Polyindene compounds, curable compositions, cured products, prepregs, circuit boards, build-up films, semiconductor encapsulants, and semiconductor devices.

Abstract

To provide a polyindane compound that exhibits a low dielectric loss tangent when cured, a curable composition containing the polyindane compound, and a cured product thereof.SOLUTION: A polyindene compound is disclosed whose reaction ingredients are an indene compound and a linear olefin compound with 3 or more carbon atoms having a leaving group at an end, which may be substituted with an alkyl or aryl group.SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to polyindene compounds, curable compositions, cured products, prepregs, circuit boards, build-up films, semiconductor encapsulating materials, and semiconductor devices.

Background Art

[0002] With the recent rapid expansion of IoT and high-capacity data communication, or the progress of various electronic devices used in sensing technologies required for autonomous driving, the need for lower dielectric materials for the materials used in these electronic devices has been increasing. For example, as a circuit board material for electronic devices, prepregs obtained by impregnating a glass cloth with a thermosetting resin such as an epoxy resin or a BT (bismaleimide-triazine) resin and heating and drying it, laminated boards obtained by heat-curing the prepregs, or multilayer boards obtained by combining the laminated boards and the prepregs and heat-curing them are widely used. Such substrates are advancing in signal speed and frequency, and there is a desire to provide a thermosetting composition that can form a cured product that maintains a sufficiently low dielectric constant and exhibits a sufficiently low dielectric tangent under these environments. In particular, since the frequency band of several hundred MHz to about 3 GHz has already been used in wireless systems such as mobile communication, it is difficult to allocate additional frequencies in this frequency band. Therefore, for the technological development for using the fifth-generation mobile communication system (5G), the use of higher frequency bands and the technologies to enable it are required.

[0003] Furthermore, recently, in various electrical material applications, especially in advanced material applications, further improvement in performance represented by dielectric properties and materials and compositions having these properties have been demanded. In response to these requirements, hydrocarbon resins have attracted attention as materials having a low dielectric tangent. However, generally, hydrocarbon materials have few industrial synthesis means and are not satisfactory in terms of handling properties (melt-kneading with various resins). For example, Patent Document 1 describes various curable resin mixtures containing a condensed ring having a cyclopentadiene structure in the molecule. The curable resin mixture has excellent curability, and its cured product is excellent in heat resistance and electrical properties, has low polarity, and becomes a highly crosslinked cured product, so it has low water absorption, high elastic properties, and low thermal expansion properties. In addition, since it has a bonding group capable of stress relaxation between crosslinked structures, it is described that it has excellent toughness.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] Generally, as the frequency increases, the transmission loss increases, so a reduction in transmission loss in the high-frequency region is required. However, various curable resin mixtures containing a condensed ring having a cyclopentadiene structure in the molecule, which is the technology of Patent Document 1, have only been studied in terms of making the dielectric tangent at 1 GHz 0.005 or less, so they are insufficient for technologies for the fifth-generation mobile communication system (5G) that use a frequency band higher than the already used frequency band (several hundred MHz to 3 GHz). Therefore, the technical problem of the present invention is to provide a polyindene compound capable of obtaining a cured product having low dielectric properties even in a frequency band higher than the already used frequency band (several hundred MHz to 3 GHz), a curable composition containing the polyindene compound and its cured product, and a prepreg, a circuit board, a build-up film, a semiconductor encapsulant, and a semiconductor device containing the cured product.

Means for Solving the Problems

[0006] The inventors, in order to solve the above problems, conducted extensive research and found that by using a compound having an indene skeleton with unsaturated double bond groups in its molecular framework and a high concentration of aromatic rings, it is possible to obtain a compound with lower dielectric properties than existing hydrocarbon resins and that is easy to synthesize industrially, thus completing the present invention. In particular, this disclosure aims to provide a polyindene compound that can produce a cured product exhibiting low dielectric properties even in the frequency band above Sub6 and having excellent heat resistance, a curable composition containing the polyindene compound and its cured product, and a prepreg, circuit board, build-up film, semiconductor encapsulant, and semiconductor device containing the cured product.

[0007] This disclosure relates to a polyindene compound, which is reacted with an indene compound and a chain-like olefin compound having 3 or more carbon atoms and having a terminal leaving group, which may be substituted with an alkyl or aryl group. [Effects of the Invention]

[0008] According to this disclosure, it is possible to provide a polyindene compound that can produce a cured product with low dielectric properties even in frequency bands higher than those already in use (hundreds of MHz to 3 GHz). According to this disclosure, it is possible to provide a curable composition containing a polyindene compound that can exhibit low dielectric properties even in the frequency band of Sub6 or higher when cured, a cured product exhibiting low dielectric properties, and a prepreg, circuit board, build-up film, semiconductor encapsulant, and semiconductor device containing the cured product. [Brief explanation of the drawing]

[0009] [Figure 1] Figure 1(a) shows the GPC chart of the polyindene compound synthesized in Example 1, Figure 1(b) shows the 13C-NMR chart of the polyindene compound synthesized in Example 1, and Figure 1(c) shows the MS chart of the polyindene compound synthesized in Example 1. [Figure 2]Figure 2(a) shows the GPC chart of the polyindene compound synthesized in Example 2, Figure 2(b) shows the 13C-NMR chart of the polyindene compound synthesized in Example 2, Figure 2(c) shows the MS chart of the polyindene compound synthesized in Example 2, and Figure 2(d) shows a magnified view of the low molecular weight side of the MS chart shown in Figure 2(c). [Figure 3] Figure 3(a) shows the GPC chart of the polyindene compound synthesized in Example 3, Figure 3(b) shows the 13C-NMR chart of the polyindene compound synthesized in Example 3, Figure 3(c) shows the MS chart of the polyindene compound synthesized in Example 3, and Figure 3(d) shows a magnified view of the low molecular weight side of the MS chart shown in Figure 3(c). [Figure 4] Figure 4(a) shows the GPC chart of the polyindene compound synthesized in Example 4, Figure 4(b) shows the 13C-NMR chart of the polyindene compound synthesized in Example 4, Figure 4(c) shows the MS chart of the polyindene compound synthesized in Example 4, and Figure 4(d) shows a magnified view of the low molecular weight side of the MS chart shown in Figure 4(c). [Modes for carrying out the invention]

[0010] The embodiments of this disclosure (hereinafter referred to as "these embodiments") will be described in detail below, but this disclosure is not limited to the following description and can be implemented in various modifications within the scope of its gist.

