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

Abstract

The invention provides a curable resin, a curable resin composition, a cured product, a prepreg, a circuit board, a deposition film, a semiconductor sealing material, and a semiconductor device. The curable resin composition according to the present invention provides a cured product that simultaneously satisfies low dielectric properties (low dielectric constant and low dielectric loss tangent), good dielectric properties after moisture absorption, high adhesion to a copper foil, and high heat resistance. A curable resin containing a structural unit represented by formula (1), a terminal (meth) acryloyl group, and at least one of a structural unit represented by formula (2) and a structural unit represented by formula (3).

Description

Technical Field

[0001] This invention relates to curable resins, curable resin compositions containing the curable resin, and cured products obtained from the curable resin compositions. Furthermore, this invention relates to prepregs, circuit boards, deposited films, semiconductor sealing materials, and semiconductor devices. Background Technology

[0002] With the increase in information communication volume in recent years, information communication in the high-frequency band has become prevalent. In order to achieve better electrical characteristics, especially to reduce transmission loss in the high-frequency band, it is required to have electrical insulating materials with low dielectric properties (low dielectric constant and low dielectric loss tangent), excellent dielectric properties after moisture absorption, and high adhesion to low roughness copper foil.

[0003] Furthermore, printed circuit boards and electronic components using these electrical insulating materials are exposed to high-temperature reflow soldering during assembly, thus requiring heat resistance and materials with high glass transition temperatures. Especially recently, from an environmental perspective, the use of high-melting-point lead-free solders has further tightened the requirements for heat resistance.

[0004] To address these requirements, various vinyl benzyl ether-based thermosetting resins have been proposed, and attempts have been made to improve the resin structure by introducing an indane backbone (Patent Document 1). Regarding resins with an indane backbone, a technique has also been proposed to improve heat resistance and low dielectric properties by making the terminal part (meth)acryloyl group (Patent Document 2).

[0005] On the other hand, as a thermosetting resin with (meth)acrylyl groups at the end, there is Noryl (trademark) SA9000 resin, which is commercially available from Sabic Corporation.

[0006] However, these thermosetting resins cannot be said to be resins that simultaneously satisfy low dielectric properties (low dielectric constant and low dielectric loss tangent), good dielectric properties after moisture absorption, high adhesion to copper foil, and high heat resistance. Further improvements in these properties are expected.

[0007] Existing technical documents

[0008] Patent documents

[0009] Patent Document 1: Japanese Patent Application Publication No. 6-172242

[0010] Patent Document 2: International Publication No. 2021 / 205806 Summary of the Invention

[0011] The problem that the invention aims to solve

[0012] Therefore, the problem to be solved by the present invention is to provide a curable resin that simultaneously satisfies the following properties: low dielectric properties (low dielectric constant and low dielectric loss tangent), good dielectric properties after moisture absorption, high adhesion to copper foil (high peel strength), and high heat resistance.

[0013] Methods for solving problems

[0014] Therefore, the inventors conducted in-depth research to solve the above-mentioned problems and found that a curable resin with both an indimite skeleton and specific structural units can produce a cured product that simultaneously satisfies low dielectric properties (low dielectric constant and low dielectric loss tangent), good dielectric properties after moisture absorption, high adhesion to copper foil (high peel strength) and high heat resistance, thus completing the present invention.

[0015] [1] A curable resin comprising at least one of the structural units shown in formula (1), formula (2), and formula (3), and a terminal (meth)acryloyl group.

[0016] [Chemistry 1]

[0017]

[0018] In formula (1), Ra is independently an alkyl, aryl, aralkyl or cycloalkyl group with 1 to 12 carbon atoms, and k is independently an integer from 0 to 4.

[0019] Rb is independently an alkyl, aryl, aralkyl, or cycloalkyl group having 1 to 12 carbon atoms, l1 is independently an integer from 0 to 4, and l2 is independently an integer from 0 to 3.

[0020] n is the average number of repeating units, which is a value ranging from 0.5 to 20.

[0021] m are independent integers from 0 to 2.

[0022] * indicates a bonding bond.

[0023] [Chemistry 2]

[0024]

[0025] (In equation (2), * represents a bonding bond.)

[0026] [Chemistry 3]

[0027]

[0028] In formula (3), Rc is independently an alkyl, aryl, aralkyl, or cycloalkyl group with 1 to 12 carbon atoms, and p is an integer from 0 to 4.

[0029] * indicates a bonding bond.

[0030] [2] The curable resin of [1] further comprises at least one of the structural units shown in formula (4) and formula (5) below.

[0031] [Chemistry 4]

[0032]

[0033] (In formula (4), Rd is independently an alkyl, aryl, aralkyl or cycloalkyl group with 1 to 12 carbon atoms. When q is 2 or more, two adjacent Rd can form a ring together. q is an integer from 0 to 5. * represents a bonding bond.)

[0034] [Chemistry 5]

[0035]

[0036] In formula (5), Re is a single bond, -O-, -S-, -S(=O)-, -S(=O)2-, -C(=O)-, or a hydrocarbon group that may have substituents.

[0037] Ar1 is independently:

[0038] [Chemistry 6]

[0039]

[0040] or

[0041] [Chemistry 7]

[0042]

[0043] Rf is independently an alkyl, aryl, aralkyl, or cycloalkyl group having 1 to 12 carbon atoms, and r is an integer from 0 to 4.

[0044] Rg is independently an alkyl, aryl, aralkyl, or cycloalkyl group having 1 to 12 carbon atoms, and s is an integer from 0 to 6.

[0045] Ar2 is independently:

[0046] [Chemistry 8]

[0047]

[0048] or

[0049] [Chemistry 9]

[0050]

[0051] Rh are independently alkyl, aryl, aralkyl, or cycloalkyl groups having 1 to 12 carbon atoms, and t is an integer from 0 to 3.

[0052] Ri is independently an alkyl, aryl, aralkyl, or cycloalkyl group having 1 to 12 carbon atoms, and u is an integer from 0 to 5.

[0053] n5 is the average number of repeating units, which is a value from 0 to 20.

[0054] * indicates a bonding bond.

[0055] [3] For the curable resins of [1] or [2], the structural unit shown in the above formula (1) is the structural unit shown in the following formula (1-1).

[0056] [Chemistry 10]

[0057]

[0058] In formula (1-1), R1 and R2 are independently hydrogen atoms, alkyl groups having 1 to 12 carbon atoms, aryl groups, aralkyl groups, or cycloalkyl groups.

[0059] n1 is the average number of repeating units, ranging from 0.5 to 20.

[0060] * indicates a bonding bond.

[0061] [4] For any of the curable resins in [1] to [3], it has the structural unit shown in formula (6).

[0062] [Chemistry 11]

[0063]

[0064] In equation (6), R3 can be the structural unit shown in equation (1-1) or the structural unit shown in equation (5) above, respectively.

[0065] R5 can be independently represented by the structural unit shown in equation (1-2), the structural unit shown in equation (4), the structural unit shown in equation (5-2), or Y.

[0066] Here, Y stands for (meth)acryloyl.

[0067] n6 is the average number of repeating units, which is a value between 0 and 5.

[0068] * indicates a bonding bond.

[0069] The curable resin described above has at least one of the structural units shown in formula (1-1) above and the structural units shown in formula (1-2) below.

[0070] The aforementioned curable resin contains at least one γ.

[0071] [Chemistry 12]

[0072]

[0073] (In equation (1-2), R1, R2, n1, and Y are the same as above.)

[0074] * indicates a bonding bond.

[0075] [Chemistry 13]

[0076]

[0077] (In equation (5-2), Re, Ar1, Ar2, Y, and n5 are the same as above.)

[0078] * indicates a bonding bond.

[0079] [5] For any of the curable resins in [1] to [4], there is a structural unit as shown in formula (7).

[0080] [Chemistry 14]

[0081]

[0082] (In equation (7), R7 is the structural unit shown in equation (1-1) above or the structural unit shown in equation (5) above.)

[0083] R8 is the structural unit shown in equation (1-2), the structural unit shown in equation (4), the structural unit shown in equation (5-2), or Y.

[0084] n7 is the average number of repeating units, which is a value between 0 and 5.

[0085] The curable resin described above has at least one of the structural units shown in formula (1-1) and formula (1-2).

[0086] The aforementioned curable resin contains at least one γ.

[0087] [6] A curable resin composition comprising any one of [1] to [5] curable resins.

[0088] [7] A cured product of a curable resin composition of [6].

[0089] [8] A prepreg having a reinforcing substrate and a semi-cured product of a curable composition [6] impregnated in the reinforcing substrate.

[0090] [9] A circuit board, which is a laminate of prepreg and copper foil of [8].

[0091]

[10] A stacked film comprising a curable composition of [6].

[0092]

[11] A semiconductor sealing material comprising a curable composition containing [6].

[0093]

[12] A semiconductor device comprising a cured semiconductor sealing material of

[11] .

[0094] Invention Effects

[0095] The curable resin of the present invention can produce a cured product that simultaneously satisfies low dielectric properties (low dielectric constant and low dielectric loss tangent), good dielectric properties after moisture absorption, high adhesion to copper foil (high peel strength), and high heat resistance, and is therefore useful. Attached Figure Description

[0096] Figure 1 The results are obtained by gel permeation chromatography (GPC) of the curable resin synthesized in Example 1.

[0097] Figure 2 The results are GPC measurements of the curable resin synthesized in Example 2.

[0098] Figure 3 The results are GPC measurements of the curable resin synthesized in Example 3.

[0099] Figure 4 The results are GPC measurements of the curable resin synthesized in Example 4.

[0100] Figure 5 The results are GPC measurements of the curable resin synthesized in Example 5.

[0101] Figure 6 The results are GPC measurements of the curable resin synthesized in Example 6.

[0102] Figure 7 It is the curable resin synthesized in Example 6. 1 ¹H-NMR measurement results.

[0103] Figure 8 It is the curable resin synthesized in Example 6. 13 C-NMR measurement results.

[0104] Figure 9 The results are IR measurements of the curable resin synthesized in Example 6.

[0105] Figure 10 The results are GPC measurements of the curable resin synthesized in Example 7.

[0106] Figure 11 The results are GPC measurements of the curable resin synthesized in Example 8.

[0107] Figure 12 The results are GPC measurements of the curable resin synthesized in Example 9.

[0108] Figure 13 It is the curable resin synthesized in Example 9. 1 ¹H-NMR measurement results.

[0109] Figure 14 It is the curable resin synthesized in Example 9. 13 C-NMR measurement results.

[0110] Figure 15 The results are IR measurements of the curable resin synthesized in Example 9.

[0111] Figure 16 The results are GPC measurements of the curable resin synthesized in Example 10.

[0112] Figure 17 The results are GPC measurements of the curable resin synthesized in Example 11.

[0113] Figure 18 The results are GPC measurements of the curable resin synthesized in Example 12.

[0114] Figure 19 The results are GPC measurements of the curable resin synthesized in Example 13.

[0115] Figure 20 The results are GPC measurements of the curable resin synthesized in Comparative Example 1.

[0116] Figure 21 The results are IR measurements of the curable resin synthesized in Comparative Example 1.

[0117] Figure 22 The results are GPC measurements of the curable resin synthesized in Comparative Example 2. Detailed Implementation

[0118] The following describes in detail the methods for implementing the present invention, but the present invention is not limited to the following description and can be implemented in various ways within its scope.

[0119] [the term]

[0120] In this specification, "structural unit" refers to the (repeating) unit of a chemical structure formed during a reaction or polymerization. In other words, it refers to the part of the structure other than the chemical bonds involved in the reaction or polymerization in the resulting compound, i.e., the so-called residue.

[0121] The alkyl group in this specification can be either straight-chain or branched, and can be 1 to 12 carbon atoms, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, sec-pentyl, tert-pentyl, neopentyl, pentyl, cyclopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, etc.

[0122] In this specification, aryl refers to a monovalent aromatic hydrocarbon group, and examples of aryl groups include 6 to 20 carbon atoms, such as phenyl, naphthyl, biphenyl, phenanthrene, etc.

[0123] In this specification, aryl groups are alkyl groups substituted by one or more, preferably one or two, particularly one aryl group. The descriptions of aryl and alkyl groups described above are applicable to aryl and alkyl groups. Examples include benzyl, phenethyl, cumyl, etc.

[0124] In this specification, cycloalkyl groups can be monocyclic or polycyclic groups, and can be 3 to 30 in terms of carbon atom number, such as cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, methylcyclohexyl, ethylcyclohexyl, etc.

[0125] The ring in this specification can be monocyclic or polycyclic, and can be aromatic (e.g., benzene ring, naphthalene ring, etc.) or non-aromatic (e.g., cycloalkanes). Furthermore, it can be a carbocyclic or heterocyclic ring. Moreover, it can have substituents on the ring.

[0126] In this specification, (meth)acryloyl group is a general term encompassing acryloyl group and methacryloyl group, which may be either one or both.

[0127] The number-average molecular weight (Mn) and weight-average molecular weight (Mw) in this specification are set as values ​​measured using gel permeation chromatography (GPC) under the measurement conditions described in the examples described later.

