Curable resin, curable resin composition, cured product, prepreg, circuit board, build-up film, semiconductor sealing material, and semiconductor device

Abstract

To provide a curable resin composition which gives a cured product simultaneously satisfying low dielectric characteristics (low dielectric constant and low dielectric loss tangent), good dielectric characteristics after moisture absorption, high adhesion to a copper foil, and high heat resistance.SOLUTION: A curable resin contains a structural unit represented by formula (1), at least one of a structural unit represented by formula (2) and a structural unit represented by formula (3), and a terminal (meth)acryloyl group.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a curable resin, a curable resin composition containing the curable resin, and a cured product obtained from the curable resin composition.The present invention also relates to a prepreg, a circuit board, a build-up film, a semiconductor encapsulant, and a semiconductor device. [Background technology]

[0002] With the recent increase in the volume of information and communication, information and communication in the high frequency band has become more prevalent. In order to achieve better electrical properties, particularly to reduce transmission loss in the high frequency band, there is a demand for electrical insulating materials that have low dielectric properties (low dielectric constant and low dielectric dissipation factor), excellent dielectric properties after moisture absorption, and high adhesion to low-roughness copper foil.

[0003] Furthermore, printed circuit boards and electronic components that use these electrical insulating materials are exposed to high-temperature solder reflow during assembly, so heat resistance is required, and materials with a high glass transition temperature are required. In particular, the recent trend toward the use of lead-free solder with a high melting point due to environmental concerns has led to stricter heat resistance requirements.

[0004] In response to these demands, various vinylbenzyl ether-based thermosetting resins have been proposed, and attempts to improve the resin structure by introducing an indane skeleton into the resin structure have been known (Patent Document 1). For resins into which an indane skeleton has been introduced, a technique has also been proposed in which the end is made into a (meth)acryloyl group, thereby improving heat resistance and low dielectric properties (Patent Document 2). On the other hand, Noryl (trademark) SA9000 resin is commercially available from Sabic as a thermosetting resin having a (meth)acryloyl group at its terminal.

[0005] However, these thermosetting resins do not provide cured products that simultaneously satisfy low dielectric properties (low dielectric constant and low dielectric dissipation factor), good dielectric properties after moisture absorption, high adhesion to copper foil, and high heat resistance, and further improvement in properties has been desired. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 6-172242 [Patent Document 2] International Publication No. 2021 / 205806 Summary of the Invention [Problem to be solved by the invention]

[0007] Therefore, an object of the present invention is to provide a curable resin that provides a cured product that simultaneously satisfies low dielectric properties (low dielectric constant and low dielectric dissipation factor), good dielectric properties after moisture absorption, high adhesion to copper foil (high peel strength), and high heat resistance. [Means for solving the problem]

[0008] Therefore, the present inventors conducted extensive research to solve the above problems and found that a curable resin having both a structural unit having an indane skeleton and a specific structural unit can provide a cured product that simultaneously satisfies low dielectric properties (low dielectric constant and low dielectric dissipation factor), good dielectric properties after moisture absorption, high adhesion to copper foil (high peel strength), and high heat resistance, thereby completing the present invention.

[0009] [1] A structural unit represented by the following formula (1): At least one of a structural unit represented by the following formula (2) and a structural unit represented by the following formula (3), a terminal (meth)acryloyl group; A curable resin containing [ka] (In formula (1), Each Ra is independently an alkyl group, an aryl group, an aralkyl group, or a cycloalkyl group having 1 to 12 carbon atoms; each k is independently an integer of 0 to 4; Rb's each independently represent an alkyl group, an aryl group, an aralkyl group, or a cycloalkyl group having 1 to 12 carbon atoms; l1's each independently represent an integer of 0 to 4; and l2's each independently represent an integer of 0 to 3. n is the average number of repeating units and is a number from 0.5 to 20; m's each independently represent an integer of 0 to 2, * is a bond.) [ka] (In formula (2), * represents a bond.) [ka] (In formula (3), Rc's each independently represent an alkyl group, an aryl group, an aralkyl group, or a cycloalkyl group having 1 to 12 carbon atoms, and p represents an integer of 0 to 4. * is a bond.) [2] The curable resin according to [1], further comprising at least one of a structural unit represented by the following formula (4) and a structural unit represented by the following formula (5): [ka] (In formula (4), Rd's each independently represent an alkyl group, an aryl group, an aralkyl group, or a cycloalkyl group having 1 to 12 carbon atoms, and when q is 2 or greater, two adjacent Rd's may be joined together to form a ring, and q is an integer of 0 to 5; * is a bond.) [ka] (In formula (5), Re is a single bond, —O—, —S—, —S(═O)—, —S(═O)2-, —C(═O)—, or a hydrocarbon group which may have a substituent; Ar1 is independently [ka] or [ka] and Rf's each independently represent an alkyl group, an aryl group, an aralkyl group, or a cycloalkyl group having 1 to 12 carbon atoms, and r represents an integer of 0 to 4. Rg's each independently represent an alkyl group, an aryl group, an aralkyl group, or a cycloalkyl group having 1 to 12 carbon atoms, and s represents an integer of 0 to 6. Ar2 is independently [ka] or [ka] and Rh each independently represents an alkyl group, an aryl group, an aralkyl group, or a cycloalkyl group having 1 to 12 carbon atoms; t represents an integer of 0 to 3; Ri each independently represents an alkyl group, an aryl group, an aralkyl group, or a cycloalkyl group having 1 to 12 carbon atoms, and u represents an integer of 0 to 5; n5 is the average number of repeating units and is a number from 0 to 20; * is a bond.) [3] The curable resin according to [1] or [2], wherein the structural unit represented by the formula (1) is a structural unit represented by the following formula (1-1): [ka] (In formula (1-1), R1 and R2 each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, or a cycloalkyl group; n1 is the average number of repeating units and is a value of 0.5 to 20; * is a bond.) [4] A curable resin according to any one of [1] to [3], which has a structural unit represented by formula (6). [ka] (In formula (6), R3 each independently represents a structural unit represented by the formula (1-1) or a structural unit represented by the formula (5), R5 each independently represents a structural unit represented by the following formula (1-2), a structural unit represented by the formula (4), a structural unit represented by the following formula (5-2), or Y, where Y is a (meth)acryloyl group, n6 is the average number of repeating units and is a number from 0 to 5; * is a bond, The curable resin has at least one of a structural unit represented by the formula (1-1) and a structural unit represented by the following formula (1-2): At least one Y is contained in the curable resin.) [ka] (In formula (1-2), R1, R2, n1 and Y are the same as above, * is a bond.) [ka] (In formula (5-2), Re, Ar1, Ar2, Y, and n5 are the same as above; * is a bond.) [5] A curable resin according to any one of [1] to [4], which has a structural unit represented by formula (7). [ka] (In formula (7), R7 is a structural unit represented by the formula (1-1) or a structural unit represented by the formula (5), R8 is a structural unit represented by the formula (1-2), a structural unit represented by the formula (4), a structural unit represented by the formula (5-2), or Y; n7 is the average number of repeating units and is a number from 0 to 5; However, the curable resin has at least one of a structural unit represented by the formula (1-1) and a structural unit represented by the formula (1-2), At least one Y is contained in the curable resin.) [6] A curable resin composition containing the curable resin according to any one of [1] to [5]. [7] A cured product of the curable resin composition of [6]. [8] A prepreg having a reinforcing substrate and a semi-cured product of the curable composition of [6] impregnated into the reinforcing substrate. [9][8] A circuit board that is a laminate of prepreg and copper foil.

[10] A build-up film containing the curable composition of [6].

[11] A semiconductor encapsulant containing the curable composition of [6].

[12] A semiconductor device comprising the cured product of the semiconductor encapsulant according to

[11] . [Effects of the Invention]

[0010] The curable resin of the present invention is useful because it can provide a cured product that simultaneously satisfies low dielectric properties (low dielectric constant and low dielectric dissipation factor), good dielectric properties after moisture absorption, high adhesion to copper foil (high peel strength), and high heat resistance. [Brief explanation of the drawings]

[0011] [Figure 1] 1 shows the results of gel permeation chromatography (GPC) measurement of the curable resin synthesized in Example 1. [Figure 2] 1 shows the results of GPC measurement of the curable resin synthesized in Example 2. [Figure 3] 1 shows the results of GPC measurement of the curable resin synthesized in Example 3. [Figure 4] 1 shows the results of GPC measurement of the curable resin synthesized in Example 4. [Figure 5] 1 shows the results of GPC measurement of the curable resin synthesized in Example 5. [Figure 6] 1 shows the results of GPC measurement of the curable resin synthesized in Example 6. [Figure 7]1 shows the results of 1H-NMR measurement of the curable resin synthesized in Example 6. [Figure 8] 1 shows the results of 13C-NMR measurement of the curable resin synthesized in Example 6. [Figure 9] 1 shows the results of IR measurement of the curable resin synthesized in Example 6. [Figure 10] 1 shows the results of GPC measurement of the curable resin synthesized in Example 7. [Figure 11] 1 shows the results of GPC measurement of the curable resin synthesized in Example 8. [Figure 12] 1 shows the results of GPC measurement of the curable resin synthesized in Example 9. [Figure 13] 1 shows the results of 1H-NMR measurement of the curable resin synthesized in Example 9. [Figure 14] 13C-NMR measurement results of the curable resin synthesized in Example 9. [Figure 15] 1 shows the results of IR measurement of the curable resin synthesized in Example 9. [Figure 16] 1 shows the results of GPC measurement of the curable resin synthesized in Example 10. [Figure 17] 1 shows the results of GPC measurement of the curable resin synthesized in Example 11. [Figure 18] 1 shows the results of GPC measurement of the curable resin synthesized in Example 12. [Figure 19] 1 shows the results of GPC measurement of the curable resin synthesized in Example 13. [Figure 20] 1 shows the results of GPC measurement of the curable resin synthesized in Comparative Example 1. [Figure 21] 1 shows the results of IR measurement of the curable resin synthesized in Comparative Example 1. [Figure 22] 1 shows the results of GPC measurement of the curable resin synthesized in Comparative Example 2. DETAILED DESCRIPTION OF THE INVENTION

[0012] Hereinafter, the embodiments for carrying out the present invention will be described in detail, but the present invention is not limited to the following description and can be carried out in various modified forms within the scope of the gist thereof.

[0013] [term] The term "structural unit" as used herein refers to a (repeating) unit of a chemical structure formed during a reaction or polymerization; in other words, it refers to a partial structure, other than the structure of the chemical bonds involved in the reaction or polymerization, in a product compound formed by a reaction or polymerization, and is a so-called residue.

[0014] The alkyl group in this specification may be either a straight-chain or branched type, and examples of the alkyl group include those having 1 to 12 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, a sec-pentyl group, a tert-pentyl group, a neopentyl group, an amyl group, a cyclopentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, and a dodecyl group. The aryl group in this specification is a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, such as a phenyl group, a naphthyl group, a biphenyl group, or a phenanthryl group. The aralkyl group in this specification refers to an alkyl group substituted with one or more, preferably one or two, particularly one, aryl group, and the above descriptions of the aryl group and alkyl group apply to the aralkyl group and the alkyl group, such as a benzyl group, a phenethyl group, and a cumyl group. The cycloalkyl group in this specification may be a monocyclic group or a polycyclic group, and examples of the cycloalkyl group include those having 3 to 30 carbon atoms, such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, an adamantyl group, a methylcyclohexyl group, and an ethylcyclohexyl group. The ring in this specification may be a monocyclic or polycyclic ring, an aromatic ring (e.g., a benzene ring, a naphthalene ring, etc.) or a non-aromatic ring (e.g., a cycloalkane ring), a carbocyclic ring or a heterocyclic ring, and may further have a substituent on the ring. In this specification, the (meth)acryloyl group is a general term including an acryloyl group and a methacryloyl group, and may be either one or both. The number average molecular weight (Mn) and weight average molecular weight (Mw) in this specification are values ​​measured using gel permeation chromatography (GPC) under the measurement conditions described in the examples below.

[0015] [Curable resin] The curable resin of the present invention comprises a structural unit represented by the following formula (1): At least one of a structural unit represented by the following formula (2) and a structural unit represented by the following formula (3), a terminal (meth)acryloyl group; It has.

[0016] <Structural unit represented by formula (1)> The curable resin of the present invention has a structural unit represented by formula (1): Formula (1) is as shown below and is a structural unit having an indane skeleton. [ka]

[0017] In formula (1), Each Ra is independently an alkyl group, an aryl group, an aralkyl group, or a cycloalkyl group having 1 to 12 carbon atoms; each k is independently an integer of 0 to 4; Rb's each independently represent an alkyl group, an aryl group, an aralkyl group, or a cycloalkyl group having 1 to 12 carbon atoms; l1's each independently represent an integer of 0 to 4; and l2's each independently represent an integer of 0 to 3. n is the average number of repeating units and is a number from 0.5 to 20; m's each independently represent an integer of 0 to 2, * is a bond. Here, Ra, Rb, *-O, and the line from a carbon atom to an aromatic ring indicate that the bond may be to any position on the aromatic ring. The same applies to other chemical structural formulas.

