Polyfunctional vinylbenzyl compound, resin composition, prepreg, resin film, metal-clad laminate, printed wiring board, and semiconductor package

Abstract

The polyfunctional vinyl benzyl compound is obtained by reacting a compound having an aromatic fused ring, a compound having a biphenylene group, and a compound having a vinyl benzyl group. Also, a resin composition, a prepreg, a resin film, a metal-clad laminate, a printed wiring board, and a semiconductor package are obtained using the polyfunctional vinylbenzyl compound.

Description

Technical Field

[0001] The present invention relates to a multifunctional vinylbenzyl compound, a resin composition, a prepreg, a resin film, a metal-clad laminate, a printed wiring board and a semiconductor package. Background Art

[0002] Metal-clad laminates represented by copper-clad laminates, prepregs that can be used for metal-clad laminates, and semiconductor packages using metal-clad laminates are used in various electronic devices such as portable communication devices such as smartphones, personal computers, industrial computers, servers, large servers, routers, and portable base stations. In addition, they are also used in electronic devices installed in home appliances, automobiles, etc. Among them, the demand for electronic communication equipment to process large amounts of data at high speed has increased due to the popularization of 5G.

[0003] In electronic devices, when processing a large amount of data at high speed, substrate materials with low transmission loss in the high-frequency region are required. Substrate materials use resins with excellent dielectric properties to provide substrates with low transmission loss, but due to the development of communication technology in recent years, there is a demand for the development of resins with even better dielectric properties.

[0004] In recent years, as people's awareness of environmental issues has increased, environmental considerations are also indispensable for electronic devices and electronic components. Therefore, as additives in substrate materials, the demand for halogen-free phosphorus flame retardants has increased instead of the previous halogen-containing flame retardants. However, when a large amount of phosphorus flame retardants are included in the substrate material in order to improve flame retardancy, it is worried that the dielectric properties of the substrate material will be reduced.

[0005] Patent Document 1 proposes a resin composition comprising a modified polyphenylene ether compound, a cross-linking curing agent and a flame retardant as a resin composition having excellent heat resistance and flame retardancy of a cured product while maintaining the excellent dielectric properties of polyphenylene ether, wherein the flame retardant comprises a compatible phosphorus compound compatible with a mixture of the modified polyphenylene ether compound and the cross-linking curing agent and an incompatible phosphorus compound incompatible with the mixture.

[0006] Prior art literature

[0007] Patent Literature

[0008] Patent Document 1: Japanese Patent Application Publication No. 2015-86330 Summary of the invention

[0009] Problems to be solved by the invention

[0010] In the technology disclosed in patent document 1, by using compatible phosphorus compounds and incompatible phosphorus compounds as flame retardants, the hindrance of the curing reaction of modified polyphenylene ether compounds and cross-linking curing agents is suppressed, and the flame retardancy of cured products is improved. On the other hand, in the resin composition disclosed in patent document 1, the modified polyphenylene ether comprises a polyphenylene ether chain, and a substituent with a carbon-carbon unsaturated double bond replaces the hydrogen atom of a phenolic group and bonds with the oxygen atom of a phenolic group. Such modified polyphenylene ether comprises a large amount of ether bonds, and therefore may not be able to withstand the requirements of more stringent dielectric properties in recent years. In addition, in the technology disclosed in patent document 1, the flame retardancy of thermosetting resin itself is not studied.

[0011] An object of the present invention is to provide a multifunctional vinylbenzyl compound for providing a product showing high flame retardancy and excellent dielectric properties, a resin composition comprising the multifunctional vinylbenzyl compound, a prepreg, a resin film, a metal-clad laminate, a printed wiring board and a semiconductor package composed of the resin composition.

[0012] Means for solving problems

[0013] The present invention includes the following embodiments. However, the present invention is not limited to the following embodiments.

[0014] One embodiment relates to a polyfunctional vinylbenzyl compound obtained by reacting a compound having an aromatic fused ring, a compound having a biphenylene group, and a compound having a vinylbenzyl group.

[0015] Another embodiment relates to a multifunctional vinylbenzyl compound comprising a unit having an aromatic condensed ring and a unit having a biphenylene group,

[0016] The polyfunctional vinylbenzyl compound has a structure in which the aromatic condensed ring is bonded to two carbon atoms on the biphenylene ring directly or via a linking group, and the linking group is a divalent hydrocarbon group.

[0017] The polyfunctional vinylbenzyl compound has a vinylbenzyl group directly bonded to a carbon atom on the aromatic condensed ring.

[0018] Another embodiment relates to a polyfunctional vinylbenzyl compound, which is a compound represented by the following formula (1).

[0019] [Chemical formula 1]

[0020]

[0021] (In formula (1),

[0022] R 1 are each independently a monovalent group having 1 to 30 carbon atoms or a hydrogen atom,

[0023] R 2 Each independently represents a monovalent group having 1 to 30 carbon atoms, a hydrogen atom, or a bonding site to another structure,

[0024] X is each independently an alkylene group having 1 to 4 carbon atoms or a single bond,

[0025] n is an integer greater than or equal to 1.)

[0026] Effects of the Invention

[0027] According to the present invention, there can be provided a polyfunctional vinylbenzyl compound for providing a product showing high flame retardancy and excellent dielectric properties, a resin composition containing the polyfunctional vinylbenzyl compound, a prepreg composed of the resin composition, a resin film, a metal-clad laminate, a printed wiring board and a semiconductor package. DETAILED DESCRIPTION

[0028] Hereinafter, the present invention will be described in detail using several embodiments. However, the present invention is not limited to the following embodiments.

[0029] In the present invention, the numerical range represented by "~" indicates a range including the numerical values ​​recorded before and after "~" as the minimum value and the maximum value, respectively. In the numerical range recorded in stages in the present invention, the upper limit or lower limit of a certain numerical range can be replaced by the upper limit or lower limit of other numerical ranges. In addition, the upper limit or lower limit of the numerical range recorded in the present invention can be replaced by the value shown in the embodiment. In the present invention, unless otherwise specified, each component may contain one or more corresponding substances. In the present invention, regarding the content of each component in the resin composition, when there are multiple substances equivalent to each component in the resin composition, unless otherwise specified, it refers to the total amount of the multiple substances present in the resin composition.

[0030] In the present invention, unless otherwise specified, the weight average molecular weight (Mw) and number average molecular weight (Mn) of a polymer are values ​​measured by the following measurement methods.

[0031] The weight average molecular weight (Mw) and the number average molecular weight (Mn) were calculated by gel permeation chromatography (GPC) based on a calibration curve using standard polystyrene. The calibration curve used standard polystyrene: TSKstandard POLYSTYRENE (model: A-500, A-2500, A-5000, F-2, F-2, F-4, F-40, F-128, F-288) [manufactured by Tosoh Corporation, trade name], and was approximated by a cubic formula. The conditions of GPC are shown below.

[0032] Device: High-speed GPC device "HLC-8320GPC" (Tosoh Corporation, trade name)

[0033] Detector: Ultraviolet absorption detector "UV-8320" (Tosoh Corporation, trade name)

[0034] Column: guard column; TSKgel guardcolumn Super(HZ)-M+, column; TSKgel SuperMultiporeHZ-M (2 pieces), reference column; TSKgel SuperH-RC (2 pieces) (all Tosoh Corporation, trade names)

[0035] Column size: 4.6×20mm (guard column), 4.6×150mm (column), 6.0×150mm (reference column)

[0036] Eluent: Tetrahydrofuran

[0037] Sample concentration: 10mg / 1mL

[0038] Injection volume: 2μL

[0039] Flow rate: 0.35mL / min

[0040] Measurement temperature: 40℃

[0041] "Multifunctional vinylbenzyl compounds"

[0042] According to one embodiment, a multifunctional vinylbenzyl compound is provided, which is obtained by reacting a compound having an aromatic condensed ring, a compound having a biphenylene group, and a compound having a vinylbenzyl group.

