Method for producing aryl-alkylated indene composition, curable resin material, prepreg, resin film, metal-clad laminated plate, printed wiring board, and semiconductor package

Abstract

This method for producing an aryl-alkylated indene composition involves: adding an arylalkyl group having a polymerizable unsaturated bond-containing group to an indene compound; and adding an arylalkyl group having no polymerizable unsaturated bond-containing group to the indene compound to which the arylalkyl group having a polymerizable unsaturated bond-containing group is added.

Description

Method for producing arylalkylated indene composition, curable resin material, prepreg, resin film, metal-clad laminate, printed wiring board, and semiconductor package

[0001] The present disclosure relates to a method for producing an arylalkylated indene composition, a curable resin material, a prepreg, a resin film, a metal-clad laminate, a printed wiring board, and a semiconductor package.

[0002] Metal-clad laminates, such as copper-clad laminates, prepregs that can be used with metal-clad laminates, and semiconductor packages that use metal-clad laminates are used in a variety of electronic devices, including mobile communication devices such as smartphones, their base station equipment, servers, routers, large servers, and other network infrastructure devices, as well as large computers, personal computers, and industrial computers. They are also used in electronic devices installed in home appliances, automobiles, and other devices. With the spread of 5G, there is a growing demand for electronic communication devices to process massive amounts of data at high speeds.

[0003] When electronic devices process huge amounts of data at high speed, they require circuit board materials with low transmission loss in the high-frequency range. While resins with low dielectric constants and low dielectric loss tangents are used as circuit board materials and provide circuit boards with low transmission loss, recent advances in communication technology have created a demand for the development of resins with even lower dielectric constants and dielectric loss tangents.

[0004] Patent Document 1 discloses a compound having an indene ring structure into which a vinylbenzyl group has been introduced, as a curable vinylbenzyl compound that can give a cured product excellent in low dielectric constant, low dielectric dissipation factor, high heat resistance, and low water absorption.

[0005] Japanese Patent Application Laid-Open No. 2003-277440

[0006] An object of the present disclosure is to provide a method for producing an arylalkylated indene composition having high heat resistance in the cured product, a curable resin material, and prepregs, resin films, metal-clad laminates, printed wiring boards, and semiconductor packages using these.

[0007] The present disclosure includes the following embodiments. The present disclosure is not limited to the following embodiments. One embodiment relates to a method for producing an arylalkylated indene composition, which includes adding an arylalkyl group having a polymerizable unsaturated bond-containing group to an indene compound, and adding an arylalkyl group not having a polymerizable unsaturated bond-containing group to the indene compound to which the arylalkyl group having the polymerizable unsaturated bond-containing group has been added.

[0008] The present disclosure provides a method for producing an arylalkylated indene composition having high heat resistance in the cured product, a curable resin material, and prepregs, resin films, metal-clad laminates, printed wiring boards, and semiconductor packages using these.

[0009] Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments.

[0010] In the present disclosure, a numerical range indicated using "to" indicates a range that includes the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In the numerical ranges described in stages in the present disclosure, the upper or lower limit of a certain numerical range may be replaced with the upper or lower limit of another numerical range. Furthermore, the upper or lower limit of a numerical range described in the present disclosure may be replaced with a value shown in an example.

[0011] In the present disclosure, unless otherwise specified, each component may contain one or more corresponding substances.

[0012] In the present disclosure, the content of each component in a curable resin material means the total amount of the multiple substances present in the curable resin material when multiple substances corresponding to each component are present in the curable resin material, unless otherwise specified.

[0013] [Method for Producing Aryl Alkylated Indene Composition] A method for producing an aryl alkylated indene composition (hereinafter, may be referred to as an "indene composition"), which is one embodiment of the present disclosure, is a method for producing an aryl alkylated indene composition, comprising adding an aryl alkyl group having a polymerizable unsaturated bond-containing group to an indene compound, and adding an aryl alkyl group not having a polymerizable unsaturated bond-containing group to the indene compound to which the aryl alkyl group having the polymerizable unsaturated bond-containing group has been added.

[0014] The indene compound is not particularly limited in terms of its specific structure, as long as it has an indene ring structure and has multiple hydrogen atoms on the indene ring that can be substituted with arylalkyl groups. A single indene compound may be used, or two or more indene compounds may be used in combination. Since the addition reaction of an arylalkyl group to an indene ring occurs primarily on the carbon atoms at the 1st, 2nd, and 3rd positions of the indene ring, a preferred indene compound is one that does not have a substituent on these carbon atoms. Examples of such compounds include compounds represented by the following general formula (2):

[0015] [In general formula (2), R ４ represents a monovalent substituent, and n is 0 or an integer of 1 to 4. When n is an integer of 2 or more, a plurality of R ４ may all be different, or some or all may be the same.]

[0016] R in general formula (2) ４is a monovalent substituent, specific examples of which include a halogen atom, an alkyl group, and an alkoxy group. Specific examples of halogen atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The alkyl group may be either linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but may be, for example, in the range of 1 to 6. Examples of alkyl groups having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a sec-butyl group, a pentyl group, an isopentyl group, a neopentyl group, a hexyl group, and a cyclohexyl group. The alkyl group may be an alkyl group having 1 to 3 carbon atoms, or may be a methyl group. Examples of alkoxy groups include a group represented by R—O—, where R is an alkyl group as described above. In the compound represented by general formula (2), n may be 0.

[0017] In an arylalkyl group having a polymerizable unsaturated bond-containing group (hereinafter, this may be referred to as "arylalkyl group (1)"), the arylalkyl group is a structural moiety in which one hydrogen atom in an alkyl group is substituted with an aryl group. In the arylalkyl group (1), the substitution position of the polymerizable unsaturated group-containing group is not particularly limited, but for example, it may be substituted on the aryl group in the arylalkyl group.

[0018] The alkyl group in the arylalkyl group (1) may be either linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but may be, for example, in the range of 1 to 6. Examples of alkyl groups having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a sec-butyl group, a pentyl group, an isopentyl group, a neopentyl group, a hexyl group, and a cyclohexyl group. The alkyl group may be an alkyl group having 1 to 3 carbon atoms, or may be a methyl group.

[0019] Examples of the aryl group in the arylalkyl group (1) include a phenyl group, a naphthyl group, an anthryl group, and those having one or more substituents on the aromatic ring. The aryl group in the arylalkyl group may be a phenyl group or a naphthyl group, or may be a phenyl group. Examples of the substituent on the aromatic ring include a halogen atom, an alkyl group, and an alkoxy group. Specific examples of the halogen atom, the alkyl group, and the alkoxy group are R in the general formula (2). ４ Examples include those exemplified as follows.

