl aralkyl type epoxy resin), MDEA: 4,0.5 parts of 4'-methylenebis(2-ethyl-6-methylaniline) (manufactured by Tokyo Chemical Industry Co., Ltd., amine compound), 1 part of DICY: dicyandiamide (manufactured by Tokyo Chemical Industry Co., Ltd., amide compound), 0.5 parts of KAYAHARD MCD (manufactured by Nippon Kayaku Co., Ltd., acid anhydride compound), KAYAHARD 0.5 parts of GPH-65 (manufactured by Nippon Kayaku Co., Ltd., biphenylaralkyl type phenol resin), 0.5 parts of Unifiner W-575 (manufactured by Unitika Corporation, activated ester resin), 0.5 parts of G4-142MHR (manufactured by Nippon Kayaku Co., Ltd., carboxylic acid compound), 2.5 parts of MIR-3000-70MT (manufactured by Nippon Kayaku Co., Ltd., maleimide compound), 2.5 parts of MIZ-001 (manufactured by Nippon Kayaku Co., Ltd., maleimide compound), 0.5 parts of Phenylmaleimide (manufactured by Tokyo Chemical Industry Co., Ltd., maleimide compound), 0.5 parts of SYTESTER TA (manufactured by Mitsubishi Gas Chemical Company, bisphenol A type cyanate resin), OPE-2st 60 parts of 2200 (a polyphenylene ether compound manufactured by Mitsubishi Gas Chemical Co., Ltd.), 3 parts of the compound described in Example 10 of Japanese Patent No. 6951829 (a compound having an ethylenically unsaturated bond), and KAYARAD 1 part R-684 (manufactured by Nippon Kayaku Co., Ltd., compound having an ethylenically unsaturated bond), 0.5 parts acenaphthylene (manufactured by Tokyo Chemical Industry Co., Ltd., compound having an ethylenically unsaturated bond), 1 part polyimide compound obtained by the method described in WO2023 / 013224A1, 1 part TAIC: triallyl isocyanurate (manufactured by Mitsubishi Chemical Corporation, allyl compound), 1 part Septon 2104 (manufactured by Kuraray Co., Ltd., modified polystyrene), 1 part P-d type benzoxazine (manufactured by Shikoku Chemicals Co., Ltd., benzoxazine compound), 0.5 parts 2E4MZ: 2-ethyl-4-methylimidazole (manufactured by Shikoku Chemicals Co., Ltd., curing accelerator), 0.5 parts TPP: triphenylphosphine (manufactured by Hokko Chemical Co., Ltd., curing accelerator), 0.1 parts Octop Zn (manufactured by Hope Pharmaceutical Co., Ltd., curing accelerator), Sun-Aid A cured product was obtained by mixing 0.1 parts of SI-B5 (manufactured by Sanshin Chemical Co., Ltd., curing accelerator), 1 part of DCP: dicumyl peroxide (manufactured by Kayaku Nurion Co., Ltd., polymerization initiator), 99.2 parts of toluene as a solvent, and 49.6 parts of tetrahydrofuran, and heating under a nitrogen atmosphere at 110°C for 10 minutes and then at 220°C for 1 hour.

[0147] [Reference Example 2] 5 parts of the curable resin (I2) obtained in Synthesis Example 2, 50 parts of NC-3000 (manufactured by Nippon Kayaku Co., Ltd., biphenyl aralkyl type epoxy resin), 10 parts of MIZ-001 (manufactured by Nippon Kayaku Co., Ltd., maleimide compound), 5 parts of the compound described in Example 10 of Japanese Patent No. 6951829 (manufactured by Nippon Kayaku Co., Ltd., compound having an ethylenically unsaturated bond), 45 parts of KAYARAD R-684 (manufactured by Nippon Kayaku Co., Ltd., compound having an ethylenically unsaturated bond), 1 part of Irgacure OXE-04 (manufactured by BASF, polymerization initiator), Irgacure BASF 290 (polymerization initiator) was added in a 1:1 ratio and coated onto a PET film to a thickness of 100 μm. Another PET film was then attached to the side not in contact with the film, and the mixture was heated under a high-pressure mercury lamp (365 nm) at a concentration of 3000 mJ / cm². ２ By irradiating it with ultraviolet light, a cured product could be obtained.