[0043] The polyfunctional vinylbenzyl compound may contain a biphenyl skeleton, which is derived from the compound having a biphenylene group. The biphenyl skeleton is a thermally and chemically stable skeleton that is not easily decomposed even at high temperatures, and can improve the flame retardancy of a cured resin obtained using the polyfunctional vinylbenzyl compound.

[0044] In addition, the biphenyl skeleton, the aromatic fused ring derived from the compound having the aromatic fused ring, and the vinylbenzyl group derived from the compound having the vinylbenzyl group form a low polarity structure, which contributes to the low dielectric constant and low dielectric loss tangent of the resin cured product obtained using the multifunctional vinylbenzyl compound, and in particular, can achieve a low dielectric loss tangent in the high frequency band.

[0045] The polyfunctional vinylbenzyl compound contains an aromatic fused ring, which has a rigid structure and a low polarity structure. Therefore, in a resin cured product obtained using the polyfunctional vinylbenzyl compound, it can contribute to a low dielectric loss tangent particularly in a high frequency band.

[0046] (Compounds having aromatic condensed rings)

[0047] In the compound having an aromatic condensed ring, the number of the aromatic condensed ring is not particularly limited, and is preferably 2 to 5 rings. The aromatic condensed ring may be a condensed ring of two or more aromatic rings. In addition, the aromatic condensed ring only needs to have at least one aromatic ring, and may be a condensed ring of at least one aromatic ring and one or more alicyclic hydrocarbons. The aromatic condensed ring may be substituted or unsubstituted. As a substituent, an alkyl group or the like may be used. The alkyl group as a substituent may have 1 to 30, 1 to 12, or 1 to 4 carbon atoms, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, and the like.

[0048] The compound having an aromatic condensed ring preferably has 9 to 40 carbon atoms, more preferably 9 to 20 carbon atoms, and even more preferably 9 to 12 carbon atoms.

[0049] Examples of the compound having an aromatic condensed ring include compounds having an indene ring, an indane ring, a phenanthrene ring, an acenaphthylene ring, a fluorene ring, etc. At least one carbon atom of these aromatic condensed rings may have a substituent.

[0050] From the viewpoint of dielectric properties and flame retardancy, the compound having an aromatic condensed ring is preferably a compound having an indene ring and a derivative thereof, more preferably a substituted or unsubstituted indene, and still more preferably an unsubstituted indene.

[0051] The compound having an aromatic condensed ring can be used alone or in combination of two or more in the reaction of the polyfunctional vinylbenzyl compound.

[0052] (Compounds Having Biphenylene Group)

[0053] The unit derived from the compound having a biphenylene group can introduce a biphenylene group into the polyfunctional vinylbenzyl compound to contribute to flame retardancy. In addition, since the polyfunctional vinylbenzyl compound contains a unit having a biphenylene group, the dielectric properties of the cured product of the resin composition can be improved.

[0054] The compound having a biphenylene group is preferably a compound having one biphenylene group and two reactive groups. For example, the compound having a biphenylene group is preferably a compound having one biphenylene group and one reactive group on each of the two benzene rings of the biphenylene group, and more preferably a compound having one biphenylene group and one reactive group on each of the 4-position and 4'-position of the biphenylene group. As the reactive group, a haloalkyl group is preferred. The number of carbon atoms of the haloalkyl group is preferably 1 to 12, more preferably 1 to 8, and further preferably 1 to 4. The haloalkyl group is preferably a haloalkyl group in which at least one hydrogen atom of the alkyl group is substituted by a halogen atom, and the halogen atom is preferably a chlorine atom or a bromine atom, and the number of substitutions of the halogen atom is preferably 1. Examples of the haloalkyl group include chloromethyl, chloroethyl, bromomethyl, bromoethyl, and the like.

[0055] In the compound having a biphenylene group, the biphenylene group may be substituted or unsubstituted. As a substituent, an alkyl group or the like may be used. As a substituent, the alkyl group may have 1 to 30, 1 to 12, or 1 to 4 carbon atoms, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, etc. The compound having a biphenylene group may contain a functional group containing a heteroatom as a substituent, and from the viewpoint of dielectric properties, it is preferred that the functional group containing a heteroatom is not contained. Among them, the compound having a biphenylene group may contain a halogen atom contained as the above-mentioned reactive group.

[0056] It should be noted that the compound having a biphenylene group is a compound different from the compound having an aromatic fused ring, and is a compound not having an aromatic fused ring.

[0057] As the compound having a biphenylene group, 4,4'-bis(halogenated alkyl)biphenyl is preferably included. As the compound having a biphenylene group, for example, 4,4'-bis(chloromethyl)biphenyl, 3,4'-bis(chloromethyl)biphenyl, 3,3'-bis(chloromethyl)biphenyl, 4,4'-bis(bromomethyl)biphenyl, 3,4'-bis(bromomethyl)biphenyl, 3,3'-bis(bromomethyl)biphenyl, etc. can be mentioned.

[0058] The compound having a biphenylene group can be used alone or in combination of two or more in the reaction of the polyfunctional vinylbenzyl compound.

[0059] (Compound having a vinylbenzyl group)

[0060] The unit derived from the compound having a vinylbenzyl group can provide a polymerizable functional group in the multifunctional vinylbenzyl compound, which contributes to the thermosetting property. In addition, the multifunctional vinylbenzyl compound can also contribute to the dielectric properties and flame retardancy of the cured product of the resin composition by introducing a polymerizable functional group derived from the compound having a vinylbenzyl group.

[0061] In the polyfunctional vinylbenzyl compound, the vinylbenzyl group of the compound having the vinylbenzyl group is preferably bonded to the aromatic condensed ring of the compound having the aromatic condensed ring, and more specifically, the vinylbenzyl group of the compound having the vinylbenzyl group is preferably directly bonded to a carbon atom on the ring of the aromatic condensed ring of the compound having the aromatic condensed ring.

[0062] From such a viewpoint, the compound having a vinylbenzyl group is preferably a vinylbenzyl halide. The halogen atom of the vinylbenzyl halide is preferably a chlorine atom or a bromine atom.

[0063] For example, examples of the vinylbenzyl halide include vinylbenzyl chloride and vinylbenzyl bromide, and vinylbenzyl chloride is preferred.

[0064] The vinylbenzyl group may be any of o-vinylbenzyl, m-vinylbenzyl and p-vinylbenzyl, preferably m-vinylbenzyl or p-vinylbenzyl, and more preferably p-vinylbenzyl. For example, 4-vinylbenzyl chloride and the like may be mentioned. When a compound containing a p-vinylbenzyl group is used, a mixture of a compound containing a p-vinylbenzyl group and a compound containing a m-vinylbenzyl group may be used. In the mixture, the mass ratio of the compound containing a p-vinylbenzyl group to the compound containing a m-vinylbenzyl group may be 20 to 80 to 80:20, or 40:60 to 60:40.

[0065] In the compound having a vinylbenzyl group, the vinylbenzyl group may be substituted or unsubstituted. As a substituent, an alkyl group or the like may be used. The alkyl group as a substituent may have 1 to 30, 1 to 12, or 1 to 4 carbon atoms, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and sec-butyl.

[0066] It should be noted that the compound having a vinylbenzyl group is a compound different from the compound having an aromatic condensed ring and the compound having a biphenylene group, and is a compound having neither an aromatic condensed ring nor a biphenylene group.

[0067] The compound having a vinylbenzyl group can be used alone or in combination of two or more in the reaction of the polyfunctional vinylbenzyl compound.

[0068] The method for reacting a compound having an aromatic condensed ring, a compound having a biphenylene group, and a compound having a vinyl benzyl group is not particularly limited. For example, a compound having an aromatic condensed ring, a compound having a biphenylene group, and a compound having a vinyl benzyl group can be mixed, and the reaction can be carried out by heating and stirring as required. The reaction can be carried out in a solvent, and the solvent is not particularly limited, for example, it can be appropriately selected from the organic solvents exemplified as solvents for the resin composition described later. The reaction temperature is preferably 20 to 80° C. During the reaction, additives such as a phase transfer catalyst and an inhibitor can be further added to the mixture.