[0020] The specific structure of the polymerizable unsaturated bond-containing group is not particularly limited, and examples thereof include a structural moiety in which one or more C-C bonds in the alkyl group or alkoxy group described above are replaced with a double bond or triple bond, a structural moiety in which one or more hydrogen atoms in the alkyl group or alkoxy group described above are replaced with a (meth)acryloyloxy group, a (meth)acryloyl group, a (meth)acryloyloxy group, etc. The polymerizable unsaturated bond-containing group may be any of an allyl group, an allyloxy group, a vinyl group, a vinyloxy group, a (meth)acryloyl group, and a (meth)acryloyloxy group, and may be a vinyl group or a vinyloxy group, or may be a vinyl group. The number of polymerizable unsaturated bond-containing groups in the arylalkyl group (1) may be 1 or more, and may be 1 or 2, or may be 1.

[0021] The specific structure of the arylalkyl group (1) is not particularly limited, but a preferred example is a vinylbenzyl group. The vinylbenzyl group may be any of o-vinylbenzyl, m-vinylbenzyl, and p-vinylbenzyl. The vinylbenzyl group may be p-vinylbenzyl or m-vinylbenzyl, or may be both p-vinylbenzyl and m-vinylbenzyl. The proportion of p-vinylbenzyl groups among the vinylbenzyl groups added to the indene compound may be 10 mol% or more, 20 mol% or more, or 30 mol% or more. It may also be 100 mol% or less, 80 mol% or less, or 70 mol% or less. The proportion of p-vinylbenzyl groups among the vinylbenzyl groups added to the indene compound may be in the range of 10 to 100 mol%. When the proportion of p-vinylbenzyl groups among the vinylbenzyl groups added to the indene compound is less than 100 mol%, the remainder may be m-vinylbenzyl groups.

[0022] Regarding an arylalkyl group that does not have a polymerizable unsaturated bond-containing group (hereinafter, this may be referred to as an “arylalkyl group (2)”), the arylalkyl group is a structural moiety in which one of the hydrogen atoms in an alkyl group is substituted with an aryl group.

[0023] The alkyl group in the arylalkyl group (2) may be either linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but may be, for example, in the range of 1 to 6. Examples of alkyl groups having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a sec-butyl group, a pentyl group, an isopentyl group, a neopentyl group, a hexyl group, and a cyclohexyl group. The alkyl group may be an alkyl group having 1 to 3 carbon atoms, or may be a methyl group.

[0024] Examples of the aryl group in the arylalkyl group (2) include a phenyl group, a naphthyl group, an anthryl group, and these groups having one or more substituents on the aromatic ring. The aryl group in the arylalkyl group may be a phenyl group or a naphthyl group, or may be a phenyl group. Examples of the substituent on the aromatic ring include a halogen atom, an alkyl group, and an alkoxy group. Specific examples of the halogen atom, the alkyl group, and the alkoxy group are R in the general formula (2). ４ Examples include those exemplified as follows.

[0025] The specific structure of the arylalkyl group (2) is not particularly limited, but a preferred example is a tolylmethyl group. The tolylmethyl group may be any of an o-tolylmethyl group, an m-tolylmethyl group, and a p-tolylmethyl group, and may also be a p-tolylmethyl group or an m-tolylmethyl group. The proportion of p-tolylmethyl groups among the tolylmethyl groups added to the indene compound may be 60 mol % or more, 80 mol % or more, 90 mol % or more, or even 100 mol %.

[0026] In one embodiment, the ratio of the number of moles of arylalkyl group (1) to the total number of moles of arylalkyl group (1) and the number of moles of arylalkyl group (2) may be 50 mol% or more, 55 mol% or more, or 60 mol% or more, since this further improves the moisture resistance of the cured product and more significantly enhances the effect of exhibiting excellent dielectric properties even when exposed to a high-humidity environment. Also, it may be 95 mol% or less, 90 mol% or less, or 80 mol% or less. The ratio of the number of moles of arylalkyl group (1) to the total number of moles of arylalkyl group (1) and the number of moles of arylalkyl group (2) may be in the range of 50 to 95 mol%.

[0027] On the other hand, the ratio of the number of moles of arylalkyl group (2) added to the total number of moles of arylalkyl group (1) and the number of moles of arylalkyl group (2) may be 5 mol% or more, 10 mol% or more, or 20 mol% or more. It may also be 50 mol% or less, 45 mol% or less, or 40 mol% or less. The ratio of the number of moles of arylalkyl group (2) added to the total number of moles of arylalkyl group (1) and the number of moles of arylalkyl group (2) added may be in the range of 5 to 50 mol%.

[0028] The total number of moles of the arylalkyl group (1) and the arylalkyl group (2) added per mole of the indene compound is preferably 2 moles or more, more preferably 2.3 moles or more, particularly preferably 2.5 moles or more, and even more preferably 2.8 moles or more. Alternatively, it may be 3 moles or less. The total number of moles of the arylalkyl group (1) and the arylalkyl group (2) added per mole of the indene compound may be in the range of 2 to 3 moles.

[0029] The method for adding the arylalkyl group (1) to the indene compound is not particularly limited, and any chemical reaction may be used. One example is a method in which a compound having a leaving group such as a halogen atom or a tosyl group is used as an aryl alkylating agent having a polymerizable unsaturated bond-containing group (hereinafter, this may be referred to as "aryl alkylating agent (1)") and the indene compound are reacted with the aryl alkylating agent in the presence of a basic compound.

[0030] Specific examples of the aryl alkylating agent (1) include compounds represented by the following general formula (3):

[0031] [In the general formula (3), X is a halogen atom or a tosyl group. ５ is an alkylene group, and Ar １ is an aryl group having a polymerizable unsaturated bond-containing group.

[0032] R in general formula (3) ５is an alkylene group, and specific examples thereof include alkylene groups corresponding to those exemplified above as the alkyl group in the arylalkyl group (1). １ is an aryl group having a polymerizable unsaturated bond-containing group. Specific examples of the aryl group include those exemplified above as the aryl group in the arylalkyl group (1), and examples of the polymerizable unsaturated bond-containing group include those exemplified above. Specific examples of the aryl alkylating agent (1) include halomethylstyrene, etc.

[0033] The reaction ratio of the indene compound to the aryl alkylating agent (1) is not particularly limited, but since this results in an aryl alkylated indene composition with higher heat resistance in the cured product, the number of moles of aryl alkylating agent (1) per mole of indene compound is preferably 1 mole or more, more preferably 1.5 moles or more, particularly preferably 1.8 moles or more, and even more preferably 2.0 moles or more. Furthermore, in order to leave reaction sites with the arylalkyl group not having a polymerizable unsaturated bond-containing group, the number of moles of aryl alkylating agent (1) per mole of indene compound is preferably 2.8 moles or less, more preferably 2.5 moles or less, and particularly preferably 2.3 moles or less. The number of moles of aryl alkylating agent (1) per mole of indene compound may be in the range of 1 to 2.8 moles.