[0148] [Reference Example 3] Five parts of the curable resin (I4) obtained in Synthesis Example 4, 20 parts of NC-3000 (manufactured by Nippon Kayaku Co., Ltd., biphenyl aralkyl type epoxy resin), MDEA: 4,0.5 parts of 4'-methylenebis(2-ethyl-6-methylaniline) (manufactured by Tokyo Chemical Industry Co., Ltd., amine compound), 1 part of DICY: dicyandiamide (manufactured by Tokyo Chemical Industry Co., Ltd., amide compound), 0.5 parts of KAYAHARD MCD (manufactured by Nippon Kayaku Co., Ltd., acid anhydride compound), KAYAHARD 0.5 parts of GPH-65 (manufactured by Nippon Kayaku Co., Ltd., biphenylaralkyl type phenol resin), 0.5 parts of Unifiner W-575 (manufactured by Unitika Corporation, activated ester resin), 0.5 parts of G4-142MHR (manufactured by Nippon Kayaku Co., Ltd., carboxylic acid compound), 2.5 parts of MIR-3000-70MT (manufactured by Nippon Kayaku Co., Ltd., maleimide compound), 2.5 parts of MIZ-001 (manufactured by Nippon Kayaku Co., Ltd., maleimide compound), 0.5 parts of Phenylmaleimide (manufactured by Tokyo Chemical Industry Co., Ltd., maleimide compound), 0.5 parts of SYTESTER TA (manufactured by Mitsubishi Gas Chemical Company, bisphenol A type cyanate resin), OPE-2st 60 parts of 2200 (a polyphenylene ether compound manufactured by Mitsubishi Gas Chemical Co., Ltd.), 3 parts of the compound described in Example 10 of Japanese Patent No. 6951829 (a compound having an ethylenically unsaturated bond), and KAYARAD 1 part R-684 (manufactured by Nippon Kayaku Co., Ltd., compound having an ethylenically unsaturated bond), 0.5 parts acenaphthylene (manufactured by Tokyo Chemical Industry Co., Ltd., compound having an ethylenically unsaturated bond), 1 part polyimide compound obtained by the method described in WO2023 / 013224A1, 1 part TAIC: triallyl isocyanurate (manufactured by Mitsubishi Chemical Corporation, allyl compound), 1 part Septon 2104 (manufactured by Kuraray Co., Ltd., modified polystyrene), 1 part P-d type benzoxazine (manufactured by Shikoku Chemicals Co., Ltd., benzoxazine compound), 0.5 parts 2E4MZ: 2-ethyl-4-methylimidazole (manufactured by Shikoku Chemicals Co., Ltd., curing accelerator), 0.5 parts TPP: triphenylphosphine (manufactured by Hokko Chemical Co., Ltd., curing accelerator), 0.1 parts Octop Zn (manufactured by Hope Pharmaceutical Co., Ltd., curing accelerator), Sun-Aid A cured product was obtained by mixing 0.1 parts of SI-B5 (manufactured by Sanshin Chemical Co., Ltd., curing accelerator), 1 part of DCP: dicumyl peroxide (manufactured by Kayaku Nurion Co., Ltd., polymerization initiator), 99.2 parts of toluene as a solvent, and 49.6 parts of tetrahydrofuran, and heating under a nitrogen atmosphere at 110°C for 10 minutes and then at 220°C for 1 hour.

[0149] [Reference Example 4] 5 parts of the curable resin (I4) obtained in Synthesis Example 4, 50 parts of NC-3000 (manufactured by Nippon Kayaku Co., Ltd., biphenyl aralkyl type epoxy resin), 10 parts of MIZ-001 (manufactured by Nippon Kayaku Co., Ltd., maleimide compound), 5 parts of the compound described in Example 10 of Japanese Patent No. 6951829 (manufactured by Nippon Kayaku Co., Ltd., compound having an ethylenically unsaturated bond), 45 parts of KAYARAD R-684 (manufactured by Nippon Kayaku Co., Ltd., compound having an ethylenically unsaturated bond), 1 part of Irgacure OXE-04 (manufactured by BASF, polymerization initiator), Irgacure BASF 290 (polymerization initiator) was added in a 1:1 ratio and coated onto a PET film to a thickness of 100 μm. Another PET film was then attached to the side not in contact with the film, and the mixture was heated under a high-pressure mercury lamp (365 nm) at a concentration of 3000 mJ / cm². ２ By irradiating it with ultraviolet light, a cured product could be obtained.