[0011] (Explanation of terms) Unless otherwise specified in this specification, the following terms may be applied: In this specification, the "aromatic group" preferably has an aromatic ring having 3 to 30 carbon atoms, and more preferably has an aromatic ring having 4 to 26 carbon atoms. Furthermore, in this specification, the hydrogen atoms of the aromatic ring in the "aromatic group" may be substituted with substituents, such as alkyl groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, or halogen atoms. In addition, the "aromatic group" may include heteroaromatic compounds, and the -CH2- or -CH= atoms in the "aromatic group" may be substituted with -O-, -S-, or -N= such that they are not adjacent to each other. Examples of the aromatic rings include monocyclic aromatic rings, fused aromatic rings, and ring-aggregated aromatic rings. Examples of monocyclic aromatic rings include benzene, furan, pyrrole, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, pyridazine, pyrazine, and triazine. Examples of fused aromatic rings include naphthalene, anthracene, phenalene, phenanthrene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indole, benzimidazole, benzofuran, and acridine. Examples of ring-aggregated aromatic rings include biphenyl, binaphthalene, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, and quaterphenyl. Furthermore, the hydrogen atoms of the aromatic rings in the aromatic group may be substituted with, for example, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen atom. A monovalent aromatic group is an aromatic group from which one hydrogen atom has been removed, a divalent aromatic group is an aromatic group from which two hydrogen atoms have been removed, and a trivalent to hexavalent aromatic group is an aromatic group from which three to six hydrogen atoms have been removed. In this specification, "aryl group" refers to, for example, a phenyl group, naphthyl group, phenalenyl group, phenantrenyl group, anthryl group, azlenyl group, indenyl group, indanyl group, tetralinyl group, etc. Furthermore, the hydrogen atoms of the aromatic ring in the "aryl group" may be substituted with, for example, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, or a halogen atom. The "arylene group" refers to a divalent group obtained by removing one arbitrary hydrogen atom from the "aryl group" mentioned above. Examples of "aralkyl groups" as used herein include benzyl groups, diphenylmethyl groups, biphenyl groups, naphthylmethyl groups, and the like. The hydrogen atoms of the aromatic ring in the aralkyl group may be substituted with, for example, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen atom. An "aralkylene group" is a divalent group obtained by removing one arbitrary hydrogen atom from the "aralkyl group" as described above. In this specification, "alkyl group" refers to, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a tert-pentyl group, a neopentyl group, a 1,2-dimethylpropyl group, an n-hexyl group, an isohexyl group, an (n-)heptyl group, an (n-)octyl group, an (n-)nonyl group, an (n-)decyl group, an (n-)undecyl group, an (n-)dodecyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, or a cyclononyl group. "Alkylene group" refers to a divalent group obtained by removing one arbitrary hydrogen atom from the aforementioned "alkyl group". In this specification, "alkenyl group" refers to groups such as ethynyl, 1-propynyl, 2-propynyl, 2-butynyl, pentynyl, hexynyl, vinyl, allyl, and isopropenyl. "Alkenylene group" refers to a divalent group obtained by removing one arbitrary hydrogen atom from the aforementioned "alkenyl group". In this specification, "alkoxy group" refers to, 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, a nonyloxy group, and the like. In this specification, "halogen atoms" include, for example, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, and the like. In this specification, "linear or branched alkylene groups" include, for example, methylene groups, ethylene groups, propylene groups, 1-methylmethylene groups, 1,1-dimethylmethylene groups, 1-methylethylene groups, 1,1-dimethylethylene groups, 1,2-dimethylethylene groups, propylene groups, butylene groups, 1-methylpropylene groups, 2-methylpropylene groups, pentylene groups, hexylene groups, heptylene groups, octylene groups, nonylene groups, decylene groups, undecylene groups, dodecylene groups, and the like. In this specification, "linear or branched alkylene ether groups" include, for example, oxymethylene groups, oxyethylene groups, oxypropylene groups, oxy(1-methylmethylene) groups, oxy(1,1-dimethylmethylene) groups, oxy(1-methylethylene) groups, oxy(1,1-dimethylethylene) groups, oxy(1,2-dimethylethylene) groups, oxybutylene groups, oxy(1-methylpropylene) groups, oxy(2-methylpropylene) groups, oxypentylene groups, oxyhexylene groups, oxyheptylene groups, oxyoctylene groups, oxynonylene groups, oxydecylen groups, oxyundecylen groups, oxidedodecylen groups, and the like.

[0012] [Polyindene compounds] This disclosure relates to a polyindene compound, which is reacted with an indene compound and a chain-like olefin compound having 3 or more carbon atoms and having a leaving group at its terminus, which may be substituted with an alkyl or aryl group (hereinafter also referred to as an olefin compound). This makes it possible to provide a polyindene compound that can produce a cured product with excellent low dielectric properties. In particular, it is possible to obtain a cured product that exhibits low dielectric properties even in the frequency band above Sub6. In other words, the polyindene compound according to this embodiment preferably has a structure in which a structural unit derived from the indene compound in the reaction raw material and a group having an unsaturated bond derived from the olefin compound excluding the leaving group in the reaction raw material are chemically linked. Furthermore, the above-mentioned "structural unit derived from indene compound" refers to a group obtained by removing one or more hydrogen atoms from the condensed aromatic ring of an indene compound. For example, if the indene compound is represented by the general formula (a) described below, the group obtained by removing one or two hydrogen atoms from the indene ring of general formula (a) is called a structural unit derived from an indene compound. Furthermore, the above-mentioned "group having an unsaturated bond derived from an olefin compound excluding a leaving group" refers to a group obtained by removing only the leaving group from a chain-like olefin compound having three or more carbon atoms and having a leaving group at its terminal, which may be substituted with an alkyl group or an aryl group. As will be described later, the leaving group in the olefin compound may be a hydroxyl group, a halogen atom, or an ester group (-OCO-R). a ), sulfate ester group (-OSO2-R b ) or phosphate ester group (-OP(=O)-(OR c )2) are examples of the above. a , R b and R c Each of these independently represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. In the polyindene compound of this embodiment, all atoms constituting the polyindene compound molecule are carbon atoms and hydrogen atoms only, and there are no polar functional groups in the polyindene compound molecule, so the dielectric loss tangent is extremely low.

