Indan ring-containing compound, curable composition, cured product, prepreg, circuit board, build-up film, semiconductor sealant and semiconductor device

Abstract

To provide an indan ring-containing compound demonstrating excellent heat resistance and low dielectric loss tangents, a curable composition containing the indan ring-containing compound, and a cured product thereof.SOLUTION: An indan ring-containing compound contains a structural unit represented by the general formula (1a) and a structural unit represented by the general formula (2) or (3), with at least one of terminal sites being an alkenyl group.SELECTED DRAWING: Figure 7

Description

[Technical Field]

[0001] The present disclosure relates to an indane ring-containing compound, a curable composition, a cured product, a prepreg, a circuit board, a build-up film, a semiconductor encapsulant, and a semiconductor device. [Background technology]

[0002] Prepregs, obtained by impregnating glass cloth with thermosetting resins such as epoxy resins or BT (bismaleimide-triazine) resins and then heating and drying them, laminates obtained by heat-curing the prepregs, and multilayer boards obtained by combining the laminates and prepregs and heat-curing them, are widely used as circuit board materials for electronic devices. In particular, package substrates, a type of printed wiring board that serves as an interposer for mounting semiconductors, are becoming thinner. Warping of package substrates during mounting is becoming a problem, and materials with high heat resistance are needed to suppress warping of package substrates during mounting. In particular, given the recent demand for high-frequency substrates that can reduce transmission loss, there is an increasing demand for resin materials with low dielectric loss tangents, which are closely related to reducing transmission loss. For example, Patent Document 1 discloses a low-dielectric material made of a polyindane derivative having a specific indane skeleton as a suitable interlayer insulating film material that has a low dielectric constant even without introducing vacancies. Patent Document 1 also describes that a low dielectric constant is achieved by reducing the polarizability of the molecule by reducing the number of π electrons and hydrogen atoms in the molecule, and therefore hydrocarbon groups other than hydrogen atoms are substituted at the benzene ring sites of the specific indane skeleton. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2007-311732 Summary of the Invention [Problem to be solved by the invention]

[0004] However, although the technology of Patent Document 1 has investigated low dielectric constant and heat resistance, the heat resistance in particular does not reach the level required for advanced material applications. Furthermore, in the low dielectric material made of a polyindane derivative obtained by the technology of Patent Document 1, the amount of vinyl groups remaining in the molecule is limited, which may affect the developability when the low dielectric material is cured. Therefore, the technical problem to be solved by the present disclosure is to provide an indan ring-containing compound and a method for producing the same, an indan-based mixture containing an indan ring-containing compound, a curable composition containing an indan ring-containing compound and a cured product thereof, all of which exhibit excellent heat resistance and a low dielectric dissipation factor, as well as prepregs, circuit boards, build-up films, semiconductor encapsulants, and semiconductor devices using the cured products. [Means for solving the problem]

[0005] As a result of extensive research aimed at solving the above-mentioned problems, the present inventors have found that by using an indan ring-containing compound having a structural unit represented by the following general formula (1a) and a structural unit represented by the following general formula (2) or general formula (3), and having an alkenyl group in at least one terminal position, it is possible to obtain an indan ring-containing compound that can achieve both a low dielectric tangent and excellent heat resistance at a high level, an indan-based mixture containing the indan ring-containing compound, a curable composition containing the indan ring-containing compound, and a cured product thereof, and have completed the present invention. [ka] (In the above general formula (1a), R 11 , R 12 and R 13 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n 12 represents the average number of repeating units.) [ka] (In the above general formula (2), R 14each independently represents an amino group, a fluoroalkyl group, or an alkyl group having 1 to 3 carbon atoms; n 2 represents an integer between 0 and 3.) (In the above general formula (3), R 15 each independently represents an amino group, a fluoroalkyl group, or an alkyl group having 1 to 3 carbon atoms; n 3 represents an integer between 0 and 4.) [Effects of the Invention]

[0006] According to the present disclosure, it is possible to provide an indan ring-containing compound, an indan-based mixture containing an indan ring-containing compound, a curable composition containing an indan ring-containing compound, and a cured product thereof, which exhibit an extremely low dielectric tangent and excellent heat resistance. According to the present disclosure, the method for producing an indan ring-containing compound using an aniline compound in the presence of an acid catalyst can omit a dehydration treatment or reduce the number of times the dehydration treatment is performed. According to the present disclosure, it is possible to provide prepregs, circuit boards, build-up films, semiconductor encapsulants, and semiconductor devices that combine low dielectric properties and excellent heat resistance to a high degree by using cured products that use indan ring-containing compounds that exhibit extremely low dielectric tangents and excellent heat resistance. [Brief explanation of the drawings]

[0007] [Figure 1] FIG. 1 shows a GPC chart of the indan ring-containing compound (A-1) obtained in Example 1. [Figure 2] FIG. 2 shows a GPC chart of the indan ring-containing compound (A-2) obtained in Example 2. [Figure 3] FIG. 3 shows a GPC chart of the indan ring-containing compound (A-3) obtained in Example 3. [Figure 4] FIG. 4 shows a GPC chart of the indan ring-containing compound (A-4) obtained in Example 4. [Figure 5] FIG. 5 shows a GPC chart of the indan ring-containing compound (A-5) obtained in Example 5. [Figure 6]FIG. 6 shows the FD-MS chart of the indan ring-containing compound (A-1) obtained in Example 1. [Figure 7] FIG. 7 shows the 13C-NMR chart of the indan ring-containing compound (A-1) obtained in Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0008] The following describes in detail an embodiment of the present invention (hereinafter referred to as the "present embodiment"); however, the present disclosure is not limited to the following description and can be implemented in various modifications within the scope of its gist.

[0009] "term" In this specification, the term "reaction raw material" refers to a compound that is used to obtain a target compound through a chemical reaction such as synthesis or decomposition and that partially constitutes the chemical structure of the target compound, and excludes substances that serve as chemical reaction auxiliaries, such as solvents and catalysts. In particular, in this specification, the term "reaction raw material" refers to a precursor for obtaining a target indan ring-containing compound or a mixture containing one or more indan ring-containing compounds through a chemical reaction. The "alkyl group" in this specification may be linear, branched, or cyclic, and examples thereof include a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, tert-pentyl group, neopentyl group, 1,2-dimethylpropyl group, n-hexyl group, isohexyl group, (n-)heptyl group, (n-)octyl group, (n-)nonyl group, (n-)decyl group, (n-)undecyl group, (n-)dodecyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, and cyclononyl group. As used herein, the term "cycloalkyl group" includes a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a norbornyl group, an adamantyl group, and the like.

[0010] As used herein, the term "alkenyl group" includes a 1-propynyl group, a 2-propynyl group, a 2-butynyl group, a pentynyl group, a hexynyl group, a vinyl group, an allyl group, an isopropenyl group, and the like. As used herein, the term "alkoxy group" includes, for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a 2-ethylhexyloxy group, an octyloxy group, and a nonyloxy group. In the present specification, the term "aryl group" includes a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and the like. As used herein, the term "aryloxy group" includes a phenoxy group, a naphthyloxy group, an anthryloxy group, a phenanthryloxy group, a pyrenyloxy group, and the like. As used herein, the term "halogen atom" includes, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like. The "alkylene group" in this specification may be linear, branched, or cyclic, and includes groups in which one hydrogen atom has been removed from any position of the above-mentioned exemplified groups of the "alkyl group." Examples include a methylene group, an ethylene group, a propylene group, a 1-methylmethylene group, a 1,1-dimethylmethylene group, a 1-methylethylene group, a 1,1-dimethylethylene group, a 1,2-dimethylethylene group, an isopropylene group, an isopropylidene group, a propylidene group, a butylene group, a 1-methylpropylene group, a 2-methylpropylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, and a dodecylene group.

[0011] In this specification, a "fluoroalkyl group" is an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. The "fluoroalkyl group" may be a straight-chain or branched fluoroalkyl group. The number of fluorine atoms contained in the "fluoroalkyl group" may be 1 or more, preferably 1 to 11. The "fluoroalkyl group" also includes a perfluoroalkyl group in which all hydrogen atoms in the alkyl group are substituted with fluorine atoms. As used herein, the term "perfluoroalkyl group" includes, for example, a trifluoromethyl group (-CF3), a pentafluoroethyl group (-C2F5), a heptafluoropropyl group (-CF2CF2CF3), and a heptafluoroisopropyl group (-CF(CF3)2). Examples of the "fluoroalkyl group" in this specification include a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a perfluoroethyl group, a tetrafluoropropyl group, a hexafluoropropyl group, a perfluorobutyl group, an octafluoropentyl group, a perfluoropentyl group, and a perfluorohexyl group. The term "structural unit" as used herein refers to a (repeating) unit of a chemical structure formed during a reaction or polymerization; in other words, it refers to a partial structure other than the structure of the chemical bonds involved in the reaction or polymerization in a product compound formed through a reaction or polymerization, and is a so-called residue.

[0012] "Indane ring-containing compounds" The indan ring-containing compound according to the present disclosure has a structural unit represented by the following general formula (1a) and a structural unit represented by the following general formula (2) or general formula (3), and at least one of the terminal moieties is an alkenyl group. [ka] (In the above general formula (1a), R 11 , R 12 and R 13 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n 12 represents the average number of repeating units.) [ka] (In the above general formula (2), R 14 each independently represents an amino group, a fluoroalkyl group, or an alkyl group having 1 to 3 carbon atoms; n 2 represents an integer between 0 and 3.) (In the above general formula (3), R 15each independently represents an amino group, a fluoroalkyl group, or an alkyl group having 1 to 3 carbon atoms; n 3 represents an integer between 0 and 4.)

[0013] The indan ring-containing compound of this embodiment has an aromatic ring containing at least one amino group in its molecule and an unsaturated bond at at least one of its molecular terminals. Therefore, the indan ring-containing compound exhibits thermosetting properties, making it suitable for a variety of reactions or applications. Furthermore, due to the extremely high proportion of carbon atoms and hydrogen atoms among the constituent atoms of the indan ring-containing compound of this embodiment, the indan ring-containing compound as a whole exhibits low polarity, resulting in an extremely low dielectric loss tangent. Furthermore, the fused ring structure of the indan ring provides excellent chemical thermal stability. This is believed to enable the compound to achieve both excellent heat resistance and low dielectric loss tangent to a high degree. As described above, the indan ring-containing compound according to the present disclosure has a group represented by general formula (2) or general formula (3) and an unsaturated bond at at least one of the molecular terminals. Therefore, when all of the terminals of the indan ring-containing compound are alkenyl groups, the molecule has an aniline skeleton represented by general formula (2). Furthermore, since the indan ring-containing compound has an aromatic ring with an aniline skeleton, it can be easily used in combination with various thermosetting resins such as epoxy resins and bismaleimide resins to further improve heat resistance.