[0150] The curable resin of the present invention is suitably used in electrical and electronic components such as semiconductor encapsulants, printed circuit boards, build-up laminates, and optical waveguide devices.

[0151] [Note] As described above, this embodiment includes the following disclosures: [1] A curable resin represented by the following formula (1). In formula (1), R １ Each of these independently represents a saturated hydrocarbon group having 1 to 5 carbon atoms. Each of these independently represents a structure expressed by the following formula (a0). m is an integer from 0 to 4. n is an integer from 0 to 3, and n is the average value of n. ａｖｅ is 0.1 ≤ n ａｖｅ The value is ≤ 3. In formula (a0), * represents the bonding position of the indene structure to the five-membered ring in formula (1). ２ Each of these independently represents a saturated hydrocarbon group having 1 to 5 carbon atoms. q represents an integer from 0 to 3. When q is 0, p is an integer from 0 to 5; when q is 1, p is an integer from 0 to 7; when q is 2, p is an integer from 0 to 9; and when q is 3, p is an integer from 0 to 11. j is an integer of 0 or 1.

[0152] The curable resin may contain molecules having both the structure represented by formula (a0) and the structure represented by the following formula (b). In formula (b), * represents the bonding position of the indene structure to the five-membered ring in formula (1). ３ Each of these independently represents a hydrocarbon group with 1 to 5 carbon atoms. l is an integer from 0 to 4.

[0153] [2] A curable resin represented by the following formula (1), comprising a molecule having both the structure represented by the following formula (a0) and the structure represented by the following formula (b). In formula (1), R １ Each of these independently represents a saturated hydrocarbon group having 1 to 5 carbon atoms. Each of these independently represents a structure represented by the following formula (a0) or the following formula (b). m is an integer from 0 to 4. n is an integer from 0 to 3, and n is the average value of n. ａｖｅ is 0.1 ≤ n ａｖｅ The value is ≤ 3. In formula (a0), * represents the bonding position of the indene structure to the five-membered ring in formula (1). ２ Each of these independently represents a saturated hydrocarbon group having 1 to 5 carbon atoms. q represents an integer from 0 to 3. When q is 0, p is an integer from 0 to 5; when q is 1, p is an integer from 0 to 7; when q is 2, p is an integer from 0 to 9; and when q is 3, p is an integer from 0 to 11. j is an integer of 0 or 1. In formula (b), * represents the bonding position of the indene structure to the five-membered ring in formula (1). ３ Each of these independently represents a hydrocarbon group having 1 to 5 carbon atoms. l is an integer from 0 to 4. [3] The curable resin according to [1] or [2], wherein formula (a0) is represented by formula (a). In formula (a), * represents the bonding position of the indene structure to the five-membered ring in formula (1). ２ Each of these independently represents a saturated hydrocarbon group having 1 to 5 carbon atoms. q represents an integer from 0 to 3. When q is 0, p is an integer from 0 to 5; when q is 1, p is an integer from 0 to 7; when q is 2, p is an integer from 0 to 9; and when q is 3, p is an integer from 0 to 11. j is an integer of 0 or 1.

[0154] [4] The curable resin according to [3], wherein formula (a) is represented by formula (a1) or formula (a2). In formulas (a1) and (a2), * represents the bonding position of the indene structure in formula (1) to the five-membered ring. ２ Each of these independently represents a saturated hydrocarbon group having 1 to 5 carbon atoms. p is an integer from 0 to 5.

[0155] [5] The curable resin according to [3], wherein formula (a) is represented by formula (a3). In formula (a3), * represents the bonding position of the indene structure to the five-membered ring in formula (1). ２ Each of these independently represents a saturated hydrocarbon group having 1 to 5 carbon atoms. q is an integer from 1 to 3. When q is 1, p is an integer from 0 to 7; when q is 2, p is from 0 to 9; and when q is 3, p is from 0 to 11.