[0069] Phase transfer catalyst is used when the reaction system contains organic solvent and water. The organic solvent is preferably an organic solvent that does not show compatibility with water, and for example, toluene can be mentioned. As a phase transfer catalyst, for example, tetra-n-butylammonium chloride, tetra-n-butylammonium bromide, tetraethylammonium chloride, tetraethylammonium bromide, tetrapropylammonium chloride, tetrapropylammonium bromide, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltributylammonium chloride, benzyltributylammonium bromide, benzyldimethyltetradecylammonium chloride, trioctylmethylammonium chloride, tetradecyltrimethylammonium bromide, hexadecyltrimethylammonium bromide, trioctylmethylammonium chloride, tetra-n-butylammonium hydrogen sulfate and other quaternary ammonium salts can be mentioned; tetra-n-butylphosphonium chloride, tetra-n-butylphosphonium bromide, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, benzyltriphenylphosphonium chloride, benzyltriphenylphosphonium bromide and other quaternary phosphonium salts.

[0070] The phase transfer catalyst may be used alone or in combination of two or more.

[0071] The polymerization inhibitor is added to the reaction system to adjust the polymerization degree of the polyfunctional vinylbenzyl compound. 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, 4-tert-butylcatechol, pyrogallol, 4-methoxyphenol, thiophenol, 1,4-di-tert-butylphenol, 2,6-di-tert-butylphenol, cresol, catechol, 4-tert-butylcatechol, pyrogallol, 4-methoxyphenol, 1,4-di-tert-butylphenol, 2,4-di-tert-butylphenol, 2,6-di-tert-butylphenol, cresol, pyrocatechol, 4-tert-butylcatech ...2,4-di-tert-butylphenol, 2,6-di-tert-butylphenol, Diphenylamine, phenothiazine, 3,7-dioctylphenothiazine, 3,7-dicumylphenothiazine, 2,2,6,6-tetramethylpiperidin-1-oxyl free radical, 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl free radical, 4-benzoyloxy-2,2,6,6-tetramethylpiperidin-1-oxyl free radical, bis(2,2,6,6-tetramethyl-1-piperidinyloxy-4-yl)sebacate, and the like.

[0072] In addition, from the viewpoint of reaction control, the reaction can be carried out under alkalinity. For example, a basic compound can be added to the mixture. As the basic compound, alkali metal hydroxides, alkali metal alkoxides, etc. can be mentioned, specifically, sodium hydroxide, etc. can be mentioned.

[0073] The product obtained by the reaction can be purified by a known method such as concentration, reprecipitation, washing, etc., as necessary.

[0074] The polyfunctional vinylbenzyl compound preferably has a partial structure formed by bonding a compound with an aromatic condensed ring, a compound with biphenylene and a compound with vinylbenzyl, thereby having a unit (A) with an aromatic condensed ring and a unit (B) with biphenylene like ABA. In the partial structure of the ABA, it is more preferred that vinylbenzyl is bonded on the aromatic condensed ring of at least one of 2 A. For example, the polyfunctional vinylbenzyl compound is a compound shown in ABA, preferably a compound of vinylbenzyl bonded on the aromatic condensed ring of 2 A respectively. According to these structures, dielectric properties are improved, particularly low dielectric loss tangent, and flame retardancy can be obtained.

[0075] The polyfunctional vinylbenzyl compound may be a compound formed by reacting a compound having an aromatic condensed ring with a compound having a biphenylene group in an equimolar manner, or may be a compound formed by reacting a compound having a biphenylene group in an amount of 100 mole parts, 80 mole parts, 60 mole parts, or 50 mole parts or less relative to 100 mole parts of a compound having an aromatic condensed ring. More specifically, it may be a compound formed by reacting a compound having a biphenylene group in an amount of 10 to 100 mole parts, 20 to 80 mole parts, 30 to 60 mole parts, or 40 to 50 mole parts relative to 100 mole parts of a compound having an aromatic condensed ring. In the reaction, the degree of polymerization can be increased by increasing the proportion of the compound having a biphenylene group, but from the viewpoint of promoting the reaction, the proportion can be limited. It should be noted that when the molecular weight of the polyfunctional vinylbenzyl compound is small, the terminal structure is preferably a unit derived from a compound having an aromatic condensed ring. From this viewpoint, it is sufficient to satisfy the range of these molar ratios.

[0076] The polyfunctional vinylbenzyl compound may be a compound formed by reacting a compound having an aromatic condensed ring with a compound having a vinylbenzyl group in an equimolar ratio, or may be a compound formed by reacting a compound having a vinylbenzyl group in an amount of 200 mol parts or less, 140 mol parts or less, 120 mol parts or less, or 100 mol parts or less relative to 100 parts of the compound having an aromatic condensed ring. More specifically, it may be a compound formed by reacting a compound having a vinylbenzyl group in an amount of 50 to 200 mol parts, 60 to 140 mol parts, 80 to 120 mol parts, or 90 to 100 mol parts relative to 100 mol parts of the compound having an aromatic condensed ring. In the reaction, by introducing one or more vinylbenzyl groups to one aromatic condensed ring, the curing of the resin composition can be more favorably promoted.

[0077] (Another embodiment)

[0078] According to another embodiment, a multifunctional vinylbenzyl compound is provided, which includes a unit having an aromatic condensed ring and a unit having a biphenylene group, and has a structure in which two carbon atoms on the ring of the biphenylene group are respectively bonded to the aromatic condensed ring directly or via a connecting group, and the connecting group is a divalent hydrocarbon group, and the multifunctional vinylbenzyl compound has a vinylbenzyl group directly bonded to a carbon atom on the ring of the aromatic condensed ring.

[0079] In the polyfunctional vinylbenzyl compound, it is preferred that the unit having an aromatic condensed ring has an indene ring, and the vinylbenzyl group is directly bonded to at least one carbon atom at the 1-position, 2-position, and 3-position of the indene ring.

[0080] The polyfunctional vinylbenzyl compound of this embodiment is not limited to its synthesis method, and can be obtained, for example, by reacting the compound having an aromatic condensed ring, a compound having a biphenylene group, and a compound having a vinylbenzyl group.

[0081] (Another Implementation Method)

[0082] According to another embodiment, a polyfunctional vinylbenzyl compound is provided, which is a compound represented by the following formula (1).

[0083] [Chemical formula 2]

[0084]

[0085] (In formula (1),

[0086] R 1 are each independently a monovalent group having 1 to 30 carbon atoms or a hydrogen atom,

[0087] R 2Each independently represents a monovalent group having 1 to 30 carbon atoms, a hydrogen atom, or a bonding site to another structure,

[0088] X is each independently an alkylene group having 1 to 4 carbon atoms or a single bond,

[0089] n is an integer greater than or equal to 1.)

[0090] The polyfunctional vinylbenzyl compound of this embodiment is not limited by its synthesis method, and can be obtained by reacting substituted or unsubstituted indene, substituted or unsubstituted 4,4'-bis(halogenated alkyl)biphenyl and substituted or unsubstituted vinylbenzyl halide as described above. 1 or R 2 Represents the group.

[0091] In formula (1), R 1 Each R is independently a monovalent group having 1 to 30 carbon atoms or a hydrogen atom. 1 The monovalent group shown is preferably a saturated or unsaturated chain or cyclic hydrocarbon group. 1 The monovalent group shown may have 1 to 30, 1 to 12, or 1 to 4 carbon atoms. 1 The monovalent group shown may be an alkyl group, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, etc. In formula (1), a plurality of R 1 They may all be the same, or some or all may be different. 1 Preferably, some or all of them are hydrogen atoms.

[0092] In formula (1), R 2 Each independently represents a monovalent group having 1 to 30 carbon atoms, a hydrogen atom, or a bonding position to another structure. 2 Can be independently R 1 Alternatively, R 2 It may be a bonding site with a unit having a biphenyl group, a unit having a vinylbenzyl group, or the like. 2 They may all be the same, or some or all may be different. 2 Preferably, one or both are R 1 The group shown is more preferably a hydrogen atom.