[0014] In the above general formula (1a), R 11 , R 12 and R 13 are each independently preferably an alkyl group having 1 to 4 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. 11 , R 12 and R 13 are preferably the same alkyl groups. In the above general formula (1a), n 12represents the average number of repeating units, and specifically, is preferably in the range of 0.5 to 20, more preferably in the range of 0.8 to 15, and even more preferably in the range of 1 to 10. Average number of repeating units n 12 is preferably in the range of 0.5 to 20, since it is possible to form a compound containing an indan ring with a relatively high molecular weight. 12 In the above range, the distance between crosslinking points becomes relatively short, which is preferable from the viewpoint of improving heat resistance due to a high crosslink density. In addition, since the proportion of carbon atoms and hydrogen atoms in the constituent atoms of the indan ring-containing compound of the present embodiment becomes high, the indan ring-containing compound as a whole tends to exhibit low polarity, and the dielectric loss tangent can be further reduced.

[0015] In the above general formula (2), R 14 are preferably each independently an amino group, a fluoroalkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 3 carbon atoms. 2 is preferably 0 or 1. In the above general formula (3), R 15 are preferably each independently an amino group, a fluoroalkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 3 carbon atoms. 3 is preferably 0, 1 or 2.

[0016] The indan ring-containing compound in this embodiment has an alkenyl group at at least one terminal of its molecular chain and an aniline skeleton in its molecular chain, which makes the indan ring-containing compound thermosetting, and thus applicable to various reactions or uses. The alkenyl group at the terminal position of the molecular chain of the indan ring-containing compound in this embodiment is preferably a linear or branched alkenyl group having 2 to 10 carbon atoms, more preferably a linear or branched alkenyl group having 2 to 6 carbon atoms, and even more preferably a linear or branched alkenyl group having 2 to 4 carbon atoms. In this embodiment, the alkenyl group may be any of various alkenyl groups as described in the "Definition" section above. Among these, an alkenyl group having at least one quaternary carbon is preferred, an alkenyl group having at least one quaternary carbon and in which one bond of the quaternary atom is chemically bonded directly or indirectly to a structural unit represented by general formula (1a) is more preferred, and an alkenyl group represented by the following general formula (i) is even more preferred. [ka] (In the above general formula (i), R i1 represents an alkyl group having 1 to 6 carbon atoms, and R i2 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and * represents a bond that chemically bonds to another atom.)

[0017] The indan ring-containing compound in this embodiment has an alkenyl group at at least one terminal site of its molecular chain, and as long as it has at least one aniline skeleton in the molecule, there are no particular limitations on the other terminal sites of the molecular chain, and examples thereof include a hydrogen atom, a halogen atom, an amino group, or a monovalent organic group. From the viewpoint of exhibiting excellent thermosetting properties, it is preferable that many alkenyl groups are introduced into the terminal sites of the molecular chain of the indan ring-containing compound in this embodiment, and ideally, all of the terminal sites of the molecular chain of the indan ring-containing compound are alkenyl groups. For example, when the structural unit represented by general formula (1a) is present in an amount of (n 11 =10), and preferably has one or more alkenyl groups. In the present embodiment, the number of alkenyl groups (unsaturated bonds) per molecule of the indan ring-containing compound is preferably in the range of 1 to 10 on average. The method for quantifying the alkenyl group (unsaturated bond) is calculated using the "method for quantifying double bonds" described in JP-A-2012-214728, as will be described in the Examples section below.

[0018] In this specification, the term "monovalent organic group" refers to an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms. In the aryl group having 6 to 20 carbon atoms, one or more hydrogen atoms may be substituted with a halogen atom, an amino group, an alkyl group, an alkenyl group, or an alkoxy group. In this specification, the term "amino group" refers not only to -NH2 but also to substituted amino groups, such as -NR a R b (R a and R b each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

[0019] The indan ring-containing compound in this embodiment preferably has a linear or branched molecular chain, and the molecular chain is preferably configured with the structural unit represented by the above general formula (1a) as the main chain. More specifically, when the indan ring-containing compound of this embodiment has a linear molecular chain, a preferred embodiment of the indan ring-containing compound has a chemical structure in which structural units represented by the general formula (1a) are linearly linked, an alkenyl group is bonded to at least one end of the linearly linked structural units represented by the general formula (1a), and at least one aniline skeleton is present within the molecule. The group at the other end of the linearly linked structural units represented by the general formula (1a) is not particularly limited as long as at least one aniline skeleton is present within the molecule, and examples thereof include a hydrogen atom, a halogen atom, an amino group, or a monovalent organic group. Preferably, the group at the other end of the linearly linked structural units represented by the general formula (1a) is an alkenyl group. The molecule may contain two or more aniline skeletons, not just at the end. On the other hand, when the indan ring-containing compound in this embodiment has a branched molecular chain, a preferred embodiment of the indan ring-containing compound has three or more fused ring-containing molecular chains in which structural units represented by the above general formula (1a) are linearly linked, and one end of the three or more fused ring-containing molecular chains is chemically bonded to a trivalent or higher organic group or a carbon atom of a benzene ring in the above general formula (1a), and the other end of the three or more fused ring-containing molecular chains has a chemical structure in which it is chemically bonded to a hydrogen atom, a halogen atom, an amino group, an alkenyl group, or a monovalent organic group, and further at least one of the other end of the three or more fused ring-containing molecular chains is chemically bonded to an alkenyl group, and further has a structure comprising at least one aniline skeleton in the molecule. In this specification, the term "trivalent organic group" refers to a group obtained by removing two hydrogen atoms at any position from the above-mentioned "monovalent organic group." The indan ring-containing compound in this embodiment is more preferably composed of a linear molecular chain. Having an indan skeleton in a linear chain is preferred because it is expected to have better flexibility and improved brittleness resistance.

[0020] The number-average molecular weight (Mn) of the indan ring-containing compound of the present disclosure is preferably in the range of 320 to 3,000, more preferably in the range of 350 to 2,000.The weight-average molecular weight (Mw) of the indan ring-containing compound is preferably in the range of 350 to 7,000, more preferably in the range of 400 to 4,000. In view of excellent heat resistance and dielectric properties, the indan ring-containing compound of the present disclosure preferably has a molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) calculated from gel permeation chromatography (GPC) measurement in the range of 1.1 to 15, more preferably 1.1 to 10, and even more preferably 1.1 to 8. Note that when the molecular weight distribution is wide and there are many high molecular weight components as seen from the GPC chart obtained from the GPC measurement, the proportion of high molecular weight components that contribute to flexibility increases, and therefore, compared to cured products using conventional indan ring-containing compounds, a cured product with reduced brittleness and excellent flexibility and pliability can be obtained, which is a preferred embodiment. The number average molecular weight (Mn), weight average molecular weight (Mw) and molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the indan ring-containing compound of this embodiment are measured using gel permeation chromatography (hereinafter abbreviated as "GPC") under the measurement conditions described in the examples described later.

[0021] The amine equivalent of the indan ring-containing compound of the present disclosure is preferably in the range of 300 to 30,000 g / equivalent, more preferably in the range of 500 to 25,000 g / equivalent. When the amine equivalent is in the above range, it becomes easier to use the compound in combination with various thermosetting resins such as epoxy resins and bismaleimide resins to further improve heat resistance. The amine equivalent is calculated using the method shown in the Examples section below.

[0022] A preferred embodiment of the indan ring-containing compound in this embodiment will be described below using as an example a chemical structure in which the indan ring-containing compound has a linear molecular chain, i.e., in which structural units represented by the above general formula (1a) are linearly linked, an alkenyl group is bonded (directly or indirectly) to at least one terminal of the linearly linked structural units represented by the general formula (1a), and at least one aniline skeleton is present in the molecule.

[0023] -Preferred form of indan ring-containing compound- The indan ring-containing compound in this embodiment is represented by the following general formula (1b): [ka] (In the above general formula (1b), R 11 , R 12 and R 13 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Q 11 , Q 12 , L 11 and L 12 each independently represents a single bond or an alkylene group having 1 to 8 carbon atoms, P11 and P 12 each independently represents an alkenyl group having 2 to 10 carbon atoms or a group represented by the following general formula (3): M 11 and M 12 each independently represents a single bond or a group represented by the following general formula (4): n 12 represents the average number of repeating units, and n 11 and n 13 Each independently represents a value from 0 to 20. However, P 11 and P 12 At least one of the above is an alkenyl group having 2 to 10 carbon atoms, and n 11 M 11 and n 13 M 12 and P 11 and P 12 and at least one group is substituted with an amino group. [ka] [In the above general formula (3), R 15 each independently represents an amino group, a fluoroalkyl group, or an alkyl group having 1 to 3 carbon atoms; n 3 represents an integer between 0 and 4.] [In the above general formula (4), R 16 each independently represents an amino group, a fluoroalkyl group, or an alkyl group having 1 to 3 carbon atoms; n 4 represents an integer between 0 and 4.] In the above general formulas (3) and (4), * represents a bond to another atom.

[0024] In the general formula (1b) of this embodiment, n 12 If there are two or more R 11 , R 12 and R 13 may be the same or different from each other independently. 11 If there are two or more M 11may be the same or different from each other independently. 11 may be independently the same or different from each other. Furthermore, n 13 If there are two or more M 12 may be the same or different from each other independently. 12 may be independently the same or different from each other.

[0025] In the above general formula (3), n 3 If there are two or more R 15 may be independently the same or different from each other. In the above general formula (4), n 4 If there are two or more R 16 may be independently the same or different from each other.

[0026] In the general formula (1b) above, R 11 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. 12 If there are two or more R 11 may be the same or different. Particularly preferred R in general formula (1b) 11 is a methyl group, an ethyl group, or an n-propyl group. 11 The benzene ring to which is bonded corresponds to the benzene ring of the aromatic compound (A) described below.

[0027] In the general formula (1b) above, R 12 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. 12 If there are two or more R 12may be the same or different. Particularly preferred R in general formula (1b) 12 is a methyl group, an ethyl group, or an n-propyl group. 12 The benzene ring to which is bonded corresponds to the benzene ring of the aromatic compound (A) described below.

[0028] In the general formula (1b) above, R 13 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. 12 If there are two or more R 13 may be the same or different. Particularly preferred R in general formula (1b) 13 is a methyl group, an ethyl group, or an n-propyl group. 13 The benzene ring to which is bonded corresponds to the benzene ring of the aromatic compound (A) described below.