[0034] Examples of the basic compound include alkali metal hydroxides and alkali metal alkoxides. One type of basic compound may be used alone, or two or more types may be used in combination. The basic compound may be used as a solid or as an aqueous solution. The amount of the basic compound added may be 1.1 moles or more, or 1.5 moles or more, per mole of the aryl alkylating agent, from the viewpoint of allowing the reaction to proceed sufficiently. The amount of the basic compound added may be 3.0 moles or less, 2.5 moles or less, or 2.2 moles or less, from the viewpoint of suppressing side reactions such as hydrolysis of the aryl alkylating agent. The amount of the basic compound added may be in the range of 1.1 to 3 moles per mole of the aryl alkylating agent.

[0035] A phase transfer catalyst may be used in the above reaction. The phase transfer catalyst may be used alone or in combination of two or more. Examples of the phase transfer catalyst include quaternary ammonium salts such as tetra-n-butylammonium chloride, tetra-n-butylammonium bromide (tetra-n-butylammonium bromide), tetraethylammonium chloride, tetraethylammonium bromide, tetrapropylammonium chloride, tetrapropylammonium bromide, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltributylammonium chloride, benzyltributylammonium bromide, benzyldimethyltetradecylammonium chloride, tricaprylmethylammonium chloride, tetradecyltrimethylammonium bromide, hexadecyltrimethylammonium bromide, trioctylmethylammonium chloride, and tetra-n-butylammonium hydrogen sulfate; and quaternary phosphonium salts such as tetra-n-butylphosphonium chloride, tetra-n-butylphosphonium bromide, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, benzyltriphenylphosphonium chloride, and benzyltriphenylphosphonium bromide. The amount of the phase transfer catalyst added may be 1 mol % or more, or 3 mol % or more, relative to 1 mole of the indene compound, from the viewpoint of reaction rate. Furthermore, from the viewpoint of reducing the amount of the phase transfer catalyst remaining in the product, it may be 20 mol % or less, 18 mol % or less, or 15 mol % or less. The amount of the phase transfer catalyst added may be in the range of 1 to 20 mol % relative to 1 mole of the indene compound.

[0036] A polymerization inhibitor may be used in the above reaction. One type of polymerization inhibitor may be used alone, or two or more types may be used in combination. Examples of the polymerization inhibitor include hydroquinone, methylhydroquinone, tert-butylhydroquinone, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, hydroquinone monomethyl ether, 1,4-benzoquinone, 2-tert-butyl-1,4-benzoquinone, 2-tert-butylphenol, 2,4-di-tert-butylphenol, 2,6-di-tert-butylphenol, cresol, catechol, and 4-tert-butylcatechol. Examples of suitable polymerization inhibitors include chol, pyrogallol, 4-methoxyphenol, thiodiphenylamine, phenothiazine, 3,7-dioctylphenothiazine, 3,7-dicumylphenothiazine, 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl, and bis(2,2,6,6-tetramethyl-1-piperidinyloxy-4-yl)sebacate. The amount of the polymerization inhibitor added may be 0.1 mol % or more, or even 0.2 mol % or more, relative to 1 mole of the indene compound, from the viewpoint of inhibiting the polymerization reaction of the polymerizable unsaturated bond-containing group during the production of the indene composition. Furthermore, from the viewpoint of inhibiting inhibition of curing of the resulting indene composition, the amount may be 2 mol % or less, 1.8 mol % or less, or 1.5 mol % or less. The amount of the polymerization inhibitor added may be in the range of 0.1 to 2 moles per mole of the indene compound.

[0037] The reaction may be carried out in a solvent. Examples of the solvent include aromatic hydrocarbon solvents such as toluene and xylene. One type of solvent may be used alone, or two or more types may be used in combination. The amount of solvent used may be, for example, an amount such that the proportion of non-solvent components in the reaction mixture falls within the range of 5 to 90 mass %.

[0038] The reaction is preferably carried out under heated conditions in order to proceed more efficiently, and may be heated, for example, to a temperature range of 30 to 70°C.

[0039] After the reaction is complete, the reaction product may be purified by a known method such as concentration, reprecipitation, or washing, if necessary.

[0040] The reaction product of the indene compound and the aryl alkylating agent (1) may be a mixture containing a plurality of compounds having different numbers of arylalkyl groups (1) per molecule. Specifically, it may be a mixture of compounds having one arylalkyl group, two arylalkyl groups, or three arylalkyl groups per molecule.

[0041] The method for adding an arylalkyl group not having a polymerizable unsaturated bond-containing group to an indene compound having an arylalkyl group having a polymerizable unsaturated bond-containing group added thereto (hereinafter, this may be referred to as "indene compound (α)") is not particularly limited, and any chemical reaction may be used. One example includes a method in which a compound having a leaving group such as a halogen atom or a tosyl group is used as an aryl alkylating agent not having a polymerizable unsaturated bond-containing group (hereinafter, this may be referred to as "aryl alkylating agent (2)"), and this is reacted with the indene compound (α) in the presence of a basic compound.

[0042] As described above, after the indene compound (α) is obtained by reacting an indene compound with an aryl alkylating agent (1), a purification operation can be carried out as necessary, and the purified indene compound (α) may be reacted with an aryl alkylating agent (2). Alternatively, as a method for more efficiently producing the target indene composition, the aryl alkylating agent (2) may be added to the reaction mixture obtained after the reaction of the indene compound with the aryl alkylating agent (1), and the reaction may be carried out continuously.

[0043] Specific examples of the aryl alkylating agent (2) include compounds represented by the following general formula (4):

[0044] [In the general formula (4), X is a halogen atom or a tosyl group. ６ is an alkylene group, and Ar ２ is an aryl group that does not have a polymerizable unsaturated bond-containing group.

[0045] R in general formula (4) ６is an alkylene group, and specific examples thereof include alkylene groups corresponding to those exemplified above as the alkyl group in the arylalkyl group (2). ２ is an aryl group having no polymerizable unsaturated bond-containing group, and specific examples of the aryl group include those exemplified above as the aryl group in the arylalkyl group (2). ２ may be a phenyl group or a phenyl group having one or more substituents on the aromatic ring. The substituent on the aromatic ring may be a halogen atom, an alkyl group, or an alkoxy group, as exemplified above. Specific examples of the aryl alkylating agent (2) include α-haloxylene.

[0046] The amount of aryl alkylating agent (2) used in the reaction is adjusted appropriately depending on the reaction ratio between the indene compound and the aryl alkylating agent (1), etc. However, since this not only provides excellent heat resistance in the cured product but also effectively suppresses deterioration of dielectric properties when exposed to a high-humidity environment, the number of moles of aryl alkylating agent (2) per mole of the indene compound used in the reaction is preferably 0.1 moles or more, more preferably 0.2 moles or more, and particularly preferably 0.6 moles or more. Furthermore, the number of moles is preferably 2.0 moles or less, more preferably 1.5 moles or less, and particularly preferably 1.2 moles or less. The number of moles of aryl alkylating agent (2) per mole of the indene compound may be in the range of 0.1 to 2.0 moles.