[0093] In formula (1), X is independently an alkylene group having 1 to 4 carbon atoms or a single bond. For example, it is a methylene group, an ethylene group, a trimethylene group, an isopropylene group, an n-butylene group, an isobutylene group, a tert-butylene group, and a sec-butylene group. In formula (1), a plurality of Xs may be all the same, or some or all of them may be different. In formula (1), preferably some or all of Xs are methylene groups or single bonds, and more preferably methylene groups.

[0094] In formula (1), n ​​is an integer greater than or equal to 1. n is an integer and is preferably 1 to 10, more preferably 1 to 5, and more preferably 1 to 4. n may be 1. In formula (1), n ​​may be an integer appropriately determined according to the weight average molecular weight (Mw) of the polyfunctional vinylbenzyl compound described below.

[0095] In formula (1), the bonding site of the indene ring and the vinylbenzyl group is preferably the 1-position of the indene ring. In addition, the bonding site of the indene ring and X is preferably the 1-position or 2-position of the indene ring. In addition, the vinylbenzyl group may be any of o-vinylbenzyl, m-vinylbenzyl and p-vinylbenzyl, and p-vinylbenzyl is more preferred. In formula (1), it is preferred that a part or all of the vinylbenzyl groups are p-vinylbenzyl groups.

[0096] The polyfunctional vinylbenzyl compound represented by the formula (1) is preferably a compound including a partial structure represented by the following formula (2).

[0097] [Chemical formula 3]

[0098]

[0099] In formula (2), R 3 Each independently represents a monovalent group having 1 to 30 carbon atoms, a hydrogen atom, or a bonding position to another structure. 3 The details of R are as shown in formula (1) 2 The other structures are the same as those described in formula (1).

[0100] In formula (2), multiple R 3 They may all be the same, or may be partially or completely different. In formula (2), R 3 Preferably, one or both of them are R of formula (1) 1 The group shown is more preferably a hydrogen atom.

[0101] The polyfunctional vinylbenzyl compound represented by formula (1) comprises repeating units of units having aromatic condensed rings and units having biphenylene groups, so that in terms of molar ratio, the units having biphenylene groups may be 50 to 150 parts by mole, 50 to 100 parts by mole, 50 to 80 parts by mole, or 50 to 60 parts by mole relative to 100 parts of units having aromatic condensed rings. It should be noted that, when the molecular weight of the polyfunctional vinylbenzyl compound is small, the terminal structure is preferably a unit derived from a compound having an aromatic condensed ring. From this viewpoint, it is sufficient to satisfy the range of these molar ratios.

[0102] The polyfunctional vinylbenzyl compound represented by formula (1) comprises a structure in which a unit having a vinylbenzyl group is bonded to a unit having an aromatic condensed ring. Therefore, in terms of molar ratio, the unit having a vinylbenzyl group may be 50 to 200 parts by mole, 100 to 150 parts by mole, or 100 to 120 parts by mole relative to 100 parts of the unit having an aromatic condensed ring.

[0103] Hereinafter, the weight average molecular weight (Mw) of the polyfunctional vinylbenzyl compound will be described.

[0104] The weight average molecular weight (Mw) of the polyfunctional vinylbenzyl compound may be 100,000 or less, 50,000 or less, 10,000 or less, 5,000 or less, or 2,000 or less. Within these ranges, better solvent solubility and coating properties can be obtained in the state of the resin composition, and better moldability and flexibility can be obtained in the state of the coating film, semi-cured product, and cured product.

[0105] The weight average molecular weight (Mw) of the polyfunctional vinylbenzyl compound may be 400 or more, 500 or more, 800 or more, or 1,000 or more. Within these ranges, better solvent solubility and coating properties can be obtained in the state of the resin composition, and better moldability and flexibility can be obtained in the state of the coating film, semi-cured product, and cured product.

[0106] For example, the weight average molecular weight (Mw) of the polyfunctional vinylbenzyl compound may be 400 to 100,000, 400 to 50,000, 500 to 10,000, 800 to 5,000, or 1,000 to 2,000.

[0107] "Resin composition"

[0108] The resin composition of one embodiment includes a polyfunctional vinylbenzyl compound. The details of the polyfunctional vinylbenzyl compound are as described above.

[0109] The resin composition may contain a polyfunctional vinylbenzyl compound obtained by reacting a compound having an aromatic condensed ring, a compound having a biphenylene group, and a compound having a vinylbenzyl group. The polyfunctional vinylbenzyl compound may be contained as a reaction product. In this case, the resin composition may contain a plurality of polyfunctional vinylbenzyl compounds having different molecular weights and molecular structures.

[0110] The resin composition is not limited to the synthesis method of the multifunctional vinylbenzyl compound, and may also include a multifunctional vinylbenzyl compound, wherein the multifunctional vinylbenzyl compound includes a unit having an aromatic condensed ring and a unit having a biphenylene group, and has a structure in which two carbon atoms on the ring of the biphenylene group are respectively bonded to an aromatic condensed ring directly or via a connecting group, and the connecting group is a divalent hydrocarbon group, and the multifunctional vinylbenzyl compound has a vinylbenzyl group directly bonded to a carbon atom on the ring of the aromatic condensed ring, and may also include a compound represented by formula (1).

[0111] The resin composition containing such a polyfunctional vinylbenzyl compound can have excellent dielectric properties and flame retardancy in its cured product.

[0112] The resin composition may further contain at least one of a thermosetting resin and a thermoplastic resin as other resin component in addition to the polyfunctional vinylbenzyl compound.

[0113] As thermosetting resins, for example, epoxy resins, maleimide compounds, modified polyphenylene ether resins, phenolic resins, polyimide resins, cyanate resins, isocyanate resins, benzoxazine resins, oxetane resins, amino resins, unsaturated polyester resins, allyl resins, dicyclopentadiene resins, silicone resins, triazine resins, and melamine resins can be cited. When the thermosetting resin is heated in the presence of a polymerization initiator or the like as required, it can be polymerized and / or cured. The thermosetting resin can be used alone or in combination of two or more.

[0114] As a thermoplastic resin, an elastomer can be included. Elastomers include diene elastomers, olefin elastomers, polysulfide elastomers, silicone elastomers, fluorine elastomers, urethane elastomers, ether elastomers, etc. In more detail, as diene elastomers, styrene butadiene rubber (SBR), butadiene rubber (BR), styrene isoprene rubber, isoprene rubber (IR), chloroprene rubber (CR), acrylonitrile butadiene rubber (NBR), etc. can be mentioned. As olefin elastomers, butyl rubber (IIR), ethylene propylene rubber, ethylene vinyl acetate rubber, chlorosulfonated polyethylene, acrylic rubber, etc. can be mentioned. These elastomers can be non-hydrogenated or hydrogenated. Elastomers can be used alone or in combination of two or more.

[0115] The polyfunctional vinylbenzyl compound may be 10 to 100 mass %, 30 to 90 mass %, 50 to 80 mass %, or 60 to 80 mass % relative to the total mass of the resin components of the resin composition. In the present invention, the total mass of the resin components of the resin composition is the total mass of the polymer, and the polymerizable oligomers and monomers.

[0116] The total mass of the polyfunctional vinylbenzyl compound and other thermosetting resins may be 10 to 100 mass %, 30 to 90 mass %, 50 to 80 mass %, or 60 to 80 mass % relative to the total mass of the resin components of the resin composition.

[0117] The total mass of the thermoplastic resin may be 1 to 90 mass %, 10 to 70 mass %, or 20 to 50 mass % relative to the total mass of the resin components of the resin composition.

[0118] The total mass of the resin components may be 10 to 80 mass %, 30 to 70 mass %, or 40 to 60 mass % relative to the total mass of the resin composition.

[0119] The resin composition may be a solvent-free composition, but may also contain a solvent. The solvent can adjust the viscosity of the resin composition and further improve the coating property. As the solvent, an organic solvent is preferred.