[0029] In the above general formula (1b), Q 11 represents a single bond or an alkylene group having 1 to 8 carbon atoms, preferably a single bond or an alkylene group having 1 to 6 carbon atoms, and more preferably a single bond or an alkylene group having 1 to 4 carbon atoms. Particularly preferred Q in general formula (1b) 11 is a single bond, a methylene group, an ethylene group, an n-propylene group, an isopropylene group, an isopropylidene group, a propylidene group, an n-butylene group, an isobutylene group, a sec-butylene group, a tert-butylene group, an n-pentylene group, an isopentylene group, a tert-pentylene group, a neopentylene group, or a 1,2-dimethylpropylene group. 12 represents a single bond or an alkylene group having 1 to 8 carbon atoms, preferably a single bond or an alkylene group having 1 to 6 carbon atoms, and more preferably a single bond or an alkylene group having 1 to 4 carbon atoms. Particularly preferred Q in general formula (1b) 12 is the particularly preferred Q 11 is the same as:

[0030] In the general formula (1b) above, L11 represents a single bond or an alkylene group having 1 to 8 carbon atoms, preferably a single bond or an alkylene group having 1 to 6 carbon atoms, and more preferably a single bond or an alkylene group having 1 to 4 carbon atoms. Particularly preferred L in general formula (1b) 11 is a single bond, a methylene group, an ethylene group, an n-propylene group, an isopropylene group, an isopropylidene group, a propylidene group, an n-butylene group, an isobutylene group, a sec-butylene group, a tert-butylene group, an n-pentylene group, an isopentylene group, a tert-pentylene group, a neopentylene group, or a 1,2-dimethylpropylene group.

[0031] In the general formula (1b) above, L 12 represents a single bond or an alkylene group having 1 to 8 carbon atoms, preferably a single bond or an alkylene group having 1 to 6 carbon atoms, and more preferably a single bond or an alkylene group having 1 to 4 carbon atoms. Particularly preferred L in general formula (1b) 12 is a single bond, a methylene group, an ethylene group, an n-propylene group, an isopropylene group, an isopropylidene group, a propylidene group, an n-butylene group, an isobutylene group, a sec-butylene group, a tert-butylene group, an n-pentylene group, an isopentylene group, a tert-pentylene group, a neopentylene group, or a 1,2-dimethylpropylene group.

[0032] In the general formula (1b) above, P 11 and P 12 are each independently an alkenyl group having 2 to 10 carbon atoms or a group represented by the following general formula (3): [ka] (In the above general formula (3), R 15 each independently represents an amino group, a fluoroalkyl group, or an alkyl group having 1 to 3 carbon atoms; n 3 represents an integer between 0 and 4.) The alkenyl group having 2 to 10 carbon atoms is preferably an alkenyl group having at least one quaternary atom, and one of the bonds of the quaternary atom is L. 11or L 12 More preferably, it is an alkenyl group bonded to the following, and even more preferably an alkenyl group represented by the following general formula (3-2). [ka] (In the above general formula (3-2), R 33 represents an alkyl group having 1 to 6 carbon atoms, and R 34 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and in the above general formula (3-2), * represents a bond chemically bonded to the aromatic ring. In the general formula (1b) above, P 11 or P 12 At least one of the groups is preferably an alkenyl group represented by general formula (3-2), and P 11 and P 12 and (3-2) are more preferably alkenyl groups represented by the general formula (3-2), which tends to improve the heat resistance since the indan ring-containing compound exhibits higher thermosetting properties. In this embodiment, P 11 or P 12 is a group represented by the above general formula (3), a preferred embodiment of the indan ring-containing compound is 15 each independently represents an amino group, a fluoroalkyl group having 1 to 3 carbon atoms, or an alkyl group having 1 to 3 carbon atoms; n 3 can represent an integer between 0 and 4. 11 and P 12 When at least one of the above is a group represented by general formula (3), homopolymerization of the other alkenyl group can be suppressed to some extent. The benzene ring in the general formula (3) can correspond to the benzene ring of an aniline compound described below.

[0033] In the general formula (1b) above, M 11 and M 12 are each independently a single bond or a group represented by the following general formula (4): [ka] (In the above general formula (4), R 16 each independently represents an amino group, a fluoroalkyl group, or an alkyl group having 1 to 3 carbon atoms; n 4 represents an integer of 0 to 4. Preferably, R 16 are each independently an amino group, a fluoroalkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 3 carbon atoms, and n 4 is 0, 1 or 2.) M in the above general formula (1b) 11 is preferably a single bond, or, as shown in the above general formula (4), a phenylene group which may be substituted with an amino group, a fluoroalkyl group, or an alkyl group having 1 to 3 carbon atoms. Examples of the phenylene group include a 1,2-phenylene group, a 1,3-phenylene group, and a 1,4-phenylene group. Similarly, M in the above general formula (1b) 12 is preferably a single bond, or, as shown in the above general formula (4), a phenylene group which may be substituted with an amino group, a fluoroalkyl group, or an alkyl group having 1 to 3 carbon atoms. Examples of the phenylene group include a 1,2-phenylene group, a 1,3-phenylene group, and a 1,4-phenylene group. The benzene ring in the general formula (4) may correspond to the benzene ring of an aniline compound described below.

[0034] In the above general formula (1b), "n 11 M 11 and n 13 M 12 and P 11 and P 12 and at least one group is substituted with an amino group." means that the indan ring-containing compound represented by general formula (1b) has at least one aromatic ring having one or more amino groups in one molecule. More specifically, the indan ring-containing compound represented by general formula (1b) has n 11 M 11 and n 13 M 12 and one P 11 and one P 12 And these "n 11 M11 , n 13 M 12 , 1 P 11 and 1 P 12 " total n 11 +n 13 + means that at least one of the two groups is an aromatic ring having an amino group (for example, an aniline skeleton). Therefore, M in general formula (1b) 11 or M 12 When the group represented by is substituted with an amino group, M 11 or M 12 are each independently a group represented by general formula (2). In other words, M in general formula (1b) 11 or M 12 When the group represented by is substituted with an amino group, M 11 or M 12 is a group represented by general formula (4), and n 4 is an integer greater than or equal to 1, and n 4 R exists 16 At least one R 16 is an amino group. 11 or P 12 If the group represented by is substituted with an amino group, P 11 or P 12 One of them may be a group represented by general formula (3), and the other may be an alkenyl group having 2 to 10 carbon atoms.

[0035] In the above general formula (1b), n 12 represents the average number of repeating units, and is preferably in the range of 0.5 to 20, more preferably in the range of 0.8 to 15, and even more preferably in the range of 1 to 10. The average number of repeating units, n 12 When is within the above range, the proportion of carbon atoms and hydrogen atoms in the constituent atoms of the indan ring-containing compound of this embodiment is high, so that the indan ring-containing compound as a whole tends to exhibit low polarity, and the dielectric loss tangent can be further reduced. In the above general formula (1b), n 11represents the average number of repeating units, and is preferably in the range of 0 to 20, more preferably in the range of 0 to 15, and even more preferably in the range of 0 to 10. The average number of repeating units, n 11 When is within the above range, the proportion of carbon atoms and hydrogen atoms in the constituent atoms of the indan ring-containing compound of this embodiment is high, so that the indan ring-containing compound as a whole tends to exhibit low polarity, and the dielectric loss tangent can be further reduced. Since the number of amine skeletons in the constituent atoms of the indan ring-containing compound of this embodiment can also be increased, it becomes easier to use the compound in combination with various thermosetting resins such as epoxy resins and bismaleimide resins to further improve heat resistance. In the above general formula (1b), n 13 represents the average number of repeating units, and is preferably in the range of 0 to 20, more preferably in the range of 0 to 15, and even more preferably in the range of 0 to 10. The average number of repeating units, n 13 When is within the above range, the proportion of carbon atoms and hydrogen atoms in the constituent atoms of the indan ring-containing compound of this embodiment is high, so that the indan ring-containing compound as a whole tends to exhibit low polarity, and the dielectric loss tangent can be further reduced. Since the number of amine skeletons in the constituent atoms of the indan ring-containing compound of this embodiment can also be increased, it becomes easier to use the compound in combination with various thermosetting resins such as epoxy resins and bismaleimide resins to further improve heat resistance.

[0036] In this embodiment, the number of alkenyl groups (unsaturated bonds) per molecule of the indan ring-containing compound is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3. The lower limit of the number of alkenyl groups (unsaturated bonds) is preferably 1 or more, and more preferably 2 or more. The upper limit of the number of alkenyl groups (unsaturated bonds) is preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less. By allowing an average of two or more alkenyl groups (for example, vinyl groups or isopropenyl groups) to remain in one molecule of the indan ring-containing compound of this embodiment, the resulting indan ring-containing compound is more likely to exhibit thermosetting properties, and therefore an indan-based mixture containing the indan ring-containing compound or a curable composition containing the indan ring-containing compound is more likely to cure with high sensitivity. The method for quantifying the alkenyl group (unsaturated bond) is calculated using the "method for quantifying double bonds" described in JP-A-2012-214728, as will be described in the Examples section below.

[0037] The indan ring-containing compound in this embodiment preferably contains structural units represented by general formula (1b) in an amount of 50% by mass or more, more preferably 55% by mass or more but less than 100% by mass, and even more preferably 55% by mass or more and 85% by mass or less, based on the total amount (100% by mass) of the indan ring-containing compound. When the proportion of the structural unit represented by general formula (1b) in the indan ring-containing compound is 55 mass % or more, the fused ring structure of the indan skeleton can provide better chemical thermal stability.

[0038] "Indan-based mixture" Another aspect of this embodiment is an indane-based mixture containing an indane ring-containing compound having a structural unit represented by the above general formula (1a) and a structural unit represented by the above general formula (2) or general formula (3), and at least one terminal moiety is an alkenyl group, and an indane ring-containing compound having a structural unit represented by the above general formula (1a) and at least one terminal moiety is an alkenyl group. In other words, the indane-based mixture of this embodiment contains one or more indane ring-containing compounds represented by general formula (1b). The indan-based mixture of the present embodiment contains an indan ring-containing compound that exhibits excellent heat resistance and a low dielectric loss tangent, and therefore can be used as a curable composition in the same manner as the indan ring-containing compound.

[0039] The indan-based mixture in this embodiment is represented by the following general formula (1a): [ka] (In the above general formula (1a), R 11 , R 12 and R 13 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n 11 represents the average number of repeating units.) It is composed of an indan ring component having a structural unit represented by The indan ring-containing compound, which is contained as the indan ring component and in which at least one of the terminal moieties bonded to the structural unit is an alkenyl group, is represented by the following general formula (1b): [ka] (In the above general formula (1b), R 11 , R 12 and R 13 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Q 11 , Q 12 , L 11 and L 12 each independently represents a single bond or an alkylene group having 1 to 8 carbon atoms, P 11 and P 12 each independently represents an alkenyl group having 2 to 10 carbon atoms or the following general formula (3): M 11 and M 12 each independently represents a single bond or the following general formula (4): n 12 represents the average number of repeating units, and n 11 and n 13 Each independently represents a value from 0 to 20. However, P 11 and P 12 At least one of the above is an alkenyl group having 2 to 10 carbon atoms, and n 11 M 11 and n 13 M 12 and P 11 and P 12At least one of the above has an amino group. [ka] [In the above general formula (3), R 15 each independently represents an amino group, a fluoroalkyl group, or an alkyl group having 1 to 3 carbon atoms; n 3 represents an integer between 0 and 4.] [In the above general formula (4), R 16 each independently represents an amino group, a fluoroalkyl group, or an alkyl group having 1 to 3 carbon atoms; n 4 represents an integer between 0 and 4.] In addition, * in the general formulas (3) and (4) represents a bond to another atom.