[0047] The ratio of the aryl alkylating agent (1) to the total number of moles of the aryl alkylating agent (1) and the aryl alkylating agent (2) may be 50 mol% or more, 55 mol% or more, or 60 mol% or more, since this further improves the moisture resistance of the cured product and more significantly enhances the effect of exhibiting excellent dielectric properties even when exposed to a high-humidity environment. The ratio may also be 95 mol% or less, 90 mol% or less, or 80 mol% or less. The ratio of the aryl alkylating agent (1) to the total number of moles of the aryl alkylating agent (1) and the aryl alkylating agent (2) may be in the range of 50 to 95 mol%.

[0048] On the other hand, the ratio of the aryl alkylating agent (2) to the total number of moles of the aryl alkylating agent (1) and the aryl alkylating agent (2) may be 5 mol% or more, 10 mol% or more, or 20 mol% or more. It may also be 50 mol% or less, 45 mol% or less, or 40 mol% or less. The ratio of the aryl alkylating agent (2) to the total number of moles of the aryl alkylating agent (1) and the aryl alkylating agent (2) may be in the range of 5 to 50 mol%.

[0049] The total number of moles of the aryl alkylating agent (1) and the aryl alkylating agent (2) per mole of the indene compound is preferably 2 moles or more, more preferably 2.3 moles or more, particularly preferably 2.5 moles or more, and even more preferably 2.8 moles or more. It may also be 3 moles or less. The total number of moles of the aryl alkylating agent (1) and the aryl alkylating agent (2) per mole of the indene compound may be in the range of 2 to 3 moles.

[0050] The reaction conditions for the indene compound (α) and the aryl alkylating agent (2), specifically, the type and amount of the basic compound, the type and amount of the optionally used phase transfer catalyst, the type and amount of the optionally used polymerization inhibitor, the type and amount of the optionally used solvent, the reaction temperature, etc., may be the same as those for the reaction between the indene compound and the aryl alkylating agent (1). When the aryl alkylating agent (2) is added to the reaction mixture obtained after the reaction of the indene compound and the aryl alkylating agent (1) and reacted continuously, the basic compound, the phase transfer catalyst, the polymerization inhibitor, etc. may be additionally added, or the reaction may be carried out without additionally adding them.

[0051] After the reaction is complete, the reaction product may be purified by a known method such as concentration, reprecipitation, or washing, if necessary.

[0052] The indene composition obtained by the method for producing an indene composition according to one embodiment may be a mixture containing a plurality of compounds having different total numbers of arylalkyl groups (1) and arylalkyl groups (2) in one molecule. Specifically, the indene composition may be a mixture of a compound having either one of the arylalkyl groups (1) or the arylalkyl group (2) in one molecule (hereinafter, this may be referred to as "indene compound (1)"), a compound having a total of two arylalkyl groups (1) and two arylalkyl groups (2) in one molecule (hereinafter, this may be referred to as "indene compound (2)"), and a compound having a total of three arylalkyl groups (1) and three arylalkyl groups (2) in one molecule (hereinafter, this may be referred to as "indene compound (3)").

[0053] The indene composition obtained by the method for producing an indene composition according to one embodiment may be, for example, a composition containing a plurality of compounds represented by the following general formula (1) each having a different number of aryl alkyl groups in one molecule:

[0054] [In formula (1), R １ , R ２ and R ３ R each independently represents a hydrogen atom, an arylalkyl group having a polymerizable unsaturated bond-containing group, or an arylalkyl group not having a polymerizable unsaturated bond-containing group. ４ represents a monovalent substituent, and n is 0 or an integer of 1 to 4. When n is an integer of 2 or more, a plurality of R ４ may all be different, or some or all may be the same.]

[0055] In the general formula (1), an arylalkyl group having a polymerizable unsaturated bond-containing group, an arylalkyl group not having a polymerizable unsaturated bond-containing group, R ４ has the same meaning as explained above.

[0056] The content of each compound in the indene composition is not particularly limited and can be adjusted appropriately depending on the desired performance, etc. As an example, since the arylalkylated indene composition has higher heat resistance in the cured product, the content of indene compound (1) in the indene composition is preferably 1% or less as calculated from the area ratio in the GPC chart. Furthermore, it may be 0.85% or less, or even 0.8% or less. Furthermore, the content of indene compound (1) in the indene composition may be below the detection limit. While the indene composition does not necessarily contain indene compound (1), it may contain 0.05% or more, or even 0.1% or more of indene compound (1). The content of indene compound (1) in the indene composition may be in the range of 0.05 to 1%.

[0057] In the present disclosure, the GPC conditions for calculating the content of each compound in the indene composition are as follows.

[0058] Apparatus: High-speed GPC apparatus "HLC-8420GPC" (Tosoh Corporation, trade name) Detector: Ultraviolet absorption detector "UV-8420" (Tosoh Corporation, trade name) Column: Guard column; TSKgel guard column SuperHZ-L, Column; TSKgel SuperHZ4000 + TSKgel SuperHZ2500 + TSKgel SuperHZ1000 (3 columns), Reference column; None (Resistor tube) (all Tosoh Corporation, trade names) Column size: 4.6 x 20 mm (guard column), 4.6 x 150 mm (column) Eluent: Tetrahydrofuran Sample concentration: 1 mg / 1 mL Injection volume: 2 μL Flow rate: 0.35 mL / min Measurement temperature: 40°C

[0059] The content of the indene compound (2) in the indene composition may be 3% or more, 5% or more, or 10% or more, as calculated from the area ratio in the GPC chart. It may also be 25% or less, 20% or less, or 19% or less. The content of the indene compound (2) in the indene composition may be in the range of 3 to 25%.

[0060] The content of the indene compound (3) in the indene composition is preferably 80% or more as calculated from the area ratio in the GPC chart. Alternatively, it may be 95% or less, 90% or less, or 85% by mass or less. The content of the indene compound (3) in the indene composition may be in the range of 80 to 95%.

[0061] The total content of the indene compound (2) and the indene compound (3) in the indene composition may be 99% or more as calculated from the area ratio in the GPC chart.

[0062] [Curable Resin Material] A curable resin material according to one embodiment of the present disclosure includes an arylalkylated indene composition obtained by the manufacturing method according to one embodiment described above. Examples of components other than the arylalkylated indene composition that may be included in the curable resin material include other curable compounds other than the indene composition, elastomers, fillers, curing accelerators, flame retardants, antioxidants, heat stabilizers, antistatic agents, UV absorbers, pigments, colorants, lubricants, and solvents. Each of these other components may be used singly or in combination.

[0063] Examples of other curable compounds include compounds having a polymerizable unsaturated bond, epoxy resins, phenolic resins, cyanate resins, isocyanate resins, benzoxazine resins, oxetane resins, amino resins, dicyclopentadiene resins, silicone resins, triazine resins, melamine resins, etc. Examples of the compound having a polymerizable unsaturated bond include compounds having a maleimide group, polyarylene ether compounds having a polymerizable unsaturated bond-containing group, styrene, divinylbenzene, triallyl isocyanurate, etc.

[0064] Examples of compounds having a maleimide group include compounds having one or more N-substituted maleimide groups and derivatives thereof.