[0128] [Curing Resin]

[0129] The curable resin of the present invention has a structural unit shown in formula (1), at least one of the structural units shown in formula (2) and formula (3), and a terminal (meth)acryloyl group.

[0130] <Structural unit shown in equation (1)>

[0131] The curable resin of the present invention has a structural unit as shown in formula (1). As described below, formula (1) is a structural unit having an indene skeleton.

[0132] [Chemistry 15]

[0133]

[0134] In formula (1), Ra is independently an alkyl, aryl, aralkyl, or cycloalkyl group having 1 to 12 carbon atoms, and k is independently an integer from 0 to 4.

[0135] Rb is independently an alkyl, aryl, aralkyl, or cycloalkyl group having 1 to 12 carbon atoms, l1 is independently an integer from 0 to 4, and l2 is independently an integer from 0 to 3.

[0136] n is the average number of repeating units, which is a value ranging from 0.5 to 20.

[0137] m are independent integers from 0 to 2.

[0138] * indicates a bonding bond.

[0139] Here, the straight lines from Ra, Rb, *-O, and carbon atoms toward the aromatic ring indicate that they can be bonded to any part of the aromatic ring. The same applies to other chemical structural formulas.

[0140] By incorporating indimium framework structural units with a high hydrocarbon content into the curable resin, excellent low dielectric properties are achieved even after moisture absorption. The indimium framework also provides excellent flexibility and suppleness, and is expected to suppress thermal expansion.

[0141] In formula (1), Ra is independently an alkyl, aryl, aralkyl, or cycloalkyl group having 1 to 12 carbon atoms, preferably an alkyl, aryl, or cycloalkyl group having 1 to 4 carbon atoms. By using an alkyl group having 1 to 12 carbon atoms, it is expected that the planarity near any of the benzene ring, naphthalene ring, and anthracene ring described later will decrease, the crystallinity will decrease, thereby increasing the solvent solubility and lowering the melting point, which is therefore preferred.

[0142] In equation (1), k is an integer from 0 to 4, preferably an integer from 0 to 2. From the viewpoint of reactivity, the above range is preferred. It is speculated that by having Ra, steric hindrance is formed, and molecular mobility is further reduced. From the perspective of expecting the cured material to have a lower dielectric loss tangent, k is particularly preferred to be 1 or 2.

[0143] In formula (1), Rb is independently an alkyl, aryl, aralkyl or cycloalkyl group having 1 to 12 carbon atoms, preferably an alkyl, aryl or cycloalkyl group having 1 to 4 carbon atoms.

[0144] In equation (1), l1 is an integer from 0 to 4, preferably an integer from 0 to 2. Additionally, l2 is an integer from 0 to 3, preferably an integer from 0 to 2. From a reactivity point of view, the above range is preferred.

[0145] In formula (1), m is an integer from 0 to 2, that is, when m is 0, it is a benzene ring; when m is 1, it is a naphthalene ring; when m is 2, it is an anthracene ring; and preferably, it is a benzene ring with m being 0. From the viewpoint of solvent solubility, the above range is preferred.

[0146] In formula (1), n ​​is the average number of repeating units, which 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 perspective of obtaining a cured product with good dielectric loss tangent even after moisture absorption and solvent solubility of the cured resin.

[0147] As for equation (1), the preferred equation is (1-1).

[0148] [Chemistry 16]

[0149]

[0150] In formula (1-1), R1 and R2 are independently hydrogen atoms, alkyl, aryl, aralkyl or cycloalkyl with 1 to 12 carbon atoms, and R1 and R2 are not both hydrogen atoms at the same time. n1 is the average number of repeating units, which is a value of 0.5 to 20.

[0151] In formula (1-1), R1 and R2 are independently hydrogen atoms, alkyl, aryl, aralkyl, or cycloalkyl groups having 1 to 12 carbon atoms, preferably alkyl, aryl, or cycloalkyl groups having 1 to 4 carbon atoms. By using alkyl groups having 1 to 12 carbon atoms, the planarity near the benzene ring decreases, the crystallinity decreases, thereby increasing solvent solubility and lowering the melting point. Therefore, it is preferable that neither of them is simultaneously hydrogen atoms. It is conceivable that by having R1 and R2, the steric hindrance increases (however, if not hydrogen atoms), and the molecular mobility further decreases, resulting in a cured product with a lower dielectric loss tangent, which is therefore preferred.

[0152] In formula (1-1), n1 is the average number of repeating units, which is a value of 0.5 to 20, preferably 0.5 to 7, and more preferably 3.0 to 4.5. The above range is preferred from the perspective of obtaining a cured product with good dielectric loss tangent even after moisture absorption and solvent solubility of the cured resin.

[0153] <At least one of the structural unit shown in equation (2) and the structural unit shown in equation (3)>

[0154] The curable resin of the present invention has at least one of the structural units shown in formula (2) and formula (3). Formulas (2) and (3) are described below, 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 units shown in formula (2) and formula (3) into the curable resin, high adhesion (high peel strength) to copper foil can be imparted to the cured product.

[0155] For improving the adhesion of copper foil by introducing the structural unit shown in formula (2) or formula (3), it is expected that with the introduction of these structural units, the proportion of polar groups in the curable resin will increase and the molecular weight will increase. Thus, the effects of (a) and (b) below can be expected, and these effects are considered to complement each other and comprehensively bring about an increase in peel strength or interlayer peel strength.

[0156] (a) The van der Waals interactions between resin / copper foil and resin / glass cloth are enhanced through polar groups.

[0157] (b) By increasing the molecular weight, the entanglement between resin molecules becomes stronger, and the cohesion of the cured product becomes stronger.

[0158] Among the structural units shown in Equation (2) and Equation (3), the structural unit shown in Equation (2) has symmetry, which is therefore more advantageous in terms of low dielectric properties.

[0159] [Chemistry 17]

[0160]

[0161] In equation (2), * represents a bonding bond.

[0162] [Chemistry 18]

[0163]

[0164] In formula (3), Rc is independently an alkyl, aryl, aralkyl, or cycloalkyl group having 1 to 12 carbon atoms, preferably an alkyl, aryl, or cycloalkyl group having 1 to 4 carbon atoms. For solubility, methyl is preferred, as it is an alkyl group having 1 to 12 carbon atoms.

[0165] In equation (3), p is an integer from 0 to 4, preferably an integer from 0 to 2. From the viewpoint of solubility, the above range is preferred.

[0166] In equation (3), the two -C(=O)-* can be any of the ortho, meta, and para positions. From the perspective of the reactivity of the polymerization reaction, the meta or para position is preferred.

[0167] In equation (3), * represents a bonding bond.

[0168] <Terminal (methyl)acryloyl>

[0169] The curable resin of the present invention has terminal (meth)acryloyl groups. The (meth)acryloyl group is a crosslinking group, resulting in a cured product with low molecular mobility and a low dielectric loss tangent compared to other crosslinking groups (e.g., vinyl benzyl ether (styrene), dihydroxyphenyl, etc.). In particular, in the case of methacryloyl groups, it is presumed that the inclusion of a methyl group in the structure increases steric hindrance, further reducing molecular mobility, and is expected to result in a cured product with an even lower dielectric loss tangent. Therefore, methacryloyl groups are preferred among the (meth)acryloyl groups. Furthermore, when there are multiple crosslinking groups, the crosslinking density increases, and the heat resistance improves; therefore, the curable resin preferably has multiple terminal (meth)acryloyl groups.

[0170] (Meth)acryloyl groups can be bonded to the bonding bonds of the structural units shown in formula (1) to form the end of a curable resin.

[0171] <Structural unit shown in equation (4)>

[0172] The curable resin of the present invention may have the structural unit shown in formula (4). Formula (4) is described below, for example, formed by bonding to the structural unit shown in formula (2) or formula (3) to form the end of the curable resin. By introducing the structural unit shown in formula (4) into the curable resin, the molecular weight, double bond equivalent, and content of the structural unit shown in formula (2) or formula (3) can be adjusted. This method allows for appropriate adjustment of the balance of fluidity, adhesion, etc., which is advantageous. Furthermore, when the curable resin has the structural unit shown in formula (2), the degree of branching can also be adjusted by bonding to the bonding in formula (2), resulting in good separation properties for use in the cleaning step of purification, thereby easily reducing the amount of ionic impurities remaining in the resin.

[0173] [Chemistry 19]

[0174]

[0175] In formula (4), Rd is independently an alkyl, aryl, aralkyl, or cycloalkyl group having 1 to 12 carbon atoms, preferably an alkyl, aryl, or cycloalkyl group having 1 to 4 carbon atoms. Since it is an alkyl group having 1 to 12 carbon atoms, it becomes a resin with excellent solubility, and is therefore preferred. Furthermore, from the perspective of the ease of obtaining industrial raw materials, methyl is more preferred.

[0176] In equation (4), q is an integer from 0 to 5, preferably an integer from 0 to 2. From the viewpoint of solubility, the above range is preferred.

[0177] When q is 2 or more, two adjacent Rd atoms can form a ring together, for example, a benzene ring. The benzene ring can have substituents, such as alkyl groups having 1 to 12 carbon atoms.

[0178] In equation (4), * represents a bonding bond.

[0179] <Structural unit shown in equation (5)>

[0180] The curable resin of the present invention can have the structural unit shown in formula (5). Formula (5) is described below, for example, it can be bonded to the bonding bonds of the structural unit shown in formula (2) or formula (3). By introducing the structural unit shown in formula (5) into the curable resin, the molecular weight and double bond equivalent can be adjusted, thereby increasing the content of the structural unit shown in formula (2) or formula (3), which can enhance the adhesion and is advantageous.

[0181] [Chemistry 20]

[0182]

[0183] In formula (5), Re is a single bond, -O-, -S-, -S(=O)-, -S(=O)2-, -C(=O)-, or a hydrocarbon group that may have substituents.

[0184] Examples of hydrocarbon groups include alkylene groups with 1 to 20 carbon atoms, cycloalkylene groups with 3 to 20 carbon atoms, arylene groups with 6 to 20 carbon atoms, or arylene groups with 8 to 20 carbon atoms. They may have substituents, such as halogen atoms (fluorine atoms, etc.).

[0185] Specifically, examples of Re include -CH2-, -CH(CH3)-, -C(CH3)2-, -C(CF3)2-, -CHPh-, -C(CH3)Ph-, 1,1-cyclopropylene, 1,1-cyclobutylene, 1,1-cyclopentylene, 1,1-cyclohexylene, 4-methyl-1,1-cyclohexylene, 3,3,5-trimethyl-1,1-cyclohexylene, 1,1-cyclooctylene, and 1,1-cyclohexylene. Nonyl, 1,2-ethylene, 1,2-cyclopropylene, 1,2-cyclobutylene, 1,2-cyclopentylene, 1,2-cyclohexylene, 1,2-phenylene, 1,3-propylene, 1,3-cyclobutylene, 1,3-cyclopentylene, 1,3-cyclohexylene, 1,3-phenylene, 1,4-butylene, 1,4-cyclohexylene, 1,4-phenylene, 1,1-fluorenyl, 1,2-xylene, 1,4-xylene, etc. In the above, Ph represents phenyl.

[0186] [Chemistry 21]

[0187]

[0188] In the formula, n 1 It can be 0 or 1.

[0189] R 1Each of these can be independently an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, or an aralkyl group.

[0190] n 2 It is an integer between 0 and 1 to 4.

[0191] R 2 It can be a hydrogen atom or a methyl group.

[0192] R 3 It is an alkylene group, oxygen atom, sulfur atom or carbonyl group having 1 to 4 carbon atoms.

[0193] n 3 It is an integer from 1 to 4.

[0194] Re is preferably a hydrocarbon group.

[0195] In equation (5), Ar1 is:

[0196] [Chemistry 22]

[0197]

[0198] or

[0199] [Chemistry 23]

[0200]

[0201] In formula (5), Rf is independently an alkyl, aryl, aralkyl, or cycloalkyl group having 1 to 12 carbon atoms, preferably an alkyl, aryl, or cycloalkyl group having 1 to 4 carbon atoms. By using the above-mentioned alkyl groups having 1 to 12 carbon atoms, the electrical properties become better, and therefore it is preferred.

[0202] In equation (5), r is an integer from 0 to 4, preferably an integer from 0 to 2. From the viewpoint of solubility, the above range is preferred.

[0203] In formula (5), Rg is independently an alkyl, aryl, aralkyl, or cycloalkyl group having 1 to 12 carbon atoms, preferably an alkyl, aryl, or cycloalkyl group having 1 to 4 carbon atoms. By using the above-mentioned alkyl groups having 1 to 12 carbon atoms, the electrical properties become better, and therefore it is preferred.

[0204] In equation (5), s is an integer from 0 to 6, preferably an integer from 0 to 4. From the viewpoint of solubility, the above range is preferred.

[0205] Ar2 is independently:

[0206] [Chemistry 24]

[0207]

[0208] or

[0209] [Chemistry 25]

[0210]

[0211] In formula (5), Rh is independently an alkyl, aryl, aralkyl, or cycloalkyl group having 1 to 12 carbon atoms, preferably an alkyl, aryl, or cycloalkyl group having 1 to 4 carbon atoms. By using the above-mentioned alkyl groups having 1 to 12 carbon atoms, the electrical properties become better, and therefore it is preferred.