[0040] Each compound constituting the indan-based mixture of this embodiment essentially contains an indan ring component having an indan ring skeleton with a very high proportion of atoms composed of carbon atoms and hydrogen atoms. Therefore, the indan-based mixture as a whole exhibits an extremely low dielectric loss tangent, similar to the indan ring-containing compounds. Furthermore, each compound constituting the indan-based mixture of this embodiment has excellent chemical thermal stability due to the fused ring structure of the indan ring. This is believed to enable both excellent heat resistance and low dielectric loss tangent to be achieved to a high degree. In particular, since the indan-based mixture is a blend of two or more indan ring-containing compounds, it is believed that both excellent heat resistance and low dielectric loss tangent can be achieved to a high degree depending on the composition ratio of the blended indan ring-containing compounds. Furthermore, since the indan-based mixture of the present embodiment has an aromatic ring having an aniline skeleton, it is preferable from the viewpoint of enabling its use in combination with various thermosetting resins such as epoxy resins and bismaleimide resins to further improve heat resistance.

[0041] In the indan mixture of this embodiment, the proportion of the indan ring component having the structural unit represented by general formula (1a), i.e., the indan ring-containing compound represented by general formula (1b), relative to 100% by mass of the total amount of the indan mixture, is preferably in the range of 0.5 to 95% by mass, more preferably in the range of 10 to 90% by mass, even more preferably in the range of 15 to 80% by mass, and particularly preferably in the range of 20 to 70% by mass. When the proportion of the indan ring-containing compound represented by general formula (1b) is in the range of 20 to 70 mass % relative to the total indan ring components having the structural unit represented by general formula (1a), better heat resistance and a low dielectric tangent are more likely to be exhibited.

[0042] A preferred composition example of the indan-based mixture of this embodiment is a compound represented by the following general formula (1c): [ka] (In the above general formula (1c), M 13 and M 14 each independently represents a single bond or a group represented by the following general formula (2) or general formula (4), [ka] [In the above general formula (2), R 14 each independently represents an amino group, a fluoroalkyl group, or an alkyl group having 1 to 3 carbon atoms; n 2 represents an integer between 0 and 4.] [In the above general formula (4), R 16 each independently represents an amino group, a fluoroalkyl group, or an alkyl group having 1 to 3 carbon atoms; n 4 represents an integer between 0 and 4.] Z 11 and Z 12 each independently represents an alkenyl group having 2 to 10 carbon atoms. However, n 11 +n 13 is greater than or equal to 1, and n 11 M 13 and n 13 M14 At least one of the groups is a group represented by general formula (2). 11 , R 12 , R 13 , Q 11 , Q 12 , L 11 and L 12 , and n 11 , n 12 and n 13 " is the same as "R 11 , R 12 , R 13 , Q 11 , Q 12 , L 11 and L 12 , and n 11 , n 12 and n 13 The indan ring-containing compound (1c) represented by the formula (I) is preferably in the range of 0.5 to 95 mass%, more preferably in the range of 10 to 90 mass%, further preferably in the range of 15 to 80 mass%, and particularly preferably in the range of 20 to 70 mass%, relative to 100 mass% of the total amount of the indan mixture. When the content of the indan ring-containing compound (1c) represented by general formula (1c) is within the range of 20 to 70 mass %, the indan-based mixture as a whole exhibits high thermosetting properties, and therefore tends to have further improved heat resistance.

[0043] Another preferred composition example of the indan-based mixture of this embodiment is a compound represented by the general formula (1d): [ka] (In the above general formula (1d), G 11 and G 12 each independently represents an alkenyl group having 2 to 10 carbon atoms or the above general formula (2), G 11 and G 12 is an alkenyl group having 2 to 10 carbon atoms, and G 11 and G 12The other is a group represented by the general formula (3), and the symbol "R 11 , R 12 , R 13 , Q 11 , Q 12 , L 11 , L 12 , M 11 and M 12 , and n 11 , n 12 and n 13 " is the same as "R 11 , R 12 , R 13 , Q 11 , Q 12 , L 11 , L 12 , M 11 and M 12 , and n 11 , n 12 and n 13 " is synonymous with ". ) is preferably in the range of 0.5 to 95 mass%, more preferably in the range of 10 to 90 mass%, further preferably in the range of 15 to 80 mass%, and particularly preferably in the range of 20 to 70 mass%, relative to 100 mass% of the total amount of the indan mixture. The indan ring-containing compound (1d) represented by general formula (1d) has an aminophenyl group derived from an aniline compound at its terminal, which is preferable from the viewpoint of enabling its use in combination with various thermosetting resins such as epoxy resins and bismaleimide resins to further improve heat resistance. Furthermore, when the indan ring-containing compound has an aminophenyl group or the indan mixture contains the compound represented by general formula (1d), when it is combined with other thermosetting resins, for example, a normal addition reaction proceeds with an epoxy group-containing thermosetting resin, or a Michael addition-type curing reaction proceeds with a maleimide group-containing thermosetting resin, and therefore an improvement in physical heat resistance (Tg) can be expected.

[0044] Another preferred composition example of the indan mixture of this embodiment preferably contains 20 to 90 mass % of the indan ring-containing compound (1c) and 0.5 to 70 mass % of the indan ring-containing compound (1d).

[0045] <Preferred Forms of Indan Ring-Containing Compounds> Preferred embodiments of the indan ring-containing compound of the present disclosure will be described below. In this embodiment, the indan ring-containing compound is preferably represented by the following general formula (1b). [ka] (In the above general formula (1b), R 11 , R 12 and R 13 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Q 11 , Q 12 , L 11 and L 12 each independently represents a single bond, a methylene group, an ethylene group, an n-propylene group, an isopropylene group, an isopropylidene group, a propylidene group, an n-butylene group, an isobutylene group, a sec-butylene group, a tert-butylene group, an n-pentylene group, an isopentylene group, a tert-pentylene group, a neopentylene group, or a 1,2-dimethylpropylene group; M 11 and M 12 each independently represents a single bond, a 1,2-phenylene group optionally substituted with an amino group, a 1,3-phenylene group optionally substituted with an amino group, or a 1,4-phenylene group optionally substituted with an amino group; P 11 and P 12 each independently represents a group represented by the following general formula (3) or an alkenyl group represented by the following general formula (3-2), n 12 is the average number of repeating units, ranging from 1 to 10, and n 11 and n 13 Each independently represents a value from 0 to 20. However, P 11 and P12 At least one of the above is an alkenyl group represented by the general formula (3-2), and n 11 M 11 and n 13 M 12 and P 11 and P 12 At least one of the groups is substituted with an amino group. [ka] (In the above general formula (3), R 15 each independently represents a hydrogen atom, an amino group, a fluoroalkyl group, or an alkyl group having 1 to 3 carbon atoms; n 3 represents an integer of 0 or more and 4 or less, and in the above general formula (3), * represents a bond to another atom. [ka] (In the above general formula (3-2), R 33 represents an alkyl group having 1 to 4 carbon atoms, and R 34 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and in the above general formula (3-2), * represents a bond chemically bonded to the aromatic ring. In addition, in the general formula (1b), n 12 If there are two or more R 11 , R 12 and R 13 may be independently the same or different from each other. In addition, in the general formula (3), n 3 If there are two or more R 15 may be independently the same or different from each other. This makes it possible to provide an indan ring-containing compound that exhibits better heat resistance and a low dielectric loss tangent. The above is a description of the indan ring-containing compound or indan-based mixture of the present disclosure. Hereinafter, a method for producing the indan ring-containing compound or indan-based mixture of the present disclosure will be described.

[0046] <Method of producing indan ring-containing compound> An example of a method for producing an indane ring-containing compound of the present embodiment includes a step of reacting an aromatic compound (A) having a substituent that forms a carbocation (hereinafter also simply referred to as aromatic compound (A)), more preferably an aromatic compound (A) having two or more substituents that form a carbocation bonded to a benzene ring, with an aniline compound in the presence of an acid. An example of a method for producing an indan ring-containing compound of the present disclosure includes a production method including the following step (1): Step (1): A step of reacting an aromatic compound (A) as a reaction raw material in the presence of an aniline compound and an acid (preferably in the presence of a solid acid catalyst) to obtain an indane ring-containing compound or an indane mixture of the present disclosure. Specifically, the method for producing an indan ring-containing compound or an indan mixture of the present embodiment preferably includes a step of reacting aromatic compounds (A) each having two or more carbocation-forming substituents bonded to a benzene ring in the presence of an aniline compound and an acid (preferably in the presence of a solid acid catalyst). By using an aniline compound, it is possible to suppress the increase in molecular weight due to runaway cationic polymerization, and to obtain an indane ring-containing compound having a terminal double bond (e.g., an isopropenyl group) in the relatively low to medium molecular weight range. Furthermore, the use of an aniline-based compound can suppress or prevent gelation. In particular, when an aromatic compound (A) having a structure in which a hydroxyl group is bonded to the α-carbon and, for example, a group represented by the following general formula (3-1) is used as a reaction raw material as a substituent that forms a carbocation, water is generated as the reaction proceeds during the temperature rise process, and violent heat is generated with bumping. Therefore, a dehydration treatment is generally required before the reaction temperature reaches, for example, 180 to 200°C. However, the use of an aniline-based compound can omit the dehydration treatment or reduce the number of dehydration treatments.

[0047] In the method for producing an indan ring-containing compound of this embodiment, after the step (1), a known purification step (e.g., washing with a reaction solvent, adsorption, fractional distillation, ion exchange resin treatment, reprecipitation, crystallization, filtration, or distillation of the reaction solvent under heating or reduced pressure, etc.) may be carried out, if necessary. This removes the reaction solvent, low-molecular-weight components such as unreacted substances, ionic impurities, etc., and can further improve the dielectric properties.

[0048] In this embodiment, the reaction product obtained in the step (1) may be a mixture containing indan ring-containing compounds, i.e., the indan-based mixture described above. Therefore, after the step (1) or the purification step, a known separation means can be used, if necessary, to recover an indan ring-containing compound having a specific molecular weight, an indan ring-containing compound having a specific functional group, or an indan ring-containing compound having alkenyl groups at both ends. Examples of the separation method include fractional distillation, chromatography, adsorption with an adsorbent, crystallization, extraction, and reprecipitation. Examples include a crystallization step in which a poor solvent is added to the reaction product obtained in step (1) and then cooled to precipitate the target product as crystals; a step in which the target product is separated from a liquid mobile phase containing the reaction product using chromatography (high-performance liquid chromatography, column chromatography, gel permeation chromatography, etc.); and a step in which the target product or unnecessary substances are adsorbed and separated using an adsorbent such as activated carbon, silica gel, alumina, or Celite. More specifically, when recovering an indan ring-containing compound having a specific molecular weight, separation is preferably performed using gel filtration chromatography. When recovering an indan ring-containing compound having a specific functional group (e.g., an amine group), separation is preferably performed using ion exchange chromatography.