[0065] Examples of the compound having one or more N-substituted maleimide groups include aromatic maleimide compounds which are compounds having an N-substituted maleimide group directly bonded to an aromatic ring, aromatic bismaleimide compounds which are compounds having two N-substituted maleimide groups directly bonded to an aromatic ring, aromatic polymaleimide compounds which are compounds having three or more N-substituted maleimide groups directly bonded to an aromatic ring, and aliphatic maleimide compounds which are compounds having an N-substituted maleimide group directly bonded to an aliphatic hydrocarbon.

[0066] Specific examples of the compound having one or more N-substituted maleimide groups include N,N'-ethylene bismaleimide, N,N'-hexamethylene bismaleimide, N,N'-(1,3-phenylene)bismaleimide, N,N'-[1,3-(2-methylphenylene)]bismaleimide, N,N'-[1,3-(4-methylphenylene)]bismaleimide, N,N'-(1,4-phenylene)bismaleimide, bis(4-maleimidophenyl)methane, bis(3-methyl-4-maleimidophenyl)methane, 3,3'-dimethyl-5, 5'-Diethyl-4,4'-diphenylmethane bismaleimide, bis(4-maleimidophenyl)ether, bis(4-maleimidophenyl)sulfone, bis(4-maleimidophenyl)sulfide, bis(4-maleimidophenyl)ketone, bis(4-maleimidocyclohexyl)methane, 1,4-bis(4-maleimidophenyl)cyclohexane, 1,4-bis(maleimidomethyl)cyclohexane, 1,4-bis(maleimidomethyl)benzene, 1,3-bis(4-maleimidophenoxy)benzene, 1,3-bis (3-maleimidophenoxy)benzene, bis[4-(3-maleimidophenoxy)phenyl]methane, bis[4-(4-maleimidophenoxy)phenyl]methane, 1,1-bis[4-(3-maleimidophenoxy)phenyl]ethane, 1,1-bis[4-(4-maleimidophenoxy)phenyl]ethane, 1,2-bis[4-(3-maleimidophenoxy)phenyl]ethane, 1,2-bis[4-(4-maleimidophenoxy)phenyl]ethane, 2,2-bis[4-(3-maleimidophenoxy)phenyl]propanol Pan, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, 2,2-bis[4-(3-maleimidophenoxy)phenyl]butane, 2,2-bis[4-(4-maleimidophenoxy)phenyl]butane, 2,2-bis[4-(3-maleimidophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis[4-(4-maleimidophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 4,4-bis(3-maleimidophenoxy)biphenyl, 4,4-bis(4-maleimidophenoxy)biphenyl, bis[4-(3-maleimidophenoxy)phenyl]ketone, bis[4-(4-maleimidophenoxy)phenyl]ketone, bis(4-maleimidophenyl)disulfide, bis[4-(3-maleimidophenoxy)phenyl]sulfide, bis[4-(4-maleimidophenoxy)phenyl]sulfide, bis[4-(3-maleimidophenoxy)phenyl]sulfoxide, bis Bis[4-(4-maleimidophenoxy)phenyl]sulfoxide, bis[4-(3-maleimidophenoxy)phenyl]sulfone, bis[4-(4-maleimidophenoxy)phenyl]sulfone, bis[4-(3-maleimidophenoxy)phenyl]ether, bis[4-(4-maleimidophenoxy)phenyl]ether, 1,4-bis[4-(4-maleimidophenoxy)-α,α-dimethylbenzyl]benzene, 1,3-bis[ 4-(4-maleimidophenoxy)-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(3-maleimidophenoxy)-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(3-maleimidophenoxy)-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(4-maleimidophenoxy)-3,5-dimethyl-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4-maleimidophenoxy)- 3,5-dimethyl-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(3-maleimidophenoxy)-3,5-dimethyl-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(3-maleimidophenoxy)-3,5-dimethyl-α,α-dimethylbenzyl]benzene, polyphenylmethane maleimide, aromatic bismaleimide compounds having an indane skeleton, biphenylaralkyl maleimide compounds, etc.

[0067] Examples of derivatives of compounds having one or more N-substituted maleimide groups include aminomaleimide compounds containing structural units derived from the above-described compounds having one or more N-substituted maleimide groups and structural units derived from diamine compounds.

[0068] Examples of derivatives of compounds having one or more N-substituted maleimide groups include aminomaleimide compounds containing structural units derived from the above-described compounds having one or more N-substituted maleimide groups and structural units derived from diamine compounds.

[0069] Regarding the polyarylene ether compound having a polymerizable unsaturated bond-containing group, the arylene group is not particularly limited, and examples thereof include a phenylene group, a naphthylene group, and structures in which one or more alkyl groups, alkyloxy groups, halogen atoms, etc. are substituted on the aromatic carbon of these groups. Examples of the polymerizable unsaturated bond-containing group include a vinyl group, a vinyloxy group, an allyl group, an allyloxy group, a (meth)acryloyl group, a (meth)acryloyloxy group, a vinylbenzyl group, and a vinylbenzyloxy group. The polyarylene ether compound having a polymerizable unsaturated bond-containing group may have a structural moiety other than the polyarylene ether structure. Specifically, the molecular chain may contain an acrylic polymerization moiety, a (poly)urethane moiety, a (poly)ester moiety, etc. The number of polymerizable unsaturated bond-containing groups in one molecule of the polyarylene ether compound is not particularly limited, and the substitution position of the polymerizable unsaturated bond-containing group is also not particularly limited. For example, the polyarylene ether compound may have a polymerizable unsaturated bond-containing group at the molecular terminal, or may have a polymerizable unsaturated bond-containing group at both terminals.

[0070] Specific examples of the polyarylene ether compound having a polymerizable unsaturated bond-containing group include compounds represented by the following general formula (5).

[0071] [In general formula (5), R ７ is a hydrogen atom or a methyl group; l and m are integers of 1 or more; and Y is a divalent organic group.

[0072] Y in general formula (5) is a divalent organic group, and the specific structure is not particularly limited. Examples of the divalent organic group include a hydrocarbon group having 1 to 6 carbon atoms, a halogenated hydrocarbon group, an oxygen atom, a sulfur atom, a carbonyl group, and a sulfonyl group.

[0073] The molecular weight of the polyarylene ether compound having a radical polymerizable group is not particularly limited, but the number average molecular weight (Mn) may be in the range of 1,000 to 5,000, for example.

[0074] The ratio of the indene composition to the total mass of the curable components of the curable resin material is arbitrary, but may be, for example, 10 mass% or more, 30 mass% or more, 50 mass% or more, 80 mass% or more, or 100 mass%.

[0075] Examples of the elastomer include polyether elastomers, styrene elastomers, conjugated diene elastomers, urethane elastomers, polyester elastomers, polyamide elastomers, acrylic elastomers, and silicone elastomers.