[0156] [6] A curable resin obtained by reacting a compound represented by the following formula (A0) with a compound represented by the following formula (C). In formula (A0), R ２ Each of these independently represents a saturated hydrocarbon group with 1 to 5 carbon atoms. q represents an integer from 0 to 3. When q is 0, p is an integer from 0 to 5; when q is 1, p is an integer from 0 to 7; when q is 2, p is from 0 to 9; and when q is 3, p is from 0 to 11. j is an integer of 0 or 1, and Y represents a halogen atom. In formula (C), R １ Each of these independently represents a saturated hydrocarbon group with 1 to 5 carbon atoms. m is an integer from 0 to 4.

[0157] The curable resin may be obtained by reacting the compound represented by formula (A0) and the compound represented by formula (C) with the compound represented by formula (B) shown below. In equation (B), there are multiple R ３ Each of these independently represents a hydrocarbon group with 1 to 5 carbon atoms. l is an integer from 0 to 4. Y represents a halogen atom.

[0158] [7] A curable resin obtained by reacting a compound represented by the following formula (A0), a compound represented by the following formula (B), and a compound represented by the following formula (C). In formula (A0), R ２Each of these independently represents a saturated hydrocarbon group with 1 to 5 carbon atoms. q represents an integer from 0 to 3. When q is 0, p is an integer from 0 to 5; when q is 1, p is an integer from 0 to 7; when q is 2, p is from 0 to 9; and when q is 3, p is from 0 to 11. j is an integer of 0 or 1, and Y represents a halogen atom. In formula (B), R ３ Each of these independently represents a hydrocarbon group with 1 to 5 carbon atoms. l is an integer from 0 to 4. Y represents a halogen atom. In formula (C), R １ Each of these independently represents a saturated hydrocarbon group with 1 to 5 carbon atoms. m is an integer from 0 to 4.

[0159] [8] The curable resin according to [6] or [7], wherein formula (A0) is represented by formula (A). In formula (A), R ２ Each of these independently represents a saturated hydrocarbon group with 1 to 5 carbon atoms. q represents an integer from 0 to 3. When q is 0, p is an integer from 0 to 5; when q is 1, p is an integer from 0 to 7; when q is 2, p is from 0 to 9; and when q is 3, p is from 0 to 11. j is an integer of 0 or 1, and Y represents a halogen atom.

[0160] [9] The curable resin according to [8], wherein formula (A) is represented by formula (A1) or formula (A2). In formulas (A1) and (A2), R ２ Each of these independently represents a saturated hydrocarbon group with 1 to 5 carbon atoms. p is an integer from 0 to 5, and Y represents a halogen atom.

[0161]

[10] The curable resin according to [8], wherein formula (A) is represented by formula (A3). In formula (A3), R ２ Each of these independently represents a saturated hydrocarbon group having 1 to 5 carbon atoms. q is an integer from 1 to 3. When q is 1, p is an integer from 0 to 7; when q is 2, p is from 0 to 9; and when q is 3, p is from 0 to 11.

[0162]

[11] A curable resin composition containing the curable resin described in any one of [1] to

[10] .

[0163]

[12] The curable resin composition according to

[11] further comprising one or more of the following: a curing accelerator, a polymerization initiator, an epoxy resin, an active ester compound, a phenol resin, a polyphenylene ether compound, an amine resin, a compound having an ethylenically unsaturated bond, an isocyanate resin, a polyamide resin, a maleimide compound, a cyanate ester resin, a polyimide resin, a polybutadiene and a modified thereof, polystyrene and a modified thereof, polyethylene and a modified thereof, and a benzoxazine compound.

[0164]

[13] A cured product obtained by curing any one of the curable resins described in [1] to

[10] .

[0165]

[14] A cured product obtained by curing the curable resin composition described in

[11] or

[12] .