[0049] The reaction raw materials, aniline compounds, acid catalysts, and reaction conditions used in the method for producing an indan ring-containing compound of the present disclosure will be described below in order. <Aromatic compounds (A)> In the method for producing an indan ring-containing compound of the present disclosure, it is preferable to use, as a reaction raw material, an aromatic compound (A) having a substituent that forms a carbocation. More specifically, the aromatic compound (A) has, as a main component, a compound (a1) having two or more substituents that form a carbocation bonded to an aromatic ring. The term "main component" means that the compound (a1) accounts for 50% by mass or more and 100% by mass or less of the entire aromatic compound (A).

[0050] In this embodiment, the substituent that forms a carbocation is preferably a group represented by the following general formula (3-1) or an alkenyl group having 2 to 10 carbon atoms. [ka] (In the above general formula (3-1), X 31 represents a polar group, and R 31 or R 32 each independently represents an alkyl group having 1 to 6 carbon atoms. In the above general formula (3-1), * represents a bond that chemically bonds to the aromatic ring. In the general formula (3-1), examples of the polar group include a hydroxyl group, an alkoxy group, and a halogen atom. 31 is relatively easily eliminated, and the polar group X 31 The α-carbon bonded to X in the general formula (3-1) can form a carbocation. 31 As the alkyl group, a hydroxyl group is particularly preferred.

[0051] In the substituent that forms a carbocation of this embodiment, the alkenyl group having 2 to 10 carbon atoms is preferably an alkenyl group having 2 to 10 carbon atoms and having at least one quaternary carbon, more preferably an alkenyl group having 2 to 10 carbon atoms and having at least one quaternary carbon atom, in which one bond of the quaternary carbon atom is chemically bonded directly or indirectly to a structural unit represented by general formula (1a), and even more preferably a group represented by the following general formula (3-2). [ka] (In the above general formula (3-2), R 33 represents an alkyl group having 1 to 6 carbon atoms, and R 34 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. In the above general formula (3-2), * represents a bond that chemically bonds to the aromatic ring. In the case of an alkenyl group having 2 to 10 carbon atoms represented by general formula (3-2), the quaternary carbon can form a carbocation in a relatively stable manner. In the above general formula (3-2), R 33 R is preferably a linear alkyl group having 1 to 3 carbon atoms. 34 is preferably a hydrogen atom or a linear alkyl group having 1 to 3 carbon atoms.

[0052] In this embodiment, the aromatic compound (A) having a substituent that forms a carbocation may be a monomer that forms a structural unit of the indane ring-containing compound represented by general formula (1a). In this embodiment, the aromatic compound (A) having a substituent that forms a carbocation preferably includes a compound (a1) represented by the following general formula (I): [ka] (In the above general formula (I), R 43 each independently represents an alkyl group or an alkoxy group having 1 to 6 carbon atoms; R 41 and R 42 are each independently a substituent that forms a carbocation, and n 41 represents an integer between 1 and 5, and n 42 represents an integer between 0 and 4. However, n 41 +n 42 is less than or equal to 5.) In the above general formula (I), R 41 and R 42 may be the same or different from each other. 41 If is between 2 and 5, there are multiple R 42 may be the same or different from each other.42 If there are two or more R 43 may be the same as or different from each other. In the above general formula (I), n 41 is preferably 1, 2 or 3, more preferably 1 or 2. 42 is preferably 0, 1 or 2, and more preferably 0 or 1. In this embodiment, the compound (a1) represented by the general formula (I) is a compound represented by the general formula (I) 41 and R 42 and are preferably the same group.

[0053] In this embodiment, a preferred embodiment of the compound (a1) represented by the general formula (I) is n 41 is 1, R 41 and R 42 are each preferably substituted. 41 is 2, R 41 and two R's 42 and are each preferably substituted, which reduces steric hindrance and allows the molecular weight or yield of the indan ring-containing compound to be further improved.

[0054] In this embodiment, the aromatic compound (A) having a substituent that forms a carbocation may further include, in addition to the compound (a1) represented by the above general formula (I), an aromatic compound (a2) having one substituent that forms a carbocation (for example, a group represented by the above general formula (3-1)). The aromatic compound (a2) is preferably represented by the following general formula (II): [ka] (In the above general formula (II), R 51is a substituent that forms a carbocation (for example, preferably an alkenyl group having 2 to 10 carbon atoms, a group represented by the above general formula (3-1) or a group represented by the general formula (3-2)), and R 52 each independently represents an alkyl group having 1 to 6 carbon atoms, and n 51 represents an integer between 0 and 5.)

[0055] . <Aniline compounds> The aniline-based compound in this embodiment reduces the tendency of aromatic compounds having a substituent that forms a carbocation to polymerize in the presence of an acid catalyst through cationic polymerization. Depending on the amount of aniline-based compound added, it is possible to significantly increase the number-average molecular weight (Mn) of approximately 3,000 or less and the weight-average molecular weight (Mw) of approximately 7,000 or less as the main product. As a result, the presence of the terminal double bond in the terminal alkenyl structure allows the indane ring-containing compound to be used as a thermosetting resin. On the other hand, if an aniline-based compound is not used, polymerization is unavoidable, and the resulting product tends to be primarily a thermoplastic resin. In the method for producing an indan ring-containing compound or an indan mixture according to this embodiment, gelation can be suppressed or prevented by using an aniline-based compound as a co-catalyst. For example, when an aromatic compound (A) having a structure in which a hydroxyl group is bonded to the α-carbon and the group represented by the general formula (3-1) above is used as a reaction raw material, water is generated as the reaction proceeds, and therefore a dehydration treatment is generally required. However, by using an aniline-based compound, the dehydration treatment can be omitted or the number of dehydration treatments can be reduced. The aniline compound is used as a cocatalyst and may be incorporated into a structural unit of the indan ring-containing compound of the present disclosure. The aniline compound is preferably represented by the following general formula (III): [ka] (In the above general formula (III), R 61each independently represents an amino group, a fluoroalkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms; n 61 represents an integer between 0 and 5.) In the above general formula (III), n 61 If is between 2 and 5, there are multiple R 61 are independent of each other, and there are multiple R 61 may be the same as or different from each other. In the above general formula (III), the fluoroalkyl group having 1 to 6 carbon atoms is preferably a perfluoroalkyl group having 1 to 6 carbon atoms.

[0056] A preferred embodiment of the aniline compound of this embodiment is a compound represented by the general formula (III) above, n 61 is an integer between 1 and 4, and R is an integer between 1 and 4 61 Preferably, each independently represents an amino group, a fluoroalkyl group having 1 to 3 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. Examples of the aniline-based compound of this embodiment include aniline, dimethylaniline, diethylaniline, diisopropylaniline, ethylmethylaniline, cyclobutylaniline, cyclopentylaniline, cyclohexylaniline, toluidine, ethylaniline, propylaniline, butylaniline, 2-methyl-3-ethylaniline, 2-methyl-4-isopropylaniline, 2,6-diethylaniline, 2-ethyl-5-tert-butylaniline, 2,4-diisopropylaniline, trimethylaniline (e.g., 2,4,6-trimethylaniline), and diethyltoluenediamine. The propyl group includes n-propyl and isopropyl, and the butyl group includes n-butyl, tert-butyl, and sec-butyl. The aniline-based compounds of this embodiment may be used alone or in combination of two or more.

[0057] In the present embodiment, the blending ratio of the aromatic compound (A) and the aniline-based compound is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 15 parts by mass, per 100 parts by mass of the aromatic compound (A), taking into consideration the balance of physical properties such as moldability during production of the resulting cured product and curability.

[0023] In addition, specific methods for carrying out the above step (1) generally include charging all raw materials at once and reacting them as they are at a predetermined temperature, or charging either the aromatic compound (A) or the aniline compound, an acid catalyst, and a reaction solvent, and reacting them while maintaining the temperature at a predetermined level and adding dropwise the other of the aromatic compound (A) or the aniline compound. After the reaction, if a solvent is used, the solvent and unreacted materials can be distilled off, if necessary, to obtain the target indan ring-containing compound. If no solvent is used, the target indan ring-containing compound can be obtained by distilling off the unreacted materials.

[0058] <Acid catalyst> Examples of the acid catalyst used in step (1) of this embodiment include inorganic salts such as acetates, chlorides, bromides, sulfates, and nitrates of nickel, cobalt, sodium, calcium, iron, lithium, manganese, and the like; inorganic acids such as phosphoric acid, hydrochloric acid, and sulfuric acid; organic acids such as oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid, and fluoromethanesulfonic acid; solid acids such as activated clay, acid clay, silica alumina, zeolite, and strongly acidic ion exchange resins; and heteropolyhydrochloric acids. From the viewpoint of handling, however, solid acids that allow the catalyst to be easily removed by filtration after the reaction are preferred. When other acids are used, it is preferable to neutralize them with a base and wash them with water after the reaction. The amount of the acid catalyst to be added is preferably within a range of 0.1 to 50 parts by mass relative to 100 parts by mass of the total amount of the raw materials (aromatic compound (A) having a substituent that forms a carbocation) to be charged, and more preferably within a range of 1 to 30 parts by mass from the viewpoints of handleability and economy.

[0059] <Reaction conditions> In the method for producing an indan ring-containing compound in this embodiment, a reaction solvent does not necessarily have to be used, but an organic solvent can also be used as the reaction solvent. Examples of organic solvents that can be used in the production method of this embodiment include ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, cyclohexanone, and acetophenone; aprotic solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, acetonitrile, and sulfolane; cyclic ethers such as dioxane and tetrahydrofuran; esters such as ethyl acetate and butyl acetate; and aromatic solvents such as benzene, toluene, and xylene. These may be used alone or in combination. In step (1) of the present embodiment, the amount of the organic solvent used is preferably in the range of 10 to 3,000 parts by mass, more preferably 50 to 1,000 parts by mass, per 100 parts by mass of the aromatic compound (A) having a substituent that forms a carbocation. Furthermore, in order to react the aromatic compound (A) as a raw material, a method may be employed in which, if necessary, water contained in the catalyst or the like is azeotropically dehydrated using a solvent capable of azeotropic dehydration, such as toluene, xylene, or chlorobenzene, and the water is then distilled off, followed by carrying out the reaction within the reaction temperature range described below.