[0076] The filler may be either an organic filler or an inorganic filler, but an inorganic filler is preferred. Examples of inorganic fillers include silica (SiO ２ ), alumina (Al ２ O ３ ), titanium oxide, barium titanate, strontium titanate, potassium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum hydroxide, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, aluminum borate, silicon carbide, mica, beryllia, clay, talc, etc. Silica is preferred from the viewpoint of dielectric properties.

[0077] The shape and size of the filler are not particularly limited. The average particle size of the filler may be, for example, 0.01 to 20 μm, or 0.1 to 10 μm. Here, the average particle size of the filler is the particle size at a point corresponding to an integrated value of 50% in a volume-based particle distribution measured by a laser diffraction scattering method.

[0078] As the curing accelerator, for example, a radical polymerization initiator can be used. The radical polymerization initiator may be a thermal radical polymerization initiator or a photoradical polymerization initiator, but a thermal radical polymerization initiator is preferred. Specific examples of the polymerization initiator include azo-based polymerization initiators and organic peroxide-based polymerization initiators. Examples of azo-based polymerization initiators include 2,2'-azobis(2,4,4-trimethylpentane), dimethyl 2,2'-azobis(2-methylpropionate), 2,2'-azobis(N-butyl-2-methylpropionamide), 2,2'-azobis[N-(2-propenyl)-2-methylpropionamide], 1,1'-azobis(cyclohexane-1-carbonitrile), and dimethyl 1,1'-azobis(1-cyclohexanecarboxylate). , 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2-methylpropanenitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 4,4'-azobis(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl 4-cyanopentanoate), and the like. Examples of organic peroxide polymerization initiators include dicumyl peroxide, dibenzoyl peroxide, 2-butanone peroxide, tert-butyl perbenzoate, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, α,α'-di(t-butylperoxy)diisopropylbenzene, and tert-butyl hydroperoxide.

[0079] Examples of the flame retardant include phosphorus-based flame retardants, nitrogen-based flame retardants, silicone-based flame retardants, and inorganic flame retardants.

[0080] The curable resin material may be solvent-free or may contain a solvent. The solvent can adjust the viscosity of the curable resin material to further improve the coatability. The solvent is preferably an organic solvent.

[0081] Examples of the organic solvent include alcohol-based solvents such as ethanol, propanol, butanol, methyl cellosolve, ethylene glycol monobutyl ether, and propylene glycol monomethyl ether; ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether-based solvents such as tetrahydrofuran; aromatic hydrocarbon-based solvents such as toluene, xylene, and mesitylene; nitrogen-containing solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone; sulfur-containing solvents such as dimethyl sulfoxide; and ester-based solvents such as γ-butyrolactone.

[0082] The method for producing the curable resin material is not particularly limited. One example of a method for producing the curable resin material is a method in which an indene composition and optional components used as needed are added and mixed. When mixing, the indene composition and optional components used as needed may be directly blended and mixed, or the indene composition and optional components used as needed may be dissolved or dispersed in a solvent and mixed. The conditions for mixing the components, such as the order of mixing, temperature, and time, are not particularly limited and may be appropriately adjusted depending on the type of raw materials, production scale, production equipment, etc.

[0083] [Prepreg] According to one embodiment, a prepreg containing a curable resin material or a semi-cured product of a curable composition can be provided. This prepreg can be formed, for example, using a curable resin material and a fibrous substrate. With regard to the semi-cured product of the curable resin material, in the present disclosure, the B-stage state in JIS K 6800 (1985) can be cited as one indicator of the semi-cured product. The prepreg may, for example, contain a curable resin material or a semi-cured product of the curable resin material and a fibrous substrate such as a sheet-like fibrous substrate. In the prepreg, the curable resin material may be in an uncured state, or the curable resin material may be partially or entirely semi-cured.

[0084] Prepregs can be obtained, for example, by impregnating a fiber substrate with a curable resin material and then drying the fiber substrate impregnated with the curable resin material. Drying is preferably carried out at a temperature at which volatile components such as solvents that may be contained in the curable resin material are removed, or at a temperature at which the curable components contained in the curable resin material are semi-cured, depending on the application. Furthermore, drying is preferably adjusted so that the thermosetting resin contained in the curable resin material is not completely cured. From this perspective, the drying temperature may be, for example, 80 to 200°C, and the drying time may be, for example, 1 to 30 minutes, depending on the drying temperature, drying equipment, and its scale.

[0085] The fiber substrate may be any of woven fabric, knitted fabric, and nonwoven fabric. The fiber substrate may be provided in the form of chopped strand mat, roving, etc. The fiber material may be any of inorganic fiber and organic fiber. Examples of inorganic fiber include glass fiber and carbon fiber. Examples of glass fiber include E-glass, NE-glass, D-glass, S-glass, Q-glass, etc. Examples of organic fiber include polyimide, polyester, tetrafluoroethylene, etc. The fiber substrate may be made of one type of these fibers alone or a combination of two or more types of these fibers. From the viewpoints of dielectric properties and heat resistance, the material of the fiber substrate is preferably inorganic fiber, and more preferably glass fiber.

[0086] The fiber substrate may be appropriately selected depending on the application of the prepreg, but a sheet-like fiber substrate is preferred. Examples of the sheet-like fiber substrate include various sheet-like fiber substrates used in known laminates for electrical insulating materials. The thickness of the sheet-like fiber substrate is not particularly limited, but is preferably 0.01 to 0.1 mm, for example. Here, the thickness is measured at five points at equal distances across the entire surface of the sheet-like fiber substrate, and the arithmetic average of the five measurements is used.

[0087] [Resin Film] According to one embodiment, a resin film containing a curable resin material or a semi-cured product of the curable resin material can be provided. The resin film can be obtained, for example, by applying a curable resin material to a substrate and drying or semi-curing the material. Drying or semi-curing can be performed in the same manner as in the prepreg manufacturing method described above. After drying the resin film on the substrate, a product can be provided as a combination of the resin film and the substrate. For example, this method can provide a resin film as a surface protective film, interlayer insulating film, etc. in a printed wiring board. In another method, after drying the resin film on the substrate, the resin film can be peeled off from the substrate to provide the resin film as a product.

[0088] The substrate may be either an inorganic substrate or an organic substrate, and examples thereof include glass substrates, metal substrates such as metal foils and metal plates, plastic substrates such as plastic plates and plastic films, and paper substrates, as well as the fiber substrates described above for the prepreg. A substrate having a release layer formed on its surface may be used so that the resin film can be peeled off from the substrate.

[0089] [Metal-clad laminate] According to one embodiment, a metal-clad laminate can be provided, which includes a cured product of a curable resin material and a metal foil. Regarding the cured product of the curable resin material, in the present disclosure, one indicator of the cured product is the C-stage state according to JIS K 6800 (1985).