[0013] -Preferred form of polyindene compound- The polyindene compound of this embodiment preferably has a structural unit represented by the following general formula (i). [ka] (In the above general formula (i), R i1 Each of these independently consists of a hydrogen atom, an alkyl group, an alkoxy group, an allyl group, an aryl group, an aryloxy group, an aralkyl group, or R i2 Represents Ri2 each independently represents a linear alkenyl group having 3 or more carbon atoms, which may be substituted with an alkyl group or an aryl group, and R i3 each independently represents an indanyl group or an indenyl group, and p i1 represents an integer of 1 or more and 4 or less, and p i2 represents an integer of 1 or more and 3 or less, and p i3 represents an integer of 0 or more and 2 or less, and p i2 +p i2 represents an integer of 1 or more and 3 or less, and * represents a bond to another atom.) The condensed ring in perylene in the general formula (i) is a structural unit derived from an indene compound. In the general formula (i), * is a bond representing a bond to another atom. Also, the dashed line in the general formula (i) represents absence or a single bond. When the dashed line is absent, the condensed ring in perylene in the general formula (i) can be an indane ring. On the other hand, when the dashed line is a single bond, a double bond including the dashed line portion is formed (unsaturated bond between the 2-position carbon atom and the 3-position carbon atom), so the condensed ring in perylene in the general formula (i) can be an indene ring.) In the general formula (i), R i1 each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group, an aryloxy group, an aralkyl group, or R i2 is preferably represented. More preferably, it represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, or R i2 is represented. Examples of the alkyl group, aryloxy group, or aralkyl group having 1 to 12 carbon atoms include the groups described in the column of the above definition. R i1The preferred aryl group may be unsubstituted or substituted with an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, or a halogen atom. Examples of such aryl groups include phenyl, naphthyl, phenalenyl, phenantrenyl, anthryl, azlenyl, indenyl, indanyl, or tetralinyl groups. The preferred aryl group is a phenyl, naphthyl, phenalenyl, phenantrenyl, anthryl, azlenyl, indenyl, or indanyl group, which may be unsubstituted or substituted with an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, or a halogen atom.

[0014] In the above general formula (i), R i1 The position can be any of positions 1 through 7 of the fused ring (indane ring or indene ring), for example, positions 1, 2, 3, 4, and 7 are preferred. In the above general formula (i), R i2 Each of these independently represents a chain-like alkenyl group having 3 or more carbon atoms, which may be substituted with an alkyl or aryl group. Considering the correspondence with the reaction raw materials, R i2 R is a group that may be substituted with an alkyl group or an aryl group, and is a group from which the terminal leaving group is removed from a chain-like olefin compound having 3 or more carbon atoms and having a terminal leaving group, and is also called a structural unit derived from an olefin compound. i2 The position can be any of positions 1 through 7 of the fused ring (indane ring or indene ring), for example, positions 1, 2, 3, 4, and 7 are preferred. In the above general formula (i), R i3 The position can be any of positions 1 through 7 of the fused ring (indane ring or indene ring), for example, positions 1, 2, 3, 4, and 7 are preferred.

[0015] In this embodiment, R in general formula (i) i2 This is expressed by the following general formula (ii): [ka] (In the above general formula (ii), R iia , R iib and R iic Each of these independently represents a hydrogen atom, an alkyl group, or an aryl group, and p ii1 It is preferable to represent it as follows: where represents an integer of 1 or more, and * represents a bond with another atom. The group represented by the above general formula (ii) preferably represents a group (in other words, a structural unit derived from an olefin compound) from which the terminal leaving group has been removed, from a chain-like olefin compound having 3 or more carbon atoms and having a terminal leaving group, and which may be substituted with an alkyl group or an aryl group. In the above general formula (ii), * represents a bond with another atom, and the bond position of the group represented by the above general formula (ii) to the fused ring (indane ring or indene ring) in the above general formula (i) may be any of positions 1 to 7, for example, positions 1, 2, 3, 4, and 7 are preferred.

[0016] In the above general formula (ii), the aryl group may be a phenyl group, a naphthyl group, a phenalenyl group, a phenantrenyl group, anthryl group, an azulenyl group, an indenyl group, an indanyl group, or a tetralinyl group. The hydrogen atoms of the aromatic ring of these aryl groups may be substituted with, for example, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen atom. In the above general formula (ii), the alkyl group can be a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a tert-pentyl group, a neopentyl group, a 1,2-dimethylpropyl group, an n-hexyl group, an isohexyl group, an (n-)heptyl group, an (n-)octyl group, an (n-)nonyl group, an (n-)decyl group, an (n-)undecyl group, an (n-)dodecyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, or a cyclononyl group.

[0017] In the above general formula (ii), p ii1It is preferable that it represents an integer between 1 and 10, more preferably an integer between 1 and 8, and even more preferably an integer between 1 and 6. A preferred form of general formula (ii) in this embodiment is R iia or R iib Each of these is preferably independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a phenyl group, a naphthyl group, a phenalenyl group, a phenantrenyl group, or an anthyl group. A preferred form of general formula (ii) in this embodiment is R iic It is preferable that this is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a phenyl group, or a naphthyl group. In this embodiment, an example of a group represented by general formula (ii) is, for example, represented by the following general formulas (ii-1) to (ii-4). [ka] (In the above general formulas (ii-1) to (ii-4), p ii1 Each of these independently represents an integer between 1 and 15 (inclusive).

[0018] In the above general formula (i), p i1 It is preferable that it represents an integer between 1 and 4, more preferably an integer between 1 and 3, and even more preferably an integer between 1 and 2. In the above general formula (i), p i2 represents an integer between 1 and 3, and is more preferably an integer between 1 and 3. In the above general formula (i), p i3 p represents an integer between 0 and 2, and is more preferably 0 or 1. Also, in the above general formula (i), p i2 +p i3 It is preferable that the value is between 1 and 3.

[0019] In the polyindene compound of this embodiment, the number of groups having unsaturated bonds derived from the olefin compound, excluding the leaving group, that are chemically bonded to one condensed ring represented by the above general formula (i), is preferably 1 to 4. If the group derived from the olefin compound chemically bonded to one condensed ring is within the above range, the crosslinking density can be improved as a thermosetting resin. The average value of unsaturated groups derived from olefin compounds, excluding leaving groups, for each condensed ring is shown in the Examples section below. 1 H-NMR and 13 The calculation is performed using 1C-NMR.

[0020] In this embodiment, the proportion of the structural unit represented by the general formula (i) to the total polyindene compound is preferably 10 mol% or more, more preferably 20 mol% or more, and even more preferably 25 mol% or more. The method for calculating the proportion of structural units represented by the above general formula (i) is shown in the section on examples below. 1 H-NMR and 13 The calculation is performed using 1C-NMR.

[0021] In this embodiment, R in general formula (i) i3 Each of these is independently an indenyl group or an indanyl group, and the hydrogen atoms of the indenyl group or the aromatic ring of the indanyl group may be substituted, for example, with an alkyl group having 1 to 12 carbon atoms.

[0022] (Reaction materials) The following describes the indene compound and a chain-like olefin compound having three or more carbon atoms and having a leaving group at its terminus, which may be substituted with an alkyl group or aryl group, as components of the reaction raw materials for the polyindene compound of this embodiment. Then, a method for producing the polyindene compound will be described. <Indene compound> The indene compound in this embodiment only needs to have an indene ring, and is preferably represented by the following general formula (a). [ka] (In the above general formula (a), R a1Each of these independently represents a hydrogen atom, an alkyl group, an alkoxy group, an allyl group, an aryl group, an aryloxy group, or an aralkyl group, and p a1 (This represents an integer between 0 and 7, inclusive.) In addition, in the above general formula (a), R is applied to the entire set of square brackets. a1 The configuration in which R is bonded is such that R is attached to any of the carbon atoms at positions 1 to 7 of the indene ring within the square brackets. a1 This indicates that chemical bonding may be permitted. In this embodiment, preferred indene compounds include p in the general formula (a) above. a1 Examples include indens where the value is 0.