[0166]

[15] A method for producing a curable resin, comprising reacting a compound represented by the following formula (A0) with a compound represented by the following formula (C) in an aprotic polar solvent in the presence of a basic catalyst. In formula (A0), R ２ Each of these independently represents a saturated hydrocarbon group with 1 to 5 carbon atoms. q represents an integer from 0 to 3. When q is 0, p is an integer from 0 to 5; when q is 1, p is an integer from 0 to 7; when q is 2, p is from 0 to 9; and when q is 3, p is from 0 to 11. j is an integer of 0 or 1, and Y represents a halogen atom. In formula (C), R １ Each of these independently represents a saturated hydrocarbon group with 1 to 5 carbon atoms. m is an integer from 0 to 4.

[0167] The method for producing the curable resin may also be a method for producing a curable resin in which a compound represented by formula (A0), a compound represented by formula (C), and a compound represented by formula (B) below are reacted in an aprotic polar solvent in the presence of a basic catalyst to obtain a curable resin.

[0168] In equation (B), there are multiple R ３ Each of these independently represents a hydrocarbon group with 1 to 5 carbon atoms. l is an integer from 0 to 4. Y represents a halogen atom.

[0169]

[16] A method for producing a curable resin obtained by reacting a compound represented by the following formula (A0), a compound represented by the following formula (B), and a compound represented by the following formula (C) in an aprotic polar solvent in the presence of a basic catalyst. In formula (A0), R ２ each independently represents a saturated hydrocarbon group having 1 to 5 carbon atoms. q represents an integer of 0 to 3. p when q is 0 is an integer of 0 to 5, p when q is 1 is an integer of 0 to 7, p when q is 2 is 0 to 9, and p when q is 3 is 0 to 11. j is an integer of 0 or 1, and Y represents a halogen atom. In formula (B), R ３ each independently represents a hydrocarbon group having 1 to 5 carbon atoms. l is an integer of 0 to 4. Y represents a halogen atom. In formula (C), R １ each independently represents a saturated hydrocarbon group having 1 to 5 carbon atoms. m is an integer of 0 to 4.

[0170]

[17] The method for producing a curable resin according to

[15] or

[16] , wherein the formula (A0) is represented by the formula (A). In formula (A), R ２ each independently represents a saturated hydrocarbon group having 1 to 5 carbon atoms. q represents an integer of 0 to 3. p when q is 0 is an integer of 0 to 5, p when q is 1 is an integer of 0 to 7, p when q is 2 is 0 to 9, and p when q is 3 is 0 to 11. j is an integer of 0 or 1, and Y represents a halogen atom.

[0171]

[18] The method for producing a curable resin according to

[17] , wherein the formula (A) is represented by the formula (A1) or the formula (A2). In formulas (A1) and (A2), * represents the bonding position to the 5-membered ring of the indene structure of formula (1). R ２ each independently represents a saturated hydrocarbon group having 1 to 5 carbon atoms. p is an integer of 0 to 5, and Y represents a halogen atom.

[0172]

[19] The method for producing a curable resin according to

[17] , wherein the formula (A) is represented by the formula (A3). In formula (A3), R ２Each of these independently represents a saturated hydrocarbon group having 1 to 5 carbon atoms. q is an integer from 1 to 3. When q is 1, p is an integer from 0 to 7; when q is 2, p is from 0 to 9; and when q is 3, p is from 0 to 11.

Claims

1. A curable resin represented by the following formula (1). In formula (1), R １ Each of these independently represents a saturated hydrocarbon group having 1 to 5 carbon atoms. Each of these independently represents a structure expressed by the following formula (a0). m is an integer from 0 to 4. n is an integer from 0 to 3, and n is the average value of n. ａｖｅ is 0.1 ≤ n ａｖｅ The value is ≤ 3. In formula (a0), * represents the bonding position of the indene structure to the five-membered ring in formula (1). ２ Each of these independently represents a saturated hydrocarbon group having 1 to 5 carbon atoms. q represents an integer from 0 to 3. When q is 0, p is an integer from 0 to 5; when q is 1, p is an integer from 0 to 7; when q is 2, p is an integer from 0 to 9; and when q is 3, p is an integer from 0 to 11. j is an integer of 0 or 1.