[0212] In equation (5), t is an integer from 0 to 3, preferably an integer from 0 to 2. From the viewpoint of solubility, the above range is preferred.

[0213] In formula (5), Ri is independently an alkyl, aryl, aralkyl, or cycloalkyl group having 1 to 12 carbon atoms, preferably an alkyl, aryl, or cycloalkyl group having 1 to 4 carbon atoms. By using the above-mentioned alkyl groups having 1 to 12 carbon atoms, the electrical properties become better, and therefore it is preferred.

[0214] In equation (5), u represents an integer from 0 to 5, preferably an integer from 0 to 4. From the viewpoint of solubility, the above range is preferred.

[0215] In equation (5), * represents a bonding bond.

[0216] As for equation (5), the preferred one is equation (5-1) when n5 is 0.

[0217] [Chemistry 26]

[0218]

[0219] In equation (5-1), Ar1 and * are the same as above, and the examples and preferred examples described above can be applied.

[0220] <Structure of Curing Resins>

[0221] The curable resin of the present invention has at least one of the structural units shown in formula (1), formula (2), and formula (3), and a (meth)acryloyl group.

[0222] In this case, relative to 1 mole of the structural unit shown in formula (1), the structural unit shown in formula (2) can be set to 0 to 0.46 moles, the structural unit shown in formula (3) can be set to 0 to 0.86 moles, and the (meth)acryloyl group can be set to more than 0 moles and less than 1 mole. Among them, the structural units shown in formula (2) and formula (3) are not 0 moles.

[0223] For example, the curable resin of the present invention may be composed of the structural unit shown in formula (1), the structural unit shown in formula (2), and (meth)acryloyl groups.

[0224] At this point, it can be composed of (meth)acryloyl groups.

[0225] In this case, relative to 1 mole of the structural unit shown in formula (1), the structural unit shown in formula (2) can be set to 0.33 to 0.46 moles, and the (meth)acryloyl group can be set to 0.62 to 1 mole.

[0226] For example, the curable resin of the present invention may be composed of the structural unit shown in formula (1), the structural unit shown in formula (3), and (meth)acryloyl groups.

[0227] In this case, relative to 1 mole of the structural unit shown in formula (1), the structural unit shown in formula (3) can be set to 0.5 to 0.86 moles, and the (meth)acryloyl group can be set to 0.29 to 1 mole.

[0228] For example, the curable resin of the present invention may be composed of the structural unit shown in formula (1), the structural unit shown in formula (2), the structural unit shown in formula (4), and (meth)acryloyl groups.

[0229] In this case, relative to 1 mole of the structural unit shown in formula (1), the structural unit shown in formula (2) can be set to 0.33 to 1.2 moles, the structural unit shown in formula (4) can be set to more than 0 moles and less than 1.4 moles, and the (meth)acryloyl group can be set to 0.2 to 1 mole.

[0230] For example, the curable resin of the present invention may be composed of the structural unit shown in formula (1), the structural unit shown in formula (2), the structural unit shown in formula (4), the structural unit shown in formula (5), and (meth)acryloyl groups.

[0231] In this case, relative to 1 mole of the structural unit shown in formula (2), the structural unit shown in formula (1) can be set to 0.16 to 3 moles, the structural unit shown in formula (4) can be set to more than 0 moles and less than 2 moles, and the (meth)acryloyl group can be set to 0.16 to 3 moles.

[0232] The number-average molecular weight (Mn) of the curable resin of the present invention can be in the range of 500 to 15,000, preferably in the range of 1,000 to 5,000. Furthermore, the weight-average molecular weight (Mw) of the curable resin can be in the range of 1,200 to 100,000, preferably in the range of 1,800 to 25,000.

[0233] 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 to 20, preferably 1.7 to 10.

[0234] 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.

[0235] <A curable resin having the structural unit shown in formula (6)>

[0236] Examples of curable resins of the present invention include curable resins having the structural unit shown in formula (6).

[0237] [Chemistry 27]

[0238]

[0239] In equation (6), R3 is independently the structural unit shown in equation (1-1) or the structural unit shown in equation (5).

[0240] [Chemistry 28]

[0241]

[0242] In equation (1-1), R1, R2, n1 and * are the same as above, and the examples and preferred examples described above can be applied.

[0243] In equation (5), Ar1, Ar2, Re, n5 and * are the same as above, and the examples and preferred examples described above can be applied.

[0244] In formula (6), R5 is independently the structural unit shown in formula (1-2), the structural unit shown in formula (4), or the structural unit shown in formula (5-2) or Y (Y is (meth)acryloyl).

[0245] [Chemistry 29]

[0246]

[0247] In formula (1-2), R1, R2, n1 and * are the same as in formula (1-1) above, and the examples and preferred examples described in formula (1-1) above can be applied, and Y is (meth)acryloyl group.

[0248] In equation (4), Rd, q and * are the same as above, and the examples and preferred examples described above can be applied.

[0249] In formula (5-2), Ar1, Ar2, Re, n5 and * are the same as in formula (5) above, and the examples and preferred examples described in formula (5) above can be applied, and Y is (meth)acryloyl group.

[0250] As in equation (5-2), it is preferable that n5 is equivalent to the following equation which is 0.

[0251] [Chemistry 30]

[0252]

[0253] In the formula, Ar1, Re, and Y are the same as those mentioned above.

[0254] In equation (6), n6 is the average number of repeating units, which is a value of 0 to 5, preferably a value of 0 to 3.

[0255] The curable resin having the structural unit shown in formula (6) has at least one of the structural units shown in formula (1-1) and formula (1-2).

[0256] Additionally, at least one Y group as a (meth)acryloyl group is included in the curable resin having the structural unit shown in formula (6). Preferably, at least two Y groups are included, more preferably two to eight. When the curable resin having the structural unit shown in formula (6) includes the structural unit shown in formula (1-2) or formula (5-2), the Y group included in the curable resin may be the Y group constituting the structural unit shown in formula (1-2) or formula (5-2).

[0257] In equation (6), the bonding bond of the triazine ring can be bonded to the structural unit shown in equation (1-2) or the structural unit shown in equation (5-2).

[0258] In addition, in equation (6), the bonding bond of the triazine ring can also be further bonded to the triazine ring via R3. The bonding bond of the triazine ring can, for example, have the same repeating unit enclosed in n6 and terminal R5 as the main chain of equation (6).

[0259] <A curable resin having the structural unit shown in formula (7)>

[0260] Examples of curable resins of the present invention include curable resins having the structural unit shown in formula (7).

[0261] [Chemistry 31]

[0262]

[0263] In equation (7), R7 is the structural unit shown in equation (1-1) or the unit shown in equation (5).

[0264] [Chemistry 32]

[0265]

[0266] In equation (1-1), R1, R2, n1 and * are the same as above, and the examples and preferred examples described above can be applied.

[0267] In equation (5), Ar1, Ar2, Re, n5 and * are the same as above, and the examples and preferred examples described above can be applied.

[0268] In formula (7), R8 is the structural unit shown in formula (1-2), the structural unit shown in formula (4), the structural unit shown in formula (5-2), or Y (Y is (meth)acryloyl).

[0269] [Chemistry 33]

[0270]

[0271] In formula (1-2), R1, R2, n1, and * are the same as in formula (1-1) above, and the examples and preferred examples described in formula (1-1) above can be applied. Y is (meth)acryloyl. In formula (4), Rd, q, and * are the same as above, and the examples and preferred examples described above can be applied.

[0272] In formula (5-2), Ar1, Ar2, Re, n5 and * are the same as in formula (5) above, and the examples and preferred examples described in formula (5) above can be applied, and Y is (meth)acryloyl group.

[0273] In equation (7), n7 is the average number of repeating units, which is a value of 0 to 5, preferably a value of 0 to 3.

[0274] [Manufacturing method of curable resin]

[0275] The curable resin of the present invention can be obtained by reacting at least one of a phenolic compound corresponding to a structural unit of formula (1), a triazine compound and a phthalic acid compound, a (meth)acrylating agent, and, depending on the circumstances, at least one of a phenolic compound corresponding to a structural unit of formula (4) and a phenolic compound corresponding to a structural unit of formula (5).

[0276] <Phenolic compounds corresponding to the structural units of formula (1)>

[0277] Phenolic compounds corresponding to the structural units of formula (1) can be represented by the following formula (1A).

[0278] [Chemistry 34]

[0279]

[0280] In equation (1A), Ra, Rb, k, l1, l2, m and n are the same as in equation (1), and the examples and preferred examples described in equation (1) can be applied.

[0281] The compound shown in formula (1A) can be prepared by the method described in International Publication No. 2021 / 205806.

[0282] As for equation (1A), the preferred equation is (1-1A).

[0283] [Chemistry 35]

[0284]

[0285] In equation (1-1A), R1, R2 and n1 are the same as in equation (1-1), and the examples and preferred examples described in equation (1-1) can be applied.

[0286] The phenolic compound shown in formula (1A) may also be reacted, without impairing the effects of the present invention, as a mixture of compounds containing at least one structural unit selected from the structural units shown in formula (8) and formula (9) below (hereinafter also referred to as "other compounds").

[0287] [Chemistry 36]

[0288]

[0289] In the formula, Rb and l2 are the same as in formula (1).

[0290] * indicates a bonding bond.

[0291] As other compounds, examples include compounds obtained by replacing at least a portion of the indimium skeleton structural unit enclosed in n of formula (1A) with the structural unit shown in formula (8) or formula (9).

[0292] When the phenolic compound of formula (1A) is used as a mixture of other compounds for reaction, the curable resin of the present invention may contain at least one structural unit selected from the structural units of formula (8) and formula (9).

[0293] For example, in the case of other compounds in which at least a portion of the structural unit of the indimium skeleton enclosed in n of formula (1A) is replaced by the structural unit shown in formula (8) or formula (9), the curable resin of the present invention may contain the structural unit in which at least a portion of the structural unit of the indimium skeleton enclosed in n of formula (1) is replaced by the structural unit shown in formula (8) or formula (9).

[0294] <At least one of a triazine compound and a phthalic acid compound>

[0295] 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, with cyanuric chloride being preferred. Cyanuric chloride is a compound represented by the following formula (2A).

[0296] [Chemistry 37]

[0297]

[0298] As a phthalic acid compound, the compound shown in the following formula (3A) can be used.

[0299] [Chemistry 38]

[0300]

[0301] In equation (3A), Rc and p are the same as in equation (3), and the examples and preferred examples described in equation (3) can be applied.

[0302] The compounds shown in formula (3A) are preferably isophthalic acid compounds and terephthalic acid compounds, such as isophthalic acid and terephthalic acid.

[0303] Compounds of formula (3A) in the form of esters (e.g., methyl esters) and halides (e.g., chlorides, bromides) can also be used as phthalic acid compounds. Among them, isophthaloyl chloride and terephthaloyl chloride are preferred.

[0304] <(Meth)Acrylate>

[0305] There are no particular limitations on (meth)acrylic agents, as long as they are compounds capable of reacting with phenolic hydroxyl groups to introduce (meth)acryloyl groups. Examples of (meth)acrylic agents include (meth)acrylic anhydride, (meth)acryloyl chloride, (meth)acrylic acid, and (meth)acrylates. Examples of (meth)acrylates include alkyl esters of (meth)acrylic acid (e.g., alkyl esters with 1 to 4 carbon atoms).

[0306] Here, (meth)acrylic anhydride includes methacrylic anhydride and acrylic anhydride, and (meth)acryloyl chloride includes methacryloyl chloride and acryloyl chloride. (meth)acrylic acid includes methacrylic acid and acrylic acid, and (meth)acrylate includes methacrylate and acrylate. When the (meth)acrylating agent is methacrylic anhydride, methacryloyl chloride, methacrylic acid, methacrylate, etc., a methacryloyl group is introduced; when it is acrylic anhydride, acryloyl chloride, acrylic acid, acrylate, etc., an acryloyl group is introduced.

[0307] <Phenolic compounds corresponding to the structural units of formula (4)>

[0308] Phenolic compounds corresponding to the structural units of formula (4) can be represented by the following formula (4A).

[0309] [Chemistry 39]

[0310]

[0311] In equation (4A), Rd and q are the same as in equation (4), and the examples and preferred examples described in equation (4) can be applied.

[0312] Examples of compounds represented by formula (4A) include phenol; monoalkyl-substituted phenols such as o-cresol, m-cresol, p-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; and 1-naphthol and 2-naphthol. Among these, 2,6-dimethylphenol is preferred from the perspective of low dielectric loss tangent.

[0313] <Phenolic compounds corresponding to the structural units of formula (5)>

[0314] Phenolic compounds corresponding to the structural units of formula (5) can be represented by the following formula (5A).

[0315] [Chemistry 40]

[0316]

[0317] In equation (5A), Ar1, Ar2, Re, and n5 are the same as in equation (5), and the examples and preferred examples described in equation (5) can be applied.

[0318] As in formula (5A), it is preferable that n5 is equivalent to 0 in the following formula.