[0023] <Olefin compounds> In this embodiment, a linear olefin compound having 3 or more carbon atoms and having a leaving group at its terminus, which may be substituted with an alkyl or aryl group, is an olefin compound having 3 or more carbon atoms and having a linear or branched molecular structure having at least one leaving group and at least one unsaturated bond at its terminus, which may be substituted with an alkyl or aryl group. The number of carbon atoms in the olefin compound is preferably 3 to 30, more preferably 4 to 26, and even more preferably 5 to 22.

[0024] In this embodiment, the olefin compound is preferably represented by the following general formula (b). [ka] (In the above general formula (b), R iia , R iib and R iic Each of these independently represents a hydrogen atom, an alkyl group, or an aryl group, and p ii1 (where represents an integer greater than or equal to 1, and X represents a leaving group.)

[0025] In the above general formula (b), X represents a leaving group, specifically a hydroxyl group, a halogen atom, or an ester group (-OCO-R a ), sulfate ester group (-OSO2-Rb ) or phosphate ester group (-OP(=O)-(OR c )2) is preferable. When the leaving group is one of the groups listed above, the reaction proceeds smoothly in the presence of an acid or base, and electrophilic reactions and the like proceed more easily with respect to the indene ring of the indene compound.

[0026] In the above general formula (b), the leaving group X is an ester group or a sulfate ester group (-OSO2-R b ) If R a and R b The alkyl group is preferably a group having 1 to 12 carbon atoms, and more preferably 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, or isohexyl group.

[0027] In the above general formula (b), the leaving group X is a phosphate ester group (-OP(=O)-(OR c )2) If so, there are two R c These groups may be the same or different from each other, and are preferably alkyl groups having 1 to 12 carbon atoms, more preferably methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, 1,2-dimethylpropyl, n-hexyl, or isohexyl.

[0028] In the above general formula (b), when the leaving group X is a halogen atom, X is preferably a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an astatine atom, and more preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. In the above general formula (b), R iia , R iib , R iic and p ii1The embodiments and preferred embodiments are the same as those of the general formula (ii) above, and are therefore omitted here.

[0029] Preferred olefin compounds in this embodiment include, for example, those represented by general formulas (b-1) to (b-4). [ka] (In the above general formulas (b-1) to (b-4), X is a halogen atom, an ester group (-OCO-R a ), sulfate ester group (-OSO2-R b ) or phosphate ester group (-OP(=O)-(OR c )2) represents R a ~R c Each of these independently represents an alkyl group having 1 to 12 carbon atoms, and p ii1 (This is an integer between 1 and 15, inclusive.)

[0030] In this embodiment, the molar ratio of the olefin compound to the indene compound in the reaction raw materials of the polyindene compound (olefin compound / indene compound) is preferably 0.5 to 5 / 1, and more preferably 1 to 4 / 1. When the molar ratio of the olefin compound to the indene compound in the reaction raw materials of the polyindene compound is within the above range, it is preferable in that a lower dielectric loss tangent can be achieved.

[0031] The number-average molecular weight (Mn) of the polyindene compound of this disclosure is preferably in the range of 100 to 10000, and more preferably in the range of 100 to 5000. The lower limit of the number-average molecular weight (Mn) of the polyindene compound is preferably 100, 150, 180, 200, or 250, and the upper limit of the number-average molecular weight (Mn) of the polyindene compound is preferably 10000, 5000, 3000, 2000, 1500, 1200, or 980. Furthermore, the weight-average molecular weight (Mw) of the polyindene compound is preferably in the range of 100 to 30,000, and more preferably in the range of 100 to 10,000. The lower limit of the weight-average molecular weight (Mw) of the polyindene compound is preferably 100, 250, 280, 320, or 350, and the upper limit of the weight-average molecular weight (Mw) of the polyindene compound is preferably 30,000, 10,000, 6,000, 4,000, 2,500, 1,200, or 990. The preferred ranges for the number-average molecular weight (Mn) and weight-average molecular weight (Mw) mentioned above may be any combination of the above upper and lower limits. It is preferable that the number-average molecular weight or weight-average molecular weight of the polyindene compound be within the above range, as this allows for the achievement of a lower dielectric loss tangent. The polyindene compounds of this disclosure are preferably in the range of 1 to 10, more preferably 1 to 7, and even more preferably 1 to 5, in terms of their excellent low dielectric properties and heat resistance, as determined by gel permeation chromatography (GPC) measurements. 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 polymaleimide compound in this embodiment were measured using gel permeation chromatography (hereinafter abbreviated as "GPC") under the measurement conditions described in the examples below.

[0032] (Method for producing polyindene compounds) The method for producing the polyindene compound described herein will be explained below. The polyindene compound of this embodiment is not particularly limited in its manufacturing method and may be manufactured using an indene compound and an olefin compound as reaction raw materials, or in any way as long as it has a structural unit represented by the general formula (i) above. An example of a manufacturing method for the polyindene compound of this disclosure is a manufacturing method that includes the following steps. Step: A step of reacting an indene compound with a chain-like olefin compound having 3 or more carbon atoms and having a leaving group at the terminal, which may be substituted with an alkyl group or aryl group, in the presence of an acid or a base, to obtain the polyindene compound of this embodiment. Regarding the mixing ratio of the indene compound and the olefin compound, considering the balance of moldability and curability properties during the production of the resulting cured product, it is preferable that the molar ratio of the olefin compound is 0.5 to 5 moles, and more preferably 1 to 4 moles, per mole of the indene compound. Furthermore, the specific methods for carrying out the above reaction generally involve either charging all reaction materials together and reacting them at a predetermined temperature, or charging the olefin compound and an acid group or base, and reacting them dropwise while maintaining the predetermined temperature with the indene compound or other compounds. In this case, the dropwise addition time is usually 0.1 to 12 hours, preferably 6 hours or less. After the reaction, if a solvent is used, the target polyindene compound can be obtained by distilling off the solvent and unreacted products as needed. If no solvent is used, the target polyindene compound can be obtained by distilling off the unreacted products.