[0018] By including a structural unit having an indane skeleton with a high hydrocarbon content in the curable resin, the cured product can have excellent low dielectric properties, even after absorbing moisture. The indane skeleton is expected to provide excellent flexibility and pliability, as well as suppress thermal expansion.

[0019] In formula (1), Ra are each independently an alkyl group, aryl group, aralkyl group or cycloalkyl group having 1 to 12 carbon atoms, and preferably an alkyl group, aryl group or cycloalkyl group having 1 to 4 carbon atoms. An alkyl group or the like having 1 to 12 carbon atoms is preferred because it reduces the planarity near any of the benzene ring, naphthalene ring or anthracene ring described below, and the reduced crystallinity is expected to improve solvent solubility and lower the melting point.

[0020] In formula (1), k is independently an integer of 0 to 4, preferably an integer of 0 to 2. From the viewpoint of reactivity, the above range is preferable. It is presumed that the presence of Ra causes steric hindrance, further reducing molecular mobility, and the cured product is expected to have a lower dielectric loss tangent, so k is particularly preferably 1 or 2.

[0021] In formula (1), Rb's each independently represent an alkyl group, aryl group, aralkyl group or cycloalkyl group having 1 to 12 carbon atoms, and preferably an alkyl group, aryl group or cycloalkyl group having 1 to 4 carbon atoms.

[0022] In formula (1), l1 is an integer of 0 to 4, and preferably an integer of 0 to 2. Furthermore, l2 is an integer of 0 to 3, and preferably an integer of 0 to 2. From the viewpoint of reactivity, the above ranges are preferred.

[0023] In formula (1), m is an integer of 0 to 2, that is, when m is 0 it is a benzene ring, when m is 1 it is a naphthalene ring, and when m is 2 it is an anthracene ring, preferably a benzene ring when m is 0. From the viewpoint of solvent solubility, the above range is preferred.

[0024] In formula (1), n ​​is the average number of repeating units and is a value of 0.5 to 20, preferably 0.5 to 7, and more preferably 3 to 4.5. The above range is preferred from the viewpoints of obtaining a cured product having a good dielectric tangent even after moisture absorption and of the solvent solubility of the curable resin.

[0025] Formula (1) is preferably formula (1-1). [ka]

[0026] In formula (1-1), R1 and R2 each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, or a cycloalkyl group, provided that R1 and R2 are not both hydrogen atoms at the same time; n1 represents the average number of repeating units and is a value of 0.5 to 20.

[0027] In formula (1-1), R1 and R2 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, or a cycloalkyl group, preferably an alkyl group, aryl group, or cycloalkyl group having 1 to 4 carbon atoms. An alkyl group having 1 to 12 carbon atoms or the like reduces the planarity in the vicinity of the benzene ring, which reduces crystallinity and improves solvent solubility while lowering the melting point; therefore, it is preferable that both are not hydrogen atoms. The presence of R1 and R2 is presumed to increase steric hindrance (unless they are hydrogen atoms), further reducing molecular mobility, and thus allowing a cured product with a lower dielectric loss tangent to be obtained, which is preferable.

[0028] In formula (1-1), n1 is the average number of repeating units and is a value from 0.5 to 20, preferably from 0.5 to 7, and more preferably from 3.0 to 4.5. The above range is preferred from the viewpoints of obtaining a cured product having a good dielectric tangent even after moisture absorption and of the solvent solubility of the curable resin.

[0029] <At least one of a structural unit represented by formula (2) and a structural unit represented by formula (3)> The curable resin of the present invention has at least one of a structural unit represented by formula (2) and a structural unit represented by formula (3). Formulas (2) and (3) are as follows, where formula (2) is a structural unit having a triazine ring, and formula (3) is a structural unit derived from phthalic acid. By introducing at least one of the structural unit represented by formula (2) and the structural unit represented by formula (3) into the curable resin, it is possible to impart high adhesion (high peel strength) to copper foil to the cured product.

[0030] The improvement in adhesion to copper foil due to the introduction of the structural units represented by formula (2) and formula (3) is expected to occur because the introduction of these structural units increases the proportion of polar groups in the curable resin and increases the molecular weight, which is expected to result in the following effects (a) and (b), which, combined, are thought to result in an overall improvement in peel strength and interlayer delamination strength. (a) The polar groups strengthen the van der Waals interactions between the resin and copper foil and between the resin and glass cloth. (b) As the molecular weight increases, the entanglement between resin molecules becomes stronger, and the cohesive strength of the cured product increases.

[0031] Of the structural unit represented by formula (2) and the structural unit represented by formula (3), the structural unit represented by formula (2) has symmetry and is therefore more advantageous in terms of low dielectric properties.

[0032] [ka]

[0033] In formula (2), * represents a bond.

[0034] [ka]

[0035] In formula (3), Rc's each independently represent an alkyl group, aryl group, aralkyl group, or cycloalkyl group having 1 to 12 carbon atoms, and are preferably an alkyl group, aryl group, or cycloalkyl group having 1 to 4 carbon atoms. A methyl group is preferred for the alkyl group having 1 to 12 carbon atoms, as this improves solubility.

[0036] In formula (3), p is an integer of 0 to 4, and preferably an integer of 0 to 2. From the viewpoint of solubility, the above range is preferred.

[0037] In formula (3), the two -C(=O)-* may be in any of the ortho, meta, and para positions, but are preferably in the meta or para position from the viewpoint of reactivity in the polymerization reaction.

[0038] In formula (3), * represents a bond.

[0039] <Terminal (meth)acryloyl group> The curable resin of the present invention has a terminal (meth)acryloyl group. The (meth)acryloyl group is a crosslinking group, and compared with other crosslinking groups (e.g., vinylbenzyl ether group (styryl group), dihydroxybenzene group, etc.), it has lower molecular mobility and can produce a cured product with a low dielectric dissipation factor. In particular, the methacryloyl group contains a methyl group in its structure, which is thought to increase steric hindrance and further reduce molecular mobility, and is expected to produce a cured product with an even lower dielectric dissipation factor. Therefore, among (meth)acryloyl groups, the methacryloyl group is preferred. Furthermore, since multiple crosslinking groups increase crosslink density and improve heat resistance, it is preferable that the curable resin have multiple terminal (meth)acryloyl groups.

[0040] The (meth)acryloyl group can be bonded to a bond of the structural unit represented by formula (1) to form the terminal of the curable resin.

[0041] <Structural unit represented by formula (4)> The curable resin of the present invention can have a structural unit represented by formula (4). Formula (4) is as follows, and can be bonded to a bond of a structural unit represented by formula (2) or (3) to form an end of the curable resin. By introducing the structural unit represented by formula (4) into the curable resin, it is possible to adjust the molecular weight, double bond equivalent, and content of the structural unit represented by formula (2) or (3), which is advantageous in that it is possible to suitably adjust the balance between fluidity, adhesion, etc. Furthermore, when the curable resin has a structural unit represented by formula (2), it is possible to adjust the degree of branching by bonding to the bond of formula (2), which can improve the liquid separation in the washing step for purification and ultimately facilitate reducing the amount of ionic impurities remaining in the resin.

[0042] [ka]

[0043] In formula (4), Rd's each independently represent an alkyl group, aryl group, aralkyl group, or cycloalkyl group having 1 to 12 carbon atoms, and are preferably an alkyl group, aryl group, or cycloalkyl group having 1 to 4 carbon atoms. An alkyl group or the like having 1 to 12 carbon atoms is preferred because it results in a resin with excellent solubility. Furthermore, a methyl group is more preferred because of the ease of industrially obtaining raw materials.

[0044] In formula (4), q is an integer of 0 to 5, and preferably an integer of 0 to 2. From the viewpoint of solubility, the above range is preferred.

[0045] When q is 2 or greater, two adjacent Rds may be joined together to form a ring, such as a benzene ring. The benzene ring may have a substituent, and examples of the substituent include an alkyl group having 1 to 12 carbon atoms.

[0046] In formula (4), * represents a bond.

[0047] <Structural unit represented by formula (5)> The curable resin of the present invention can have a structural unit represented by formula (5). Formula (5) is as follows, and can be bonded to a bond of a structural unit represented by formula (2) or (3), for example. By introducing the structural unit represented by formula (5) into the curable resin, the molecular weight and double bond equivalent can be adjusted, which increases the content of the structural unit represented by formula (2) or (3) and advantageously strengthens adhesion.

[0048] [ka]

[0049] In formula (5), Re is a single bond, -O-, -S-, -S(=O)-, -S(=O)2-, -C(=O)- or a hydrocarbon group which may have a substituent.

[0050] Examples of the hydrocarbon group include an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, and an aralkylene group having 8 to 20 carbon atoms. These may have a substituent, and examples of the substituent include a halogen atom (such as a fluorine atom).

[0051] Specific examples of Re include -CH2-, -CH(CH3)-, -C(CH3)2-, -C(CF3)2-, -CHPh-, -C(CH3)Ph-, 1,1-cyclopropylene group, 1,1-cyclobutylene group, 1,1-cyclopentylene group, 1,1-cyclohexylene group, 4-methyl-1,1-cyclohexylene group, 3,3,5-trimethyl-1,1-cyclohexylene group, 1,1-cyclooctylene group, 1,1-cyclononylene group, 1,2-ethylene group, Examples include 1,2-cyclopropylene group, 1,2-cyclobutylene group, 1,2-cyclopentylene group, 1,2-cyclohexylene group, 1,2-phenylene group, 1,3-propylene group, 1,3-cyclobutylene group, 1,3-cyclopentylene group, 1,3-cyclohexylene group, 1,3-phenylene group, 1,4-butylene group, 1,4-cyclohexylene group, 1,4-phenylene group, 1,1-fluorene group, 1,2-xylylene group, 1,4-xylylene group, etc. In the above, Ph represents a phenyl group.

[0052] [ka] In the formula, n 1 is 0 or 1, R 1 each independently represents an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, or an aralkyl group, n 2 is 0 or an integer from 1 to 4, R 2 is a hydrogen atom or a methyl group, R 3 represents an alkylene group having 1 to 4 carbon atoms, an oxygen atom, a sulfur atom, or a carbonyl group, n 3 is an integer between 1 and 4.)

[0053] Re is preferably a hydrocarbon group.

[0054] In formula (5), Ar1 is [ka] or [ka] is.

[0055] In formula (5), Rf's each independently represent an alkyl group, aryl group, aralkyl group, or cycloalkyl group having 1 to 12 carbon atoms, and are preferably an alkyl group, aryl group, or cycloalkyl group having 1 to 4 carbon atoms. The alkyl group or the like having 1 to 12 carbon atoms is preferred because it provides good electrical properties.

[0056] In formula (5), r is an integer of 0 to 4, and preferably an integer of 0 to 2. From the viewpoint of solubility, the above range is preferred.

[0057] In formula (5), Rg's each independently represent an alkyl group, aryl group, aralkyl group, or cycloalkyl group having 1 to 12 carbon atoms, and are preferably an alkyl group, aryl group, or cycloalkyl group having 1 to 4 carbon atoms. The alkyl group or the like having 1 to 12 carbon atoms is preferred because it improves the electrical properties.

[0058] In formula (5), s is an integer of 0 to 6, and preferably an integer of 0 to 4. From the viewpoint of solubility, the above range is preferred.

[0059] Ar2 is independently [ka] or [ka] is.

[0060] In formula (5), Rh's each independently represent an alkyl group, aryl group, aralkyl group, or cycloalkyl group having 1 to 12 carbon atoms, and are preferably an alkyl group, aryl group, or cycloalkyl group having 1 to 4 carbon atoms. The alkyl group or the like having 1 to 12 carbon atoms is preferred because it improves the electrical properties.

[0061] In formula (5), t is an integer of 0 to 3, and preferably an integer of 0 to 2. From the viewpoint of solubility, the above range is preferred.

[0062] In formula (5), Ri are each independently an alkyl group, aryl group, aralkyl group or cycloalkyl group having 1 to 12 carbon atoms, and preferably an alkyl group, aryl group or cycloalkyl group having 1 to 4 carbon atoms. The alkyl group or the like having 1 to 12 carbon atoms is preferred because it improves the electrical properties.

[0063] In formula (5), u represents an integer of 0 to 5, and preferably an integer of 0 to 4. From the viewpoint of solubility, the above range is preferred.

[0064] In formula (5), * represents a bond.

[0065] As formula (5), formula (5-1) corresponding to the case where n5 is 0 is preferable. [ka]

[0066] In formula (5-1), Ar1 and * are the same as above, and the examples and preferred examples described above apply.

[0067] <Configuration of curable resin> The curable resin of the present invention has a structural unit represented by formula (1), at least one of a structural unit represented by formula (2) and a structural unit represented by formula (3), and a (meth)acryloyl group. In this case, the structural units represented by formula (2) can be 0 to 0.46 moles, the structural units represented by formula (3) can be 0 to 0.86 moles, and the (meth)acryloyl group can be more than 0 moles but not more than 1 mole, relative to 1 mole of the structural units represented by formula (1). However, the structural units represented by formula (2) and the structural units represented by formula (3) cannot both be 0 moles.