[0060] In step (1) of the present embodiment, the reaction temperature for the cyclization reaction between aromatic compounds (A) each having a substituent that forms a carbocation is preferably in the range of 80 to 250°C, more preferably 100 to 220°C. In step (1) of the present embodiment, the reaction time of the aromatic compound (A) having a substituent that forms a carbocation, i.e., the reaction time of the cyclization reaction between the aromatic compounds (A), is usually in the range of 0.5 to 20 hours in total under the reaction temperature conditions, and preferably in the range of 1 to 10 hours in total, because the reaction does not proceed completely if it is short and side reactions such as thermal decomposition of the product occur if it is long. Preferred reaction conditions for step (1) of this embodiment include charging the aromatic compound (A), the aniline compound, the acid catalyst, and the organic solvent, reacting them at a temperature preferably in the range of 80 to 250°C, more preferably 100 to 220°C, for 0.5 to 20 hours, preferably 1.0 to 10 hours, and then further increasing the reaction temperature to a temperature range of 100 to 220°C, preferably 120 to 210°C, and then reacting them for 0.5 to 20 hours, preferably 1.0 to 10 hours. In step (1) of this embodiment, if necessary, a dehydrating agent may be used, such as a lower aliphatic carboxylic acid anhydride such as acetic anhydride, propionic anhydride, or butyric anhydride; an oxide such as phosphorus pentoxide, calcium oxide, or barium oxide; an inorganic acid such as sulfuric acid; or a porous ceramic such as a molecular sieve. Alternatively, instead of using the dehydrating agent, distilled water may be removed during the reaction.

[0061] [Curable composition] The indan ring-containing compound or indan-based mixture of the present disclosure can be used to prepare a curable composition. The curable composition of the present disclosure preferably contains the above-described indan ring-containing compound or indan-based mixture. The indan ring-containing compound or indan-based mixture of this embodiment has excellent solvent solubility, fluidity when heated and melted, and handleability, and further contributes to dimensional stability, low moisture absorption, brittleness resistance, heat resistance, and a low dielectric constant and low dielectric loss tangent. Therefore, a cured product obtained from a curable composition containing the indan ring-containing compound or indan-based mixture has excellent heat resistance and dielectric properties.

[0062] The curable composition of the present disclosure may contain a curing agent, and further, if necessary, various compounding agents such as a curing accelerator, a silane coupling agent, a release agent, a pigment, an emulsifier, a non-halogen flame retardant, an inorganic filler, a flame retardant (e.g., an inorganic phosphorus-based flame retardant, an organic phosphorus-based flame retardant, a halogen-based flame retardant), a solvent, etc. In addition to the indane ring-containing compound or indane-based mixture, it is also possible to appropriately compound epoxy resins, phenolic resins, active ester resins, maleimide resins, cyanate resins, polyphenylene ether resins, benzoxazine resins, styrene-maleic anhydride copolymers, polybutadiene and modified products thereof, polyacetal resins, polyvinyl alcohol resins, liquid crystal polymers, fluororesins, polystyrene, polyethylene, polyimide resins, silicone gels, silicone oils, etc., within the scope of the present disclosure.

[0063] [Cured product] The cured product of the present disclosure is preferably obtained from the curable composition. The cured product can be obtained by subjecting the curable composition to a curing reaction. The curable composition can be obtained by uniformly mixing the above-described components (e.g., curing agent, compounding agent), and can be easily cured by a method similar to a conventionally known method. Examples of the cured product include molded cured products such as laminates, cast products, adhesive layers, coating films, and films.

[0064] [Semiconductor encapsulation materials] The present disclosure relates to a semiconductor encapsulation material containing the curable composition of the present embodiment. The semiconductor encapsulation material obtained using the curable composition of the present embodiment has improved low dielectric loss tangent or heat resistance due to the use of the indan ring-containing compound or indan-based mixture of the present disclosure, and therefore has excellent processability, moldability, and reflow resistance in the manufacturing process, making it a preferred embodiment. The curable composition of this embodiment used in the semiconductor encapsulation material may contain an inorganic filler. The inorganic filler may be used in an amount of, for example, 0.5 to 1,200 parts by mass per 100 parts by mass of the curable composition of this embodiment. Examples of the inorganic filler include barium sulfate, barium titanate, amorphous silica, crystalline silica, Neuburg silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, silicon nitride, and aluminum nitride.

[0065] Examples of a method for obtaining the semiconductor encapsulating material include a method in which the curable composition of the present embodiment and optional additives are further melt-mixed, as necessary, using an extruder, kneader, rolls, or the like until the mixture becomes homogeneous.

[0066] [Semiconductor Devices] The present disclosure relates to a semiconductor device including a cured product of the semiconductor encapsulation material. The semiconductor device obtained using the curable composition of the present embodiment has low viscosity and excellent flowability due to the use of the indane ring-containing compound or indane mixture of the present disclosure, and further has improved moisture absorption, hot elastic modulus, and adhesion to metal materials, resulting in excellent processability, moldability, and reflow resistance in the manufacturing process, making it a preferred embodiment.

[0067] The semiconductor device can be obtained by molding the semiconductor encapsulating material using a casting machine, a transfer molding machine, an injection molding machine, or the like, and then heat-curing the material at a temperature ranging from room temperature (20°C) to 250°C.

[0068] [Prepreg] The present disclosure relates to a prepreg having a reinforcing substrate and a semi-cured product of the curable composition of the present embodiment impregnated into the reinforcing substrate. A method for obtaining a prepreg from the curable composition includes blending an organic solvent (described below) to form a varnish of the curable composition, impregnating a reinforcing substrate (such as paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, or glass roving cloth) with the curable composition, and then heating the curable composition at a temperature appropriate for the solvent used, preferably 50 to 170°C, to semi-cure (or uncur) the curable composition to obtain a prepreg. The mass ratio of the curable composition to the reinforcing substrate used in this case is not particularly limited, but it is generally preferable to prepare the prepreg so that the resin content in the prepreg is 20 to 60% by mass. In this embodiment, the semi-cured product of the curable composition can be obtained by adjusting the heating temperature and heating time to stop the curing reaction before it is completed. For example, the semi-cured product may have a degree of cure of, for example, 5% or more and 85% or less. On the other hand, the cured product in this embodiment may have a higher degree of cure than the semi-cured product. The degree of cure of the semi-cured product can be calculated from the following formula by measuring the amount of heat generated during curing when the curable composition is heated and the amount of heat generated during curing of the semi-cured product by DSC. Degree of cure (%) = [1 - (cure heat release amount of semi-cured product / cure heat release amount of curable composition)] x 100

[0069] Examples of organic solvents used in producing the prepreg include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, and propylene glycol monomethyl ether acetate. The selection and appropriate amount of the organic solvent can be determined appropriately depending on the application. For example, when a printed circuit board is further produced from the prepreg as described below, it is preferable to use a polar solvent with a boiling point of 160°C or less, such as methyl ethyl ketone, acetone, or dimethylformamide, and it is also preferable to use it in a proportion such that the non-volatile content is 40 to 80% by mass.

[0070] [Circuit board] The present disclosure relates to a circuit board that is a laminate of the prepreg and copper foil. A method for obtaining a printed circuit board from the curable composition of this embodiment includes laminating the prepreg by a conventional method, overlaying copper foil as appropriate, and subjecting the laminate to heat-pressure bonding at 170 to 300°C under a pressure of 1 to 10 MPa for 10 minutes to 3 hours.

[0071] [Build-up film] The present disclosure relates to a build-up film containing the curable composition of the present embodiment. A method for producing the build-up film of the present embodiment includes applying the curable composition to a support film to form a curable composition layer, thereby forming an adhesive film for a multilayer printed wiring board.

[0072] When a build-up film is produced from the curable composition, it is essential that the film softens under the lamination temperature conditions (usually 70 to 140°C) in the vacuum lamination method, and exhibits fluidity (resin flow) that allows resin to fill via holes or through holes present in the circuit board simultaneously with lamination of the circuit board. It is preferable to blend the above-mentioned components so as to exhibit such properties.

[0073] Here, the diameter of the through-holes in the multilayer printed wiring board is usually 0.1 to 0.5 mm, and the depth is usually 0.1 to 1.2 mm, and it is usually preferable to make it possible to fill the resin within this range. When laminating both sides of the circuit board, it is desirable to fill about half of the through-holes.

[0074] Specifically, the adhesive film can be produced by preparing the curable composition in a varnish form, applying the varnish to the surface of the support film (Y), and then drying the organic solvent by heating or blowing hot air or the like to form a composition layer (X) made of the curable composition.

[0075] The thickness of the composition layer (X) to be formed is preferably equal to or greater than the thickness of the conductor layer. Since the thickness of the conductor layer of a circuit board is usually in the range of 5 to 70 μm, the thickness of the resin composition layer is preferably 10 to 100 μm.

[0076] The composition layer (X) in this embodiment may be protected with a protective film described below. By protecting the resin composition layer with a protective film, adhesion of dust and the like to the surface of the resin composition layer and scratches can be prevented.

[0077] Examples of the support film (Y) and protective film include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate, polycarbonate, polyimide, and even release paper and metal foils such as copper foil and aluminum foil. The support film and protective film may be subjected to a mud treatment, a corona treatment, or a release treatment.

[0078] The thickness of the support film is not particularly limited, but is usually in the range of 10 to 150 μm, preferably 25 to 50 μm, and the thickness of the protective film is preferably 1 to 40 μm.

[0079] The support film (Y) is peeled off after laminating it onto the circuit board or after forming an insulating layer by heat curing. If the support film (Y) is peeled off after the adhesive film is heat cured, adhesion of dust and the like during the curing process can be prevented. When peeling off after curing, the support film is usually subjected to a release treatment in advance.

[0080] <Heat-resistant materials and electronic materials> The cured products obtained from the curable compositions containing the indan ring-containing compounds of the present disclosure exhibit low moisture absorption and excellent heat resistance and dielectric properties, making them suitable for use in heat-resistant or electronic components. They are particularly suitable for use in prepregs, circuit boards, semiconductor encapsulants, semiconductor devices, build-up films, build-up boards, adhesives using conductive pastes, and resist materials. They are also suitable for use as matrix resins for fiber-reinforced resins, making them particularly suitable for highly heat-resistant prepregs. Furthermore, the indan ring-containing compounds having an indane skeleton contained in the curable compositions exhibit excellent solubility in various solvents, making them suitable for use in paints. The heat-resistant or electronic components thus obtained can be used in a variety of applications, including, but not limited to, industrial machine parts, general machine parts, automobile, railway, and vehicle parts, aerospace and aviation-related parts, electronic and electrical components, building materials, containers and packaging materials, household goods, sports and leisure goods, and housing materials for wind power generation. [Example]

[0081] The present invention will be described in more detail with reference to Examples and Comparative Examples, in which "parts" and "%" are by mass unless otherwise specified. The physical properties of the synthesized indan ring-containing compounds were measured as follows, and the results are shown in Table 1.