[0033] In the method for producing polyindene compounds according to this embodiment, the choice of acid or base is appropriately selected depending on the type of olefin compound used. For example, if the olefin compound used as a reaction material is an olefin compound that satisfies the condition that the leaving group X in the above general formula (b) is a halogen atom (i.e., an olefin compound having a halogen atom such as an allyl halide), then by reacting the reaction material containing the olefin compound having the halogen atom and the indene compound with a base, the group represented by the above general formula (ii) (for example, an allyl group) modifies the indene ring of the indene compound. At that time, the polymerization of the indene compound may also proceed simultaneously with the hydrogen halide generated. Furthermore, for example, if the olefin compound used as a reaction raw material is an olefin compound that satisfies the condition that the leaving group X in the above general formula (b) is a hydroxyl group (i.e., an olefin compound having a hydroxyl group such as allyl alcohol), then by reacting the reaction raw material containing the olefin compound having a hydroxyl group and the indene compound with an acid (e.g., Brønsted acid), the group represented by the above general formula (ii) (e.g., a cinnamyl group) modifies the indene ring of the indene compound. In this case, the dehydration reaction of the alcohol by the acid (e.g., Brønsted acid) and the polymerization of the indene compound can proceed simultaneously.

[0034] In this embodiment, either an organic or inorganic base can be used. Examples of organic bases include alkali metal alkoxides such as sodium methoxide, lithium methoxide, sodium ethoxide, lithium ethoxide, sodium tert-leaf toxide, and potassium tert-leaf toxide; trialkylamines such as triethylamine and ethyldiisopropylamine; aniline derivatives having alkyl groups with 1 to 4 carbon atoms, such as N,N-dimethylaniline and N,N-diethylaniline; pyridine derivatives, such as pyridine and 2,6-lutidine, which may have alkyl substituents with 1 to 4 carbon atoms; and nitrogen-containing heterocyclic compounds such as 1,8-diazabicyclo[5.4.0]-7-undecene. On the other hand, examples of the inorganic bases mentioned above include alkali metal hydrides such as sodium hydride and lithium hydride; alkaline earth metal hydrides such as calcium hydride; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; carbonates or bicarbonates of alkali metals or alkaline earth metals such as sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate; and halogenated compounds of alkali metals or alkaline earth metals such as potassium fluoride, cesium fluoride, and potassium iodide. These bases may be used individually or in combination of two or more. In this embodiment, preferred bases are alkyl metal alkoxides, nitrogen-containing heterocyclic compounds, alkali metals, or alkaline earth metal hydroxides, with potassium tertifoxide or sodium tertifoxide being more preferred. The amount of base added is preferably in the range of 1 to 15 times (moles) the number of moles of the olefin compound.

[0035] In this embodiment, any acid that can be used is an organic acid, an inorganic acid, or a solid acid, with Brønsted acid being preferred. Examples of the organic acid include aliphatic sulfonic acids such as methanesulfonic acid or fluoromethanesulfonic acid; aromatic sulfonic acids such as 3-morpholinopropanesulfonic acid, piperazine-1,4-bis(2-ethanesulfonic acid), 10-camphorsulfonic acid, 4-chlorobenzenesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, or trifluoromethanesulfonic acid; alkyl phosphates such as dimethyl phosphate or diethyl phosphate; alkyl sulfuric acids such as dimethyl sulfate, diethyl sulfate, and lauryl sulfate; aromatic sulfuric acids such as phenyl sulfate and phenyl fluoride sulfate; and various other acids such as oxalic acid. Examples of the inorganic acids mentioned above include phosphoric acid, hydrochloric acid, sulfuric acid, nitric acid, and boric acid. Examples of the solid acids mentioned above include activated clay, acid clay, silica alumina, zeolite, and strongly acidic ion exchange resin. These acids may be used individually or in combination of two or more. In this embodiment, preferred Brønsted acids include hydrochloric acid, sulfuric acid, fluorosulfonic acid, chlorosulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, 2-aminoethanesulfonic acid, 2-[4-(2-hydroxyethyl)-1-piperazinyl]ethanesulfonic acid, 3-morpholinopropanesulfonic acid, piperazine-1,4-bis(2-ethanesulfonic acid), 10-camphorsulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, 4-chlorobenzenesulfonic acid, sulfanilic acid, 3-pyridinesulfonic acid, 2-aminoethanesulfinic acid, benzenesulfinic acid, and 4-methylbenzenesulfinic acid. The amount of the acid added is preferably in the range of 0.5 to 15 mol% relative to the number of moles of the olefin compound.

[0036] In this embodiment, the reaction temperature between the olefin compound and the indene compound in the presence of an acid group or a base can be in the range of 40 to 200°C, and more preferably 60 to 180°C. Furthermore, the reaction temperature can be appropriately selected depending on the type of catalyst, reaction conditions, or reaction raw materials used. For example, when reacting an olefin compound with an indene compound in the presence of a base, the reaction temperature is preferably 20 to 180°C. On the other hand, when reacting an olefin compound with an indene compound in the presence of an acid, for example, the reaction temperature is preferably 60 to 180°C. In this embodiment, the reaction time between the olefin compound and the indene compound in the presence of an acidic group or a base is usually in the range of 0.5 to 24 hours, but the reaction time can be appropriately selected depending on the catalyst used, reaction conditions, or type of reaction raw material. For example, when reacting the olefin compound and the indene compound in the presence of a base, the reaction time is preferably 0.5 to 24 hours. On the other hand, for example, when reacting the olefin compound and the indene compound in the presence of an acid, the reaction time is preferably 0.5 to 24 hours. The reaction atmosphere between the olefin compound and the indene compound can be appropriately selected from air or an inert gas (nitrogen, argon, helium, etc.).

[0037] In the method for producing the indene compound in this embodiment, the indene compound (e.g., indene or its derivative) also serves as the solvent, so it is not necessarily required to use other solvents, but it is possible to use a solvent. For example, a method may be employed in which an azeotropic dehydration solvent such as toluene, xylene, or chlorobenzene is used, and if necessary, water contained in the catalyst, etc. is azeotropically dehydrated, the solvent is then removed by distillation, and the reaction is carried out within the above reaction temperature range.

[0038] [Curable composition] The polyindene compounds of this disclosure can be used to prepare curable compositions. The curable compositions of this disclosure preferably contain the polyindene compounds described above. The polyindene compounds of this embodiment have excellent solvent solubility, fluidity when heated and melted, and handling properties, and further contribute to dimensional stability, low hygroscopicity, brittleness, heat resistance, and low dielectric constant / low dielectric loss tangent. Therefore, cured products obtained from curable compositions containing the polyindene compounds have excellent dimensional stability, hygroscopicity, and dielectric properties.