[0319] [Chemistry 41]

[0320]

[0321] In the formula, Ar1 and Re are the same as above.

[0322] Examples of compounds represented by formula (5A) include the following compounds.

[0323] [Chemistry 42]

[0324]

[0325] Here, n5 is the same as above.

[0326] [Chemistry 43]

[0327]

[0328] <Manufacturing of a curable resin having the structural unit shown in formula (6)>

[0329] By reacting at least a phenolic compound, a triazine compound, and a (meth)acrylic agent corresponding to the structural unit of formula (1), a curable resin of the present invention having the structural unit shown in formula (2) can be obtained. This curable resin includes curable resins having the structural unit shown in formula (6).

[0330] By using a triazine compound, the structural unit of formula (2) can be introduced into a curable resin. At this time, the phenolic compound, triazine compound and (meth)acrylating agent corresponding to the structural unit of formula (1) can be mixed together and reacted (reaction 1-1), or the phenolic compound and triazine compound corresponding to the structural unit of formula (1) can be reacted to obtain an intermediate phenolic compound, and then the intermediate phenolic compound can be reacted with the (meth)acrylating agent (reaction 1-2).

[0331] (Reaction 1-1)

[0332] When a phenolic compound, a triazine compound, and a (meth)acrylating agent corresponding to the structural unit of formula (1) are mixed together and reacted, the reaction can be carried out under the following conditions.

[0333] For the phenolic compound, triazine compound and (meth)acrylating agent corresponding to the structural unit of formula (1), 1 mole of triazine compound relative to the hydroxyl group of phenolic compound can be set to 0.01 to 0.33 moles, and 1 mole of (meth)acrylating agent relative to the hydroxyl group of phenolic compound can be set to 0.01 to 3.0 moles.

[0334] The reaction can be carried out in the presence of a basic catalyst.

[0335] Examples of basic catalysts include trimethylamine, triethylamine, N,N-diisopropylmethylamine, 1,8-diazabicyclo[5,4,0]-7-undecene, 1,5-diazabicyclo[4,3,0]-5-nonene, pyridine, and dimethylaminopyridine, among other amine-containing compounds; 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. From the viewpoint of catalytic activity, triethylamine, N,N-diisopropylmethylamine, dimethylaminopyridine, and pyridine are preferred. These catalysts can be used alone or in combination of two or more.

[0336] During the reaction, the basic catalyst is preferably used at a rate of 0.01 to 2.00 moles relative to 1 mole of hydroxyl groups. These catalysts can be added all at once or in batches.

[0337] From the viewpoint of avoiding side reactions, it is preferable to mix the phenolic compound and triazine compound corresponding to the structural unit of formula (1) with the basic catalyst and then add the (meth)acrylating agent.

[0338] The reaction temperature can be set from 0 to 80°C, but from a reactivity point of view, 20 to 80°C is preferred. The reaction time can be from 1 to 48 hours.

[0339] The reaction is preferably carried out in an organic solvent. Examples of suitable 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 a solubility perspective, toluene, xylene, mesitylene, aromatic oil solvents, dimethyl sulfoxide, dimethylformamide, and dimethylacetamide are preferred. These organic solvents can be used in any ratio, one or more of them.

[0340] The amount of organic solvent used is not particularly limited, but it is preferably set to 50 to 2000 by mass relative to the total amount of phenolic compound, triazine compound and (meth)acrylating agent corresponding to the structural unit of formula (1).

[0341] After the reaction is complete, the curable resin of the present invention can be obtained by reprecipitation, recrystallization, water washing, distillation, etc.

[0342] (Reaction 1-2)

[0343] After reacting the phenolic compound corresponding to the structural unit of formula (1) with a triazine compound to obtain an intermediate phenolic compound, the reaction of the intermediate phenolic compound with a (meth)acrylating agent can be carried out under the following conditions.

[0344] For the preparation of intermediate phenolic compounds, the phenolic compounds and triazine compounds corresponding to the structural units of formula (1) used, the amount of 1 mole of triazine compound relative to the hydroxyl group of phenolic compound can be set to 0.01 mole to 0.33 mole.

[0345] The reaction can be carried out in the presence of a base catalyst and, depending on the circumstances, a phase transfer catalyst.

[0346] Examples of base 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 a reactivity point of view, sodium hydroxide or potassium hydroxide is preferred. The amount of base catalyst used relative to 1 mole of the triazine compound can be set to 3.0 to 4.5 moles. These catalysts can be used in the form of 1 to 50% by mass aqueous solutions.

[0347] Phase transfer catalysts can be used in the reaction. Examples of ammonium-based phase transfer catalysts include tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium, tetrabutylammonium iodide, tetrabutylammonium hydroxide, benzyltriethylammonium chloride, benzyltriethylammonium bromide, benzyltriethylammonium iodide, and benzyltriethylammonium hydroxide; phosphonium-based catalysts include tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, tetrabutylphosphonium iodide, and tetrabutylphosphonium hydroxide; and crown ether-based catalysts include 12-crown-4-ether, 15-crown-5-ether, 18-crown-6-ether, and tribenzo-18-crown-6-ether. From a reactivity point of view, tetrabutylammonium bromide, tetrabutylammonium iodide, benzyltriethylammonium chloride, and benzyltriethylammonium iodide are preferred. Phase transfer catalysts can be used alone or in combination of two or more. The amount of phase transfer catalyst used relative to 1 mole of the hydroxyl group of the phenolic compound can be set to 0.0003 to 0.1 moles.

[0348] The reaction is preferably carried out in an organic solvent. Examples of suitable 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 aromatic oils; 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 a solubility perspective, toluene, xylene, mesitylene, aromatic oils, dimethyl sulfoxide, dimethylformamide, and dimethylacetamide are preferred. These organic solvents can be used in any ratio, one or more of them.

[0349] The amount of organic solvent used is not particularly limited, but it is preferably set to 50 to 2000 by mass relative to the phenolic compound and triazine compound corresponding to the structural unit of formula (1).

[0350] The reaction temperature can be set from 0 to 80°C, but from a reactivity point of view, 20 to 80°C is preferred. The reaction time can be set from 1 to 48 hours.

[0351] The phenolic compound, triazine compound, base catalyst, and phase transfer catalyst corresponding to the structural unit of formula (1) can be mixed at 0–40°C, and then the temperature can be raised to 20–80°C to carry out the reaction. From the viewpoint of reactivity, 40–80°C is preferred.

[0352] After the reaction is complete, the intermediate phenolic compound can be separated. For example, it can be separated into an upper and lower layer, and the lower layer, which is an aqueous layer, can be removed to obtain the intermediate phenolic compound. At this point, water can be added as needed to dissolve the insoluble salt and remove the lower layer. Furthermore, this aqueous layer can be alkaline, neutralized, or acidic. Examples of neutralizing agents include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, sodium dihydrogen phosphate, and ammonium chloride; and organic acids such as methanesulfonic acid, p-toluenesulfonic acid, and oxalic acid. These acid catalysts can be used alone or in combination of two or more.

[0353] Next, the obtained intermediate phenolic compound is reacted with a (meth)acrylating agent to introduce a (meth)acryloyl group.

[0354] Regarding the amounts of intermediate phenolic compounds and (meth)acrylating agents used in the reaction, the (meth)acrylating agent can be set to 1 to 3 moles relative to 1 mole of hydroxyl groups contained in the intermediate phenolic compound.

[0355] The reaction can be carried out in the presence of either a basic or acidic catalyst. Examples of basic catalysts include: trimethylamine, triethylamine, N,N-diisopropylmethylamine, 1,8-diazabicyclo[5,4,0]-7-undecene, 1,5-diazabicyclo[4,3,0]-5-nonene, pyridine, dimethylaminopyridine, and other amine-containing compounds; 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. From the viewpoint of catalytic activity, triethylamine, N,N-diisopropylmethylamine, dimethylaminopyridine, and pyridine are preferred. The above catalysts can be used alone or in combination of two or more.

[0356] The amount of basic or acidic catalyst is preferably 0.5 to 2.0 moles relative to 1 mole of hydroxyl group contained in the intermediate phenolic compound. These catalysts can be added all at once or in batches.

[0357] The reaction temperature can be set from 0 to 80°C, but from a reactivity point of view, 40 to 80°C is preferred. The reaction time can be set from 1 to 48 hours.

[0358] The reaction is preferably carried out in an organic solvent. Examples of suitable 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 aromatic oils; 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 a solubility perspective, toluene, xylene, mesitylene, aromatic oils, dimethyl sulfoxide, dimethylformamide, and dimethylacetamide are preferred. These organic solvents can be used in any ratio, one or more of them.

[0359] There is no particular limitation on the amount of organic solvent used, but it is preferably set to 50 to 2000 by mass relative to the total amount of phenolic resin and (meth)acrylic agent added as intermediates.

[0360] After the reaction is complete, the curable resin of the present invention can be obtained by reprecipitation, recrystallization, water washing, distillation, etc.

[0361] An example of reaction 1-2 is shown below (a representative reaction in reaction 1-2).

[0362] [Chemistry 44]

[0363]

[0364] (Reactions 1-3)

[0365] When using a phenolic compound corresponding to a structural unit of formula (4), a triazine compound and a phenolic compound corresponding to a structural unit of formula (4) can be reacted, and a structural unit of formula (4) can be introduced into the triazine compound beforehand. Next, a phenolic compound corresponding to a structural unit of formula (1) is mixed and reacted to form an intermediate phenolic compound. This intermediate phenolic compound is then reacted with a (meth)acrylating agent to produce the curable resin of the present invention.

[0366] At this point, regarding the triazine compound, the phenolic compound corresponding to the structural unit of formula (4) and the phenolic compound corresponding to the structural unit of formula (1), the amount of 1 mole of hydroxyl group of the phenolic compound corresponding to the structural unit of formula (4) relative to the phenolic compound corresponding to the structural unit of formula (1) can be set to 0.01 to 1.0 moles, and the total amount of 1.0 mole of hydroxyl group of the triazine compound relative to the phenolic compound corresponding to the structural unit of formula (1) and the phenolic compound corresponding to the structural unit of formula (4) can be set to 0.01 to 1.0 moles.

[0367] In an organic solvent, a phenolic compound, a triazine compound, a base catalyst, and a phase transfer catalyst, depending on the situation, corresponding to the structural unit of formula (4), can be mixed to pre-introduce the structural unit of formula (4) into the triazine compound. The reaction can be carried out at 0–80°C, and from the viewpoint of reactivity, 0–60°C is preferred.

[0368] Here, the types and amounts of the base catalyst, phase transfer catalyst, and organic solvent can be the same as in reaction 1-2.

[0369] A phenolic compound corresponding to a structural unit of formula (1) is mixed into a reaction mixture containing a triazine compound incorporating a structural unit of formula (4), and then the reaction is carried out at 20–80 °C to obtain an intermediate phenolic compound. From a responsiveness point of view, it is preferable to raise the temperature to 40–80 °C.

[0370] From the viewpoint of promoting the reaction, when mixing with a phenolic compound corresponding to a structural unit of formula (1), it is preferable to add an additional base catalyst and, depending on the situation, a phase transfer catalyst. The amount of the additional base catalyst used can be set to 0.50 to 1.0 moles per mole of the hydroxyl group of the phenolic compound corresponding to the structural unit of formula (1). In addition, when using an additional phase transfer catalyst, its amount can be set to 0.0003 to 0.1 moles per mole of the hydroxyl group of the phenolic compound corresponding to the structural unit of formula (1).

[0371] After the reaction is complete, an intermediate phenolic compound can be obtained. For example, it can be appropriately separated into upper and lower layers in the same manner as in reactions 1-2, and the lower layer, which is the aqueous layer, can be removed to obtain the intermediate phenolic compound.

[0372] Next, similar to reactions 1-2, the resulting intermediate phenolic compound is reacted with a (meth)acrylating agent to introduce a (meth)acryloyl group.

[0373] An example of reaction 1-3 is shown below (a representative reaction in reaction 1-3).

[0374] [Chemistry 45]

[0375]

[0376] (Reactions 1-4)

[0377] When using phenolic compounds corresponding to structural units of formula (4) and formula (5), a triazine compound and a phenolic compound corresponding to structural units of formula (4) can be reacted. After introducing the phenolic compound corresponding to structural units of formula (4) into the triazine compound, the phenolic compound corresponding to structural units of formula (5) is reacted beforehand. Next, a phenolic compound corresponding to structural units of formula (1) is mixed and reacted to form an intermediate phenolic compound. This intermediate phenolic compound is then reacted with a (meth)acrylic agent to produce the curable resin of the present invention.

[0378] At this point, among the triazine compound, the phenolic compound corresponding to the structural unit of formula (4), the phenolic compound corresponding to the structural unit of formula (5), and the phenolic compound corresponding to the structural unit of formula (1), the amount of 1 mole of hydroxyl group of the phenolic compound corresponding to the structural unit of formula (4) relative to the phenolic compound corresponding to the structural unit of formula (1) can be set to 0.01 to 1.0 moles, the amount of 1 mole of hydroxyl group of the phenolic compound corresponding to the structural unit of formula (5) relative to the phenolic compound corresponding to the structural unit of formula (1) can be set to 0.01 to 2.0 moles, and the amount of 1.0 mole of hydroxyl group of the triazine compound relative to the total amount of hydroxyl group of the phenolic compounds corresponding to the structural units of formulas (1), (4), and (5) can be set to 0.01 to 1.0 moles.