[0082] (1) GPC measurement The number average molecular weight (Mn), weight average molecular weight (Mw), and molecular weight distribution (Mw / Mn) of the indan ring-containing compounds or indan-based mixtures obtained in the examples and comparative examples were calculated using the following measuring devices and conditions. "Measuring device" Tosoh Corporation's "HLC-8320 GPC" "Measurement conditions" Column: Tosoh Corporation guard column "HXL-L" + Tosoh Corporation "TSK-GEL G2000HXL" + Tosoh Corporation "TSK-GEL G2000HXL" + Tosoh Corporation "TSK-GEL G3000HXL" + Tosoh Corporation "TSK-GEL G4000HXL" Detector: RI (differential refractometer) Data processing: Tosoh Corporation's "GPC Workstation EcoSEC-WorkStation" Measurement conditions: Column temperature 40℃ Developing solvent: Tetrahydrofuran Flow rate 1.0ml / min Standard: The following monodisperse polystyrenes with known molecular weights were used in accordance with the measurement manual for the GPC Workstation EcoSEC-WorkStation. (Polystyrene used) Tosoh Corporation "A-500" Tosoh Corporation "A-1000" Tosoh Corporation "A-2500" Tosoh Corporation "A-5000" "F-1" manufactured by Tosoh Corporation "F-2" manufactured by Tosoh Corporation "F-4" manufactured by Tosoh Corporation "F-10" manufactured by Tosoh Corporation "F-20" manufactured by Tosoh Corporation "F-40" manufactured by Tosoh Corporation Tosoh Corporation "F-80" Tosoh Corporation "F-128" Sample: A tetrahydrofuran solution of 1.0% by mass (in terms of resin solid content) of the indan ring-containing compound obtained in Synthesis Example was filtered through a microfilter (50 μl).

[0083] (2) FD-MS measurement The FD-MS spectra of the indan ring-containing compounds obtained in the examples were measured using the following measuring device and under the following measuring conditions. Measurement equipment: JMS-T100GC AccuTOF Measurement conditions Measurement range: m / z = 4.00 to 2000.00 Rate of change: 51.2mA / min Final current value: 45mA Cathode voltage: -10kV Recording interval: 0.07 seconds

[0084] (3)13 C-NMR measurement The indan ring-containing compounds obtained in the examples 13 C-NMR spectra were measured using the following measuring device and conditions. 13 C-NMR: “JNM-ECZ400S” manufactured by JEOL RESONANCE Resonance frequency: 100MHz Accumulation count: 4000 times Solvent: chloroform-d Sample concentration: 12% by mass Relaxation reagent: Chromium(III) acetylacetonate

[0085] (4) Quantitative determination of unsaturated bonds The amount of unsaturated bonds was calculated using the method for quantifying unsaturated bonds described in JP-A-2012-214728.

[0086] (5) Softening point Measurement method: The softening points (° C.) of the thermosetting resins obtained in the synthesis examples shown below were measured according to JIS K7234 (ring and ball method).

[0087] (6) Amine equivalent The amine equivalent of the indan ring-containing compound or indan-based mixture was measured by the following method. In a 500 mL Erlenmeyer flask with a stopper, weigh out approximately 2.5 g of the sample indan ring-containing compound or indan-based mixture, 7.5 g of pyridine, 2.5 g of acetic anhydride, and 7.5 g of triphenylphosphine, then attach a condenser and heat under reflux in an oil bath set to 120°C for 150 minutes. After cooling, 5.0 mL of distilled water, 100 mL of propylene glycol monomethyl ether, and 75 mL of tetrahydrofuran were added, and the mixture was titrated potentiometrically with 0.5 mol / L potassium hydroxide-ethanol solution. A blank test was performed in the same manner to correct the value. Amine equivalent (g / eq.) = (S × 2,000) / (Blank-A) S: Amount of sample (g) A: Amount of 0.5 mol / L potassium hydroxide-ethanol solution consumed (mL) Blank: Amount of 0.5 mol / L potassium hydroxide-ethanol solution consumed in the blank test (mL)

[0088] (7) Synthesis of indan ring-containing compounds Example 1: Synthesis of indan ring-containing compound (A-1) A 2L flask equipped with a thermometer, condenser, Dean-Stark trap, and stirrer was charged with 40.6g (0.30mol) of 2,4,6-trimethylaniline, 582.8g (3.0mol) of α,α'-dihydroxy-1,3-diisopropylbenzene, 600.0g of xylene, and 62.3g of activated clay. The mixture was heated to 120°C with stirring. The temperature was then raised to 200°C while removing the distillate using a Dean-Stark tube, and the reaction was continued for 8 hours. After the reaction, the mixture was air-cooled to room temperature, diluted with 500g of toluene, filtered to remove the activated clay, and distilled under reduced pressure to remove low-molecular-weight substances such as the solvent and unreacted materials, yielding 384g of indan ring-containing compound (A-1). The chemical structure and properties of the indan ring-containing compound (A-1) were analyzed using GPC, FD-MS, and 13 The number average molecular weight (Mw) of the indan ring-containing compound (A-1) was confirmed using C-NMR. As a result, the number average molecular weight (Mw) of the indan ring-containing compound (A-1) was 845. In addition, the FD-MS spectrum of the indan ring-containing compound (A-1) showed that M + Furthermore, the FD-MS spectrum of the indan ring-containing compound (A-1) showed peaks of M + Peaks at 293, 451, and 610 were also confirmed, confirming that the indan ring-containing compound (A-1) contained a compound having an aniline skeleton (corresponding to general formula (2) or general formula (3)). The indan ring-containing compound (A-1) exhibited thermosetting properties. It was also confirmed that the number of alkenyl groups (unsaturated bonds) per molecule of the obtained indan ring-containing compound (A-1) was in the range of 1 to 10 on average. For reference, the GPC chart (FIG. 1), FD-MS chart (FIG. 6), and FT-MS chart (FIG. 7) of the indan ring-containing compound (A-1) obtained in Example 1 are shown below. 13 The C-NMR chart (Figure 7) is shown. Therefore, from the results of MS and NMR measurements, it is believed that the indan ring-containing compound (A-1) obtained in Example 1 is a mixture of a compound represented by the following formula (A-1.1) and a compound represented by the above general formula (1b). [ka]

[0089] Example 2: Synthesis of indan ring-containing compound (A-2) A 2L flask equipped with a thermometer, condenser, Dean-Stark trap, and stirrer was charged with 56.7g (0.40mol) of 2,4,6-trimethylaniline, 666.7g (4.20mol) of diisopropenylbenzene, 700.0g of xylene, and 133.3g of activated clay, and heated to 120°C with stirring. The temperature was further increased to 180°C while removing the distillate water using a Dean-Stark tube, and the reaction was carried out for 5 hours. After the reaction, the mixture was air-cooled to room temperature, diluted with xylene, and the activated clay was removed by filtration. Low-molecular-weight substances such as the solvent and unreacted materials were distilled off under reduced pressure to obtain an indan ring-containing compound (A-2). The chemical structure and properties of the indan ring-containing compound (A-2) were analyzed using GPC, FD-MS, and 13 The number average molecular weight (Mw) of the indan ring-containing compound (A-2) was confirmed using C-NMR. As a result, the number average molecular weight (Mw) of the indan ring-containing compound (A-2) was 814. The FD-MS spectrum of the indan ring-containing compound (A-2) showed that M + Furthermore, peaks at M = 316, 474, and 632 were confirmed in the FD-MS spectrum of the indan ring-containing compound (A-2). + Peaks at 293, 451, and 610 were also observed, confirming that the indan ring-containing compound (A-2) contained a compound having an aniline skeleton (corresponding to general formula (2) or general formula (3)). The indan ring-containing compound (A-2) exhibited thermosetting properties. It was also confirmed that the number of alkenyl groups (unsaturated bonds) per molecule of the obtained indan ring-containing compound (A-2) was in the range of 1 to 10 on average. For reference, Figure 2 shows a GPC chart of the indan ring-containing compound (A-2) obtained in Example 2. The indan ring-containing compound (A-2) obtained in Example 2 was also reacted with the compound (A-3) in the same manner as in Example 1. 13 C-NMR measurement revealed a peak chart similar to that of the indan ring-containing compound (A-1) in Example 1. Therefore, the indan ring-containing compound (A-2) is considered to be a mixture of a compound represented by the following formula (A-2.1) and a compound represented by the above general formula (1b). [ka]

[0090] Example 3: Synthesis of indan ring-containing compound (A-3) A 2L flask equipped with a thermometer, condenser, Dean-Stark trap, and stirrer was charged with 25.3g (0.13mol) of 2-trifluoromethylaniline, 333.3g (1.73mol) of α,α'-dihydroxy-1,3-diisopropylbenzene, 340.0g of xylene, and 66.7g of activated clay, and heated to 120°C with stirring. The temperature was further increased to 180°C while removing the distillate water using a Dean-Stark tube, and the reaction was continued for 5 hours. After the reaction, the mixture was air-cooled to room temperature, diluted with xylene, filtered to remove the activated clay, and low-molecular-weight substances such as the solvent and unreacted materials were distilled off under reduced pressure to obtain an indan ring-containing compound (A-3). The chemical structure and properties of the indan ring-containing compound (A-3) were analyzed using GPC, FD-MS, and 13 The number average molecular weight (Mw) of the indan ring-containing compound (A-3) was confirmed using C-NMR. As a result, the number average molecular weight (Mw) of the indan ring-containing compound (A-3) was 689. The FD-MS spectrum of the indan ring-containing compound (A-3) showed that M + Furthermore, peaks at M = 316, 474, and 632 were confirmed in the FD-MS spectrum of the indan ring-containing compound (A-3). +Peaks at 319, 478, and 636 were also observed, confirming that the indan ring-containing compound (A-3) contained a compound having an aniline skeleton (corresponding to general formula (2) or general formula (3)). The indan ring-containing compound (A-3) exhibited thermosetting properties. It was also confirmed that the number of alkenyl groups (unsaturated bonds) per molecule of the obtained indan ring-containing compound (A-3) was in the range of 1 to 10 on average. For reference, a GPC chart of the indan ring-containing compound (A-3) obtained in Example 3 is shown in Figure 3. The indan ring-containing compound (A-3) obtained in Example 3 was also synthesized in the same manner as in Example 1. 13 C-NMR measurement revealed a peak chart similar to that of the indan ring-containing compound (A-1) in Example 1. Therefore, the indan ring-containing compound (A-3) is considered to be a mixture of a compound represented by the following formula (A-3.1) and a compound represented by the above general formula (1b). [ka]