2. A curable resin represented by the following formula (1), the curable resin containing a molecule having both a structure represented by the following formula (a0) and a structure represented by the following formula (b). In formula (1), R １ each independently represents a saturated hydrocarbon group having 1 to 5 carbon atoms. X each independently represents a structure represented by the following formula (a0) or a structure represented by the following formula (b). m is an integer of 0 to 4. n is an integer of 0 to 3, and the average value n ａｖｅ is such that 0.1 ≤ n ａｖｅ ≤ 3. In formula (a0), * represents the bonding position to the 5-membered ring of the indene structure in formula (1). R ２ each independently represents a saturated hydrocarbon group having 1 to 5 carbon atoms. q represents an integer of 0 to 3. p when q is 0 is an integer of 0 to 5, p when q is 1 is an integer of 0 to 7, p when q is 2 is 0 to 9, and p when q is 3 is 0 to 11. j is an integer of 0 or 1. In formula (b), * represents the bonding position to the 5-membered ring of the indene structure in formula (1). R ３ each independently represents a hydrocarbon group having 1 to 5 carbon atoms. l is an integer of 0 to 4.

3. The curable resin according to claim 1 or 2, wherein formula (a0) is represented by formula (a). In formula (a), * represents the bonding position of the indene structure to the five-membered ring in formula (1). ２ Each of these independently represents a saturated hydrocarbon group having 1 to 5 carbon atoms. q represents an integer from 0 to 3. When q is 0, p is an integer from 0 to 5; when q is 1, p is an integer from 0 to 7; when q is 2, p is an integer from 0 to 9; and when q is 3, p is an integer from 0 to 11. j is an integer of 0 or 1.

4. The curable resin according to claim 3, wherein formula (a) is represented by formula (a1) or formula (a2). In formulas (a1) and (a2), * represents the bonding position of the indene structure in formula (1) to the five-membered ring. ２ Each of these independently represents a saturated hydrocarbon group having 1 to 5 carbon atoms. p is an integer from 0 to 5.

5. The curable resin according to claim 3, wherein formula (a) is represented by formula (a3). In formula (a3), * represents the bonding position of the indene structure to the five-membered ring in formula (1). ２ Each of these independently represents a saturated hydrocarbon group having 1 to 5 carbon atoms. q is an integer from 1 to 3. When q is 1, p is an integer from 0 to 7; when q is 2, p is from 0 to 9; and when q is 3, p is from 0 to 11.

6. A curable resin obtained by reacting a compound represented by the following formula (A0) with a compound represented by the following formula (C). In formula (A0), R ２ Each of these independently represents a saturated hydrocarbon group with 1 to 5 carbon atoms. q represents an integer from 0 to 3. When q is 0, p is an integer from 0 to 5; when q is 1, p is an integer from 0 to 7; when q is 2, p is from 0 to 9; and when q is 3, p is from 0 to 11. j is an integer of 0 or 1, and Y represents a halogen atom. In formula (C), R １ Each of these independently represents a saturated hydrocarbon group with 1 to 5 carbon atoms. m is an integer from 0 to 4.

7. A curable resin obtained by reacting a compound represented by the following formula (A0), a compound represented by the following formula (B), and a compound represented by the following formula (C). In formula (A0), R ２ Each of these independently represents a saturated hydrocarbon group with 1 to 5 carbon atoms. q represents an integer from 0 to 3. When q is 0, p is an integer from 0 to 5; when q is 1, p is an integer from 0 to 7; when q is 2, p is from 0 to 9; and when q is 3, p is from 0 to 11. j is an integer of 0 or 1, and Y represents a halogen atom. In formula (B), R ３ Each of these independently represents a hydrocarbon group with 1 to 5 carbon atoms. l is an integer from 0 to 4. Y represents a halogen atom. In formula (C), R １ Each of these independently represents a saturated hydrocarbon group with 1 to 5 carbon atoms. m is an integer from 0 to 4.

8. The curable resin according to claim 6 or 7, wherein formula (A0) is represented by formula (A). In formula (A), R ２ Each of these independently represents a saturated hydrocarbon group with 1 to 5 carbon atoms. q represents an integer from 0 to 3. When q is 0, p is an integer from 0 to 5; when q is 1, p is an integer from 0 to 7; when q is 2, p is from 0 to 9; and when q is 3, p is from 0 to 11. j is an integer of 0 or 1, and Y represents a halogen atom.