[0379] In an organic solvent, a phenolic compound, a triazine compound, an alkali metal catalyst, and a phase transfer catalyst, corresponding to the structural unit of formula (4), are mixed, and the structural unit of formula (4) is pre-introduced into the triazine compound. From a reactivity point of view, 0–60 °C is preferred. The types and amounts of the alkali catalyst, phase transfer catalyst, and organic solvent can be the same as in reactions 1–2.

[0380] A phenolic compound corresponding to a structural unit of formula (5) is mixed into a reaction mixture containing a triazine compound incorporating a structural unit of formula (4), and then the mixture is heated to 0–80°C to carry out the reaction, thereby obtaining a reaction mixture containing a compound incorporating a structural unit of formula (5). From the viewpoint of reactivity, 40–80°C is preferred.

[0381] From the viewpoint of promoting the reaction, when mixing phenolic compounds corresponding to the structural units of formula (5), it is preferable to add an additional base catalyst and, depending on the situation, a phase transfer catalyst. The amount of the additional base catalyst used can be set to 0.50 to 1.0 moles per mole of the hydroxyl group of the phenolic compound corresponding to the structural unit of formula (5). In addition, when using an additional phase transfer catalyst, its amount can be set to 0.0003 to 0.1 moles per mole of the hydroxyl group of the phenolic compound corresponding to the structural unit of formula (5).

[0382] A phenolic compound corresponding to a structural unit of formula (1) is mixed into a reaction mixture containing a compound incorporating a structural unit of formula (5), and then the mixture is heated to 0–80°C to carry out the reaction, thereby obtaining an intermediate phenolic compound. From the viewpoint of reactivity, 40–80°C is preferred.

[0383] After the reaction is complete, an intermediate phenolic compound can be obtained. For example, it can be appropriately separated into upper and lower layers in the same manner as in reactions 1-2, and the lower layer, which is the aqueous layer, can be removed to obtain the intermediate phenolic compound.

[0384] Next, similar to reactions 1-2, the resulting intermediate phenolic compound is reacted with a (meth)acrylating agent to introduce a (meth)acryloyl group.

[0385] An example of reaction 1-4 is shown below (a representative reaction in reaction 1-4).

[0386] [Chemistry 46]

[0387]

[0388] <Manufacturing of a curable resin having the structural unit shown in formula (7)>

[0389] By reacting the phenolic compound, phthalic acid compound, and (meth)acrylic agent corresponding to the structural unit of formula (1), the curable resin of the present invention having the structural unit represented by formula (3) can be obtained. This curable resin comprises a curable resin having the structural unit shown in formula (7).

[0390] (Reaction 2-1)

[0391] After reacting the phenolic compound corresponding to the structural unit of formula (1) with a phthalic acid compound to obtain an intermediate phenolic compound, it is advantageous to react the intermediate phenolic compound with a (meth)acrylating agent. This can be done under the following conditions.

[0392] For the phenolic compound and phthalic acid compound corresponding to the structural unit of formula (1) used in the preparation of intermediate phenolic compounds, the amount of 1 mole of phthalic acid compound relative to the hydroxyl group of the phenolic compound corresponding to the structural unit of formula (1) can be set to 0.01 mole to 1.0 mole.

[0393] The reaction can be carried out in the presence of a base catalyst and, depending on the circumstances, a phase transfer catalyst.

[0394] Examples of base 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 a reactivity point of view, sodium hydroxide or potassium hydroxide is preferred. The amount of base catalyst used can be set to 1 to 1.1 times the molar amount of hydroxyl groups. These catalysts can be used in the form of 1 to 50% by mass aqueous solutions.

[0395] Phase transfer catalysts can be used in the reaction. Examples of ammonium-based phase transfer catalysts include tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium, tetrabutylammonium iodide, tetrabutylammonium hydroxide, benzyltriethylammonium chloride, benzyltriethylammonium bromide, benzyltriethylammonium iodide, and benzyltriethylammonium hydroxide; phosphonium-based catalysts include tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, tetrabutylphosphonium iodide, and tetrabutylphosphonium hydroxide; and crown ether-based catalysts include 12-crown-4-ether, 15-crown-5-ether, 18-crown-6-ether, and tribenzo-18-crown-6-ether. From a reactivity point of view, tetrabutylammonium bromide, tetrabutylammonium iodide, benzyltriethylammonium chloride, and benzyltriethylammonium iodide are preferred. Phase transfer catalysts can be used alone or in combination of two or more. The amount of phase transfer catalyst used relative to the hydroxyl group of the phenolic compound corresponding to the structural unit of formula (1) can be set to 0.0003 to 0.1 moles.

[0396] The reaction is preferably carried out in an organic solvent. Examples of suitable 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 aromatic oils; 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 a solubility perspective, toluene, xylene, mesitylene, aromatic oils, dimethyl sulfoxide, dimethylformamide, and dimethylacetamide are preferred. These organic solvents can be used in any ratio, one or more of them.

[0397] The amount of organic solvent used is not particularly limited, but it is preferably set to 50 to 2000 by mass relative to the phenolic compound and phthalic acid compound corresponding to the structural unit of formula (1).

[0398] The reaction temperature can be set from 0 to 60°C, but from a reactivity point of view, 25 to 60°C is preferred. The reaction time can be from 1 to 48 hours.

[0399] The phenolic compound, phthalic acid compound, base catalyst, and phase transfer catalyst corresponding to the structural unit of formula (1) can be mixed at 0–30°C, and then the temperature can be raised to 40–80°C for reaction. From the viewpoint of reactivity, 40–60°C is preferred.

[0400] The intermediate phenolic compound can be obtained. For example, it can be appropriately separated into an upper and lower layer, and the lower layer, which is an aqueous layer, can be removed to obtain the intermediate phenolic compound. At this time, water can be added as needed to dissolve the insoluble salt and remove the lower layer. In addition, the aqueous layer can be alkaline, neutralized, or acidic. Examples of neutralizing agents include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, sodium dihydrogen phosphate, and ammonium chloride; and organic acids such as methanesulfonic acid, p-toluenesulfonic acid, and oxalic acid. These acid catalysts can be used alone or in combination of two or more.

[0401] Next, the obtained intermediate phenolic compound is reacted with a (meth)acrylating agent to introduce a (meth)acryloyl group.

[0402] The amount of intermediate phenolic compound and (meth)acrylating agent used in the reaction can be set to 1.0 to 2.0 moles of (meth)acrylating agent relative to 1 mole of hydroxyl group contained in the intermediate phenolic compound.

[0403] The reaction can be carried out in the presence of either a basic or acidic catalyst. Examples of basic catalysts include: trimethylamine, triethylamine, N,N-diisopropylmethylamine, 1,8-diazabicyclo[5,4,0]-7-undecene, 1,5-diazabicyclo[4,3,0]-5-nonene, pyridine, dimethylaminopyridine, and other amine-containing compounds; 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. From the viewpoint of catalytic activity, triethylamine, N,N-diisopropylmethylamine, dimethylaminopyridine, and pyridine are preferred. The above catalysts can be used alone or in combination of two or more.

[0404] For every 1 mole of hydroxyl group contained in the intermediate phenolic compound, the amount of basic or acidic catalyst is preferably 0.5 to 2.0 moles. These catalysts can be added all at once or in batches.

[0405] The reaction temperature can be 40–80℃. The reaction time can be 1–48 hours.

[0406] 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 aromatic oils; alcohol solvents such as methanol, ethanol, 1-propanol, isopropanol, 1-butanol, sec-butanol, and tert-butanol; cellosol solvents such as methyl cellosol and ethyl cellosol; 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 a solubility point of view, toluene, xylene, mesitylene, aromatic oils, isopropanol, dimethyl sulfoxide, dimethylformamide, and dimethylacetamide are preferred. These organic solvents can be used in any ratio, one or more of them.

[0407] There is no particular limitation on the amount of organic solvent used, but it is preferably set to 50 to 2000 by mass relative to the total amount of phenolic resin and (meth)acrylic agent added as intermediates.

[0408] After the reaction is complete, the curable resin of the present invention can be obtained by reprecipitation, recrystallization, water washing, distillation, etc.

[0409] An example of reaction 2-1 is shown below (a representative reaction in reaction 2-1).

[0410] [Chemistry 47]

[0411]

[0412] The curable resin of the present invention can be used as a thermosetting resin because it has a heat-reactive (meth)acryloyl group.

[0413] [Curing Resin Composition]

[0414] The present invention also relates to curable resin compositions containing the curable resin of the present invention.

[0415] <Other Resins>

[0416] In the curable resin composition of the present invention, resins other than the curable resin of the present invention (hereinafter also referred to as "other resins") may be used to a extent that does not impair the purpose. Other resins are not particularly limited, and examples include alkenyl compounds, such as bismaleimides, allyl ether compounds, allyl amine compounds, triallyl cyanurate, alkenylphenol compounds, vinyl-containing polyolefin compounds, divinylbenzene, polydivinylbenzene, polybutadiene, acrylate compounds, methacrylate compounds, etc. Furthermore, other thermosetting resins, such as thermosetting polyimide resins, epoxy resins, phenolic resins, reactive ester resins, benzoxazine resins, cyanate ester resins, etc., may also be appropriately formulated according to the purpose.

[0417] <Curing Accelerator>

[0418] In the curable resin composition of the present invention, a curing accelerator may also be used as needed. The curing accelerator is not particularly limited, and examples include, for instance, organic peroxides (e.g., benzoyl peroxide, cumene hydroperoxide, dicumyl peroxide, lauroyl peroxide, di-tert-butyl peroxide, tert-butyl hydroperoxide, methyl ethyl ketone peroxide, tert-butyl perbenzoate, etc.), azo compounds (azobisisobutyronitrile, etc.), and free radicals (azobisisobutyronitrile, galvanoxy radical, etc.).

[0419] <Flame retardant>

[0420] In the curable resin composition of the present invention, a flame retardant may be added as needed. Preferably, the flame retardant is a non-halogenated flame retardant that is substantially free of halogen atoms, such as phosphorus-based flame retardants, nitrogen-based flame retardants, silicone-based flame retardants, inorganic flame retardants, and organometallic salt-based flame retardants. These flame retardants may be used alone or in combination of two or more.

[0421] <filler>

[0422] In the curable resin composition of the present invention, inorganic fillers may be incorporated as needed. The inorganic fillers are not particularly limited, and examples include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide. When the amount of inorganic filler is particularly increased, fused silica is preferred. Fused silica can be either crushed or spherical, but to increase the amount of fused silica and suppress the increase in the melt viscosity of the molding material, spherical fused silica is preferred. Furthermore, to increase the amount of spherical silica incorporated, the particle size distribution of the spherical silica is preferably appropriately adjusted.

[0423] In addition, when using the curable resin composition for applications such as conductive pastes detailed below, conductive fillers such as silver powder and copper powder can be used.

[0424] <Other compounding agents>

[0425] The curable resin composition of the present invention may contain various compounding agents such as silane coupling agents, release agents, pigments, and emulsifiers as needed.

[0426] <Method for manufacturing curable resin compositions>

[0427] The curable resin composition of the present invention can be prepared by mixing the curable resin of the present invention alone, or by uniformly mixing the above-mentioned curing accelerator and other components with the curable resin of the present invention. The mixing method is not particularly limited, and known methods can be used.

[0428] [cured material]

[0429] The present invention also relates to cured products of the curable resin compositions of the present invention.

[0430] The curable resin composition of the present invention can be cured into a cured product through a curing reaction. Examples of cured products include laminates, castings, adhesive layers, coatings, films, and other molded cured products, but are not limited to these.

[0431] Examples of curing reactions include thermosetting and UV curing. The thermosetting reaction of the curable resin composition of the present invention is advantageous because it proceeds easily even without a catalyst. For faster reactions, incorporating a polymerization initiator such as an organic peroxide, an azo compound, a phosphine compound, or a basic catalyst such as a tertiary amine into the curable resin composition is effective. Examples of basic catalysts include benzoyl peroxide, dicumyl peroxide, azobisisobutyronitrile, triphenylphosphine, triethylamine, and imidazoles.

[0432] [use]

[0433] The cured product of this invention simultaneously satisfies low dielectric properties (low dielectric constant and low dielectric loss tangent), good dielectric properties after moisture absorption, high adhesion to copper foil, and high heat resistance, making it suitable for use in heat-resistant components and electronic components. It is particularly preferred for use in prepregs, circuit boards, semiconductor sealing materials, semiconductor devices, laminated films, laminated substrates, adhesives, and photoresist materials. Additionally, it is suitable as a matrix resin for fiber-reinforced resins, and is particularly suitable as a high-heat-resistant prepreg. Furthermore, the curable resin composition of this invention can be dissolved in various solvents to form a coating, and the coating is used to form a cured product. The resulting heat-resistant components and electronic components are suitable for a wide range of applications, including, but not limited to, industrial machinery parts, general machinery parts, automotive / railway / vehicle parts, aerospace-related parts, electronic / electrical parts, building materials, container / packaging components, consumer goods, sports / leisure products, and wind power generation housing components.