[0120] Examples of the organic solvent include alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, ethylene glycol monobutyl ether, and propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether solvents such as tetrahydrofuran; aromatic hydrocarbon solvents such as toluene, xylene, and mesitylene; nitrogen-containing solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone; sulfur-containing solvents such as dimethyl sulfoxide; ester solvents such as γ-butyrolactone, etc. The organic solvent may be used alone or in combination of two or more.

[0121] When the resin composition contains a solvent, the solid content of the components other than the solvent may be 10 to 80 mass %, 30 to 70 mass %, or 40 to 60 mass % relative to the total mass of the resin composition. It should be noted that the solvent does not contain a compound containing a polymerizable functional group.

[0122] The resin composition may contain an inorganic filler as an optional component. Examples of the inorganic filler include silicon dioxide (SiO2), aluminum oxide (Al2O3), 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, beryllium oxide, clay, talc, and the like.

[0123] The shape and size of the inorganic filler are not particularly limited. The average particle size of the inorganic filler can be, for example, 0.01 to 20 μm, or 0.1 to 10 μm. Here, the average particle size of the inorganic filler is the particle size corresponding to the point of 50% of the cumulative value in the volume-based particle distribution based on the laser diffraction scattering method.

[0124] The inorganic filler can be used alone or in combination of two or more.

[0125] The content of the inorganic filler may be 10 to 80% by volume, 30 to 70% by volume, or even 50 to 60% by volume based on the solid content of the resin composition.

[0126] The resin composition may further contain a curing catalyst in order to accelerate the curing of the polyfunctional vinylbenzyl compound.

[0127] As a curing catalyst, a free radical polymerization initiator can be used. As the free radical polymerization initiator, it can be a thermal free radical polymerization initiator, it can also be a photo free radical polymerization initiator, preferably a thermal free radical polymerization initiator. The free radical polymerization initiator is not particularly limited, and an azo-based polymerization initiator, an organic peroxide-based polymerization initiator, etc. can be mentioned.

[0128] The amount of the curing catalyst used may be appropriately adjusted, and for example, may be 0.01 to 5 parts by mass, 0.1 to 4 parts by mass, or 0.5 to 2 parts by mass relative to 100 parts by mass of the polyfunctional vinylbenzyl compound.

[0129] The resin composition may further include a flame retardant.

[0130] Examples of the flame retardant include phosphorus-based flame retardants, metal hydrates, and halogen-based flame retardants. From the viewpoint of environmental issues, phosphorus-based flame retardants are preferred.

[0131] The phosphorus-based flame retardant may be any of an inorganic phosphorus-based flame retardant and an organic phosphorus-based flame retardant, but an organic phosphorus-based flame retardant is preferred.

[0132] Examples of the inorganic phosphorus flame retardant include red phosphorus; ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate; inorganic nitrogen-containing phosphorus compounds such as phosphoric acid amide; phosphoric acid; and phosphine oxide.

[0133] Examples of organic phosphorus flame retardants include aromatic phosphates, monosubstituted phosphonic acid diesters, disubstituted phosphinates, metal salts of disubstituted phosphinic acids, organic nitrogen-containing phosphorus compounds, cyclic organic phosphorus compounds, etc. Examples of metal salts of disubstituted phosphinic acids include lithium salts, sodium salts, potassium salts, calcium salts, magnesium salts, aluminum salts, titanium salts, zinc salts, etc.

[0134] The flame retardant may be contained in an amount of 0.1 to 30 parts by mass, 1 to 20 parts by mass, or 5 to 10 parts by mass based on 100 parts by mass of the total mass of the resin components of the resin composition.

[0135] The resin composition may further contain additives other than the above components within a range that does not impair the effects of the present invention. Examples of the additives include curing accelerators, antioxidants, heat stabilizers, antistatic agents, ultraviolet absorbers, pigments, colorants, lubricants, and the like.

[0136] The method for producing the resin composition is not particularly limited. As an example of the method for producing the resin composition, any component can be added to the multifunctional vinyl benzyl compound as needed and mixed to obtain the resin composition. In more detail, the multifunctional vinyl benzyl compound is dissolved or dispersed in a solvent, and additives are added and mixed as needed to obtain the resin composition. The mixing order, temperature, time and other conditions of each component are not particularly limited, and can be appropriately adjusted according to the type of raw materials, manufacturing scale, manufacturing equipment, etc.

[0137] The heated residue amount ratio of the cured product of the resin composition, represented by the mass after heating at 800° C. relative to the mass before heating, is preferably 25% by mass or more, more preferably 28% by mass or more, and further preferably 30% by mass or more. Within these ranges, a product with excellent flame retardancy can be provided.

[0138] In particular, in a cured product of a resin composition containing a polyfunctional vinylbenzyl compound and containing no other solid components, the heating residue amount ratio is preferably within the above range.

[0139] In the present invention, the heating residue ratio of the cured product of the resin composition can be measured by measuring the heating residue ratio of the cured product of the resin composition under a nitrogen flow (100 ml·min -1 ), heating rate (10℃·min -1 ) is obtained by heating the cured product of the resin composition to 800° C. under the conditions of TG / DTA. For example, a TG / DTA device manufactured by Hitachi High-Tech Science Co., Ltd. can be used as a measuring device.

[0140] The test piece for measuring the heating residual amount is a test piece in which the resin composition is cured to a C-stage state in JIS K6800 (1985). Specifically, it can be prepared in the following manner: the resin composition is semi-cured to a B-stage state, a resin powder is prepared by crushing the semi-cured material, the resin powder is filled into a forming mold, and vacuum heating and pressing are performed under the conditions of a temperature of 150°C, a pressure of 1.5 to 2.0 MPa, and a time of 120 minutes, and further heat forming is performed under the conditions of a temperature of 180°C and a time of 300 minutes to form a plate-shaped cured product with a thickness of 1 mm.

[0141] The dielectric loss tangent (Df) of the cured product of the resin composition at 25°C and 10 GHz is preferably 0.0020 or less, more preferably 0.0019 or less, and further preferably 0.0017 or less. The lower the dielectric loss tangent (Df) of the cured product of the resin composition at 25°C and 10 GHz, the more preferred it is, and the lower limit thereof is not particularly limited, and in consideration of the balance with other physical properties, it may be, for example, 0.0001 or more, 0.0005 or more, or 0.0010 or more.

[0142] For example, the dielectric loss tangent (Df) of the cured product of the resin composition at a measurement temperature of 25° C. and a frequency of 10 GHz is preferably 0.0001 to 0.0020, 0.0005 to 0.0019, or 0.0010 to 0.0017.

[0143] The relative dielectric constant (Dk) of the cured product of the resin composition at 25°C and 10 GHz is preferably 4.0 or less, more preferably 3.0 or less, further preferably 2.7 or less, and further preferably 2.6 or less. The lower the relative dielectric constant (Dk) of the cured product of the resin composition at 25°C and 10 GHz, the more preferred it is. The lower limit is not particularly limited, and in consideration of the balance with other physical properties, it may be, for example, 2.3 or more, or 2.4 or more.

[0144] For example, the relative dielectric constant (Dk) of the cured product of the resin composition at a measurement temperature of 25° C. and a frequency of 10 GHz is preferably 2.3 to 4.0, 2.3 to 3.0, 2.4 to 2.7, or 2.4 to 2.6.

[0145] In particular, in a cured product of a resin composition containing a polyfunctional vinylbenzyl compound and containing no other solid components, the dielectric loss tangent (Df) and relative dielectric constant (Dk) at 25° C. and 10 GHz are preferably within the above ranges.

[0146] In the present invention, dielectric loss tangent (Df) and relative dielectric constant (Dk) are measured by cavity resonator perturbation method in 10 GHz band at 25° C. A measurement device can be “PNA Network Analyzer N5222B” (trade name) manufactured by Agilent Technologies.