9. The curable resin according to claim 8, wherein formula (A) is represented by formula (A1) or formula (A2). In formulas (A1) and (A2), R ２ Each of these independently represents a saturated hydrocarbon group with 1 to 5 carbon atoms. p is an integer from 0 to 5, and Y represents a halogen atom.

10. The curable resin according to claim 8, wherein formula (A) is represented by formula (A3). In formula (A3), R ２ Each of these independently represents a saturated hydrocarbon group having 1 to 5 carbon atoms. q is an integer from 1 to 3. When q is 1, p is an integer from 0 to 7; when q is 2, p is from 0 to 9; and when q is 3, p is from 0 to 11.

11. A curable resin composition containing the curable resin according to any one of claims 1 to 10.

12. The curable resin composition according to claim 11, further comprising one or more of the following: a curing accelerator, a polymerization initiator, an epoxy resin, an active ester compound, a phenol resin, a polyphenylene ether compound, an amine resin, a compound having an ethylenically unsaturated bond, an isocyanate resin, a polyamide resin, a maleimide compound, a cyanate ester resin, a polyimide resin, a polybutadiene and a modified thereof, polystyrene and a modified thereof, polyethylene and a modified thereof, and a benzoxazine compound.

13. A cured product obtained by curing a curable resin according to any one of claims 1 to 10.

14. A cured product obtained by curing the curable resin composition according to claim 11 or claim 12.

15. A method for producing a curable resin, comprising reacting a compound represented by the following formula (A0) with a compound represented by the following formula (C) in an aprotic polar solvent in the presence of a basic catalyst. In formula (A0), R ２ Each of these independently represents a saturated hydrocarbon group with 1 to 5 carbon atoms. q represents an integer from 0 to 3. When q is 0, p is an integer from 0 to 5; when q is 1, p is an integer from 0 to 7; when q is 2, p is from 0 to 9; and when q is 3, p is from 0 to 11. j is an integer of 0 or 1, and Y represents a halogen atom. In formula (C), R １ Each of these independently represents a saturated hydrocarbon group with 1 to 5 carbon atoms. m is an integer from 0 to 4.

16. A method for producing a curable resin obtained by reacting a compound represented by the following formula (A0), a compound represented by the following formula (B), and a compound represented by the following formula (C) in an aprotic polar solvent in the presence of a basic catalyst. In formula (A0), R ２ Each of these independently represents a saturated hydrocarbon group with 1 to 5 carbon atoms. q represents an integer from 0 to 3. When q is 0, p is an integer from 0 to 5; when q is 1, p is an integer from 0 to 7; when q is 2, p is from 0 to 9; and when q is 3, p is from 0 to 11. j is an integer of 0 or 1, and Y represents a halogen atom. In formula (B), R ３ Each of these independently represents a hydrocarbon group with 1 to 5 carbon atoms. l is an integer from 0 to 4. Y represents a halogen atom. In formula (C), R １ Each of these independently represents a saturated hydrocarbon group with 1 to 5 carbon atoms. m is an integer from 0 to 4.

17. A method for producing a curable resin according to claim 15 or 16, wherein formula (A0) is represented by formula (A). In formula (A), R ２ Each of these independently represents a saturated hydrocarbon group with 1 to 5 carbon atoms. q represents an integer from 0 to 3. When q is 0, p is an integer from 0 to 5; when q is 1, p is an integer from 0 to 7; when q is 2, p is from 0 to 9; and when q is 3, p is from 0 to 11. j is an integer of 0 or 1, and Y represents a halogen atom.

18. The method for producing a curable resin according to claim 17, wherein formula (A) is represented by formula (A1) or formula (A2). In formulas (A1) and (A2), * represents the bonding position of the indene structure in formula (1) to the five-membered ring. ２ Each of these independently represents a saturated hydrocarbon group with 1 to 5 carbon atoms. p is an integer from 0 to 5, and Y represents a halogen atom.

19. A method for producing a curable resin according to claim 17, wherein formula (A) is represented by formula (A3). In formula (A3), R ２ Each of these independently represents a saturated hydrocarbon group having 1 to 5 carbon atoms. q is an integer from 1 to 3. When q is 1, p is an integer from 0 to 7; when q is 2, p is from 0 to 9; and when q is 3, p is from 0 to 11.

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