[0434] [Example]

[0435] Next, the present invention will be specifically described through examples and comparative examples. Unless otherwise specified, "parts" and "%" refer to mass. It should be noted that the curable resin and the cured product obtained using the aforementioned curable resin were synthesized under the conditions shown below, and the cured product was then evaluated by measurement or calculation under the following conditions.

[0436] <GPC Determination (Evaluation of Number-Average Molecular Weight, Weight-Average Molecular Weight, and Average Number of Repeat Units)>

[0437] The following measurement apparatus and conditions were used to obtain the GPC spectra of the phenolic resin, phenolic resin intermediate, and cured resin. The number-average molecular weight (Mn) and weight-average molecular weight (Mw) were then determined.

[0438] For the phenolic resins synthesized in Examples 1-3, the average number of repeating units n with an indane skeleton was calculated based on the number-average molecular weight (Mn) according to the results of the GPC spectra. Specifically, for compounds with n of 0-4, an approximate straight line was drawn by plotting the theoretical molecular weight and the measured molecular weight in the GPC on a scatter plot, and the number-average molecular weight (Mn) was obtained from the point indicated by the measured value Mn(1) on the straight line, and the average number of repeating units n was calculated.

[0439] Measurement apparatus: HLC-8320GPC manufactured by Tosoh Corporation

[0440] Protective pillars: Tosoh Corporation "HXL-L" + Tosoh Corporation "TSK-GEL G2000HXL" + Tosoh Corporation "TSK-GEL G2000 HXL" + Tosoh Corporation "TSK-GEL G3000 HXL" + Tosoh Corporation "TSK-GEL G4000 HXL"

[0441] Detector: RI (Differential Refractometer)

[0442] Data processing: Tosoh Corporation's "GPC Workstation Eco SEC-Workstation"

[0443] Measurement conditions: Column temperature 40℃

[0444] Expand solvent tetrahydrofuran

[0445] Flow rate 1.0 ml / min

[0446] Standard: According to the above-mentioned "GPC Workstation Eco SEC-Workstation" test manual, use the following monodisperse polystyrene with a known molecular weight.

[0447] (Using polystyrene)

[0448] "A-500" manufactured by Tosoh Corporation

[0449] "A-1000" manufactured by Tosoh Corporation

[0450] "A-2500" manufactured by Tosoh Corporation

[0451] "A-5000" manufactured by Tosoh Corporation

[0452] "F-1" manufactured by Tosoh Corporation

[0453] "F-2" manufactured by Tosoh Corporation

[0454] "F-4" manufactured by Tosoh Corporation

[0455] "F-10" manufactured by Tosoh Corporation

[0456] "F-20" manufactured by Tosoh Corporation

[0457] "F-40" manufactured by Tosoh Corporation

[0458] "F-80" manufactured by Tosoh Corporation

[0459] "F-128" manufactured by Tosoh Corporation

[0460] Sample: 50 μl of a tetrahydrofuran solution of the curable resin with an indane skeleton obtained in the synthesis example, which was filtered through a microfilter.

[0461] < 1 H-NMR measurement >

[0462] Measurement equipment: JNM-E CA500 manufactured by Nippon Egis Corporation.

[0463] Magnetic field strength: 500MHz

[0464] Total number of times: 16

[0465] Solvent: Chloroform-d

[0466] Sample concentration: 5% by mass

[0467] < 13 C-NMR measurement >

[0468] Measurement equipment: JNM-E CA500 manufactured by Nippon Egis Corporation.

[0469] Magnetic field strength: 125MHz

[0470] Total number of times: 4000

[0471] Solvent: Chloroform-d

[0472] Sample concentration: 30% by mass

[0473] <IR Measurement>

[0474] Measurement equipment: FT / I R-4100typeA manufactured by Japan Spectrophotometry Co., Ltd.

[0475] Method: KBr tableting

[0476] Total number of times: 32

[0477] Decomposition: 4cm -1

[0478] <Hydroxy equivalent (phenol equivalent)>

[0479] The hydroxyl equivalent (phenol equivalent) of phenolic resin and phenolic resin intermediates is calculated by titration. Here, titration refers to the neutralization titration method according to JIS K0070.

[0480] Synthesize phenolic resins (A-1) to (A-3) represented by the following general formula (iA).

[0481] [Chemistry 48]

[0482]

[0483] Synthesis Example 1: Synthesis of Phenolic Resin (A-1)

[0484] In a 2L flask equipped with a thermometer, condenser, Dean-Stark separator, and stirrer, 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 were added. The mixture was heated to 120°C while stirring. Then, while removing distillate water using a Dean-Stark tube, the temperature was increased to 210°C, and the reaction was carried out for 6 hours. The mixture was then cooled to 100°C with air, diluted with 636g of toluene, and the activated clay was removed by filtration. Solvent and unreacted low molecular weight substances were removed by distillation under reduced pressure, yielding 621g of the target phenolic resin (A-1) (hydroxyl equivalent 555g / equivalent). The phenolic resin (A-1) had a Mn of 1107, a Mw of 1799, and an average repeating unit number n of 4.5.

[0485] Synthesis Example 2: Synthesis of Phenolic Resin (A-2)

[0486] In a 2L flask equipped with a thermometer, condenser, Dean-Stark separator, and stirrer, 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 were added. The mixture was heated to 120°C while stirring. Then, while removing distillate water using a Dean-Stark tube, the temperature was increased to 210°C, and the reaction was carried out for 6 hours. The mixture was then cooled to 100°C with air, diluted with 658g of toluene, and the activated clay was removed by filtration. Solvent and unreacted low molecular weight substances were removed by distillation under reduced pressure, yielding 721g of the target phenolic resin (A-2) (hydroxyl equivalent 405g / equivalent). The phenolic resin (A-2) had a Mn of 909, a Mw of 1130, and an average repeating unit number n of 3.2.

[0487] Synthesis Example 3: Synthesis of Phenolic Resin (A-3)

[0488] In a 2L flask equipped with a thermometer, condenser, Dean-Stark separator, and stirrer, 170g (1.39mol) of 2,6-dimethylphenol, 811g (4.17mol) of α,α'-dihydroxy-1,3-diisopropylbenzene, 811g of xylene, and 98g of activated clay were added. The mixture was heated to 120°C while stirring. Then, while removing distillate water using a Dean-Stark tube, the temperature was increased to 210°C, and the reaction was carried out for 6 hours. The mixture was then cooled to 100°C with air, diluted with 811g of toluene, and the activated clay was removed by filtration. Solvent and unreacted low molecular weight substances were removed by distillation under reduced pressure, yielding 727g of the target phenolic resin (A-3) (hydroxyl equivalent 816g / equivalent). The phenolic resin (A-2) had a Mn of 1667, a Mw of 3189, and an average repeating unit number n of 8.0.

[0489] The following are the synthetic thermosetting resins (B-1) to (B-15).

[0490] The structural units that thermosetting resins may contain are shown below.

[0491] [Chemistry 49]

[0492]

[0493] Example 1: Synthesis of thermosetting resin (B-1)

[0494] In a 2L flask equipped with a thermometer, condenser, Dean-Stark separator, and stirrer, 200g of phenolic resin (A-1), 1.1g (0.006mol) of cyanuric chloride, 400g of toluene, 2.4g (0.020mol) of dimethylaminopyridine, and 40.0g (0.40mol) of triethylamine were added and stirred at 60°C. When the solids were considered completely dissolved, 73.8g (0.48mol) of methacrylic anhydride was added dropwise over 1 hour. After the addition was complete, the reaction was continued at 60°C for another 3 hours. The mixture was then washed 10 times with water, and the organic layer was heated under vacuum using a rotary evaporator to remove volatile components, yielding a thermosetting resin (B-1) with methacrylamide groups at the ends. The thermosetting resin (B-1) has a Mn of 1359 and a Mw of 2044. The GPC spectrum is shown below. Figure 1 .

[0495] Example 2: Synthesis of thermosetting resin (B-2)

[0496] In a 2L flask equipped with a thermometer, condenser, Dean-Stark separator, and stirrer, 200g of phenolic resin (A-1), 2.2g (0.012mol) of cyanuric chloride, 400g of toluene, 2.4g (0.020mol) of dimethylaminopyridine, and 40.0g (0.40mol) of triethylamine were added and stirred at 60°C. When the solids were considered completely dissolved, 69.9g (0.45mol) of methacrylic anhydride was added dropwise over 1 hour. After the addition was complete, the reaction was continued at 60°C for another 3 hours. The mixture was then washed 10 times with water, and the organic layer was heated under vacuum using a rotary evaporator to remove volatile components, yielding a thermosetting resin (B-2) with methacrylamide groups at the ends. The thermosetting resin (B-2) has a Mn of 1435 and a Mw of 2261. The GPC spectrum is shown below. Figure 2 .

[0497] Example 3: Synthesis of thermosetting resin (B-3)

[0498] In a 2L flask equipped with a thermometer, condenser, Dean-Stark separator, and stirrer, 200g of phenolic resin (A-1), 3.7g (0.020mol) of cyanuric chloride, 400g of toluene, 2.4g (0.020mol) of dimethylaminopyridine, and 40.0g (0.40mol) of triethylamine were added and stirred at 60°C. At the point when the solids were considered completely dissolved, 64.9g (0.42mol) of methacrylic anhydride was added dropwise over 1 hour. After the addition was complete, the reaction was continued at 60°C for another 3 hours. The mixture was then washed 10 times with water, and the organic layer was heated under vacuum using a rotary evaporator to remove volatile components, yielding a thermosetting resin (B-3) with methacrylamide groups at the ends. The thermosetting resin (B-3) has a Mn of 1637 and a Mw of 2823. The GPC spectrum is shown below. Figure 3 .

[0499] Example 4: Synthesis of thermosetting resin (B-4)

[0500] In a 2L flask equipped with a thermometer, condenser, Dean-Stark water separator, and stirrer, 400g of phenolic resin (A-1), 16.1g (0.087mol) of cyanuric chloride, 1219g of toluene, and 0.62g (0.0019mol) of tetrabutylammonium bromide were added dropwise over 3 hours at 25°C with stirring. The temperature was then raised to 80°C, and the reaction was carried out for 5 hours. The mixture was then neutralized with a 30% (w / w) sodium dihydrogen phosphate aqueous solution and washed four times with water. The solvent and water were then removed by heating under reduced pressure to obtain the phenolic resin intermediate (hydroxyl equivalent 862g / equivalent).

[0501] In a 2L flask equipped with a thermometer, condenser, Dean-Stark separator, and stirrer, 250g of the above-mentioned phenolic resin intermediate, 500g of toluene, 2.0g (0.017mol) of dimethylaminopyridine, and 29.3g (0.29mol) of triethylamine were added and stirred at 60°C. When the solids were considered completely dissolved, 62.6g (0.41mol) of methacrylic anhydride was added dropwise over 1 hour. After the addition was complete, the reaction was further carried out at 60°C for 3 hours. The mixture was then washed 10 times with water, and the organic layer was heated under vacuum using a rotary evaporator to remove volatile components, yielding a thermosetting resin (B-4) with methacrylamide groups at the ends. The thermosetting resin (B-4) has a Mn of 1887 and a Mw of 4511. The GPC spectrum is shown below. Figure 4 .

[0502] Example 5: Synthesis of thermosetting resin (B-5)

[0503] In a 2L flask equipped with a thermometer, condenser, Dean-Stark water separator, and stirrer, 400g of phenolic resin (A-1), 22.1g (0.12mol) of cyanuric chloride, 1227g of toluene, and 0.61g (0.0019mol) of tetrabutylammonium bromide were added dropwise over 3 hours at 25°C with stirring. The temperature was then raised to 80°C, and the reaction was carried out for 5 hours. The mixture was then neutralized with a 30% (w / w) sodium dihydrogen phosphate aqueous solution and washed four times with water. The solvent and water were then removed by heating under reduced pressure to obtain the phenolic resin intermediate (hydroxyl equivalent 1299g / equivalent).

[0504] In a 2L flask equipped with a thermometer, condenser, Dean-Stark separator, and stirrer, 170g of the above-mentioned phenolic resin intermediate, 340g of toluene, 0.88g (0.0072mol) of dimethylaminopyridine, and 13.3g (0.13mol) of triethylamine were added and stirred at 60°C. When the solids were considered completely dissolved, 28.3g (0.18mol) of methacrylic anhydride was added dropwise over 1 hour. After the addition was complete, the reaction was further carried out at 60°C for 3 hours. The mixture was then washed 10 times with water, and the organic layer was heated under vacuum using a rotary evaporator to remove volatile components, yielding a thermosetting resin (B-5) with methacrylamide groups at the ends. The thermosetting resin (B-5) has a Mn of 2462 and a Mw of 8961. The GPC spectrum is shown below. Figure 5 .