[0147] The test piece for measuring the dielectric loss tangent (Df) and the relative dielectric constant (Dk) is a test piece in which the resin composition is cured to a C-stage state in JIS K 6800 (1985). Specifically, it can be prepared in the following manner: the resin composition is semi-cured to a B-stage state, a resin powder obtained by crushing the semi-cured material is prepared, the resin powder is filled into a forming mold, and vacuum heating and pressing is performed under the conditions of a temperature of 150°C, a pressure of 1.5 to 2.0 MPa, and a time of 120 minutes, and further heat-formed under the conditions of a temperature of 180°C and 300 minutes to form a plate-shaped cured product with a thickness of 1 mm.

[0148] "Prepreg"

[0149] According to one embodiment, a prepreg formed using a resin composition and a fiber base material can be provided. The details of the resin composition are as described above.

[0150] Prepreg refers to an article in which a fiber substrate is impregnated with a resin composition. In the prepreg, the resin composition may be in an uncured state, but the resin composition may also be partially or completely in a semi-cured state. For example, a molded product such as a laminate is assembled using the prepreg, and cured by heat treatment or the like to obtain a cured product.

[0151] Prepregs can be obtained, for example, by applying a resin composition to a fiber substrate and drying it. In other methods, prepregs can be obtained by impregnating a fiber substrate with a resin composition and drying the fiber substrate impregnated with the resin composition. Drying is preferably performed at a temperature above the temperature at which volatile components such as solvents that may be contained in the resin composition are removed, and may also be performed at a temperature above the temperature at which the resin composition contained in the resin composition is semi-cured, depending on the application. In addition, drying can be adjusted in a manner that the resin composition is not completely cured. From this point of view, the drying temperature can be 80 to 200°C, and the drying time can be 1 to 30 minutes depending on the drying temperature and the drying device, its scale, etc.

[0152] In the present invention, as one index of the semi-cured product, the B-stage state in JIS K 6800 (1985) can be cited.

[0153] The fiber substrate can be any of woven fabrics, knitted fabrics and non-woven fabrics. The fiber substrate can be provided in the form of chopped strand mats, rovings, etc. As the material of the fiber, it can be any of inorganic fibers and organic fibers. As inorganic fibers, glass fibers, carbon fibers, etc. can be mentioned. As glass fibers, E glass, NE glass, D glass, S glass, Q glass, etc. can be mentioned. As organic fibers, polyimide, polyester, tetrafluoroethylene, etc. can be mentioned. The fiber substrate can be a single fiber among them, or it can be a blended fiber of two or more of them. From the viewpoint of dielectric properties and flame retardancy, the fiber substrate is preferably an inorganic fiber, more preferably a glass fiber. The heat resistance and dimensional stability of the prepreg using inorganic fibers are also excellent.

[0154] The fiber substrate can be appropriately selected according to the purpose of the prepreg, and a sheet-like fiber substrate is preferred. As the sheet-like fiber substrate, for example, various sheet-like fiber substrates used in known laminated boards for electrical insulating materials can be used. The thickness of the sheet-like fiber substrate is not particularly limited, and for example, it is preferably 0.02 to 0.5 mm. Here, the thickness is the thickness measured at 5 points at equal distances on the entire surface of the sheet-like fiber substrate, and is set as the arithmetic mean of the 5 points.

[0155] In the prepreg, the total mass of the thermosetting resin and the thermoplastic resin containing the multifunctional vinylbenzyl compound can be 20 to 90% by mass, or 30 to 80% by mass relative to the total mass of the prepreg. If it is within these ranges, the resin can be more easily impregnated into the fiber substrate in the prepreg. In addition, the process of assembling the prepreg into a molded product and curing it can be more easily performed.

[0156] "Resin film"

[0157] According to one embodiment, a resin film formed using the resin composition can be provided. The details of the resin composition are as described above.

[0158] Resin film refers to an article in which a resin composition is formed into a film-like state. In the resin film, the resin composition can be in an uncured state, but the resin composition can also be partially or completely in a semi-cured state. By using heat treatment etc. to cure the resin film, a cured product can be obtained.

[0159] The resin film can be obtained, for example, by applying a resin composition to a coated material and drying it. Drying can be performed in the same manner as in the above-mentioned method for manufacturing the prepreg. It is also possible to provide a product in the form of a combination of the resin film and the coated material after drying the resin film on the coated material. For example, in this method, a resin film can be provided in order to form an insulating layer on the coated material in an electronic device, etc. In other methods, it is also possible to provide the resin film as a product by peeling the resin film from the coated material after drying the resin film on the coated material.

[0160] As the coated material, it can be any of an inorganic substrate and an organic substrate, and can include metal substrates such as glass substrates, metal foils, metal plates, plastic substrates such as plastic plates, plastic films, paper substrates, etc. The coated material can be the fiber substrate described in the above-mentioned prepreg, or it can be a prepreg. In order to provide the resin film peeled off from the coated material, the coated material having a release layer formed on the surface can be used.

[0161] "Metal-clad laminate"

[0162] According to one embodiment, a metal-clad laminate formed using a prepreg and a metal foil can be provided. According to another embodiment, a metal-clad laminate comprising a resin cured material layer and a metal foil can be provided. The resin cured material layer can be a cured material of a resin composition or a cured material of a prepreg. The details of the resin composition and the prepreg are as described above.

[0163] The metal-clad laminate preferably comprises a resin cured material layer containing a resin cured material and a metal foil formed on at least one side of the resin cured material layer. The resin cured material layer comprises a cured material of a resin composition, but may also be a cured material of the above-mentioned prepreg. As a more useful application, a metal foil is formed on at least one side of the cured material of the prepreg, and more preferably a metal foil is formed on both sides of the cured material of the prepreg. The metal-clad laminate can be manufactured by forming a metal foil on at least one side of a sheet-like prepreg, or by stacking more than two sheet-like prepregs and forming a metal foil on at least one side of the outermost surface of the laminate. As a more useful application, the metal-clad laminate is a laminate manufactured by stacking more than two sheet-like prepregs and forming a metal foil on both sides of the laminate. Specifically, for example, a metal foil can be configured on one or both sides of a sheet-like prepreg, and then heated and pressed to form. By this heated and pressed forming, the curing reaction of the sheet-like prepreg is carried out, and a metal-clad laminate containing a cured material of the prepreg can be obtained. When performing heat and pressure forming, only one prepreg may be used, or two or more prepregs may be stacked and used. Heat and pressure forming may be performed using, for example, an autoclave forming machine, a multi-stage press machine, a multi-stage vacuum press machine, a continuous forming machine, etc. The conditions for heat and pressure forming are not particularly limited, and may be, for example, a temperature of 100 to 300° C., a time of 10 to 300 minutes, and a pressure of 1.5 to 5 MPa.

[0164] The metal of 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, it can be a single metal of copper, nickel, or aluminum. By using copper as the metal foil, a copper-clad laminate can be provided.

[0165] In the assembled metal-clad laminate, the dielectric properties of the cured resin in the state where the metal foil is removed (also referred to as the dielectric properties of the metal-clad laminate) are preferably as follows. By using a resin composition containing a multifunctional vinylbenzyl compound according to one embodiment, a metal-clad laminate having excellent dielectric properties can be provided.

[0166] The dielectric loss tangent (Df) of the metal-clad laminate at a measurement temperature of 25° C. and a frequency of 10 GHz is preferably 0.0001 to 0.0020, 0.0005 to 0.0019, or 0.0010 to 0.0017.

[0167] The relative dielectric constant (Dk) of the metal-clad laminate at a measurement temperature of 25° C. and a frequency of 10 GHz is preferably 2.3 to 4.0, 2.3 to 3.0, 2.4 to 2.7, or 2.4 to 2.6.

[0168] The dielectric loss tangent (Df) and relative dielectric constant (Dk) of the metal-clad laminate may be measured in the same manner as the dielectric loss tangent (Df) and relative dielectric constant (Dk) of the cured product of the above-mentioned resin composition.

[0169] "Printed Circuit Board"

[0170] According to one embodiment, a printed wiring board including a cured product of a resin composition can be provided. The details of the resin composition are as described above.