[0090] In the metal-clad laminate, the cured product of the curable resin material may be contained as a cured product of the curable resin material itself, or may be contained in the form of a prepreg. The metal-clad laminate preferably includes a prepreg layer and a metal foil disposed on at least one side of the prepreg layer. The prepreg layer is a cured product of the prepreg described above, and may be formed by using a single prepreg or by laminating multiple prepregs. The metal-clad laminate may also be formed by disposing metal foil on one side of the cured prepreg, or by disposing metal foil on both sides of the cured prepreg. The metal-clad laminate may be manufactured by disposing metal foil on at least one side of a single sheet-like prepreg, or by laminating two or more sheet-like prepregs and disposing metal foil on at least one of the outermost surfaces of the laminate. The metal-clad laminate may also be manufactured by laminating two or more sheet-like prepregs and disposing metal foil on both sides of the laminate.

[0091] Hereinafter, as a specific example of a method for producing a metal-clad laminate, a method in which a metal foil is arranged on a laminate of two or more sheet-like prepregs will be described.

[0092] First, two or more sheet-like prepregs are laminated to obtain a laminate. In this laminate, the two or more sheet-like prepregs may be identical to each other, or some or all of them may be different. In the laminate, it is sufficient that at least one of the two or more sheet-like prepregs is obtained using the curable resin material according to one embodiment.

[0093] Next, a metal foil is placed on at least one surface of this laminate. The laminate with the metal foil placed thereon is heated and pressurized. This progresses the curing reaction of the sheet-like prepreg, resulting in a cured prepreg. Furthermore, adjacent sheet-like prepregs can be fixed together. The heating and pressurizing conditions are not particularly limited, but may be, for example, a temperature of 100 to 300°C, a time of 10 to 300 minutes, and a pressure of 0.5 to 50 MPa. Furthermore, after heating and pressurizing, reheating may be performed to further promote the curing of the prepreg. In this case, the reheating temperature may be 100 to 300°C. Examples of pressurizing methods that can be used include an autoclave molding machine, a multi-stage press, a multi-stage vacuum press, and a continuous molding machine.

[0094] The metal for the metal foil is not particularly limited, and examples thereof include copper, nickel, aluminum, gold, silver, platinum, molybdenum, ruthenium, tungsten, iron, titanium, chromium, and alloys containing two or more of these metal elements. Industrially, the metals copper, nickel, and aluminum are preferred. By using copper as the metal foil, a copper-clad laminate can be provided.

[0095] [Printed Wiring Board] According to one embodiment, a printed wiring board containing a cured product of a curable resin material can be provided. In the printed wiring board, the cured product of the curable resin material may be contained as a cured product of the curable resin material itself, or may be contained in the form of a prepreg. The printed wiring board can be manufactured using a curable resin material, a prepreg, a metal-clad laminate, or a combination thereof. For example, a printed wiring board can be provided by forming wiring using a metal-clad laminate by a known method. Details of the prepreg and the metal-clad laminate are as described above. The printed wiring board may be either a single-layer printed wiring board or a multilayer printed wiring board.

[0096] [Semiconductor Package] According to one embodiment, a semiconductor package can be provided that includes a printed wiring board and a semiconductor element. More specifically, for example, a semiconductor package can be provided that includes a printed wiring board that includes a cured product of a prepreg and a semiconductor element. The semiconductor package can be manufactured, for example, by mounting the semiconductor element, memory, etc. on the printed wiring board by a known method.

[0097] Examples of embodiments are listed below. The present invention is not limited to the following embodiments. <1> A method for producing an arylalkylated indene composition, which includes adding an arylalkyl group having a polymerizable unsaturated bond-containing group to an indene compound, and adding an arylalkyl group not having a polymerizable unsaturated bond-containing group to the indene compound to which the arylalkyl group having the polymerizable unsaturated bond-containing group has been added.

[0098] <2> The production method according to <1>, wherein the content of the compound having one arylalkyl group per molecule in the arylalkylated indene composition is 1% or less as calculated from the area ratio in a GPC chart.

[0099] <3> The production method according to <1> or <2>, wherein the ratio of the number of moles of the arylalkyl group having a polymerizable unsaturated bond-containing group to the total number of moles of the arylalkyl group having a polymerizable unsaturated bond-containing group and the number of moles of the arylalkyl group not having a polymerizable unsaturated bond-containing group is in the range of 50 to 95%.

[0100] <4> The method according to any one of <1> to <3>, wherein the arylalkylated indene composition is a composition containing a plurality of compounds represented by the following general formula (1), each of which has a different number of arylalkyl groups in one molecule:

[0101] [In general formula (1), R １ , R ２ and R ３ are each independently a hydrogen atom or an arylalkyl group. ４represents a monovalent substituent, and n is 0 or an integer of 1 to 4. When n is an integer of 2 or more, a plurality of R ４ may all be different, or some or all may be the same.]

[0102] <5> A curable resin material containing an arylalkylated indene composition obtained by the production method according to any one of <1> to <4>.

[0103] <6> A prepreg comprising the curable resin material or a semi-cured product of the curable resin material according to <5>.

[0104] <7> A resin film comprising the curable resin material according to <5> or a semi-cured product of the curable resin material.

[0105] <8> A metal-clad laminate comprising a cured product of the curable resin material according to <5> above and a metal foil.

[0106] <9> A printed wiring board comprising a cured product of the curable resin material according to <5>.

[0107] <10> A semiconductor package comprising the printed wiring board according to <9> above and a semiconductor element.

[0108] <11> A semiconductor package comprising a semiconductor element and a cured product of the curable resin material according to <5> that encapsulates the semiconductor element.

[0109] <12> A printed wiring board comprising at least one of a surface protective film and an interlayer insulating film formed from the curable resin material according to <5>.

[0110] The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to the following examples.

[0111] Example 1: Production of Indene Composition (1) A 500 ml reaction vessel equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet was charged with 26.72 parts by mass of indene, 77.23 parts by mass of chloromethylstyrene (*1), 3.71 parts by mass of tetra-n-butylammonium bromide (manufactured by Kanto Chemical Co., Inc.) as a phase transfer catalyst, 0.18 parts by mass of phenothiazine as a polymerization inhibitor, and 70.25 parts by mass of toluene as a solvent, and the mixture was heated and stirred at 40°C while blowing in nitrogen at a flow rate of 50 ml / min. Next, 100.25 parts by mass of a 48% by mass aqueous sodium hydroxide solution (manufactured by Kanto Chemical Co., Inc.) as a basic compound was added. After stirring at 70°C for 6 hours, 22.64 parts by mass of α-chloro-p-xylene was added. Stirring was then continued at 70°C for 8 hours. Nitrogen blowing was continued throughout the reaction. The reaction mixture was cooled to room temperature (25°C), neutralized with a 10% aqueous solution of hydrochloric acid, and then washed twice with pure water. Toluene was distilled off under reduced pressure, and the resulting viscous liquid was washed with methanol and dried in vacuum to obtain an indene composition (1).

[0112] (*1) Chloromethylstyrene “CMS-P”: AGC Seimi Chemical Co., Ltd., a mixture of m- and p-isomers, with an m-isomer content of approximately 50% by mass and a p-isomer content of approximately 50% by mass.