[0505] Example 6: Synthesis of thermosetting resin (B-6)

[0506] In a 2L flask equipped with a thermometer, condenser, Dean-Stark water separator, and stirrer, 413g of phenolic resin (A-2), 22.4g (0.12mol) of cyanuric chloride, 1268g of toluene, and 0.63g (0.0019mol) of tetrabutylammonium bromide were added dropwise over 3 hours at 25°C with stirring. The temperature was then raised to 80°C, and the reaction was carried out for 5 hours. The mixture was then neutralized with a 30% (w / w) sodium dihydrogen phosphate aqueous solution and washed four times with water. The solvent and water were then removed by heating under reduced pressure to obtain the phenolic resin intermediate (hydroxyl equivalent 620g / equivalent).

[0507] In a 2L flask equipped with a thermometer, condenser, Dean-Stark separator, and stirrer, 250g of the above-mentioned phenolic resin intermediate, 500g of toluene, 2.7g (0.022mol) of dimethylaminopyridine, and 40.8g (0.40mol) of triethylamine were added and stirred at 60°C. When the solids were considered completely dissolved, 87.1g (0.56mol) of methacrylic anhydride was added dropwise over 1 hour. After the addition was complete, the reaction was further carried out at 60°C for 3 hours. The mixture was then washed 10 times with water, and the organic layer was heated under vacuum using a rotary evaporator to remove volatile components, yielding a thermosetting resin (B-6) with methacrylamide groups at the ends. The thermosetting resin (B-6) has a Mn of 1442 and a Mw of 2730. The GPC spectrum is shown below. Figure 6 At the same time, 1 H-NMR measurement results 13 The C-NMR and IR measurement results are shown in Figure 7 , 8 And 9.

[0508] Example 7: Synthesis of thermosetting resin (B-7)

[0509] In a 2L flask equipped with a thermometer, condenser, Dean-Stark water separator, and stirrer, 250g of phenolic resin (A-2), 19g (0.10mol) of cyanuric chloride, 773g of toluene, and 0.39g (0.0012mol) of tetrabutylammonium bromide were added dropwise over 3 hours at 25°C with stirring. The temperature was then raised to 80°C, and the reaction was carried out for 5 hours. The mixture was then neutralized with a 30% (w / w) sodium dihydrogen phosphate aqueous solution and washed four times with water. The solvent and water were then removed by heating under reduced pressure to obtain the phenolic resin intermediate (hydroxyl equivalent 751g / equivalent).

[0510] In a 2L flask equipped with a thermometer, condenser, Dean-Stark separator, and stirrer, 200g of the above-mentioned phenolic resin intermediate, 400g of toluene, 1.8g (0.015mol) of dimethylaminopyridine, and 27.0g (0.27mol) of triethylamine were added and stirred at 60°C. When the solids were considered completely dissolved, 57.5g (0.37mol) of methacrylic anhydride was added dropwise over 1 hour. After the addition was complete, the reaction was further carried out at 60°C for 3 hours. The mixture was then washed 10 times with water, and the organic layer was heated under vacuum using a rotary evaporator to remove volatile components, yielding a thermosetting resin (B-7) with methacrylamide groups at the ends. The thermosetting resin (B-7) has a Mn of 1831 and a Mw of 5135. The GPC diagram is shown below. Figure 10 .

[0511] Example 8: Synthesis of thermosetting resin (B-8)

[0512] In a 2L flask equipped with a thermometer, condenser, Dean-Stark water separator, and stirrer, 300g of phenolic resin (A-3), 6.6g (0.036mol) of cyanuric chloride, 908g of toluene, and 0.45g (0.0014mol) of tetrabutylammonium bromide were added dropwise over 3 hours at 25°C with stirring. The temperature was then raised to 80°C, and the reaction was carried out for 5 hours. The mixture was then neutralized with a 30% (w / w) sodium dihydrogen phosphate aqueous solution and washed four times with water. The solvent and water were then removed by heating under reduced pressure to obtain the phenolic resin intermediate (hydroxyl equivalent 1161g / equivalent).

[0513] In a 2L flask equipped with a thermometer, condenser, Dean-Stark separator, and stirrer, 200g of the above-mentioned phenolic resin intermediate, 400g of toluene, 1.2g (0.0098mol) of dimethylaminopyridine, and 17.4g (0.17mol) of triethylamine were added and stirred at 60°C. When the solids were considered completely dissolved, 37.2g (0.24mol) of methacrylic anhydride was added dropwise over 1 hour. After the addition was complete, the reaction was further carried out at 60°C for 3 hours. The mixture was then washed 10 times with water, and the organic layer was heated under vacuum using a rotary evaporator to remove volatile components, yielding a thermosetting resin (B-8) with methacrylamide groups at the ends. The thermosetting resin (B-8) has a Mn of 2187 and a Mw of 5348. The GPC diagram is shown below. Figure 11 .

[0514] Example 9: Synthesis of thermosetting resin (B-9)

[0515] In a 2L flask equipped with a thermometer, condenser, Dean-Stark water separator, and stirrer, 150g of phenolic resin (A-1), 12.7g (0.063mol) of isophthaloyl dichloroisocyanurate, 474g of toluene, and 0.79g (0.0025mol) of tetrabutylammonium bromide were added dropwise over 3 hours at 25°C with stirring. The temperature was then raised to 40°C, and the reaction was carried out at the same temperature for 1 hour. The mixture was then neutralized with a 30% (w / w) sodium dihydrogen phosphate aqueous solution and washed four times with water. The solvent and water were then removed by heating under reduced pressure to obtain the phenolic resin intermediate (hydroxyl equivalent 1110g / equivalent).

[0516] In a 2L flask equipped with a thermometer, condenser, Dean-Stark separator, and stirrer, 139g of the above-mentioned phenolic resin intermediate, 280g of toluene, 0.77g (0.0063mol) of dimethylaminopyridine, and 14.0g (0.14mol) of triethylamine were added and stirred at 60°C. When the solids were considered completely dissolved, 29.0g (0.19mol) of methacrylic anhydride was added dropwise over 1 hour. After the addition was complete, the reaction was further carried out at 60°C for 3 hours. The mixture was then washed 10 times with water, and the organic layer was heated under vacuum using a rotary evaporator to remove volatile components, yielding a thermosetting resin (B-9) with methacrylamide groups at the ends. The thermosetting resin (B-9) has a Mn of 2195 and a Mw of 4940. The GPC spectrum is shown below. Figure 12 ;Will 1 H-NMR measurement results 13 The C-NMR and IR measurement results are shown in Figure 13 , 14 and 15;

[0517] Example 10: Synthesis of thermosetting resin (B-10)

[0518] In a 2L flask equipped with a thermometer, condenser, Dean-Stark water separator, and stirrer, 299g of phenolic resin (A-1), 38.0g (0.189mol) of isophthaloyl dichloroisocyanurate, 970g of toluene, and 0.48g (0.0015mol) of tetrabutylammonium bromide were added dropwise over 3 hours at 25°C with stirring. The temperature was then raised to 40°C, and the reaction was carried out at the same temperature for 1 hour. The mixture was then neutralized with a 30% (w / w) sodium dihydrogen phosphate aqueous solution and washed four times with water. The solvent and water were then removed by heating under reduced pressure to obtain the phenolic resin intermediate (hydroxyl equivalent 1848g / equivalent).

[0519] In a 2L flask equipped with a thermometer, condenser, Dean-Stark separator, and stirrer, 220g of the above-mentioned phenolic resin intermediate, 440g of toluene, 0.80g (0.0065mol) of dimethylaminopyridine, and 12.7g (0.13mol) of triethylamine were added and stirred at 60°C. When the solids were considered completely dissolved, 25.7g (0.17mol) of methacrylic anhydride was added dropwise over 1 hour. After the addition was complete, the reaction was further carried out at 60°C for 3 hours. The mixture was then washed 10 times with water, and the organic layer was heated under vacuum using a rotary evaporator to remove volatile components, yielding a thermosetting resin (B-10) with methacrylamide groups at the ends. The thermosetting resin (B-10) has a Mn of 2967 and a Mw of 8358. The GPC spectrum is shown below. Figure 16 .

[0520] Example 11: Synthesis of thermosetting resin (B-11)

[0521] In a 2L flask equipped with a thermometer, condenser, Dean-Stark water separator, and stirrer, 13.1 g (0.107 mol) of 6-dimethylphenol, 29.7 g (0.161 mol) of cyanuric chloride, 970 g of toluene, and 0.48 g (0.0015 mol) of tetrabutylammonium bromide were added dropwise over 3 hours at 20°C with stirring. Then, 298 g of phenolic resin (A-1) was added and stirred until dissolved. After complete dissolution, 77.4 g (0.39 mol) of 20% sodium hydroxide aqueous solution was added dropwise over 3 hours at 25°C with stirring. The temperature was then raised to 80°C, and the reaction was carried out for 5 hours at the same temperature. The mixture was then neutralized with 30% sodium dihydrogen phosphate aqueous solution and washed four times with water. The solvent and water were then removed by heating under reduced pressure to obtain the phenolic resin intermediate (hydroxyl equivalent 1821 g / equivalent).

[0522] In a 2L flask equipped with a thermometer, condenser, Dean-Stark separator, and stirrer, 170g of the above-mentioned phenolic resin intermediate, 340g of toluene, 0.63g (0.0052mol) of dimethylaminopyridine, and 9.5g (0.094mol) of triethylamine were added and stirred at 60°C. When the solids were considered completely dissolved, 20.2g (0.13mol) of methacrylic anhydride was added dropwise over 1 hour. After the addition was complete, the reaction was further carried out at 60°C for 3 hours. The mixture was then washed 10 times with water, and the organic layer was heated under vacuum using a rotary evaporator to remove volatile components, yielding thermosetting resin B-11 with methacrylamide groups at the ends. The thermosetting resin (B-11) has a Mn of 3063 and a Mw of 13212. The GPC spectrum is shown below. Figure 17 .

[0523] Example 12: Synthesis of thermosetting resin (B-12)

[0524] In a 2L flask equipped with a thermometer, condenser, Dean-Stark water separator, and stirrer, 21.9 g (0.179 mol) of 6-dimethylphenol, 33.1 g (0.179 mol) of cyanuric chloride, 1002 g of toluene, and 0.50 g (0.0016 mol) of tetrabutylammonium bromide were added dropwise over 3 hours at 20°C with stirring. Then, 299 g of phenolic resin (A-1) was added and stirred until dissolved. After complete dissolution, 73.9 g (0.37 mol) of 20% sodium hydroxide aqueous solution was added dropwise over 3 hours at 25°C with stirring. The temperature was then raised to 80°C, and the reaction was carried out for 5 hours at the same temperature. The mixture was then neutralized with 30% sodium dihydrogen phosphate aqueous solution and washed four times with water. Finally, the solvent and water were removed by heating under reduced pressure to obtain the phenolic resin intermediate. (Hydroxy equivalent 1965 g / equivalent).

[0525] In a 2L flask equipped with a thermometer, condenser, Dean-Stark separator, and stirrer, 200g of the above-mentioned phenolic resin intermediate, 400g of toluene, 0.68g (0.0056mol) of dimethylaminopyridine, and 10.3g (0.10mol) of triethylamine were added and stirred at 60°C. When the solids were considered completely dissolved, 22.0g (0.14mol) of methacrylic anhydride was added dropwise over 1 hour. After the addition was complete, the reaction was further carried out at 60°C for 3 hours. The mixture was then washed 10 times with water, and the organic layer was heated under vacuum using a rotary evaporator to remove volatile components, yielding a thermosetting resin (B-12) with methacrylamide groups at the ends. The thermosetting resin (B-12) has a Mn of 2452 and a Mw of 5724. The GPC spectrum is shown below. Figure 18 .

[0526] Example 13: Synthesis of thermosetting resin (B-13)

[0527] In a 2L flask equipped with a thermometer, condenser, Dean-Stark water separator, and stirrer, 31.2 g (0.255 mol) of 6-dimethylphenol, 47.1 g (0.255 mol) of cyanuric chloride, 931 g of toluene, and 0.51 g (0.0017 mol) of tetrabutylammonium bromide were added dropwise over 3 hours at 20°C with stirring. Then, 56.2 g of a dicyclopentadiene-phenol addition polymerization resin (hydroxyl equivalent: 165 g / equivalent, softening point 85°C) was added. The temperature was raised to 60°C, and 68.1 g (0.34 mol) of a 20% sodium hydroxide aqueous solution was added dropwise over 3 hours at the same temperature with stirring. Finally, 203.8 g of phenolic resin (A-1) was added and stirred until dissolved. After dissolution, 38.7 g (0.19 mol) of a 20% sodium hydroxide aqueous solution was added dropwise over 3 hours at the same temperature while stirring. The temperature was then raised to 80°C and reacted for 5 hours at the same temperature. The mixture was then neutralized with a 30% sodium dihydrogen phosphate aqueous solution and washed four times with water. The solvent and water were then removed by heating under reduced pressure to obtain the phenolic resin intermediate (hydroxyl equivalent 1886 g / equivalent).