[0171] In a printed wiring board, the cured product of a resin composition can be manufactured by using a resin composition, a prepreg, a resin film, a metal-clad laminate or a combination thereof. For example, as a substrate of a printed wiring board, a metal-clad laminate comprising a cured product of a resin composition is used, and a conductor circuit is formed by a known method, thereby providing a printed wiring board. Details about prepreg, resin film and metal-clad laminate are as described above. The printed wiring board can be any of a single-layer printed wiring board and a multilayer printed wiring board.

[0172] "Semiconductor Package"

[0173] According to one embodiment, a semiconductor package can be provided, which includes a printed circuit board and a semiconductor element containing a resin cured product, and the resin cured product is a cured product of a resin composition. The details of the resin composition are as described above. The details of the cured product of the resin composition and the printed circuit board are as described above. The semiconductor package can be manufactured, for example, by mounting a semiconductor element, a memory, etc. on a printed circuit board using a known method. As an insulating material, a sealing material, etc. of a semiconductor package, a cured resin can be used.

[0174] Examples of the embodiments are given below, but the present invention is not limited to the following embodiments.

[0175] <1> A polyfunctional vinylbenzyl compound obtained by reacting a compound having an aromatic condensed ring, a compound having a biphenylene group, and a compound having a vinylbenzyl group.

[0176] <2> according to <1> The polyfunctional vinylbenzyl compound described in , wherein the compound having an aromatic condensed ring contains indene.

[0177] <3> according to <1> or <2> The polyfunctional vinylbenzyl compound described in , wherein the compound having a biphenylene group includes 4,4'-bis(halogenated alkyl)biphenyl.

[0178] <4> according to <1> ~ <3> The polyfunctional vinylbenzyl compound according to any one of the above, wherein the compound having a vinylbenzyl group comprises a vinylbenzyl halide.

[0179] <5> A multifunctional vinylbenzyl compound comprising a unit having an aromatic condensed ring and a unit having a biphenylene group,

[0180] The polyfunctional vinylbenzyl compound has a structure in which the aromatic condensed ring is bonded to two carbon atoms on the biphenylene ring directly or via a linking group, and the linking group is a divalent hydrocarbon group.

[0181] The polyfunctional vinylbenzyl compound has a vinylbenzyl group directly bonded to a carbon atom on the aromatic condensed ring.

[0182] <6> according to <5> The polyfunctional vinylbenzyl compound described in , wherein the unit having an aromatic condensed ring has an indene ring,

[0183] The vinylbenzyl group is directly bonded to at least one carbon atom among the 1-position, 2-position and 3-position of the indene ring.

[0184] <7> A polyfunctional vinylbenzyl compound is a compound represented by the following formula (1).

[0185] [Chemical formula 4]

[0186]

[0187] (In formula (1),

[0188] R 1 are each independently a monovalent group having 1 to 30 carbon atoms or a hydrogen atom,

[0189] R 2Each independently represents a monovalent group having 1 to 30 carbon atoms, a hydrogen atom, or a bonding site to another structure,

[0190] X is each independently an alkylene group having 1 to 4 carbon atoms or a single bond,

[0191] n is an integer greater than or equal to 1.)

[0192] <8> according to <7> The polyfunctional vinylbenzyl compound described in contains a partial structure represented by the following formula (2).

[0193] [Chemical formula 5]

[0194]

[0195] (In formula (2), R 3 Each is independently a monovalent group having 1 to 30 carbon atoms, a hydrogen atom, or a bonding position to another structure.)

[0196] <9> A resin composition comprising the above <1> ~ <8> The polyfunctional vinylbenzyl compound according to any one of the above.

[0197] <10> according to <9> The resin composition described in , wherein the cured product of the resin composition has a heating residue amount ratio represented by the mass after heating at 800° C. relative to the mass before heating of 25% by mass or more.

[0198] <11> according to <9> or <10> The resin composition described in , wherein the dielectric loss tangent of the cured product of the resin composition is 0.0001 to 0.0020 at a measurement temperature of 25° C. and a frequency of 10 GHz.

[0199] <12> A prepreg comprising the above <1> ~ <8> The present invention is formed by a resin composition of a polyfunctional vinylbenzyl compound as described in any one of claims 1 to 5 and a fiber substrate.

[0200] <13> A metal-clad laminated plate, which is made by using the above <12> It is formed by prepreg and metal foil.

[0201] <14> A resin film comprising the above <1> ~ <8> The present invention is formed by a resin composition comprising a polyfunctional vinylbenzyl compound as described in any one of the above.

[0202] <15> A printed circuit board comprising the above <1> ~ <8> A cured product of a resin composition comprising a polyfunctional vinylbenzyl compound as described in any one of the above.

[0203] <16> A semiconductor package comprising a printed circuit board containing a cured resin and a semiconductor element,

[0204] The above-mentioned cured resin comprises <1> ~ <8> A cured product of a resin composition comprising a polyfunctional vinylbenzyl compound as described in any one of the above.

[0205] Example

[0206] Hereinafter, specific examples of the present invention will be described by way of examples, but the present invention is not limited to the following examples.

[0207] "Method for determining weight average molecular weight (Mw)"

[0208] The weight average molecular weight (Mw) is measured according to the following procedure.

[0209] The weight average molecular weight (Mw) is converted by gel permeation chromatography (GPC) based on a calibration curve using standard polystyrene. The calibration curve uses standard polystyrene: TSKstandard POLYSTYRENE (model; A-500, A-2500, A-5000, F-2, F-2, F-4, F-40, F-128, F-288) [manufactured by Tosoh Corporation, trade name], and is approximated by a cubic formula. The measurement conditions of GPC are shown below.

[0210] Device: High-speed GPC device HLC-8320GPC

[0211] Detector: UV-8320 ultraviolet absorption detector [manufactured by Tosoh Corporation]

[0212] Column: guard column; TSKgel1guardcolumn Super(HZ)-M+ column; TSKgel SuperMultipore HZ-M (2 pieces), reference column; TSKgel SuperH-RC (2 pieces) (all manufactured by Tosoh Corporation, trade names)

[0213] Column size: 4.6×20mm (guard column), 4.6×150mm (column), 6.0×150mm (reference column)

[0214] Eluent: Tetrahydrofuran

[0215] Sample concentration: 10mg / 1mL

[0216] Injection volume: 2μL

[0217] Flow rate: 0.35mL / min

[0218] Measuring temperature: 40℃

[0219] "Preparation of multifunctional vinylbenzyl compounds"

[0220] (Production Examples 1 to 4)

[0221] The formulation of the polyfunctional vinylbenzyl compound is shown in Table 1. The blending amounts shown in the table are parts by mass.

[0222] In a 500 mL reaction container equipped with a stirring device, a thermometer, a reflux tube and a nitrogen blowing port, indene, 4,4'-bis(chloromethyl)biphenyl, chloromethylstyrene, a phase transfer catalyst, a polymerization inhibitor, pure water and toluene as a solvent in the amounts shown in Table 1 were placed, and nitrogen was blown in at a flow rate of 50 ml / min while heating and stirring at 40°C.

[0223] Next, an aqueous sodium hydroxide (NaOH) solution (Kanto Chemical Co., Ltd.) having a concentration of 48% by mass as an alkaline compound in an amount shown in Table 1 was added dropwise over 20 minutes, and the mixture was further stirred at 60° C. for 9 hours. It should be noted that nitrogen was continuously blown in during the reaction. After cooling to room temperature (25° C.) and neutralizing with a 10% aqueous hydrochloric acid solution, the mixture was washed three times with pure water, and then the organic phase was precipitated in methanol to obtain polyfunctional vinylbenzyl compounds 1 to 4.

[0224] As chloromethylstyrene, “CMS-P” (trade name; a mixture of meta-form and para-form, with a meta-form content of about 50% by mass and a para-form content of about 50% by mass) produced by AGC Seimi Chemical Co., Ltd. was used.

[0225] As the phase transfer catalyst, tetra-n-butylammonium bromide (Kanto Chemical Co., Ltd.) was used.