[0068] For example, the curable resin of the present invention can be composed of a structural unit represented by formula (1), a structural unit represented by formula (2), and a (meth)acryloyl group. In this case, it can be composed of a (meth)acryloyl group. In this case, the structural unit represented by formula (2) can be 0.33 to 0.46 mol and the (meth)acryloyl group can be 0.62 to 1 mol per 1 mol of the structural unit represented by formula (1).

[0069] For example, the curable resin of the present invention can be composed of a structural unit represented by formula (1), a structural unit represented by formula (3), and a (meth)acryloyl group. In this case, the structural unit represented by formula (3) can be 0.5 to 0.86 mol and the (meth)acryloyl group can be 0.29 to 1 mol per 1 mol of the structural unit represented by formula (1).

[0070] For example, the curable resin of the present invention can be composed of a structural unit represented by formula (1), a structural unit represented by formula (2), a structural unit represented by formula (4), and a (meth)acryloyl group. In this case, the structural units represented by formula (2) can be 0.33 to 1.2 moles, the structural units represented by formula (4) can be more than 0 moles and 1.4 moles or less, and the (meth)acryloyl groups can be 0.2 to 1 mole, relative to 1 mole of the structural units represented by formula (1).

[0071] For example, the curable resin of the present invention can be composed of a structural unit represented by formula (1), a structural unit represented by formula (2), a structural unit represented by formula (4), a structural unit represented by formula (5), and a (meth)acryloyl group. In this case, the structural unit represented by formula (1) can be 0.16 to 3 moles, the structural unit represented by formula (4) can be more than 0 moles but not more than 2 moles, and the (meth)acryloyl group can be 0.16 to 3 moles per mole of the structural unit represented by formula (2).

[0072] The number average molecular weight (Mn) of the curable resin of the present invention can be in the range of 500 to 15,000, and preferably in the range of 1,000 to 5,000. The weight average molecular weight (Mw) of the curable resin can be in the range of 1,200 to 100,000, and preferably in the range of 1,800 to 25,000. The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the curable resin can be in the range of 1.2-20, and preferably 1.7-10.

[0073] The vinyl equivalent of the curable resin is preferably in the range of 200 to 10,000 g / equivalent, and more preferably 300 to 5,000 g / equivalent.

[0074] <Curable resin having a structural unit represented by formula (6)> The curable resin of the present invention includes a curable resin having a structural unit represented by formula (6). [ka]

[0075] In formula (6), each R3 is independently a structural unit represented by formula (1-1) or a structural unit represented by formula (5). [ka]

[0076] In formula (1-1), R1, R 2、 n1 and * are the same as above, and the examples and preferred examples explained above apply. In formula (5), Ar1, Ar2, Re 、 n5 and * are the same as above, and the examples and preferred examples explained above apply.

[0077] In formula (6), R5's each independently represent a structural unit represented by the following formula (1-2), a structural unit represented by the following formula (4), a structural unit represented by the following formula (5-2), or Y (Y is a (meth)acryloyl group). [ka]

[0078] In formula (1-2), R1, R 2、 n1 and * are the same as in the above formula (1-1), the examples and preferred examples described in the above formula (1-1) are applied, and Y is a (meth)acryloyl group. In formula (4), Rd, q, and * are the same as above, and the examples and preferred examples described above apply. In formula (5-2), Ar1, Ar2, Re 、 n5 and * are the same as in the above formula (5), the examples and preferred examples described in the above formula (5) are applied, and Y is a (meth)acryloyl group.

[0079] As formula (5-2), the following formula in which n5 corresponds to 0 is preferred. [ka]

[0080] In the formula, Ar1, Re, and Y are the same as above.

[0081] In formula (6), n6 is the average number of repeating units and is a number from 0 to 5, preferably 0 to 3.

[0082] The curable resin having the structural unit represented by formula (6) has at least one of the structural unit represented by formula (1-1) and the structural unit represented by formula (1-2).

[0083] Furthermore, at least one Y, which is a (meth)acryloyl group, is contained in the curable resin having the structural unit represented by formula (6). Preferably, at least two Ys are contained, and more preferably 2 to 8 Ys are contained. When the curable resin having the structural unit represented by formula (6) contains a structural unit represented by formula (1-2) or formula (5-2), the Y contained in the curable resin may be Y constituting the structural unit represented by formula (1-2) or formula (5-2).

[0084] In formula (6), a structural unit represented by formula (1-2) or a structural unit represented by formula (5-2) can be bonded to a bond of the triazine ring. In addition, in formula (6), another triazine ring may be bonded to the bond of the triazine ring via R3. The bond of the triazine ring may have, for example, a repeating unit bound by n6 and a terminal R5, similar to the main chain of formula (6).

[0085] <Curable resin having a structural unit represented by formula (7)> The curable resin of the present invention includes a curable resin having a structural unit represented by formula (7). [ka]

[0086] In formula (7), R7 is a structural unit represented by formula (1-1) or a unit represented by formula (5). [ka]

[0087] In formula (1-1), R1, R 2、 n1 and * are the same as above, and the examples and preferred examples explained above apply. In formula (5), Ar1, Ar2, Re 、 n5 and * are the same as above, and the examples and preferred examples explained above apply.

[0088] In formula (7), R8 is a structural unit represented by formula (1-2), a structural unit represented by formula (4), a structural unit represented by formula (5-2), or Y (Y is a (meth)acryloyl group). [ka]

[0089] In formula (1-2), R1, R 2、n1 and * are the same as in the above formula (1-1), and the examples and preferred examples described in the above formula (1-1) are applicable, and Y is a (meth)acryloyl group. In formula (4), Rd, q, and * are the same as above, and the examples and preferred examples described in the above formula (1-1) are applicable. In formula (5-2), Ar1, Ar2, Re 、 n5 and * are the same as in the above formula (5), the examples and preferred examples described in the above formula (5) are applied, and Y is a (meth)acryloyl group.

[0090] In formula (7), n7 is the average number of repeating units and is a number from 0 to 5, preferably 0 to 3.

[0091] [Method for producing curable resin] The curable resin of the present invention can be obtained by reacting a phenolic compound corresponding to the structural unit of formula (1), at least one of a triazine compound and a phthalic acid compound, a (meth)acrylation agent, and optionally at least one of a phenolic compound corresponding to the structural unit of formula (4) and a phenolic compound corresponding to the structural unit of formula (5).

[0092] <Phenol compounds corresponding to the structural units of formula (1)> A phenol compound corresponding to the structural unit of formula (1) can be represented by the following formula (1A). [ka]

[0093] In formula (1A), Ra, Rb, k, l1, l2, m, and n are the same as in formula (1), and the examples and preferred examples described in formula (1) are applied.

[0094] The compound represented by formula (1A) can be prepared by the method described in WO 2021 / 205806.

[0095] Formula (1A) is preferably formula (1-1A). [ka]

[0096] In formula (1-1A), R1, R2 and n1 are the same as in formula (1-1), and the examples and preferred examples described in formula (1-1) are applied.

[0097] The phenol compound represented by formula (1A) may be subjected to the reaction as a mixture with a compound containing at least one structural unit selected from the structural unit represented by the following formula (8) and the structural unit represented by the following formula (9) (hereinafter also referred to as "other compound"), within the scope that does not impair the effects of the present invention.

[0098] [ka] During the ceremony, Rb and l2 are the same as in formula (1), * represents a bond.

[0099] Other compounds include compounds in which at least a part of the structural units containing an indane skeleton enclosed by n in formula (1A) is replaced with structural units represented by formula (8) or structural units represented by formula (9).

[0100] When the phenol compound represented by formula (1A) is reacted as a mixture with other compounds, the curable resin of the present invention may contain at least one structural unit selected from the structural unit represented by formula (8) and the structural unit represented by formula (9). For example, when the other compound is a compound in which at least a part of the structural units containing an indane skeleton bounded by n in formula (1A) is replaced with a structural unit represented by formula (8) or a structural unit represented by formula (9), the curable resin of the present invention may contain a structural unit in which at least a part of the structural units containing an indane skeleton bounded by n in formula (1) is replaced with a structural unit represented by formula (8) or a structural unit represented by formula (9).

[0101] <At least one of triazine compound and phthalic acid compound> Examples of triazine compounds include cyanuric chloride, 2,4,6-tribromo-1,3,5-triazine, 2,4,6-trifluoro-1,3,5-triazine, and 2,4,6-trimethoxy-1,3,5-triazine, and among these, cyanuric chloride is preferred. Cyanuric chloride is a compound represented by the following formula (2A): [ka]

[0102] As the phthalic acid compound, a compound represented by the following formula (3A) can be used. [ka]

[0103] In formula (3A), Rc and p are the same as in formula (3), and the examples and preferred examples described in formula (3) are applied.

[0104] The compound represented by formula (3A) is preferably an isophthalic acid compound or a terephthalic acid compound, and examples thereof include isophthalic acid and terephthalic acid.

[0105] The compound of formula (3A) in the form of an ester (e.g., methyl ester, etc.) and a halide (e.g., chloride, bromide, etc.) can also be used as the phthalic acid compound. Among them, isophthalic acid dichloride and terephthalic acid dichloride are preferred.

[0106] <(Meth)acrylation agent> The (meth)acrylation agent is not particularly limited as long as it is a compound that can react with a phenolic hydroxyl group to introduce a (meth)acryloyl group. Examples of the (meth)acrylation agent include (meth)acrylic anhydride, (meth)acrylic acid chloride, (meth)acrylic acid, and (meth)acrylic acid esters. Examples of the (meth)acrylic acid esters include alkyl esters of (meth)acrylic acid (e.g., alkyl esters having 1 to 4 carbon atoms).

[0107] Here, (meth)acrylic anhydride includes methacrylic anhydride and acrylic anhydride, and (meth)acrylic chloride includes methacrylic chloride and acrylic chloride. (Meth)acrylic acid includes methacrylic acid and acrylic acid, and (meth)acrylic acid esters include methacrylic acid esters and acrylic acid esters. When the (meth)acrylating agent is methacrylic anhydride, methacrylic acid chloride, methacrylic acid, methacrylic acid esters, etc., a methacryloyl group is introduced, and when the (meth)acrylating agent is acrylic anhydride, acrylic acid chloride, acrylic acid, acrylic acid esters, etc., an acryloyl group is introduced.

[0108] <Phenol compounds corresponding to the structural unit of formula (4)> A phenol compound corresponding to the structural unit of formula (4) can be represented by the following formula (4A). [ka]

[0109] In formula (4A), Rd and q are the same as in formula (4), and the examples and preferred examples described in formula (4) are applied.

[0110] Examples of the compound represented by formula (4A) include phenol; monoalkyl-substituted phenols such as orthocresol, meta-cresol, para-cresol, 4-isopropylphenol, and 4-tert-butylphenol; dialkyl-substituted phenols such as 2,6-dimethylphenol, 2,5-dimethylphenol, 2,4-dimethylphenol, and 3,5-dimethylphenol; 1-naphthol, and 2-naphthol. Among these, 2,6-dimethylphenol is preferred from the viewpoint of low dielectric loss tangent.

[0111] <Phenol compounds corresponding to the structural unit of formula (5)> A phenol compound corresponding to the structural unit of formula (5) can be represented by the following formula (5A). [ka]

[0112] In formula (5A), Ar1, Ar2, Re, and n5 are the same as in formula (5), and the examples and preferred examples described in formula (5) apply.

[0113] As formula (5A), the following formula in which n5 corresponds to 0 is preferred. [ka]

[0114] In the formula, Ar1 and Re are the same as above.

[0115] Examples of the compound represented by formula (5A) include the following. [ka] Here, n5 is the same as above.

[0116] [ka]

[0117] <Production of curable resin having structural unit represented by formula (6)> The curable resin of the present invention having a structural unit represented by formula (2) can be obtained by reacting at least a phenol compound corresponding to the structural unit of formula (1), a triazine compound, and a (meth)acrylating agent. This curable resin includes a curable resin having a structural unit represented by formula (6).

[0118] By using a triazine compound, the structural unit of formula (2) can be introduced into a curable resin. In this case, a phenolic compound corresponding to the structural unit of formula (1), a triazine compound, and a (meth)acrylation agent may be mixed together and reacted (Reaction 1-1), or a phenolic compound corresponding to the structural unit of formula (1) may be reacted with a triazine compound to obtain an intermediate phenolic compound, and then this intermediate phenolic compound may be reacted with a (meth)acrylation agent (Reaction 1-2).

[0119] (Reaction 1-1) When a phenol compound corresponding to the structural unit of formula (1), a triazine compound and a (meth)acrylation agent are mixed together and reacted, the reaction can be carried out under the following conditions.

[0120] The phenol compound, triazine compound, and (meth)acrylation agent corresponding to the structural unit of formula (1) can be used in an amount of 0.01 to 0.33 mol of the triazine compound relative to 1 mol of the hydroxyl group of the phenol compound, and 0.01 to 3.0 mol of the (meth)acrylation agent relative to 1 mol of the hydroxyl group of the phenol compound.

[0121] The reaction can be carried out in the presence of a basic catalyst.