[0039] The curable composition of this disclosure may contain a curing agent, and may further contain various compounding agents as needed, such as curing accelerators, silane coupling agents, mold release agents, pigments, emulsifiers, non-halogenated flame retardants, inorganic fillers, flame retardants (e.g., inorganic phosphorus-based flame retardants, organophosphorus-based flame retardants, halogenated flame retardants), and solvents. In addition, as long as the purpose of this disclosure is not impaired, epoxy resins, phenolic resins, activated ester resins, cyanate resins, polyphenylene ether resins, benzoxazine resins, styrene-maleic anhydride copolymers, polybutadiene and its modified products, polyacetal resins, polyvinyl alcohol resins, liquid crystal polymers, fluororesins, polystyrene, polyethylene, polyimide resins, silicone gels, silicone oils, etc.

[0040] [Cured product] The cured product of this disclosure is preferably obtained by the curable composition. The cured product can be obtained by curing the curable composition. The curable composition can be obtained by uniformly mixing the above-mentioned components (e.g., curing agent, compounding agent) and can be easily cured in the same manner as conventionally known methods. Examples of the cured product include molded cured products such as laminates, cast products, adhesive layers, coatings, and films.

[0041] [Semiconductor encapsulation material] This disclosure relates to a semiconductor encapsulation material containing the curable composition of this embodiment. The semiconductor encapsulation material obtained using the curable composition of this embodiment is preferable because, by using the polyindene compound of this disclosure, its hygroscopicity, low dielectric loss tangent ratio, or dimensional stability are improved, resulting in excellent processability, moldability, and reflow resistance during the manufacturing process. The curable composition of this embodiment used in the semiconductor encapsulating material may contain an inorganic filler. The filling ratio of the inorganic filler can be, for example, 0.5 to 1200 parts by mass of the inorganic filler 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, aluminum nitride, and the like.

[0042] A method for obtaining the aforementioned semiconductor encapsulating material includes, as necessary, a method of thoroughly melting and mixing the curable composition of this embodiment with an optional additive until uniform, using an extruder, needle, roll, or the like.

[0043] [Semiconductor device] This disclosure relates to a semiconductor device comprising a cured product of the semiconductor encapsulating material. A semiconductor device obtained using the semiconductor encapsulating material obtained using the curable composition of this embodiment is preferable because, since it uses the polyindene compound of this disclosure, it has low viscosity and excellent fluidity, and furthermore, improved hygroscopicity, thermal modulus, and adhesion to metal materials, resulting in excellent processability, moldability, and reflow resistance in the manufacturing process.

[0044] Methods for obtaining the semiconductor device include casting the semiconductor encapsulating material, molding it using a transfer molding machine, injection molding machine, etc., and then heat-curing it in a temperature range of room temperature (20°C) to 250°C.

[0045] [Prepreg] This disclosure relates to a prepreg having a reinforcing substrate and a semi-cured product of the curable composition of this embodiment impregnated into the reinforcing substrate. A method for obtaining a prepreg from the curable composition includes impregnating a reinforcing substrate (paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, glass roving cloth, etc.) with a varnished curable composition made by blending it with an organic solvent, as described later, and then heating it at a heating temperature corresponding to the type of solvent used, preferably 50 to 170°C, to semi-cure (or not cure) the curable composition and obtain a prepreg. The mass ratio of the curable composition to the reinforcing substrate used at this time is not particularly limited, but it is generally preferable to prepare it so that the resin content in the prepreg is 20 to 60% by mass. In this embodiment, a semi-cured product of the curable composition is 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 curing of 85% or less and 5% or more. On the other hand, the cured product in this embodiment may have a higher degree of curing than the semi-cured product. The degree of hardening of the semi-cured product can be calculated using the following formula by measuring the heat generated during curing of the curable composition and the heat generated during curing of the semi-cured product using DSC. Degree of curing (%) = [1 - (heat generated during curing of the semi-cured material / heat generated during curing of the curable composition)] × 100

[0046] Examples of organic solvents used in the production of prepregs 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 these solvents can be appropriately chosen depending on the application. For example, when further manufacturing printed circuit boards from prepregs as described below, it is preferable to use polar solvents with a boiling point of 160°C or lower, such as methyl ethyl ketone, acetone, and dimethylformamide, and it is also preferable to use them in a proportion that results in a non-volatile content of 40 to 80% by mass.

[0047] [Circuit board] This disclosure relates to a circuit board which is a laminate of the prepreg and copper foil. A method for obtaining a printed circuit board from the curable composition of this embodiment is to laminate the prepreg by a conventional method, add copper foil as appropriate, and heat-press it at 170 to 300°C for 10 minutes to 3 hours under pressure of 1 to 10 MPa.

[0048] [Build-up film] This disclosure relates to a build-up film containing the curable composition of this embodiment. A method for manufacturing the build-up film of this embodiment is to apply the curable composition onto a support film to form a curable composition layer, thereby producing an adhesive film for multilayer printed circuit boards.

[0049] When manufacturing a build-up film from a curable composition, it is essential that the film softens under the lamination temperature conditions (usually 70-140°C) in the vacuum lamination method and exhibits fluidity (resin flow) that allows for simultaneous lamination of the circuit board and resin filling of via holes or through holes present in the circuit board. It is preferable to formulate the above-mentioned components in such a way as to exhibit these characteristics.

[0050] Here, the diameter of the through-holes in a multilayer printed circuit board is typically 0.1 to 0.5 mm, and the depth is typically 0.1 to 1.2 mm. It is generally preferable to be able to fill the holes with resin within this range. When laminating both sides of the circuit board, it is desirable to fill about half of the through-holes.

[0051] The adhesive film described above can be manufactured by first preparing a varnish-like curable composition, then applying this varnish-like composition to the surface of a support film (Y), and finally drying the organic solvent by heating or blowing hot air to form a composition layer (X) made of the curable composition.

[0052] The thickness of the formed composition layer (X) is usually preferably greater than or equal to 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.

[0053] Furthermore, the composition layer (X) in this embodiment may be protected by a protective film, which will be described later. By protecting it with a protective film, it is possible to prevent dirt and other debris from adhering to the surface of the resin composition layer and to prevent scratches.

[0054] The support film (Y) and protective film mentioned above can be made of polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate, polycarbonate, polyimide, and also release paper and metal foils such as copper foil and aluminum foil. The support film and protective film may be treated with a mat treatment, corona treatment, or release treatment.

[0055] The thickness of the support film is not particularly limited, but is usually 10 to 150 μm, and preferably in the range of 25 to 50 μm. The thickness of the protective film is preferably 1 to 40 μm.

[0056] The support film (Y) described above is peeled off after lamination to the circuit board or after an insulating layer is formed by heat curing. Peeling off the support film (Y) after heat curing the adhesive film prevents the adhesion of dust and other debris during the curing process. When peeling off after curing, the support film is usually treated with a release agent beforehand.