[0091] Example 4: Synthesis of indan ring-containing compound (A-4) A 2L flask equipped with a thermometer, condenser, Dean-Stark trap, and stirrer was charged with 31.4g (0.20mol) of diethyltoluenediamine, 333.3g (1.73mol) of α,α'-dihydroxy-1,3-diisopropylbenzene, 340.0g of xylene, and 66.7g of activated clay, and heated to 120°C with stirring. The temperature was further increased to 180°C while removing the distillate water using a Dean-Stark tube, and the reaction was continued for 5 hours. After the reaction, the mixture was air-cooled to room temperature, diluted with xylene, and the activated clay was removed by filtration. Low-molecular-weight substances such as the solvent and unreacted materials were distilled off under reduced pressure to obtain indan ring-containing compound (A-4). The chemical structure and properties of the indan ring-containing compound (A-4) were analyzed using GPC, FD-MS, and 13 The number average molecular weight (Mw) of the indan ring-containing compound (A-4) was confirmed using C-NMR. As a result, the number average molecular weight (Mw) of the indan ring-containing compound (A-4) was 393. The FD-MS spectrum of the indan ring-containing compound (A-4) showed that M +Furthermore, the FD-MS spectrum of the indan ring-containing compound (A-4) showed peaks of M + Peaks at 337, 494, and 653 were also observed, confirming that the indan ring-containing compound (A-4) contained a compound having an aniline skeleton (corresponding to general formula (2) or general formula (3)). The indan ring-containing compound (A-4) exhibited thermosetting properties. It was also confirmed that the number of alkenyl groups (unsaturated bonds) per molecule of the obtained indan ring-containing compound (A-4) was in the range of 1 to 10 on average. For reference, a GPC chart of the indan ring-containing compound (A-4) obtained in Example 4 is shown in FIG. 4. The indan ring-containing compound (A-4) obtained in Example 4 was also synthesized in the same manner as in Example 1. 13 C-NMR measurement revealed a peak chart similar to that of the indan ring-containing compound (A-1) in Example 1. Therefore, the indan ring-containing compound (A-4) is considered to be a mixture of a compound represented by the following formula (A-4.1) and a compound represented by the above general formula (1b). [ka]

[0092] Example 5: Synthesis of indan ring-containing compound (A-5) A 2 L flask equipped with a thermometer, condenser, Dean-Stark trap, and stirrer was charged with 10.2 g (0.07 mol) of 2,4,6-trimethylaniline, 100.0 g (0.51 mol) of α,α'-dihydroxy-1,4-diisopropylbenzene, 300.0 g of xylene, and 23.5 g of activated clay. The mixture was heated to 120°C with stirring. The temperature was then raised to 180°C while removing the distillate using a Dean-Stark tube, and the reaction was continued for 5 hours. After the reaction, the mixture was air-cooled to room temperature, diluted with xylene, and the activated clay was removed by filtration. The solvent and low-molecular-weight substances, such as unreacted materials, were distilled off under reduced pressure to obtain the indan ring-containing compound (A-5). The chemical structure and properties of the indan ring-containing compound (A-5) were analyzed using GPC, FD-MS, and 13The number average molecular weight (Mw) of the indan ring-containing compound (A-5) was confirmed using C-NMR. As a result, the number average molecular weight (Mw) of the indan ring-containing compound (A-5) was 1142. The FD-MS spectrum of the indan ring-containing compound (A-5) showed that M + Furthermore, peaks at M = 316, 474, and 632 were confirmed in the FD-MS spectrum of the indan ring-containing compound (A-5). + Peaks at 293, 451, and 610 were also observed, confirming that the indan ring-containing compound (A-5) contained a compound having an aniline skeleton (corresponding to general formula (2) or general formula (3)). The indan ring-containing compound (A-5) exhibited thermosetting properties. It was also confirmed that the number of alkenyl groups (unsaturated bonds) per molecule of the obtained indan ring-containing compound (A-5) was in the range of 1 to 10 on average. For reference, a GPC chart of the indan ring-containing compound (A-5) obtained in Example 5 is shown in FIG. 5. The indan ring-containing compound (A-5) obtained in Example 5 was also synthesized in the same manner as in Example 1. 13 C-NMR measurement revealed a peak chart similar to that of the indan ring-containing compound (A-1) in Example 1. Therefore, the indan ring-containing compound (A-5) is considered to be a mixture of a compound represented by the following formula (A-5.1) and a compound represented by the above general formula (1b). [ka]

[0093] <Synthesis Example 1> Synthesis of alicyclic compound (1) A flask equipped with a thermometer, condenser, and stirrer was charged with 72.0 g of norbornene, 25.0 g of the first divinylbenzene compound (DVB-810 (Nippon Steel Chemical & Material Co., Ltd., divinylbenzene purity 81%, containing 19% ethylstyrene)), and 75.0 g of the second divinylbenzene compound (DVB-570 (Nippon Steel Chemical & Material Co., Ltd., divinylbenzene purity 57%, containing 43% ethylstyrene)). The resulting mixture was mixed with 35.6 g of butyl acetate and 114.7 g of toluene and heated to 70 °C with stirring. Trifluoroborane diethyl ether complex was added and reacted at the same temperature for 6 hours. After the reaction was complete, the mixture was neutralized with aqueous sodium bicarbonate, washed with water to remove the catalyst residue, and volatiles were removed under reduced pressure at 60 °C to obtain alicyclic compound (1). <Synthesis Example 2> Synthesis of indan ring-containing compound (A-6) A 2 L flask equipped with a thermometer, a condenser, a Dean-Stark trap, and a stirrer was charged with 582.8 g (3.0 mol) of α,α'-dihydroxy-1,3-diisopropylbenzene, 600.0 g of xylene, and 62.3 g of activated clay, and the mixture was heated to 120°C with stirring. As a result, heat was generated and gelation occurred while dehydration occurred. Therefore, the indan ring-containing compound (A-6) could not be recovered by the synthesis method described in Synthesis Example 2.

[0094] <Examples 6 to 10 and Comparative Example 1> <<Preparation of Curable Composition>> The indan ring-containing compounds (A-1) to (A-4) obtained in Examples 1 to 4 above, the alicyclic compound (1) obtained in Synthesis Example 1, a maleimide resin ("BMI-TMH" manufactured by Daiwa Chemical Industry Co., Ltd., represented by the following formula (BT)), and a polymerization initiator (dicumyl peroxide: DCPO) were mixed in the compositional ratios shown in Table 1 below to prepare curable compositions. [ka] The curable compositions of Examples 6 to 9 and Comparative Example 1 were then cured under the conditions described in the "Preparation of Cured Products" section below to prepare the cured products of Examples 6 to 9 and Comparative Example 1. The physical properties of the dielectric loss tangent and thermal decomposition resistance were evaluated using the methods described below. The results are shown in Table 1 below. <<Preparation of cured product>> Curing conditions: Heat curing at 200°C for 3 hours Plate thickness after molding: 2.0mm The cured product was evaluated for various physical properties by the following methods, and the results are shown in Table 2. <<Measurement of thermal decomposition resistance>> The cured product was cut into small pieces with a thickness of 2.0 mm, and measurements were performed using a thermogravimetric analyzer (METTLER TOREDO thermogravimetric analyzer "TGA / DSC1") at a heating rate of 5°C / min under a nitrogen atmosphere to determine the temperature at which the weight lost 5% (Td5). <<Measurement of dielectric loss tangent>> In accordance with JIS-C-6481, the dielectric loss tangent of the test specimens at 1 GHz and 10 GHz was measured using the cavity resonance method with an Agilent Technologies network analyzer "E8362C" after drying and storing them in a room at 23°C and 50% humidity for 24 hours.

[0095] [Table 1]

[0096] From the results shown in Table 1 above, when Examples 6 to 9 are compared with Comparative Example 1, it is confirmed that excellent dielectric properties and thermal decomposition resistance were achieved by using the indan ring-containing compounds of Examples 1 to 4. [Industrial Applicability]

[0097] According to the present disclosure, it is possible to provide an indene ring-containing compound that exhibits a low dielectric loss tangent and excellent heat resistance, a curable composition containing the indene ring-containing compound, and a cured product thereof.

Claims

1. An indane ring-containing compound having a structural unit represented by the following general formula (1a) and a structural unit represented by the following general formula (2) or general formula (3), and at least one of the terminal sites being an alkenyl group. 【Chemical 1】 (In the above general formula (1a), R １１ , R １２ and R １３ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n １２ represents the average number of repeating units.) [Chemical Formula 2] (In the above general formula (2), R １４ each independently represents an amino group, a fluoroalkyl group, or an alkyl group having 1 to 3 carbon atoms, and n ２ represents an integer of 0 or more and 3 or less.) (In the above general formula (3), R １５ each independently represents an amino group, a fluoroalkyl group, or an alkyl group having 1 to 3 carbon atoms, and n ３ represents an integer of 0 or more and 4 or less.)

2. The indane ring-containing compound according to Claim 1, represented by the following general formula (1b). [Chemical Formula 3] (In the above general formula (1b), R １１ , R １２ and R １３ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Q １１ , Q １２ , L １１ and L １２ each independently represents a single bond or an alkylene group having 1 to 8 carbon atoms, P １１ and P １２ each independently represents an alkenyl group having 2 to 10 carbon atoms or the following general formula (3), M １１ and M １２ each independently represents a single bond or the following general formula (4): n １２ represents the average number of repeating units, and n １１ and n １３ each independently represent from 0 to 20. However, P １１ and P １２ at least one of them is an alkenyl group having 2 to 10 carbon atoms, and n １１ pieces of M １１ and n １３ pieces of M １２ and P １１ and P １２ has an amino group in at least one of them. 【Chemical Formula 4】 [In the above general formula (3), R １５ each independently represents an amino group, a fluoroalkyl group, or an alkyl group having 1 to 3 carbon atoms, and n ３ represents an integer of 0 or more and 4 or less. ] In the general formula (4) above, R １６ each independently represents an amino group, a fluoroalkyl group, or an alkyl group having 1 to 3 carbon atoms, and n ４ represents an integer of 0 or more and 4 or less.])

3. The indane ring-containing compound according to Claim 1, which is a thermosetting compound.

4. An indane-based mixture containing two or more of the indane ring-containing compounds according to Claim 1.

5. A method for producing an indane ring-containing compound, comprising a step of reacting an aromatic compound (A) having a substituent that forms a carbocation with an aniline-based compound in the presence of an acid.

6. A curable composition containing the indane ring-containing compound according to any one of Claims 1 to 3 or the indane-based mixture according to Claim 4 and a curing agent.

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

8. A prepreg having a reinforcing base material and a semi-cured product of the curable composition according to Claim 6 impregnated in the reinforcing base material.

9. A circuit board having the prepreg according to Claim 8 and a laminate with a copper foil laminated thereon.

10. A build-up film containing the curable composition according to Claim 6.

11. A semiconductor encapsulant containing the curable composition according to Claim 6.

12. A semiconductor device including a cured product of the semiconductor encapsulant according to Claim 11.

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