[0122] Examples of basic catalysts include amine-containing catalysts such as trimethylamine, triethylamine, N,N-diisopropylmethylamine, 1,8-diazabicyclo[5,4,0]-7-undecene, 1,5-diazabicyclo[4,3,0]-5-nonene, pyridine, and dimethylaminopyridine; alkaline earth metal hydroxides such as calcium hydroxide and barium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; and alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. Among these, triethylamine, N,N-diisopropylmethylamine, dimethylaminopyridine, and pyridine are preferred in terms of catalytic activity. The above catalysts may be used alone or in combination of two or more.

[0123] In the reaction, the basic catalyst is preferably used in an amount of 0.01 to 2.00 moles per mole of hydroxyl groups. The catalyst may be added all at once or in portions.

[0124] From the viewpoint of avoiding side reactions, it is preferable to mix the phenol compound and triazine compound corresponding to the structural unit of formula (1) with the basic catalyst, and then add the (meth)acrylation agent.

[0125] The reaction temperature can be set to 0 to 80° C., and from the viewpoint of reactivity, it is preferably set to 20 to 80° C. The reaction time can be set to 1 to 48 hours.

[0126] The reaction is preferably carried out in an organic solvent. Examples of organic solvents include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aromatic hydrocarbon solvents such as toluene, xylene, mesitylene, and Solvesso; ether solvents such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxane, and diethoxyethane; and aprotic polar solvents such as acetonitrile, dimethyl sulfoxide, sulfolane, dimethylformamide, and dimethylacetamide. From the viewpoint of solubility, toluene, xylene, mesitylene, Solvesso, dimethyl sulfoxide, dimethylformamide, and dimethylacetamide are preferred. These organic solvents can be used alone or in combination of two or more in any ratio. The amount of the organic solvent used is not particularly limited, but is preferably 50 to 2000% by mass based on the total amount of the phenol compound corresponding to the structural unit of formula (1), the triazine compound, and the (meth)acrylation agent.

[0127] After the reaction is completed, the curable resin of the present invention can be obtained by carrying out reprecipitation, recrystallization, washing with water, distillation, etc.

[0128] (Reaction 1-2) When an intermediate phenolic compound is obtained by reacting a phenolic compound corresponding to the structural unit of formula (1) with a triazine compound, and then this intermediate phenolic compound is reacted with a (meth)acrylation agent, the reaction can be carried out under the following conditions.

[0129] The phenol compound and triazine compound corresponding to the structural unit of formula (1) used to prepare the intermediate phenol compound can be used in an amount of 0.01 to 0.33 moles of the triazine compound per mole of the hydroxyl group of the phenol compound.

[0130] The reaction can be carried out in the presence of an alkaline catalyst and optionally a phase transfer catalyst.

[0131] Examples of alkali catalysts include lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium methoxy, sodium ethoxy, sodium tert-butoxy, potassium methoxy, potassium ethoxy, potassium tert-butoxy, triethylamine, pyridine, and dimethylaminopyridine. From the viewpoint of reactivity, sodium hydroxide or potassium hydroxide is preferred. The amount of alkali catalyst used can be 3.0 to 4.5 moles per mole of the triazine compound. These catalysts can be used as a 1 to 50 mass% aqueous solution.

[0132] A phase transfer catalyst may be used in the reaction. Examples of phase transfer catalysts include ammonium-based catalysts such as tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium, tetrabutylammonium iodide, tetrabutylammonium hydroxide, benzyltriethylammonium chloride, benzyltriethylammonium bromide, benzyltriethylammonium iodide, and benzyltriethylammonium hydroxide; phosphonium-based catalysts such as tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, tetrabutylphosphonium iodide, and tetrabutylphosphonium hydroxide; and crown ether-based catalysts such as 12-crown-4-ether, 15-crown-5-ether, 18-crown-6-ether, and tribenzo-18-crown-6-ether. From the viewpoint of reactivity, tetrabutylammonium bromide, tetrabutylammonium iodide, benzyltriethylammonium chloride, and benzyltriethylammonium iodide are preferred. The phase transfer catalysts may be used alone or in combination of two or more. The amount of the phase transfer catalyst used can be 0.0003 to 0.1 moles per mole of the hydroxyl group of the phenol compound.

[0133] The reaction is preferably carried out in an organic solvent. Examples of organic solvents include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aromatic hydrocarbon solvents such as toluene, xylene, mesitylene, and Solvesso; ether solvents such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxane, and diethoxyethane; and aprotic polar solvents such as acetonitrile, dimethyl sulfoxide, sulfolane, dimethylformamide, and dimethylacetamide. From the viewpoint of solubility, toluene, xylene, mesitylene, Solvesso, dimethyl sulfoxide, dimethylformamide, and dimethylacetamide are preferred. These organic solvents can be used alone or in combination of two or more in any ratio. The amount of the organic solvent used is not particularly limited, but is preferably 50 to 2000% by mass relative to the phenol compound and triazine compound corresponding to the structural unit of formula (1).

[0134] The reaction temperature can be set to 0 to 80° C., and from the viewpoint of reactivity, is preferably 20 to 80° C. The reaction time can be set to 1 to 48 hours.

[0135] The reaction can be carried out by mixing a phenol compound corresponding to the structural unit of formula (1), a triazine compound, an alkali catalyst, and optionally a phase transfer catalyst at 0 to 40° C., and then heating the mixture to 20 to 80° C. From the viewpoint of reactivity, a temperature of 40 to 80° C. is preferred.

[0136] After the reaction is complete, the intermediate phenol compound can be separated. For example, the intermediate phenol compound can be obtained by separating into an upper layer and a lower layer, and then removing the lower aqueous layer. If necessary, water may be added to dissolve insoluble salts and then remove the lower layer. The aqueous layer may be basic, neutralized by neutralization, or acidic. Examples of neutralizing agents used for neutralization include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, sodium monophosphate, and ammonium chloride, and organic acids such as methanesulfonic acid, paratoluenesulfonic acid, and oxalic acid. These acid catalysts may be used alone or in combination.

[0137] Next, the resulting intermediate phenol compound is reacted with a (meth)acrylation agent to introduce a (meth)acryloyl group.

[0138] The amounts of the intermediate phenol compound and (meth)acrylation agent used in the reaction can be 1 to 3 moles of the (meth)acrylation agent per mole of hydroxyl groups contained in the intermediate phenol compound.

[0139] The reaction can be carried out in the presence of a basic catalyst or an acidic catalyst. Examples of basic catalysts include amine-containing catalysts such as trimethylamine, triethylamine, N,N-diisopropylmethylamine, 1,8-diazabicyclo[5,4,0]-7-undecene, 1,5-diazabicyclo[4,3,0]-5-nonene, pyridine, and dimethylaminopyridine; alkaline earth metal hydroxides such as calcium hydroxide and barium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; and alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. Examples of acidic catalysts include sulfuric acid, methanesulfonic acid, and p-toluenesulfonic acid. Among these, triethylamine, N,N-diisopropylmethylamine, dimethylaminopyridine, and pyridine are preferred in terms of catalytic activity. The above catalysts may be used alone or in combination.

[0140] The amount of the basic or acidic catalyst used is preferably 0.5 to 2.0 moles per mole of hydroxyl groups contained in the intermediate phenol compound. These catalysts may be added all at once or in portions.

[0141] The reaction temperature can be set to 0 to 80° C., and from the viewpoint of reactivity, it is preferably set to 40 to 80° C. The reaction time can be set to 1 to 48 hours.

[0142] The reaction is preferably carried out in an organic solvent. Examples of organic solvents include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aromatic hydrocarbon solvents such as toluene, xylene, mesitylene, and Solvesso; ether solvents such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxane, and diethoxyethane; and aprotic polar solvents such as acetonitrile, dimethyl sulfoxide, sulfolane, dimethylformamide, and dimethylacetamide. From the viewpoint of solubility, toluene, xylene, mesitylene, Solvesso, dimethyl sulfoxide, dimethylformamide, and dimethylacetamide are preferred. These organic solvents can be used alone or in combination of two or more in any ratio. The amount of organic solvent used is not particularly limited, but is preferably 50 to 2000% by mass based on the total amount of the phenolic resin and (meth)acrylation agent, which are charged as intermediates.

[0143] After the reaction is completed, the curable resin of the present invention can be obtained by carrying out reprecipitation, recrystallization, washing with water, distillation, etc.

[0144] An example of Reaction 1-2 is as follows (a representative reaction among Reactions 1-2). [ka]

[0145] (Reactions 1-3) When a phenolic compound corresponding to the structural unit of formula (4) is used, the structural unit of formula (4) can be introduced into the triazine compound by reacting the triazine compound with the phenolic compound corresponding to the structural unit of formula (4). Next, a phenolic compound corresponding to the structural unit of formula (1) is mixed and reacted to form an intermediate phenolic compound, and then this intermediate phenolic compound is reacted with a (meth)acrylation agent to form the curable resin of the present invention.

[0146] In this case, the triazine compound, the phenol compound corresponding to the structural unit of formula (4), and the phenol compound corresponding to the structural unit of formula (1) can be used in an amount of 0.01 to 1.0 mol per 1 mol of hydroxyl groups in the phenol compound corresponding to the structural unit of formula (1), and the triazine compound can be used in an amount of 0.01 to 1.0 mol per 1.0 mol of the total hydroxyl groups in the phenol compound corresponding to the structural unit of formula (1) and the phenol compound corresponding to the structural unit of formula (4).

[0147] The structural unit of formula (4) can be introduced into the triazine compound by mixing a phenol compound corresponding to the structural unit of formula (4), a triazine compound, an alkali catalyst, and optionally a phase transfer catalyst in an organic solvent. The reaction can be carried out at 0 to 80°C, and preferably 0 to 60°C from the viewpoint of reactivity. Here, the types and amounts of the alkali catalyst, phase transfer catalyst, and organic solvent can be the same as those in Reaction 1-2.

[0148] An intermediate phenol compound can be obtained by mixing a phenol compound corresponding to the structural unit of formula (1) with a reaction mixture containing a triazine compound having a structural unit of formula (4) introduced therein, and then heating the mixture to 20 to 80°C to carry out the reaction. From the viewpoint of reactivity, it is preferable to heat the mixture to 40 to 80°C.

[0149] To promote the reaction, it is preferable to add an alkali catalyst and, optionally, a phase transfer catalyst when mixing the phenolic compound corresponding to the structural unit of formula (1). The amount of the additional alkali catalyst used can be 0.50 to 1.0 mol per mol of hydroxyl groups in the phenolic compound corresponding to the structural unit of formula (1). When an additional phase transfer catalyst is used, the amount can be 0.0003 to 0.1 mol per mol of hydroxyl groups in the phenolic compound corresponding to the structural unit of formula (1).

[0150] After the reaction is complete, the intermediate phenol compound can be obtained. For example, the reaction mixture can be separated into an upper layer and a lower layer as appropriate in the same manner as in Reaction 1-2, and the lower aqueous layer can be removed to obtain the intermediate phenol compound.

[0151] Next, in the same manner as in Reaction 1-2, the resulting intermediate phenol compound is reacted with a (meth)acrylation agent to introduce a (meth)acryloyl group.

[0152] An example of Reaction 1-3 is as follows (a representative reaction among Reactions 1-3). [ka]

[0153] (Reactions 1-4) When a phenolic compound corresponding to the structural unit of formula (4) and a phenolic compound corresponding to the structural unit of formula (5) are used, a triazine compound and a phenolic compound corresponding to the structural unit of formula (4) can be reacted to introduce the phenolic compound corresponding to the structural unit of formula (4) into the triazine compound, and then the phenolic compound corresponding to the structural unit of formula (5) can be reacted. Next, a phenolic compound corresponding to the structural unit of formula (1) is mixed and reacted to form an intermediate phenolic compound, and this intermediate phenolic compound can then be reacted with a (meth)acrylation agent to form the curable resin of the present invention.

[0154] In this case, the triazine compound, the phenol compound corresponding to the structural unit of formula (4), the phenol compound corresponding to the structural unit of formula (5), and the phenol compound corresponding to the structural unit of formula (1) can be used in an amount of 0.01 to 1.0 mol per 1 mol of hydroxyl groups of the phenol compound corresponding to the structural unit of formula (1), the phenol compound corresponding to the structural unit of formula (5) can be used in an amount of 0.01 to 2.0 mol per 1 mol of hydroxyl groups of the phenol compound corresponding to the structural unit of formula (1), and the triazine compound can be used in an amount of 0.01 to 1.0 mol per 1.0 mol of the total hydroxyl groups of the phenol compounds corresponding to the structural units of formula (1), formula (4), and formula (5).

[0155] The structural unit of formula (4) can be introduced into the triazine compound by mixing a phenol compound corresponding to the structural unit of formula (4), a triazine compound, an alkali catalyst, and optionally a phase transfer catalyst in an organic solvent. From the viewpoint of reactivity, the reaction temperature is preferably 0 to 60°C. The types and amounts of the alkali catalyst, phase transfer catalyst, and organic solvent can be the same as those in Reaction 1-2.

[0156] A phenol compound corresponding to the structural unit of formula (5) is mixed with a reaction mixture containing a triazine compound having a structural unit of formula (4) introduced therein, and the reaction is carried out by raising the temperature to 0 to 80°C, thereby obtaining a reaction mixture containing a compound having a structural unit of formula (5) introduced therein. From the viewpoint of reactivity, a temperature of 40 to 80°C is preferred.