[0057] [Heat-resistant materials and electronic materials] Since the cured product obtained from the curable composition containing the polyindene compound of the present disclosure exhibits low hygroscopicity and is excellent in dimensional stability and dielectric properties, it can be suitably used for heat-resistant members or electronic members. In particular, it can be suitably used for prepregs, circuit boards, semiconductor encapsulating materials, semiconductor devices, build-up films, build-up boards, adhesives using conductive pastes, resist materials, etc. It can also be suitably used as a matrix resin for fiber-reinforced resins, and is particularly suitable as a prepreg having high heat resistance or a small dimensional change rate. Further, since the polyindene compound contained in the curable composition exhibits excellent solubility in various solvents, it can be made into a paint. The heat-resistant members and electronic members thus obtained can be suitably used for various applications, for example, industrial machine parts, general machine parts, parts of automobiles, railways, vehicles, etc., space and aviation-related parts, electronic and electrical parts, building materials, container and packaging members, daily necessities, sports and leisure goods, housing members for wind power generation, etc., but are not limited thereto.

Examples

[0058] Hereinafter, the present disclosure will be described in more detail with reference to examples, but the present disclosure is not limited to the following examples. Also, in the following, "parts" and "%" are based on mass unless otherwise specified. In addition, regarding GPC measurement, 1 1H-NMR measurement, 13 13C-NMR measurement and FD-MS spectrum measurement were performed under the following conditions, etc.

[0059] (Evaluation method) <GPC measurement> Using the following measuring device and measuring conditions, GPC charts of polyindene compounds, indene compounds, and olefin compounds described in the following synthesis examples, examples, or comparative examples were obtained. From the results of the GPC charts, it was confirmed that the target product (polyindene compound) was formed from the decrease and disappearance of the raw material peaks. Measuring device: "HLC-8320 GPC" manufactured by Tosoh Corporation Columns: 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: In accordance with the measurement manual for the aforementioned "GPC Workstation EcoSEC-WorkStation," the following monodisperse polystyrenes with known molecular weights were used. (Uses polystyrene) "A-500" manufactured by Tosoh Corporation "A-1000" manufactured by Tosoh Corporation "A-2500" manufactured by Tosoh Corporation "A-5000" manufactured by Tosoh Corporation "F-1" manufactured by Tosoh Corporation "F-2" manufactured by Tosoh Corporation "F-4" manufactured by Tosoh Corporation Tosoh Corporation's "F-10" F-20 manufactured by Tosoh Corporation Tosoh Corporation's "F-40" Tosoh Corporation's "F-80" Tosoh Corporation's "F-128" Sample: A tetrahydrofuran solution containing 1.0% by mass (based on solid content) of the polyindene compound, obtained by the synthesis examples and other methods shown below, was used, filtered through a microfilter (50 μl).

[0060] < 1 H-NMR measurement> 1 H-NMR: “JNM-ECA600” manufactured by JEOL RESONANCE Magnetic field strength: 600MHz Total number of times: 32 Solvent: DMSO-d6 Sample concentration: 30% by mass The aforementioned 1 The results of the 1H-NMR chart confirmed the presence of peaks originating from the target product, thus confirming that the target product was obtained in each reaction. < 13 C-NMR measurement> 13 C-NMR: “JNM-ECA600” manufactured by JEOL RESONANCE Magnetic field strength: 150MHz Total number of times: 320 Solvent: DMSO-d6 Sample concentration: 30% by mass The aforementioned 13 The results of the 1C-NMR chart confirmed the presence of peaks originating from the target product, thus confirming that the target product was obtained in each reaction.

[0061] [Method for measuring dielectric loss tangent] A curable composition containing a polyindene compound was formulated and cured according to the composition shown in Table 1 below. The resulting cured material was measured in accordance with JIS-C-6481 using the cavity resonance method with an Agilent Technologies, Inc. network analyzer "E8362C". The dielectric loss tangent of the test specimens was measured at 1 GHz and 10 GHz after being completely dried and stored in a room at 23°C and 50% humidity for 24 hours.

[0062] (Example 1) Synthesis of polyindene compound (1) In a flask equipped with a stirrer and condenser, 116.2 parts by mass of indene, 145.9 parts by mass of potassium tert-butoxide (hereinafter referred to as tBuOK), and 814.4 parts by mass of toluene were charged and heated to 70°C to obtain a mixture. Next, 145.19 parts by mass of allyl bromide were added dropwise to the mixture while maintaining a temperature of 70-80°C, and the mixture was stirred at 70°C for 3 hours to obtain a reaction solution. After cooling the reaction solution to 80°C, the catalyst residue was removed from the reaction solution by neutralization and washing three times with 156.2 parts by mass of water. The reaction solution from which the catalyst residue had been removed was then heated to 150°C, and volatile components were removed by vacuum distillation to obtain the target product, polyindene compound (1) (Mn: 293, Mw: 597 of polyindene compound (1)). For the obtained polyindene compound (1), the GPC chart is shown in Figure 1(a) and Figure 1(b) 13 The 1C-NMR chart and the FS-MS chart are shown in Figure 1(c), respectively.

[0063] (Example 2) Synthesis of polyindene compound (2) Polyindene compound (2) was obtained by performing the same procedure as in Example 1, except that 814.4 parts by mass of toluene was replaced with 370.7 parts by mass of toluene, 145.19 parts by mass of allyl bromide was replaced with 108.7 parts by mass of 3-chloro-2-methyl-1-propene, and 156.2 parts by mass of water was replaced with 181.0 parts by mass of water (Mn: 299, Mw: 582 of polyindene compound (2)). For the obtained polyindene compound (2), the GPC chart is shown in Figure 2(a) and Figure 2(b) 13 The 1C-NMR chart and FS-MS charts are shown in Figures 2(c) and 2(d), respectively.

[0064] (Example 3) Synthesis of polyindene compound (3) In a flask equipped with a stirrer, a Dean-Stark apparatus, and a condenser, 75.7 parts by mass of indene, 131.2 parts by mass of cinnamyl alcohol, 206.9 parts by mass of toluene, and 4.14 parts by mass of p-toluenesulfonic acid monohydrate were charged and heated to obtain a reaction solution. While removing the water produced during the reaction using a Dean-Stark apparatus, the temperature was raised to reflux temperature and stirring was continued for 2 hours to obtain the reaction solution. After cooling the obtained reaction solution to 80°C, it was neutralized with 1.80 parts by mass of a 49% by mass aqueous sodium hydroxide solution. Subsequently, the organic layer was diluted with 189.3 parts by mass of methyl isobutyl ketone, and the organic layer was washed three times with 189.3 parts by mass of water to remove catalyst residue. After removing the catalyst residue from the reaction solution, the temperature was raised to 150°C and volatile components were removed by distillation under reduced pressure to obtain polyindene compound (3) (Mn: 370, Mw: 672 of polyindene compound (3)). For the obtained polyindene compound (3), Figure 3(a) shows the GPC chart, and Figure 3(b) shows the 13 The 1C-NMR chart and FS-MS charts are shown in Figures 3(c) and 3(d), respectively.