[0528] In a 2L flask equipped with a thermometer, condenser, Dean-Stark separator, and stirrer, 250g of the above-mentioned phenolic resin intermediate, 500g of toluene, 0.89g (0.0073mol) of dimethylaminopyridine, and 14.1g (0.14mol) of triethylamine were added and stirred at 60°C. When the solids were considered completely dissolved, 28.6g (0.19mol) of methacrylic anhydride was added dropwise over 1 hour. After the addition was complete, the reaction was further carried out at 60°C for 3 hours. The mixture was then washed 10 times with water, and the organic layer was heated under vacuum using a rotary evaporator to remove volatile components, yielding a thermosetting resin (B-13) with methacrylamide groups at the ends. The thermosetting resin (B-13) has a Mn of 2754 and a Mw of 10480. The GPC spectrum is shown below. Figure 19 .

[0529] Comparative Example 1: Synthesis of thermosetting resin (B-14)

[0530] In a 2L flask equipped with a thermometer, condenser, Dean-Stark separator, and stirrer, 200g of phenolic resin (A-1), 400g of toluene, 2.4g (0.020mol) of dimethylaminopyridine, and 40.0g (0.40mol) of triethylamine were added and stirred at 60°C. When the solids were considered completely dissolved, 77.8g (0.50mol) of methacrylic anhydride was added dropwise over 1 hour. After the addition was complete, the reaction was continued at 60°C for another 3 hours. The mixture was then washed 10 times with water, and the organic layer was heated under vacuum using a rotary evaporator to remove volatile components, yielding a thermosetting resin (B-14) with methacrylamide groups at the ends. The thermosetting resin (B-14) has a Mn of 1291 and a Mw of 2037. The GPC diagram is shown below. Figure 20 The IR measurement results are presented together. Figure 21 .

[0531] Comparative Example 2: Synthesis of thermosetting resin (B-15)

[0532] In a 2L flask equipped with a thermometer, condenser, Dean-Stark separator, and stirrer, 200g (0.64mol) of 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 28.5g (0.15mol) of cyanuric chloride, 400g of toluene, 8.7g (0.071mol) of dimethylaminopyridine, and 143.4g (1.42mol) of triethylamine were added and stirred at 60°C. At the point when the solids were considered completely dissolved, 178.0g (1.15mol) of methacrylic anhydride was added dropwise over 1 hour. After the addition was complete, the reaction was continued at 60°C for another 3 hours. The mixture was then washed 10 times with water, and the organic layer was heated under vacuum using a rotary evaporator to remove volatile components, yielding a thermosetting resin (B-15) with methacrylamide groups at the ends. The thermosetting resin (B-15) has a Mn of 732 and a Mw of 1025. The GPC spectrum is shown below. Figure 22 .

[0533] Examples 14-18 and Comparative Example 3

[0534] <Preparation of cured products>

[0535] In each component shown in Table 1 (the proportions in the table are parts by mass), 0.5% by mass of PERBUTYL P (manufactured by Nippon Oil Co., Ltd., α,α'-di(tert-butylperoxy)diisopropylbenzene) was added as a curing catalyst, relative to 100% by mass of the total components. After heating and mixing, the mixture was poured into a mold with a thickness of 2 mm, cured at 170°C for 30 minutes, and then cured at 200°C for 2 hours to obtain a cured product. In Comparative Example 3, Noryl (trademark) SA9000 resin manufactured by Sabic Co., Ltd. was used as the thermosetting resin. TAIC in the table refers to triallyl isocyanurate.

[0536] The physical properties of the cured material obtained as described above were evaluated as follows. The results are shown in Table 1.

[0537] <Heat resistance (DMA TgI)>

[0538] The glass transition temperature (Tg) was evaluated using a viscoelasticity measuring apparatus (Rheometric "Solid Viscoelasticity Measuring Apparatus RSAII", rectangular plate tension method: frequency 1 Hz, heating rate 3 °C / min) at the low temperature side with the largest change rate of Tanδ.

[0539] <Dielectric properties (dielectric constant, dielectric loss tangent)>

[0540] According to JIS-C-6481, using the Agilent Technologies E8362C network analyzer manufactured by Agilent Technologies, Inc., the dielectric constant and dielectric loss tangent of the test piece after absolute drying and storage in an indoor environment at 23°C and 50% humidity for 24 hours were determined by the cavity resonance method at 1 GHz and 10 GHz.

[0541] <Dielectric properties after moisture absorption (dielectric constant, dielectric loss tangent)>

[0542] After the test pieces were treated at 121°C and 100% humidity for 6 hours, the dielectric constant and dielectric loss tangent of the test pieces at 1 GHz and 10 GHz were determined by cavity resonance method using an Agilent Technologies E8362C network analyzer manufactured by JIS-C-6481 after absolute drying and storage at 23°C and 50% humidity for 24 hours.

[0543] <Current Thermal Expansion Properties (CTE)>

[0544] Thermomechanical analysis was performed using a Seiko Instruments SS-6100 thermomechanical analysis apparatus in compression mode (measurement weight: 88.8 mN, heating rate: 10 °C / min, twice; measurement temperature range: room temperature to 290 °C). The coefficient of thermal expansion in the second measurement from 40 °C to 60 °C was evaluated using α1, and the coefficient of thermal expansion in the second measurement from 230 °C to 250 °C was evaluated using α2.

[0545] [Table 1]

[0546]

[0547] Examples 19-32 and Comparative Examples 4-6

[0548] <Preparation of Curable Resin Compositions>

[0549] In the proportions shown in Table 2 (proportions in the table are parts by mass), 1.0% by mass of PERBUTYL P (manufactured by Nippon Oil, α,α'-di(tert-butylperoxy)diisopropylbenzene) as a curing catalyst was added relative to 100% by mass of the total components, and toluene was added to prepare a curable resin composition. In the table, SA9000 resin is Noryl (trademark) SA9000 resin manufactured by Sabic Corporation, and TAIC is triallyl isocyanurate.

[0550] <Fabrication of Laminated Boards>

[0551] Using the obtained curable resin composition, laminates were fabricated under the following conditions, and various evaluation tests were conducted using the methods described later. The results are shown in Table 2.

[0552] Substrate: Nitto Boshoku Co., Ltd., glass cloth "#2116" (210×280mm)

[0553] Copper foil: JTCSLC foil (18μm) manufactured by JX Metals Co., Ltd.

[0554] Fukuda Metal Foil Powder Industry Co., Ltd. manufactures CF-T4X-SV (18μm).

[0555] Fukuda Metal Foil Powder Industry Co., Ltd. manufactures CF-T9DA-SV (18μm).

[0556] Number of floors: 6

[0557] Curing conditions: 200℃, 29kg / cm² 2 1.5 hours

[0558] Thickness of the formed plate: 0.8mm

[0559] <Dielectric properties (dielectric constant and dielectric loss tangent)>

[0560] According to JIS-C-6481, using the impedance material analyzer "HP4291B" manufactured by Agilent Technologies, Inc., the dielectric constant (Dk) and dielectric loss tangent (Df) of the test piece after absolute drying and storage at 23°C and 50% humidity for 24 hours were determined at 1 GHz and 10 GHz.

[0561] <Copper Foil Adhesion (Peel Strength)>

[0562] According to JIS-6911, the previously obtained laminated board was cut into pieces with a width of 10 mm and a length of 200 mm. These pieces were used as test pieces to determine the peel strength of the copper foil and to evaluate the adhesion.

[0563] <Interlayer adhesion (interlayer peel strength)>

[0564] According to JIS-6911, the copper foil laminate obtained above was cut into pieces with a width of 10 mm and a length of 200 mm, and used as test pieces to determine the interlayer adhesion. The results are shown in Table 2.

[0565] [Table 2]

[0566]

[0567] As can be seen from the results shown in Tables 1 and 2 above, by using the various curable resins of the embodiments, a cured product can be obtained that simultaneously satisfies low dielectric properties (low dielectric constant and low dielectric loss tangent), good dielectric properties after moisture absorption, high adhesion to copper foil, and high heat resistance.

[0568] Industrial applicability

[0569] The cured product obtained using the curable resin of this invention simultaneously satisfies low dielectric properties (low dielectric constant and low dielectric loss tangent), good dielectric properties after moisture absorption, high adhesion to copper foil, and high heat resistance. Therefore, it is suitable for use in heat-resistant components, electronic components, and particularly for prepregs, semiconductor sealing materials, circuit boards, laminated films, laminated substrates, adhesives, and photoresist materials. Additionally, it is also suitable as a matrix resin for fiber-reinforced resins and as a high-heat-resistant prepreg.

Claims

1. A curable resin, characterized in that, contain: The structural unit shown in equation (1) below, At least one of the structural units shown in equation (2) and equation (3) below, and Terminal (methyl)acryloyl group, [Chemistry 1] In formula (1), Ra is independently an alkyl, aryl, aralkyl, or cycloalkyl group having 1 to 12 carbon atoms, and k is independently an integer from 0 to 4. Rb is independently an alkyl, aryl, aralkyl, or cycloalkyl group having 1 to 12 carbon atoms, l1 is independently an integer from 0 to 4, and l2 is independently an integer from 0 to 3. n is the average number of repeating units, which is a value ranging from 0.5 to 20. m are independent integers from 0 to 2. * indicates a bonding bond. [Chemistry 2] In equation (2), * represents a bonding bond. [Chemistry 3] In formula (3), Rc is independently an alkyl, aryl, aralkyl, or cycloalkyl group with 1 to 12 carbon atoms, and p is an integer from 0 to 4. * indicates a bonding bond.

2. The curable resin according to claim 1, wherein, It also includes at least one of the structural units shown in equation (4) and equation (5) below. [Chemistry 4] In formula (4), Rd is independently an alkyl, aryl, aralkyl, or cycloalkyl group with 1 to 12 carbon atoms. When q is 2 or more, two adjacent Rd groups can form a ring together. q is an integer from 0 to 5. * indicates a bonding bond. [Chemistry 5] In formula (5), Re is a single bond, -O-, -S-, -S(=O)-, -S(=O)2-, -C(=O)-, or a hydrocarbon group that may have substituents. Ar1 is independently: [Chemistry 6] or [Chemistry 7] Rf is independently an alkyl, aryl, aralkyl, or cycloalkyl group having 1 to 12 carbon atoms, and r is an integer from 0 to 4. Rg is independently an alkyl, aryl, aralkyl, or cycloalkyl group having 1 to 12 carbon atoms, and s is an integer from 0 to 6. Ar2 is independently: [Chemistry 8] or [Chemistry 9] Rh are independently alkyl, aryl, aralkyl, or cycloalkyl groups having 1 to 12 carbon atoms, and t is an integer from 0 to 3. Ri is independently an alkyl, aryl, aralkyl, or cycloalkyl group having 1 to 12 carbon atoms, and u is an integer from 0 to 5. n5 is the average number of repeating units, which is a value from 0 to 20. * indicates a bonding bond.

3. The curable resin according to claim 1, wherein, The structural unit shown in equation (1) is the structural unit shown in equation (1-1) below. [Chemistry 10] In formula (1-1), R1 and R2 are independently hydrogen atoms, alkyl groups having 1 to 12 carbon atoms, aryl groups, aralkyl groups, or cycloalkyl groups. n1 is the average number of repeating units, ranging from 0.5 to 20. * indicates a bonding bond.

4. The curable resin according to claim 1, having the structural unit shown in formula (6), [Chemistry 11] In equation (6), R3 can be independently represented by either the structural unit shown in equation (1-1) or the structural unit shown in equation (5). R5 can be independently the structural unit shown in equation (1-2), the structural unit shown in equation (4), the structural unit shown in equation (5-2), or Y. Here, Y stands for (meth)acryloyl. n6 is the average number of repeating units, which is a value between 0 and 5. * indicates a bonding bond. in, The curable resin has at least one of the structural units shown in formula (1-1) and the structural units shown in formula (1-2) below. The curable resin contains at least one Y. [Chemistry 12] In equation (1-2), R1, R2, n1, and Y are the same as above. * indicates a bonding bond. [Chemistry 13] In equation (5-2), Re, Ar1, Ar2, Y, and n5 are the same as above. * indicates a bonding bond.

5. The curable resin according to claim 1, having the structural unit shown in formula (7), [Chemistry 14] In equation (7), R7 is the structural unit shown in equation (1-1) or the structural unit shown in equation (5). R8 is the structural unit shown in equation (1-2), the structural unit shown in equation (4), the structural unit shown in equation (5-2), or Y. n7 is the average number of repeating units, which is a value between 0 and 5. in, The curable resin has at least one of the structural units shown in formula (1-1) and formula (1-2). The curable resin contains at least one Y.

6. A curable resin composition, characterized in that, The product contains any one of the curable resins according to claims 1 to 5.

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

8. A prepreg, characterized in that, A semi-cured product having a reinforcing substrate and a curable resin composition of claim 6 impregnated in the reinforcing substrate.

9. A circuit board comprising a laminate of the prepreg and copper foil as described in claim 8.

10. A deposited film, characterized in that, The curable resin composition of claim 6 is contained in the composition of claim 6.

11. A semiconductor sealing material, characterized in that, The curable resin composition of claim 6 is contained in the composition of claim 6.

12. A semiconductor device, characterized in that, A cured product comprising the semiconductor sealing material of claim 11.

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