[0157] To promote the reaction, it is preferable to add an alkali catalyst and, optionally, a phase transfer catalyst when mixing the phenolic compound corresponding to the structural unit of formula (5). The amount of the additional alkali catalyst used can be 0.50 to 1.0 mol per mol of hydroxyl groups in the phenolic compound corresponding to the structural unit of formula (5). When an additional phase transfer catalyst is used, the amount can be 0.0003 to 0.1 mol per mol of hydroxyl groups in the phenolic compound corresponding to the structural unit of formula (5).

[0158] An intermediate phenol compound can be obtained by mixing a phenol compound corresponding to the structural unit of formula (1) with a reaction mixture containing a compound having a structural unit of formula (5) introduced therein, and then heating the mixture to 0 to 80°C to carry out the reaction. From the viewpoint of reactivity, a temperature of 40 to 80°C is preferred.

[0159] After the reaction is complete, the intermediate phenol compound can be obtained. For example, the reaction mixture can be separated into an upper layer and a lower layer as appropriate in the same manner as in Reaction 1-2, and the lower aqueous layer can be removed to obtain the intermediate phenol compound.

[0160] Next, in the same manner as in Reaction 1-2, the resulting intermediate phenol compound is reacted with a (meth)acrylation agent to introduce a (meth)acryloyl group.

[0161] An example of Reaction 1-4 is as follows (a representative reaction among Reactions 1-4). [ka]

[0162] <Production of curable resin having structural unit represented by formula (7)> The curable resin of the present invention having a structural unit represented by formula (3) can be obtained by reacting a phenolic compound corresponding to the structural unit of formula (1), a phthalic acid compound, and a (meth)acrylating agent. This curable resin includes a curable resin having a structural unit represented by formula (7).

[0163] (Reaction 2-1) It is advantageous to react a phenol compound corresponding to the structural unit of formula (1) with a phthalic acid compound to obtain an intermediate phenol compound, and then react this intermediate phenol compound with a (meth)acrylation agent. In this case, the reaction can be carried out under the following conditions:

[0164] The phenol compound corresponding to the structural unit of formula (1) and the phthalic acid compound used to prepare the intermediate phenol compound can be used in an amount of 0.01 to 1.0 moles of the phthalic acid compound per mole of the hydroxyl group of the phenol compound corresponding to the structural unit of formula (1).

[0165] The reaction can be carried out in the presence of an alkaline catalyst and optionally a phase transfer catalyst.

[0166] Examples of alkali catalysts include lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium methoxy, sodium ethoxy, sodium tert-butoxy, potassium methoxy, potassium ethoxy, potassium tert-butoxy, triethylamine, pyridine, and dimethylaminopyridine. From the viewpoint of reactivity, sodium hydroxide or potassium hydroxide is preferred. The amount of alkali catalyst used can be 1 to 1.1 times the number of moles of hydroxyl groups. These catalysts can be used as a 1 to 50% by mass aqueous solution.

[0167] A phase transfer catalyst may be used in the reaction. Examples of phase transfer catalysts include ammonium-based catalysts such as tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium, tetrabutylammonium iodide, tetrabutylammonium hydroxide, benzyltriethylammonium chloride, benzyltriethylammonium bromide, benzyltriethylammonium iodide, and benzyltriethylammonium hydroxide; phosphonium-based catalysts such as tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, tetrabutylphosphonium iodide, and tetrabutylphosphonium hydroxide; and crown ether-based catalysts such as 12-crown-4-ether, 15-crown-5-ether, 18-crown-6-ether, and tribenzo-18-crown-6-ether. From the viewpoint of reactivity, tetrabutylammonium bromide, tetrabutylammonium iodide, benzyltriethylammonium chloride, and benzyltriethylammonium iodide are preferred. The phase transfer catalysts may be used alone or in combination of two or more. The amount of the phase transfer catalyst used can be 0.0003 to 0.1 moles per mole of the hydroxyl group of the phenol compound corresponding to the structural unit of formula (1).

[0168] The reaction is preferably carried out in an organic solvent. Examples of organic solvents include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aromatic hydrocarbon solvents such as toluene, xylene, mesitylene, and Solvesso; ether solvents such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxane, and diethoxyethane; and aprotic polar solvents such as acetonitrile, dimethyl sulfoxide, sulfolane, dimethylformamide, and dimethylacetamide. From the viewpoint of solubility, toluene, xylene, mesitylene, Solvesso, dimethyl sulfoxide, dimethylformamide, and dimethylacetamide are preferred. These organic solvents can be used alone or in combination of two or more in any ratio. The amount of the organic solvent used is not particularly limited, but is preferably 50 to 2000% by mass relative to the phenol compound and phthalic acid compound corresponding to the structural unit of formula (1).

[0169] The reaction temperature can be set to 0 to 60° C., and from the viewpoint of reactivity, is preferably 25 to 60° C. The reaction time can be set to 1 to 48 hours.

[0170] The reaction can be carried out by mixing a phenol compound corresponding to the structural unit of formula (1), a phthalic acid compound, an alkali catalyst, and a phase transfer catalyst at 0 to 30°C, and then heating the mixture to 40 to 80°C. From the viewpoint of reactivity, a temperature of 40 to 60°C is preferred.

[0171] An intermediate phenolic compound can be obtained. For example, the intermediate phenolic compound can be obtained by separating the mixture into upper and lower layers as appropriate and removing the lower aqueous layer. The intermediate phenolic compound can be obtained by separating the mixture into upper and lower layers as appropriate and removing the lower aqueous layer. In this process, water may be added as needed to dissolve insoluble salts and remove the lower layer. The aqueous layer may be basic, neutralized by neutralization, or acidic. Examples of neutralizing agents used for neutralization include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, sodium monophosphate, and ammonium chloride, and organic acids such as methanesulfonic acid, paratoluenesulfonic acid, and oxalic acid. These acid catalysts may be used alone or in combination of two or more.

[0172] Next, the resulting intermediate phenol compound is reacted with a (meth)acrylation agent to introduce a (meth)acryloyl group.

[0173] The amounts of the intermediate phenol compound and (meth)acrylation agent used in the reaction can be 1.0 to 2.0 moles of the (meth)acrylation agent per mole of hydroxyl groups contained in the intermediate phenol compound.

[0174] The reaction can be carried out in the presence of a basic catalyst or an acidic catalyst. Examples of basic catalysts include amine-containing catalysts such as trimethylamine, triethylamine, N,N-diisopropylmethylamine, 1,8-diazabicyclo[5,4,0]-7-undecene, 1,5-diazabicyclo[4,3,0]-5-nonene, pyridine, and dimethylaminopyridine; alkaline earth metal hydroxides such as calcium hydroxide and barium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; and alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. Examples of acidic catalysts include sulfuric acid, methanesulfonic acid, and p-toluenesulfonic acid. Among these, triethylamine, N,N-diisopropylmethylamine, dimethylaminopyridine, and pyridine are preferred in terms of catalytic activity. The above catalysts may be used alone or in combination.

[0175] The amount of the basic or acidic catalyst used is preferably 0.5 to 2.0 moles per mole of hydroxyl groups contained in the intermediate phenol compound. These catalysts may be added all at once or in portions.

[0176] The reaction temperature can be set to 40 to 80° C. The reaction time can be set to 1 to 48 hours.

[0177] The reaction is preferably carried out in an organic solvent. Examples of organic solvents include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aromatic hydrocarbon solvents such as toluene, xylene, mesitylene, and Solvesso; alcoholic solvents such as methanol, ethanol, 1-propyl alcohol, isopropyl alcohol, 1-butanol, sec-butanol, and tert-butanol; cellosolve solvents such as methyl cellosolve and ethyl cellosolve; ether solvents such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxane, and diethoxyethane; and aprotic polar solvents such as acetonitrile, dimethyl sulfoxide, sulfolane, dimethylformamide, and dimethylacetamide. From the viewpoint of solubility, toluene, xylene, mesitylene, Solvesso, isopropyl alcohol, dimethyl sulfoxide, dimethylformamide, and dimethylacetamide are preferred. These organic solvents can be used alone or in combination of two or more in any ratio. The amount of organic solvent used is not particularly limited, but is preferably 50 to 2000% by mass based on the total amount of the phenolic resin and (meth)acrylation agent, which are charged as intermediates.

[0178] After the reaction is completed, the curable resin of the present invention can be obtained by carrying out reprecipitation, recrystallization, washing with water, distillation, etc.

[0179] An example of Reaction 2-1 is as follows (a representative reaction among Reaction 2-1): [ka]

[0180] The curable resin of the present invention has a heat-reactive (meth)acryloyl group, and therefore can be used as a thermosetting resin.

[0181] [Curable resin composition] The present invention also relates to a curable resin composition containing the curable resin of the present invention.

[0182] <Other resins> The curable resin composition of the present invention can contain resins other than the curable resin of the present invention (hereinafter also referred to as "other resins"), as long as the purpose is not impaired. The other resins are not particularly limited, and examples thereof include alkenyl group-containing compounds such as bismaleimides, allyl ether compounds, allylamine compounds, triallyl cyanurate, alkenylphenol compounds, vinyl group-containing polyolefin compounds, divinylbenzene, polydivinylbenzene, polybutadiene, acrylate compounds, and methacrylate compounds. In addition, other thermosetting resins such as thermosetting polyimide resins, epoxy resins, phenolic resins, active ester resins, benzoxazine resins, and cyanate resins can also be appropriately blended depending on the purpose.

[0183] <Curing accelerator> The curable resin composition of the present invention may also contain a curing accelerator, if necessary. The curing accelerator is not particularly limited, and examples thereof include organic peroxides (e.g., benzoyl peroxide, cumene hydroperoxide, dicumyl peroxide, lauroyl peroxide, di-t-butyl peroxide, t-butyl hydroperoxide, methyl ethyl ketone peroxide, t-butyl perbenzoate, etc.), azo compounds (azobisisobutyronitrile, etc.), and free radicals (azobisisobutyronitrile, galvinoxyl, etc.).

[0184] <Flame retardant> The curable resin composition of the present invention may contain a flame retardant as needed. The flame retardant is preferably a non-halogen flame retardant that does not substantially contain halogen atoms, and examples thereof include phosphorus-based flame retardants, nitrogen-based flame retardants, silicone-based flame retardants, inorganic flame retardants, and organic metal salt-based flame retardants. These flame retardants may be used alone or in combination of two or more.

[0185] <Filler> The curable resin composition of the present invention can contain an inorganic filler as needed. The inorganic filler is not particularly limited, and examples thereof include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide. When the amount of inorganic filler to be added is particularly large, it is preferable to use fused silica. Either crushed or spherical fused silica can be used, but in order to increase the amount of fused silica added and to suppress an increase in the melt viscosity of the molding material, it is preferable to mainly use spherical silica. Furthermore, in order to increase the amount of spherical silica added, it is preferable to appropriately adjust the particle size distribution of the spherical silica. When the curable resin composition is used for applications such as a conductive paste, which will be described in detail below, a conductive filler such as silver powder or copper powder can be used.

[0186] <Other compounding agents> The curable resin composition of the present invention may contain various additives such as a silane coupling agent, a release agent, a pigment, an emulsifier, etc., as needed.

[0187] <Method for producing curable resin composition> The curable resin composition of the present invention can be prepared by uniformly mixing the curable resin of the present invention alone or in addition to the curable resin of the present invention with the above-mentioned curing accelerator and other components. The mixing method is not particularly limited, and known methods can be used.

[0188] [Cured product] The present invention also relates to a cured product of the curable resin composition of the present invention.

[0189] The curable resin composition of the present invention can be cured by a curing reaction to form a cured product, such as a laminate, a cast, an adhesive layer, a coating, or a film, but is not limited to these.

[0190] Examples of the curing reaction include a thermosetting reaction and an ultraviolet curing reaction. Among them, the thermosetting reaction of the curable resin composition of the present invention is advantageous because it easily proceeds even without a catalyst. When it is desired to react more quickly, it is effective to blend a polymerization initiator such as an organic peroxide or an azo compound, or a basic catalyst such as a phosphine-based compound or a tertiary amine into the curable resin composition. Examples of the basic catalyst include benzoyl peroxide, dicumyl peroxide, azobisisobutyronitrile, triphenylphosphine, triethylamine, imidazoles, and the like.

[0191] [Use] The cured product of the present invention simultaneously satisfies low dielectric characteristics (low dielectric constant and low dielectric tangent), good dielectric characteristics after moisture absorption, high adhesion to a copper foil, and high heat resistance, and can be suitably used for heat-resistant members and electronic members. In particular, it can be suitably used for prepregs, circuit boards, semiconductor encapsulation materials, semiconductor devices, build-up films, build-up boards, adhesives, resist materials, and the like. It can also be suitably used as a matrix resin for fiber-reinforced resins, and is particularly suitable as a high heat-resistant prepreg. It is also possible to dissolve the curable resin composition of the present invention in various solvents to form a paint, and form a cured product using this paint. The heat-resistant members and electronic members thus obtained can be suitably used for various applications, and examples include industrial machine parts, general machine parts, parts of automobiles, railways, vehicles, etc., space and aviation-related parts, electronic and electrical parts, building materials, container and packaging members, daily necessities, sports and leisure goods, housing members for wind power generation, etc., but are not limited thereto.