[0065] (Example 4) Synthesis of polyindene compound (4) In Example 3, polyindene compound (4) was obtained by performing the same procedure as in Example 3, except that 116.2 parts by mass of indene was used instead of 75.7 parts by mass of indene, 245.4 parts by mass of toluene was used instead of 206.9 parts by mass of toluene, 129.2 parts by mass of 3-methyl-2-buten-1-ol was used instead of 131.2 parts by mass of cinnamyl alcohol, 4.91 parts by mass of p-toluenesulfonic acid monohydrate was used instead of 4.14 parts by mass of p-toluenesulfonic acid monohydrate, 2.13 parts by mass of 49% sodium hydroxide was used instead of 1.80 parts by mass of 49% sodium hydroxide aqueous solution, the charging of methyl isobutyl ketone was omitted, and 109.2 parts by mass of water was used instead of 189.3 parts by mass (Mn: 297, Mw: 431 of polyindene compound (4)). For the obtained polyindene compound (4), Figure 4(a) shows the GPC chart, and Figure 4(b) shows the 13 The 1C-NMR chart and FS-MS charts are shown in Figures 4(c) and 4(d), respectively.

[0066] (Comparative Example 1) Synthesis of indene compound (C1) In a flask equipped with a thermometer, condenser, and stirrer, 72.0 parts by mass of norbornene, 25.0 parts by mass of DVB-810 (manufactured by Nippon Steel Chemical & Material Co., Ltd., containing 81% by mass of divinylbenzene and 19% by mass of ethylstyrene), and 75.0 parts by mass of DVB-570 (manufactured by Nippon Steel Chemical & Material Co., Ltd., containing 57% by mass of divinylbenzene and 43% by mass of ethylstyrene) were charged to adjust the charge amount to 0.63 moles of divinylbenzene and 0.37 moles of ethylstyrene per mole of norbornene. Subsequently, 35.6 parts by mass of butyl acetate and 114.7 parts by mass of toluene were charged, and the temperature was raised to 70°C while stirring. The trifluoroborane diethyl ether complex was added, and the reaction was carried out at the same temperature for 6 hours to obtain the reaction solution. After the reaction was complete, the solution was neutralized with an aqueous sodium bicarbonate solution, the catalyst residue was removed by washing with water, and volatile components were removed under reduced pressure at 60°C to obtain the indene compound (C1).

[0067] (Examples 5-9 and: Preparation of cured products (1)-(5)) Maleimide resin (1,6'-bismaleimide-(2,2,4-trimethyl)hexane (BMI-TMH, manufactured by Yamato Chemical Industries, Ltd.)) and polyindene compounds (1) to (4) were melt-kneaded to the composition ratio shown in Table 1 below. Dicumyl peroxide (hereinafter also referred to as DCPO) was added in a mass of 0.5 parts by mass relative to the total amount of polyindene compounds (1) to (4) and the maleimide resin. The mixture was poured into a mold processed to a thickness of 2 mm and heated and cured at 200°C for 3 hours to obtain a cured product. The "dielectric loss tangent" shown in Table 1 was then evaluated according to the procedure described in the evaluation method above. The results are shown in Table 1 below.

[0068] (Comparative Example 2: Cured product (C2)) Maleimide resin (1,6'-bismaleimide-(2,2,4-trimethyl)hexane (BMI-TMH, manufactured by Yamato Chemical Industries, Ltd.)) and an indene compound were melt-kneaded to the composition ratio shown in Table 1 below. 0.5 parts by mass of DCPO were added to the total amount of the maleimide resin, and the mixture was poured into a mold processed to a thickness of 2 mm. The mixture was then heated and cured at 200°C for 3 hours to obtain a cured product. The "dielectric loss tangent" shown in Table 1 was then evaluated according to the procedure described in the evaluation method above. The results are shown in Table 1 below.

[0069] [Table 1]

[0070] The results in Table 1 confirm that when the polyindene compound of the example was used, a cured product with superior dielectric properties was obtained compared to the comparative example. [Industrial applicability]

[0071] According to this disclosure, it is possible to provide a polyindane compound having excellent dielectric properties in the resulting cured product, a curable composition containing the polyindane compound, and cured products, prepregs, build-up films, semiconductor encapsulants, and semiconductor devices obtained using the curable composition.

Claims

1. Indene compounds, A polyindene compound, comprising a chain-like olefin compound having three or more carbon atoms and having a terminal leaving group which may be substituted with an alkyl or aryl group, as a reaction raw material, It has a structural unit derived from the indene compound represented by the following general formula (i), and a group having an unsaturated bond derived from the olefin compound represented by the following general formula (ii), 【Chemistry 1】 (In the above general formula (i), R ｉ１ each independently represents a hydrogen atom, an alkyl group, an allyl group, an aryl group, an aralkyl group, or R ｉ２ ; R ｉ２ each independently represents a group having an unsaturated hydrocarbon bond derived from the olefin compound represented by the general formula (ii) excluding the leaving group; R ｉ３ each independently represents an indenyl group or an indanyl group; p ｉ１ represents an integer of 1 or more and 3 or less; p ｉ２ represents an integer of 1 or more and 3 or less; p ｉ３ represents an integer of 0 or more and 2 or less; p ｉ２ + p ｉ３ represents an integer of 1 or more and 3 or less; * represents a bond with another atom.) 【Chemistry 2】 (In the above general formula (ii), R ｉｉa , R ｉｉｂ and R ｉｉｃ Each of these independently represents a hydrogen atom, an alkyl group, or an aryl group, and p ｉｉ１ (where * represents an integer between 1 and 6, and * represents a bond with another atom.) A polyindene compound with a weight-average molecular weight (Mw) in the range of 280 to 30,000.

2. The polyindene compound according to claim 1, wherein the number-average molecular weight (Mn) is in the range of 100 to 10000.

3. The olefin compound is the polyindene compound according to claim 1 or 2, represented by the following general formula (b). 【Transformation 3】 (In the above general formula (b), R ｉｉａ , R ｉｉｂ and R ｉｉｃ Each of these independently represents a hydrogen atom, an alkyl group, or an aryl group, and p ｉｉ１ (where represents an integer between 1 and 6, and X represents a leaving group.)

4. A polyindene compound according to any one of claims 1 to 3, which is a thermosetting compound.

5. A method for producing a polyindene compound according to any one of claims 1 to 4, comprising reacting the indene compound with the olefin compound in the presence of an acid or a base.

6. A curable composition containing a polyindene compound according to any one of claims 1 to 4 and a curing agent.

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

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

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

10. A build-up film containing the curable composition described in claim 6.

11. A semiconductor encapsulant containing the curable composition described in claim 6.

12. A semiconductor device comprising a cured product of the semiconductor encapsulant according to claim 11.

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