[0113] The indene composition (1) was analyzed using ECX400II manufactured by JEOL RESONANCE Co., Ltd. １ H-NMR spectrum (400 MHz, CDCl ３ ) was measured, a shift or disappearance of the raw material peak was observed, indicating that a reaction had occurred in which a vinylbenzyl group was bonded to one of the 1st to 3rd positions of the indene ring and a methylbenzyl group was bonded to one of the 1st to 3rd positions of the indene ring.

[0114] [Calculation of Content of Each Compound in Indene Composition (1)] The contents of each compound in the indene composition (1) were calculated from the area ratio of the GPC chart measured under the following conditions. The results were: indene compound (1) 0.5%, indene compound (2) 16.0%, and indene compound (3) 83.5%.

[0115] Apparatus: High-speed GPC apparatus "HLC-8420GPC" (Tosoh Corporation, trade name) Detector: Ultraviolet absorption detector "UV-8420" (Tosoh Corporation, trade name) Column: Guard column; TSKgel guard column SuperHZ-L, Column; TSKgel SuperHZ4000 + TSKgel SuperHZ2500 + TSKgel SuperHZ1000 (3 columns), Reference column; None (Resistor tube) All Tosoh Corporation, trade names) Column size: 4.6 x 20 mm (guard column), 4.6 x 150 mm (column) Eluent: Tetrahydrofuran Sample concentration: 1 mg / 1 mL Injection volume: 2 μL Flow rate: 0.35 mL / min Measurement temperature: 40°C

[0116] Comparative Example 1: Preparation of Indene Composition (1') A 500 ml reaction vessel equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet was charged with 26.72 parts by mass of indene, 77.23 parts by mass of the chloromethylstyrene (*1) described above, 22.64 parts by mass of α-chloro-p-xylene, 3.71 parts by mass of tetra-n-butylammonium bromide (Kanto Chemical Co., Ltd.) as a phase transfer catalyst, 0.18 parts by mass of phenothiazine as a polymerization inhibitor, and 70.25 parts by mass of toluene. The mixture was heated and stirred at 40°C while blowing in nitrogen at a flow rate of 50 ml / min. Next, 100.05 parts by mass of a 48% by mass aqueous sodium hydroxide solution (Kanto Chemical Co., Ltd.) as a basic compound was added dropwise over 20 minutes, and the mixture was stirred at 70°C for 14 hours. Nitrogen blowing was continued throughout the reaction. The mixture was cooled to room temperature (25°C), neutralized with a 10% aqueous hydrochloric acid solution, and then washed twice with pure water. Toluene was distilled off under reduced pressure, and the resulting viscous liquid was washed with methanol and dried in vacuum to obtain an indene composition (1').

[0117] [Calculation of the Content of Each Compound in Indene Composition (1′)] The contents of each compound in indene composition (1′) were calculated from the area ratios of the GPC charts measured under the above conditions, and were found to be 0.7% for indene compound (1), 15.4% for indene compound (2), and 83.9% for indene compound (3).

[0118] [Production of Cured Product] A low-profile copper foil ("SI-VSP-18" manufactured by Mitsui Mining & Smelting Co., Ltd., thickness 18 μm) was placed with the S-side (shiny side) facing up, and a Teflon (registered trademark) sheet die-cut to a size of 1.0 mm thick x 20 mm long x 20 mm wide was placed on top of it. Next, a viscous liquid of an indene composition was poured into the die-cut section, and the low-profile copper foil was placed on top of it with the S-side (shiny side) facing down (the viscous liquid side of the indene composition). The resin composition was cured by vacuum heating and pressure molding at a temperature of 150°C, a pressure of 1.5 to 2.0 MPa, and a time of 120 minutes, followed by further hot molding at a temperature of 180°C for 300 minutes. The copper foil on both sides was then peeled off to obtain a cured product (thickness of cured product: 1 mm).

[0119] [Measurement of Glass Transition Temperature (Tg)] The cured product obtained as described above was cut into a length of 30 mm and a width of 4 mm to prepare a test piece. Measurement was then performed using a dynamic mechanical analyzer (DMA) (manufactured by UBM Corporation, product name: Rheogel-E4000) in a temperature range of 30 to 350°C, with a tensile test jig, a chuck distance of 20 mm, a frequency of 10 Hz, and a heating rate of 5°C / min. The temperature at which tan δ reached its maximum was taken as the glass transition temperature.

[0120] The glass transition temperature of the indene composition (1) of Example 1, measured according to the above-mentioned method, was 228° C., and the glass transition temperature of the indene composition (1′) of Comparative Example 1 was 204.1° C. The indene composition (1) of Example 1 had a higher glass transition temperature and better heat resistance than the indene composition (1′) of Comparative Example 1.

[0121] The disclosure of this application is related to the subject matter described in Japanese Patent Application No. 2024-100310, filed on June 21, 2024, the disclosures of which are incorporated herein by reference.

Claims

1. A method for producing an arylalkylated indene composition, comprising adding an arylalkyl group having a polymerizable unsaturated bond-containing group to an indene compound, and adding an arylalkyl group not having a polymerizable unsaturated bond-containing group to the indene compound to which the arylalkyl group having a polymerizable unsaturated bond-containing group has been added.

2. The method according to claim 1, wherein the content of the compound having one arylalkyl group per molecule in the arylalkylated indene composition is 1% or less as calculated from the area ratio in the GPC chart.

3. The production method according to claim 1, wherein the ratio of the number of moles of the arylalkyl group having a polymerizable unsaturated bond-containing group to the total number of moles of the arylalkyl group having a polymerizable unsaturated bond-containing group and the number of moles of the arylalkyl group not having a polymerizable unsaturated bond-containing group is in the range of 50 to 95%.

4. The method of claim 1, wherein the arylalkylated indene composition is a composition containing a plurality of compounds represented by the following general formula (1) that have different numbers of aryl alkyl groups per molecule: [In formula (1), R １ , R ２ and R ３ R each independently represents a hydrogen atom, an arylalkyl group having a polymerizable unsaturated bond-containing group, or an arylalkyl group not having a polymerizable unsaturated bond-containing group. ４ represents a monovalent substituent, and n is 0 or an integer of 1 to 4. When n is an integer of 2 or more, a plurality of R ４ may all be different, or some or all may be the same.] 5. A curable resin material comprising an arylalkylated indene composition obtained by the method according to any one of claims 1 to 4.

6. A prepreg comprising the curable resin material according to claim 5 or a semi-cured product of said curable resin material.

7. A resin film comprising the curable resin material according to claim 5 or a semi-cured product of the curable resin material.

8. A metal-clad laminate comprising a cured product of the curable resin material according to claim 5 and a metal foil.

9. A printed wiring board comprising a cured product of the curable resin material according to claim 5.

10. A semiconductor package comprising the printed wiring board according to claim 9 and a semiconductor element.

11. A semiconductor package comprising a semiconductor element and a cured product of the curable resin material according to claim 5 that encapsulates the semiconductor element.

12. A printed wiring board comprising at least one of a surface protection film and an interlayer insulating film formed from the curable resin material according to claim 5.

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