Examples

[0192] Next, the present invention will be specifically described with reference to Examples and Comparative Examples. In the following, "parts" and "%" are based on mass unless otherwise specified. The curable resin and the cured product obtained using the curable resin were synthesized under the conditions shown below, and further, the obtained cured product was measured or calculated under the following conditions and evaluated.

[0193] <GPC Measurement (Evaluation of Number Average Molecular Weight, Weight Average Molecular Weight, and Average Repeat Unit Number)> Measurements were carried out using the following measuring equipment and under the following measuring conditions, and GPC charts were obtained for the phenolic resin, phenolic resin intermediate, and curable resin obtained below, from which the number average molecular weight (Mn) and weight average molecular weight (Mw) were determined. For the phenolic resins of Synthesis Examples 1 to 3, the average number of repeating units n of the structure having an indane skeleton was calculated based on the number average molecular weight (Mn) from the results of the GPC chart. Specifically, for compounds where n is 0 to 4, the theoretical molecular weight and each measured molecular weight in GPC were plotted on a scatter diagram, an approximation line was drawn, and the number average molecular weight (Mn) was determined from the point on the line indicated by the measured value Mn(1), and the average number of repeating units n was calculated. Measuring device: Tosoh Corporation "HLC-8320 GPC" Column: Tosoh Corporation guard column "HXL-L" + Tosoh Corporation "TSK-GEL G2000HXL" + Tosoh Corporation "TSK-GEL G2000HXL" + Tosoh Corporation "TSK-GEL G3000HXL" + Tosoh Corporation "TSK-GEL G4000HXL" Detector: RI (differential refractometer) Data processing: Tosoh Corporation's "GPC Workstation EcoSEC-WorkStation" Measurement conditions: Column temperature 40℃ Developing solvent: Tetrahydrofuran Flow rate 1.0ml / min Standard: The following monodisperse polystyrenes with known molecular weights were used in accordance with the measurement manual for the GPC Workstation EcoSEC-WorkStation. (Polystyrene used) Tosoh Corporation "A-500" Tosoh Corporation "A-1000" Tosoh Corporation "A-2500" Tosoh Corporation "A-5000" "F-1" manufactured by Tosoh Corporation "F-2" manufactured by Tosoh Corporation "F-4" manufactured by Tosoh Corporation "F-10" manufactured by Tosoh Corporation "F-20" manufactured by Tosoh Corporation "F-40" manufactured by Tosoh Corporation "F-80" manufactured by Tosoh Corporation "F-128" manufactured by Tosoh Corporation Sample: A 50 μl of a 1.0 mass% tetrahydrofuran solution of the curable resin having an indane skeleton obtained in the synthesis example, filtered through a microfilter (in terms of solid content).

[0194] < 1 1H-NMR measurement Measuring instrument: "JNM-ECA500" manufactured by JEOL Ltd. Magnetic field strength: 500 MHz Number of integrations: 16 times Solvent: chloroform-d Sample concentration: 5 mass%

[0195] < 13 13C-NMR measurement Measuring instrument: "JNM-ECA500" manufactured by JEOL Ltd. Magnetic field strength: 125 MHz Number of integrations: 4000 times Solvent: chloroform-d Sample concentration: 30 mass%

[0196] <IR measurement Measuring instrument: "FT / IR-4100 type A" manufactured by JASCO Corporation Method: KBr tablet method Number of integrations: 32 times Resolution: 4 cm -1

[0197] <Hydroxyl equivalent (phenol equivalent)> The hydroxyl equivalent (phenol equivalent) of the phenol resin and the phenol resin intermediate was calculated by titration. Here, the titration method refers to the neutral titration method based on JIS K0070.

[0198] Phenol resins (A-1) to (A-3) represented by the following general formula (iA) were synthesized.

Chemical formula

[0199] Synthesis Example 1: Synthesis of phenolic resin (A-1) A 2L flask equipped with a thermometer, condenser, Dean-Stark trap, and stirrer was charged with 200g (1.64mol) of 2,6-dimethylphenol, 636g (3.27mol) of α,α'-dihydroxy-1,3-diisopropylbenzene, 636g of xylene, and 84g of activated clay. The mixture was heated to 120°C with stirring. The temperature was then increased to 210°C while removing the distillate via a Dean-Stark tube, and the reaction was continued for 6 hours. The mixture was then air-cooled to 100°C, diluted with 636g of toluene, filtered to remove the activated clay, and the solvent and low-molecular-weight components, such as unreacted materials, were distilled off under reduced pressure to obtain 621g of the target phenolic resin (A-1). (Hydroxyl group equivalent: 555g / eq.) The Mn of the phenolic resin (A-1) was 1107, the Mw was 1799, and the average repeating unit number n was 4.5.

[0200] Synthesis Example 2: Synthesis of phenolic resin (A-2) A 2L flask equipped with a thermometer, condenser, Dean-Stark trap, and stirrer was charged with 300g (2.46mol) of 2,6-dimethylphenol, 658g (3.39mol) of α,α'-dihydroxy-1,3-diisopropylbenzene, 658g of xylene, and 96g of activated clay. The mixture was heated to 120°C with stirring. The temperature was then increased to 210°C while removing the distillate via a Dean-Stark tube, and the reaction was continued for 6 hours. The mixture was then air-cooled to 100°C, diluted with 658g of toluene, filtered to remove the activated clay, and the solvent and low-molecular-weight components, such as unreacted materials, were distilled off under reduced pressure to obtain 721g of the target phenolic resin (A-2). (Hydroxyl group equivalent: 405g / eq.) The Mn of the phenolic resin (A-2) was 909, the Mw was 1130, and the average repeating unit number n was 3.2.

[0201] Synthesis Example 3: Synthesis of phenolic resin (A-3) A 2 L flask equipped with a thermometer, condenser, Dean-Stark trap, and stirrer was charged with 170 g (1.39 mol) of 2,6-dimethylphenol, 811 g (4.17 mol) of α,α'-dihydroxy-1,3-diisopropylbenzene, 811 g of xylene, and 98 g of activated clay. The mixture was heated to 120 °C with stirring. The temperature was then increased to 210 °C while removing the distillate via a Dean-Stark tube, and the reaction was continued for 6 hours. The mixture was then air-cooled to 100 °C, diluted with 811 g of toluene, filtered to remove the activated clay, and the solvent and low-molecular-weight components, such as unreacted materials, were distilled off under reduced pressure to obtain 727 g of the target phenolic resin (A-3). (Hydroxyl group equivalent: 816 g / eq.) The Mn of the phenolic resin (A-2) was 1667, the Mw was 3189, and the average repeating unit number n was 8.0.

[0202] Thermosetting resins (B-1) to (B-15) were synthesized as follows. Structural units that can be included in the thermosetting resin are shown below. [ka]

[0203] Example 1: Synthesis of thermosetting resin (B-1) A 2 L flask equipped with a thermometer, condenser, Dean-Stark trap, and stirrer was charged with 200 g of phenolic resin (A-1), 1.1 g (0.006 mol) of cyanuric chloride, 400 g of toluene, 2.4 g (0.020 mol) of dimethylaminopyridine, and 40.0 g (0.40 mol) of triethylamine, and stirred at 60 °C. Once the solids were dissolved, 73.8 g (0.48 mol) of methacrylic anhydride was added dropwise over 1 hour. After the addition was complete, the mixture was allowed to react for an additional 3 hours at 60 °C. The mixture was then washed 10 times with water, and the organic layer was heated under vacuum in a rotary evaporator to remove volatiles, yielding thermosetting resin (B-1) with methacryloyl groups at its termini. The Mn of thermosetting resin (B-1) was 1359 and the Mw was 2044. The GPC chart is shown in Figure 1.

[0204] Example 2: Synthesis of thermosetting resin (B-2) A 2 L flask equipped with a thermometer, condenser, Dean-Stark trap, and stirrer was charged with 200 g of phenolic resin (A-1), 2.2 g (0.012 mol) of cyanuric chloride, 400 g of toluene, 2.4 g (0.020 mol) of dimethylaminopyridine, and 40.0 g (0.40 mol) of triethylamine, and stirred at 60 °C. Once the solids were dissolved, 69.9 g (0.45 mol) of methacrylic anhydride was added dropwise over 1 hour. After the addition was complete, the mixture was allowed to react for an additional 3 hours at 60 °C. The mixture was then washed 10 times with water, and the organic layer was heated under vacuum in a rotary evaporator to remove volatiles, yielding thermosetting resin (B-2) with methacryloyl groups at its termini. The Mn of thermosetting resin (B-2) was 1435 and the Mw was 2261. The GPC chart is shown in Figure 2.

[0205] Example 3: Synthesis of thermosetting resin (B-3) A 2 L flask equipped with a thermometer, condenser, Dean-Stark trap, and stirrer was charged with 200 g of phenolic resin (A-1), 3.7 g (0.020 mol) of cyanuric chloride, 400 g of toluene, 2.4 g (0.020 mol) of dimethylaminopyridine, and 40.0 g (0.40 mol) of triethylamine, and stirred at 60 °C. Once the solids appeared to be completely dissolved, 64.9 g (0.42 mol) of methacrylic anhydride was added dropwise over 1 hour. After the addition was complete, the mixture was allowed to react for an additional 3 hours at 60 °C. The mixture was then washed 10 times with water, and the organic layer was heated under vacuum in a rotary evaporator to remove volatiles, yielding thermosetting resin (B-3) with methacryloyl groups at its termini. The Mn of thermosetting resin (B-3) was 1637 and the Mw was 2823. The GPC chart is shown in Figure 3.

[0206] Example 4: Synthesis of thermosetting resin (B-4) A 2L flask equipped with a thermometer, condenser, Dean-Stark trap, and stirrer was charged with 400g of phenolic resin (A-1), 16.1g (0.087mol), cyanuric chloride 1219g, and 0.62g (0.0019mol) of tetrabutylammonium bromide. While stirring, 54.1g (0.27mol) of 20% by weight aqueous sodium hydroxide solution was added dropwise at 25°C over 3 hours. The mixture was then heated to 80°C and reacted at that temperature for 5 hours. The mixture was then neutralized with 30% by weight aqueous sodium phosphate and washed four times with water. The solvent and water were then removed by heating under reduced pressure, yielding a phenolic resin intermediate (hydroxyl equivalent: 862g / equivalent). A 2 L flask equipped with a thermometer, condenser, Dean-Stark trap, and stirrer was charged with 250 g of the above phenolic resin intermediate, 500 g of toluene, 2.0 g (0.017 mol) of dimethylaminopyridine, and 29.3 g (0.29 mol) of triethylamine, and stirred at 60 °C. Once all solids were dissolved, 62.6 g (0.41 mol) of methacrylic anhydride was added dropwise over 1 hour. After the addition was complete, the mixture was allowed to react for an additional 3 hours at 60 °C. The mixture was then washed 10 times with water, and the organic layer was heated under vacuum in a rotary evaporator to remove volatiles, yielding thermosetting resin (B-4) with methacryloyl groups at its termini. The Mn of thermosetting resin (B-4) was 1887 and the Mw was 4511. The GPC chart is shown in Figure 4.

[0207] Example 5: Synthesis of thermosetting resin (B-5) A 2L flask equipped with a thermometer, condenser, Dean-Stark trap, and stirrer was charged with 400g of phenolic resin (A-1), 22.1g (0.12mol) of cyanuric chloride, 1227g of toluene, and 0.61g (0.0019mol) of tetrabutylammonium bromide. While stirring, 74.2g (0.37mol) of 20% by weight aqueous sodium hydroxide solution was added dropwise at 25°C over 3 hours. The temperature was then raised to 80°C and the mixture was allowed to react at that temperature for 5 hours. The mixture was then neutralized with 30% by weight aqueous sodium phosphate and washed four times with water. The solvent and water were then removed by heating under reduced pressure, yielding a phenolic resin intermediate (hydroxyl equivalent: 1299g / equivalent). A 2 L flask equipped with a thermometer, condenser, Dean-Stark trap, and stirrer was charged with 170 g of the above phenolic resin intermediate, 340 g of toluene, 0.88 g (0.0072 mol) of dimethylaminopyridine, and 13.3 g (0.13 mol) of triethylamine, and stirred at 60 °C. Once the solids appeared to be completely dissolved, 28.3 g (0.18 mol) of methacrylic anhydride was added dropwise over 1 hour. After the addition was complete, the mixture was allowed to react for an additional 3 hours at 60 °C. The mixture was then washed 10 times with water, and the organic layer was heated under vacuum in a rotary evaporator to remove volatiles, yielding thermosetting resin (B-5) with methacryloyl groups at its termini. The Mn of thermosetting resin (B-5) was 2462 and the Mw was 8961. The GPC chart is shown in Figure 5.

[0208] Example 6: Synthesis of thermosetting resin (B-6) A 2L flask equipped with a thermometer, condenser, Dean-Stark trap, and stirrer was charged with 413g of phenolic resin (A-2), 22.4g (0.12mol) of cyanuric chloride, 1268g of toluene, and 0.63g (0.0019mol) of tetrabutylammonium bromide. While stirring, 75.2g (0.38mol) of 20% by weight aqueous sodium hydroxide solution was added dropwise at 25°C over 3 hours. The temperature was then raised to 80°C and the mixture was allowed to react at that temperature for 5 hours. The mixture was then neutralized with 30% by weight aqueous sodium phosphate and washed four times with water. The solvent and water were then removed by heating under reduced pressure, yielding a phenolic resin intermediate (hydroxyl equivalent: 620g / equivalent). A 2L flask equipped with a thermometer, condenser, Dean-Stark trap, and stirrer was charged with 250 g of the above phenolic resin intermediate, 500 g of toluene, 2.7 g (0.022 mol) of dimethylaminopyridine, and 40.8 g (0.40 mol) of triethylamine, and the mixture was stirred at 60°C. Once all solids appeared to have dissolved, 87.1 g (0.56 mol) of methacrylic anhydride was added dropwise over 1 hour. After the addition was complete, the mixture was allowed to react for an additional 3 hours at 60°C. The mixture was then washed 10 times with water, and the organic layer was heated under vacuum in a rotary evaporator to remove volatiles, yielding thermosetting resin (B-6) having methacryloyl groups at its termini. The Mn of thermosetting resin (B-6) was 1442 and the Mw was 2730. The GPC chart is shown in Figure 6. 1 H-NMR measurement results, 13 The results of C-NMR and IR measurements are shown in FIGS.

[0209] Example 7: Synthesis of thermosetting resin (B-7) A 2L flask equipped with a thermometer, condenser, Dean-Stark trap, and stirrer was charged with 250g of phenolic resin (A-2), 19g (0.10mol), cyanuric chloride, 773g of toluene, and 0.39g (0.0012mol) of tetrabutylammonium bromide. While stirring, 63.5g (0.32mol) of 20% by weight aqueous sodium hydroxide solution was added dropwise at 25°C over 3 hours. The temperature was then raised to 80°C and the mixture was allowed to react at that temperature for 5 hours. The mixture was then neutralized with 30% by weight aqueous sodium phosphate and washed four times with water. The solvent and water were then removed by heating under reduced pressure, yielding a phenolic resin intermediate (hydroxyl equivalent: 751g / equivalent). A 2 L flask equipped with a thermometer, condenser, Dean-Stark trap, and stirrer was charged with 200 g of the above phenolic resin intermediate, 400 g of toluene, 1.8 g (0.015 mol) of dimethylaminopyridine, and 27.0 g (0.27 mol) of triethylamine, and stirred at 60 °C. Once all solids were dissolved, 57.5 g (0.37 mol) of methacrylic anhydride was added dropwise over 1 hour. After the addition was complete, the mixture was allowed to react for an additional 3 hours at 60 °C. The mixture was then washed 10 times with water, and the organic layer was heated under vacuum in a rotary evaporator to remove volatiles, yielding thermosetting resin (B-7) with methacryloyl groups at its termini. The Mn of thermosetting resin (B-7) was 1831 and the Mw was 5135. The GPC chart is shown in Figure 10.

[0210] Example 8: Synthesis of thermosetting resin (B-8) A 2L flask equipped with a thermometer, condenser, Dean-Stark trap, and stirrer was charged with 300g of phenolic resin (A-3), 6.6g (0.036mol), cyanuric chloride, 908g of toluene, and 0.45g (0.0014mol) of tetrabutylammonium bromide. While stirring, 22.2g (0.11mol) of 20% by weight aqueous sodium hydroxide solution was added dropwise at 25°C over 3 hours. The temperature was then raised to 80°C and the mixture was allowed to react at that temperature for 5 hours. The mixture was then neutralized with 30% by weight aqueous sodium phosphate and washed four times with water. The solvent and water were then removed by heating under reduced pressure, yielding a phenolic resin intermediate (hydroxyl equivalent weight: 1161g / eq). A 2 L flask equipped with a thermometer, condenser, Dean-Stark trap, and stirrer was charged with 200 g of the above phenolic resin intermediate, 400 g of toluene, 1.2 g (0.0098 mol) of dimethylaminopyridine, and 17.4 g (0.17 mol) of triethylamine, and stirred at 60 °C. Once the solids appeared to be completely dissolved, 37.2 g (0.24 mol) of methacrylic anhydride was added dropwise over 1 hour. After the addition was complete, the mixture was allowed to react for an additional 3 hours at 60 °C. The mixture was then washed 10 times with water, and the organic layer was heated under vacuum in a rotary evaporator to remove volatiles, yielding thermosetting resin (B-8) with methacryloyl groups at its termini. The Mn of thermosetting resin (B-8) was 2187 and the Mw was 5348. The GPC chart is shown in Figure 11.

[0211] Example 9: Synthesis of thermosetting resin (B-9) A 2L flask equipped with a thermometer, condenser, Dean-Stark trap, and stirrer was charged with 150g of phenolic resin (A-1), 12.7g (0.063mol) of isophthalic acid dichloride, 474g of toluene, and 0.79g (0.0025mol) of tetrabutylammonium bromide. While stirring, 25.8g (0.13mol) of 20% by weight aqueous sodium hydroxide solution was added dropwise at 25°C over 3 hours. The temperature was then raised to 40°C and the mixture was allowed to react at that temperature for 1 hour. The mixture was then neutralized with 30% by weight aqueous sodium phosphate and washed four times with water. The solvent and water were then removed by heating under reduced pressure, yielding a phenolic resin intermediate (hydroxyl equivalent weight: 1110g / eq). A 2 L flask equipped with a thermometer, condenser, Dean-Stark trap, and stirrer was charged with 139 g of the above phenolic resin intermediate, 280 g of toluene, 0.77 g (0.0063 mol) of dimethylaminopyridine, and 14.0 g (0.14 mol) of triethylamine, and stirred at 60 °C. Once the solids appeared to be completely dissolved, 29.0 g (0.19 mol) of methacrylic anhydride was added dropwise over 1 hour. After the addition was complete, the mixture was allowed to react for an additional 3 hours at 60 °C. The mixture was then washed 10 times with water, and the organic layer was heated under vacuum in a rotary evaporator to remove volatiles, yielding thermosetting resin (B-9) with methacryloyl groups at its termini. The Mn of thermosetting resin (B-9) was 2195 and the Mw was 4940. The GPC chart is shown in Figure 12. 1 H-NMR measurement results, 13 The results of C-NMR and IR measurements are shown in FIGS.

[0212] Example 10: Synthesis of thermosetting resin (B-10) A 2L flask equipped with a thermometer, condenser, Dean-Stark trap, and stirrer was charged with 299g of phenolic resin (A-1), 38.0g (0.189mol) of isophthalic acid dichloride, 970g of toluene, and 0.48g (0.0015mol) of tetrabutylammonium bromide. While stirring, 77.6g (0.39mol) of 20% by weight aqueous sodium hydroxide solution was added dropwise at 25°C over 3 hours. The temperature was then raised to 40°C and the mixture was allowed to react at that temperature for 1 hour. The mixture was then neutralized with 30% by weight aqueous sodium phosphate and washed four times with water. The solvent and water were then removed by heating under reduced pressure, yielding a phenolic resin intermediate (hydroxyl equivalent: 1848g / eq). A 2 L flask equipped with a thermometer, condenser, Dean-Stark trap, and stirrer was charged with 220 g of the above phenolic resin intermediate, 440 g of toluene, 0.80 g (0.0065 mol) of dimethylaminopyridine, and 12.7 g (0.13 mol) of triethylamine, and stirred at 60 °C. Once all solids were dissolved, 25.7 g (0.17 mol) of methacrylic anhydride was added dropwise over 1 hour. After the addition was complete, the mixture was allowed to react for an additional 3 hours at 60 °C. The mixture was then washed 10 times with water, and the organic layer was heated under vacuum in a rotary evaporator to remove volatiles, yielding thermosetting resin (B-10) with methacryloyl groups at its termini. The Mn of thermosetting resin (B-10) was 2967 and the Mw was 8358. The GPC chart is shown in Figure 16.

[0213] Example 11: Synthesis of thermosetting resin (B-11) A 2L flask equipped with a thermometer, condenser, Dean-Stark trap, and stirrer was charged with 13.1g (0.107mol) of 2,6-dimethylphenol, 29.7g (0.161mol) of cyanuric chloride, 970g of toluene, and 0.48g (0.0015mol) of tetrabutylammonium bromide. While stirring, 22.1g (0.11mol) of 20% by weight aqueous sodium hydroxide solution was added dropwise at 20°C over 3 hours. Then, 298g of phenolic resin (A-1) was added and stirred until dissolved. After complete dissolution, 77.4g (0.39mol) of 20% by weight aqueous sodium hydroxide solution was added dropwise at 25°C over 3 hours with stirring. The mixture was then heated to 80°C and allowed to react at that temperature for 5 hours. The mixture was then neutralized with 30% by weight aqueous sodium phosphate and washed four times with water. The solvent and water were then removed by heating under reduced pressure, yielding a phenolic resin intermediate. (Hydroxyl equivalent 1821g / equivalent). A 2 L flask equipped with a thermometer, condenser, Dean-Stark trap, and stirrer was charged with 170 g of the above phenolic resin intermediate, 340 g of toluene, 0.63 g (0.0052 mol) of dimethylaminopyridine, and 9.5 g (0.094 mol) of triethylamine, and stirred at 60 °C. Once the solids appeared to be completely dissolved, 20.2 g (0.13 mol) of methacrylic anhydride was added dropwise over 1 hour. After the addition was complete, the mixture was allowed to react for an additional 3 hours at 60 °C. The mixture was then washed 10 times with water, and the organic layer was heated under vacuum in a rotary evaporator to remove volatiles, yielding thermosetting resin B-11 with methacryloyl groups at its termini. The Mn of thermosetting resin (B-11) was 3063 and the Mw was 13212. The GPC chart is shown in Figure 17.

[0214] Example 12: Synthesis of thermosetting resin (B-12) A 2L flask equipped with a thermometer, condenser, Dean-Stark trap, and stirrer was charged with 21.9g (0.179mol) of 2,6-dimethylphenol, 33.1g (0.179mol) of cyanuric chloride, 1002g of toluene, and 0.50g (0.0016mol) of tetrabutylammonium bromide. 37.0g (0.185mol) of 20% by weight aqueous sodium hydroxide solution was added dropwise at 20°C over 3 hours while stirring. 299g of phenolic resin (A-1) was then added and stirred until dissolved. After complete dissolution, 73.9g (0.37mol) of 20% by weight aqueous sodium hydroxide solution was added dropwise at 25°C over 3 hours while stirring. The mixture was then heated to 80°C and reacted at that temperature for 5 hours. The mixture was then neutralized with 30% by weight aqueous sodium phosphate and washed four times with water. The solvent and water were then removed by heating under reduced pressure, yielding a phenolic resin intermediate. (Hydroxyl equivalent 1965g / equivalent). A 2 L flask equipped with a thermometer, condenser, Dean-Stark trap, and stirrer was charged with 200 g of the above phenolic resin intermediate, 400 g of toluene, 0.68 g (0.0056 mol) of dimethylaminopyridine, and 10.3 g (0.10 mol) of triethylamine, and stirred at 60 °C. Once the solids appeared to be completely dissolved, 22.0 g (0.14 mol) of methacrylic anhydride was added dropwise over 1 hour. After the addition was complete, the mixture was allowed to react for an additional 3 hours at 60 °C. The mixture was then washed 10 times with water, and the organic layer was heated under vacuum in a rotary evaporator to remove volatiles, yielding thermosetting resin (B-12) with methacryloyl groups at its termini. The Mn of thermosetting resin (B-12) was 2452 and the Mw was 5724. The GPC chart is shown in Figure 18.

[0215] Example 13: Synthesis of thermosetting resin (B-13) A 2L flask equipped with a thermometer, condenser, Dean-Stark trap, and stirrer was charged with 31.2g (0.255mol) of 2,6-dimethylphenol, 47.1g (0.255mol) of cyanuric chloride, 931g of toluene, and 0.51g (0.0017mol) of tetrabutylammonium bromide. While stirring, 51.1g (0.256mol) of 20% by weight aqueous sodium hydroxide solution was added dropwise at 20°C over 3 hours. Then, 56.2g of a polyaddition reaction resin of dicyclopentadiene and phenol (hydroxyl group equivalent: 165g / eq, softening point 85°C) was added, heated to 60°C, and 68.1g (0.34mol) of 20% by weight aqueous sodium hydroxide solution was added dropwise over 3 hours at the same temperature. Then, 203.8g of phenolic resin (A-1) was added and stirred until dissolved. After dissolution, 38.7 g (0.19 mol) of 20% by weight aqueous sodium hydroxide solution was added dropwise over 3 hours while stirring at the same temperature. The mixture was then heated to 80°C and reacted at that temperature for 5 hours. After that, the mixture was neutralized with 30% by weight aqueous sodium phosphate solution and washed four times with water. The solvent and water were then removed by heating under reduced pressure, yielding a phenolic resin intermediate (hydroxyl group equivalent weight: 1886 g / equivalent). A 2 L flask equipped with a thermometer, condenser, Dean-Stark trap, and stirrer was charged with 250 g of the above phenolic resin intermediate, 500 g of toluene, 0.89 g (0.0073 mol) of dimethylaminopyridine, and 14.1 g (0.14 mol) of triethylamine, and stirred at 60 °C. Once all solids were dissolved, 28.6 g (0.19 mol) of methacrylic anhydride was added dropwise over 1 hour. After the addition was complete, the mixture was allowed to react for an additional 3 hours at 60 °C. The mixture was then washed 10 times with water, and the organic layer was heated under vacuum in a rotary evaporator to remove volatiles, yielding thermosetting resin (B-13) with methacryloyl groups at its termini. The Mn of thermosetting resin (B-13) was 2754 and the Mw was 10480. The GPC chart is shown in Figure 19.

[0216] Comparative Example 1: Synthesis of thermosetting resin (B-14) A 2 L flask equipped with a thermometer, condenser, Dean-Stark trap, and stirrer was charged with 200 g of phenolic resin (A-1), 400 g of toluene, 2.4 g (0.020 mol) of dimethylaminopyridine, and 40.0 g (0.40 mol) of triethylamine, and the mixture was stirred at 60 °C. Once the solids appeared to be completely dissolved, 77.8 g (0.50 mol) of methacrylic anhydride was added dropwise over 1 hour. After the addition was complete, the mixture was allowed to react for an additional 3 hours at 60 °C. The mixture was then washed 10 times with water, and the organic layer was heated under vacuum in a rotary evaporator to remove volatiles, yielding thermosetting resin (B-14) with methacryloyl groups at its termini. The Mn and Mw of thermosetting resin (B-14) were 1291 and 2037, respectively. The GPC chart is shown in Figure 20. The IR analysis results are also shown in Figure 21.

[0217] Comparative Example 2: Synthesis of thermosetting resin (B-15) A 2 L flask equipped with a thermometer, condenser, Dean-Stark trap, and stirrer was charged with 200 g (0.64 mol) of 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 28.5 g (0.15 mol) of cyanuric chloride, 400 g of toluene, 8.7 g (0.071 mol) of dimethylaminopyridine, and 143.4 g (1.42 mol) of triethylamine, and stirred at 60 °C. Once the solids appeared to be completely dissolved, 178.0 g (1.15 mol) of methacrylic anhydride was added dropwise over 1 hour. After the addition was complete, the mixture was allowed to react for an additional 3 hours at 60 °C. The mixture was then washed 10 times with water, and the organic layer was heated under vacuum in a rotary evaporator to remove volatiles, yielding a thermosetting resin (B-15) with methacryloyl groups at its termini. The thermosetting resin (B-15) had an Mn of 732 and an Mw of 1025, and its GPC chart is shown in FIG.

[0218] Examples 14 to 18 and Comparative Example 3 <Preparation of cured product> To each component in the proportions shown in Table 1 (proportions in the table are in parts by mass), Perbutyl P (α,α'-di(t-butylperoxy)diisopropylbenzene, manufactured by NOF Corporation) was added as a curing catalyst in an amount of 0.5% by mass relative to the total of 100% by mass of each component. The mixture was heated and mixed, then poured into a mold machined to a thickness of 2 mm, and cured at 170°C for 30 minutes and then at 200°C for 2 hours to obtain a cured product. In Comparative Example 3, Noryl (trademark) SA9000 resin, manufactured by Sabic, was used as the thermosetting resin. TAIC in the table stands for triallyl isocyanurate.

[0219] The physical properties of the cured product obtained as described above were evaluated as follows, and the results are shown in Table 1.

[0220] <Heat resistance (DMA TgI>) Using a viscoelasticity measuring device (Rheometrics "Solid Viscoelasticity Measuring Device RSAII", rectangular tension method: frequency 1 Hz, heating rate 3°C / min), the temperature at the lowest temperature where the rate of change in Tan δ was greatest was evaluated as the glass transition temperature (Tg).

[0221] <Dielectric properties (dielectric constant, dielectric loss tangent)> In accordance with JIS-C-6481, the dielectric constant and dielectric loss tangent of the test specimens at 1 GHz and 10 GHz were measured using the cavity resonance method with an Agilent Technologies network analyzer "E8362C" after drying and storing them in a room at 23°C and 50% humidity for 24 hours.

[0222] <Dielectric properties after moisture absorption (dielectric constant, dielectric loss tangent)> The above test specimens were treated at 121°C and 100% humidity for 6 hours, and then stored indoors at 23°C and 50% humidity for 24 hours after being completely dried. The dielectric constant and dielectric loss tangent at 1 GHz and 10 GHz were measured using the cavity resonance method using an Agilent Technologies network analyzer "E8362C" in accordance with JIS-C-6481.

[0223] <Thermal expansion characteristics (CTE)> Thermomechanical analysis was performed in compression mode using a thermomechanical analyzer (TMA: Seiko Instruments Inc. SS-6100) (measurement load: 88.8 mN, heating rate: 10°C / min twice, measurement temperature range: room temperature to 290°C). In the second measurement, the thermal expansion coefficient from 40°C to 60°C was evaluated as α1, and the thermal expansion coefficient from 230°C to 250°C as α2.

[0224] [Table 1]

[0225] Examples 19 to 32 and Comparative Examples 4 to 6 <Preparation of Curable Resin Composition> To each component in the proportions shown in Table 2 (proportions in the table are parts by mass), 1.0 mass% of Perbutyl P (α,α'-di(t-butylperoxy)diisopropylbenzene, manufactured by NOF Corporation) was added as a curing catalyst, based on a total of 100 mass% of the components, and toluene was added so that the final non-volatile content (NV) was 58 mass%, to prepare a curable resin composition. In the table, SA9000 resin is Noryl™ SA9000 resin manufactured by Sabic, and TAIC is triallyl isocyanurate.

[0226] <Fabrication of laminated plates> Using the obtained curable resin composition, a laminate was produced under the following conditions, and various evaluation tests were carried out using the methods described below. The results are shown in Table 2. Base material: Nitto Boseki Co., Ltd., glass cloth "#2116" (210 x 280 mm) Copper foil: "JTCSLC foil" (18μm) manufactured by JX Metals Co., Ltd. CF-T4X-SV (18 μm) manufactured by Fukuda Metal Foil and Powder Co., Ltd. CF-T9DA-SV (18 μm) manufactured by Fukuda Metal Foil and Powder Co., Ltd. Number of plies: 6 Curing conditions: 200℃, 29kg / cm 2 1.5 hours Plate thickness after molding: 0.8mm

[0227] <Dielectric properties (dielectric constant and dielectric loss tangent)> In accordance with JIS-C-6481, the dielectric constant (Dk) and dielectric loss tangent (Df) of the test specimens at 1 GHz and 10 GHz were measured using an Agilent Technologies Impedance Material Analyzer "HP4291B" after drying and storing them indoors at 23°C and 50% humidity for 24 hours.

[0228] <Copper foil adhesion (peel strength)> In accordance with JIS-6911, the laminate obtained above was cut into a size of 10 mm in width and 200 mm in length, and the peel strength of the copper foil was measured using this as a test piece to evaluate adhesion.

[0229] <Interlayer adhesion (interlayer peel strength)> The copper foil laminate obtained above was cut into a size of 10 mm wide and 200 mm long, and the interlayer adhesion was measured using this as a test piece in accordance with JIS-6911. The results are shown in Table 2.

[0230] [Table 2]

[0231] From the results shown in Tables 1 and 2 above, it can be seen that by using each of the curable resins of the Examples, it is possible to obtain a cured product that simultaneously satisfies low dielectric properties (low dielectric constant and low dielectric dissipation factor), good dielectric properties after moisture absorption, high adhesion to copper foil, and high heat resistance. [Industrial Applicability]

[0232] The cured product obtained using the curable resin of the present invention simultaneously satisfies low dielectric properties (low dielectric constant and low dielectric dissipation factor), good dielectric properties after moisture absorption, high adhesion to copper foil, and high heat resistance, and is therefore suitable for use in heat-resistant components and electronic components, particularly in prepregs, semiconductor encapsulants, circuit boards, build-up films, build-up boards, adhesives, and resist materials. It can also be used as a matrix resin for fiber-reinforced resins, and is suitable as a highly heat-resistant prepreg.

Claims

1. A structural unit represented by the following formula (1): At least one of a structural unit represented by the following formula (2) and a structural unit represented by the following formula (3), a terminal (meth)acryloyl group; A curable resin containing 【Chemistry 1】 (In formula (1), Each Ra independently represents an alkyl group, an aryl group, an aralkyl group, or a cycloalkyl group having 1 to 12 carbon atoms; each k independently represents an integer of 0 to 4; Rb's each independently represent an alkyl group, an aryl group, an aralkyl group, or a cycloalkyl group having 1 to 12 carbon atoms; １ are independently integers from 0 to 4, ２ are each independently an integer of 0 to 3, n is the average number of repeating units and is a number between 0.5 and 20; m is independently an integer of 0 to 2, * indicates a bond.) 【Chemistry 2】 (In formula (2), * represents a bond.) 【Transformation 3】 (In formula (3), Rc's each independently represent an alkyl group, an aryl group, an aralkyl group, or a cycloalkyl group having 1 to 12 carbon atoms; p represents an integer of 0 to 4; * indicates a bond.)

2. The curable resin according to claim 1, further comprising at least one of a structural unit represented by the following formula (4) and a structural unit represented by the following formula (5): 【Chemistry 4】 (In formula (4), Rd's each independently represent an alkyl group, an aryl group, an aralkyl group, or a cycloalkyl group having 1 to 12 carbon atoms, and when q is 2 or greater, two adjacent Rd's may be joined together to form a ring, and q is an integer of 0 to 5; * indicates a bond.) 【Transformation 5】 (In formula (5), Re is a single bond, -O-, -S-, -S(=O)-, -S(=O) ２ -, -C(=O)- or an optionally substituted hydrocarbon group, Ar １ are each independently 【Transformation 6】 or 【Transformation 7】 and Rf's each independently represent an alkyl group, an aryl group, an aralkyl group, or a cycloalkyl group having 1 to 12 carbon atoms; r represents an integer of 0 to 4; Rg's each independently represent an alkyl group, an aryl group, an aralkyl group, or a cycloalkyl group having 1 to 12 carbon atoms; s represents an integer of 0 to 6; Ar ２ are each independently 【Transformation 8】 or 【Chemistry 9】 and Rh each independently represents an alkyl group, an aryl group, an aralkyl group, or a cycloalkyl group having 1 to 12 carbon atoms; t represents an integer of 0 to 3; Ri each independently represents an alkyl group, an aryl group, an aralkyl group, or a cycloalkyl group having 1 to 12 carbon atoms; u represents an integer of 0 to 5; n ５ is the average number of repeating units, a number from 0 to 20; * indicates a bond.)

3. The curable resin according to claim 1, wherein the structural unit represented by the formula (1) is a structural unit represented by the following formula (1-1): 【Chemistry 10】 (In formula (1-1), R １ and R ２ each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, or a cycloalkyl group, n １ is the average number of repeating units, which is a number between 0.5 and 20; * indicates a bond.)

4. The curable resin according to claim 1 , having a structural unit represented by formula (6): 【Chemistry 11】 (In formula (6), R ３ are each independently a structural unit represented by the formula (1-1) or a structural unit represented by the formula (5), R ５ are each independently a structural unit represented by the following formula (1-2), a structural unit represented by the formula (4), a structural unit represented by the following formula (5-2), or Y, where Y is a (meth)acryloyl group, n ６ is the average number of repeating units, a number from 0 to 5; * is a bond, However, the curable resin has at least one of a structural unit represented by the formula (1-1) and a structural unit represented by the following formula (1-2): At least one Y is contained in the curable resin. 【Chemistry 12】 (In formula (1-2), R １ , R ２ , n １ and Y are the same as above, * indicates a bond.) 【Chemistry 13】 (In formula (5-2), Re, Ar １ , Ar ２ , Y and n ５ is the same as above, * indicates a bond.)

5. The curable resin according to claim 1 , having a structural unit represented by formula (7): 【Chemistry 14】 (In formula (7), R ７ is a structural unit represented by the formula (1-1) or a structural unit represented by the formula (5), R ８ represents a structural unit represented by the formula (1-2), a structural unit represented by the formula (4), a structural unit represented by the formula (5-2), or Y, n ７ is the average number of repeating units, a number from 0 to 5; However, the curable resin has at least one of a structural unit represented by the formula (1-1) and a structural unit represented by the formula (1-2), At least one Y is contained in the curable resin.

6. A curable resin composition comprising the curable resin according to any one of claims 1 to 5.

7. A cured product of the curable resin composition according to claim 6.

8. A prepreg comprising a reinforcing substrate and a semi-cured product of the curable composition according to claim 6 impregnated into the reinforcing substrate.

9. A circuit board which is a laminate of the prepreg according to claim 8 and copper foil.

10. A build-up film comprising the curable composition according to claim 6.

11. A semiconductor encapsulant comprising the curable composition according to claim 6.

12. A semiconductor device comprising the cured product of the semiconductor encapsulation material according to claim 11.

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