[0226] Phenothiazine was used as the polymerization inhibitor.

[0227] Table 1 shows the weight average molecular weights (Mw) of the polyfunctional vinylbenzyl compounds 1 to 4.

[0228] [Table 1]

[0229] [Table 1] Formulation and weight average molecular weight (Mw) of multifunctional vinylbenzyl compounds

[0230] Manufacturing example number 1 2 3 4 Numbering of polyfunctional vinylbenzyl compounds 1 2 3 4 Indole 44.7 34.6 37.8 36.2 4,4'-Bis(chloromethyl)biphenyl 40.5 45.8 41.7 32.0 Chloromethylstyrene 54.4 46.4 60.9 68.0 Phase transfer catalyst 9.0 7.7 8.4 8.0 Pure water 1.8 1.8 1.8 1.8 Inhibitor 0.2 0.2 0.2 0.2 Toluene 99-2 134.6 99.4 96-3 NaOH aqueous solution (concentration 48 mass%) 107.1 100.6 110.0 105.3 Weight average molecular weight (Mw) 1,000 1,900 1,200 800

[0231] (Examples 1 to 4)

[0232] The polyfunctional vinylbenzyl compounds 1 to 4 obtained in the production examples were respectively dissolved in toluene to obtain resin compositions of Examples 1 to 4 having a solid content concentration of about 60% by mass.

[0233] (Comparative Examples 1 to 3)

[0234] In Comparative Examples 1 to 3, the following compounds 1 to 3 were respectively dissolved in toluene to obtain resin compositions of Comparative Examples 1 to 3 having a solid content concentration of approximately 60% by mass.

[0235] Compound 1: 1-vinyl-4-[2-(4-vinylphenyl)ethyl]benzene (Shandong Xingshun New Materials Co., Ltd.).

[0236] Compound 2: a benzyl-type vinylbenzyl-modified resin (Nippon Kayaku Co., Ltd., trade name: STR-2000).

[0237] Compound 3: a vinylbenzyl-modified resin of an oligophenylene ether (Mitsubishi Gas Chemical Co., Ltd., trade name: OPE-2St).

[0238] The structural formulas of Compounds 1 to 3 are shown below.

[0239] [Chemical formula 6]

[0240]

[0241] [Chemical formula 7]

[0242]

[0243] [Chemical formula 8]

[0244]

[0245] "Production of resin sheets"

[0246] Each of the resin compositions obtained above was applied to a polyethylene terephthalate (PET) film (manufactured by Teijin Co., Ltd., trade name: G2000) having a thickness of 38 μm, and heated and dried at 110° C. for 5 minutes to prepare a resin film in a B-stage state. The resin film was peeled off from the PET film and then crushed to prepare a resin powder. It should be noted that since compound 1 was a powder, it was not heated and dried and crushed, and was used as a resin powder.

[0247] Next, the resin powder was placed in a Teflon (registered trademark) sheet cut into a size of 1 mm thick × 50 mm long × 30 mm wide, and a low-profile copper foil (manufactured by Mitsui Mining & Smelting Co., Ltd., trade name: SI-VSP) with a thickness of 18 μm was placed on the upper and lower sides thereof in a state where the S surface (glossy surface) was in contact with the resin powder. Next, vacuum heating and pressure molding was performed under the conditions of a temperature of 150° C., a pressure of 1.5 to 2.0 MPa, and a time of 120 minutes, and further heat molding was performed under the conditions of a temperature of 180° C. and 300 minutes, thereby curing the resin composition. Then, the copper foils on both sides were removed, thereby obtaining a resin plate (resin plate thickness: 1 mm).

[0248] "Evaluation Method"

[0249] The following evaluations were performed using the resin plates obtained above.

[0250] (Dielectric loss tangent (Df))

[0251] The resin plate obtained above was cut to prepare a test piece of 1 mm×50 mm. Next, the dielectric loss tangent (Df) of the test piece was measured at an ambient temperature of 25° C. in a 10 GHz frequency band by a cavity resonator perturbation method.

[0252] Measurement device: PNA Network Analyzer N5222B from Agilent Technologies

[0253] (Heating residue ratio)

[0254] The resin plate obtained above was cut out as a test piece. Using a TG / DTA apparatus, the sample was analyzed under a nitrogen flow (100 ml min -1 ), heating rate (10℃·min -1 ) under the condition of heating the test piece to 800° C. The heating residue amount ratio (mass %) was determined from the ratio of the mass of the test piece after heating to the mass of the test piece before heating.

[0255] Measurement device: Hitachi High-Tech Science's "TG / DTA7300"

[0256] [Table 2]

[0257] [Table 2] Evaluation results

[0258]

[0259] As shown in the table, it can be seen that Examples 1 to 4 all exhibit high flame retardancy due to a large heating residue amount ratio, and exhibit excellent dielectric properties due to a low dielectric loss tangent (Df).

[0260] The disclosure of this application is related to the subject matter described in Japanese Special Application No. 2023-074727 filed on April 28, 2023, and all of their disclosures are incorporated herein by reference. It should be noted that in addition to the contents already described, various modifications and changes may be made to the above-mentioned embodiments without departing from the novel and advantageous features of the present invention. Therefore, all such modifications and changes are included in the attached technical solutions.

Claims

1. A polyfunctional vinylbenzyl compound obtained by reacting a compound having an aromatic condensed ring, a compound having a biphenylene group, and a compound having a vinylbenzyl group.

2. The multifunctional vinylbenzyl compound according to claim 1, wherein The compound having an aromatic condensed ring includes indene.

3. The multifunctional vinylbenzyl compound according to claim 1, wherein The compound having a biphenylene group includes 4,4'-bis(halogenated alkyl)biphenyl.

4. The multifunctional vinylbenzyl compound according to claim 1, wherein The compound having a vinylbenzyl group includes a vinylbenzyl halide.

5. A polyfunctional vinylbenzyl compound comprising a unit having an aromatic condensed ring and a unit having a biphenylene group, The polyfunctional vinylbenzyl compound has a structure in which the aromatic condensed ring is bonded to two carbon atoms on the biphenylene ring directly or via a linking group, and the linking group is a divalent hydrocarbon group. The polyfunctional vinylbenzyl compound has a vinylbenzyl group directly bonded to a carbon atom on the aromatic condensed ring.

6. The multifunctional vinylbenzyl compound according to claim 5, wherein The unit having an aromatic condensed ring has an indene ring, The vinylbenzyl group is directly bonded to at least one carbon atom among the 1-position, 2-position and 3-position of the indene ring.

7. A polyfunctional vinylbenzyl compound, which is a compound represented by the following formula (1), In formula (1), R 1 are each independently a monovalent group having 1 to 30 carbon atoms or a hydrogen atom, R 2 Each independently represents a monovalent group having 1 to 30 carbon atoms, a hydrogen atom, or a bonding site to another structure, X is each independently an alkylene group having 1 to 4 carbon atoms or a single bond, n is an integer of 1 or more.

8. The polyfunctional vinylbenzyl compound according to claim 7, comprising a partial structure represented by the following formula (2): In formula (2), R 3 Each is independently a monovalent group having 1 to 30 carbon atoms, a hydrogen atom, or a bonding site to another structure. 9 . A resin composition comprising the polyfunctional vinylbenzyl compound according to claim 1 .

10. The resin composition according to claim 9, wherein The cured product of the resin composition has a heating residue amount ratio represented by a mass after heating at 800° C. relative to a mass before heating of 25% by mass or more.

11. The resin composition according to claim 9, wherein The cured product of the resin composition has a dielectric loss tangent of 0.0001 to 0.0020 at a measurement temperature of 25° C. and a frequency of 10 GHz. 12 . A prepreg formed using a resin composition comprising the polyfunctional vinylbenzyl compound according to claim 1 and a fiber base material. 13 . A metal-clad laminate formed by using the prepreg according to claim 12 and a metal foil. 14 . A resin film formed using a resin composition comprising the polyfunctional vinylbenzyl compound according to claim 1 . 15 . A printed wiring board comprising a cured product of a resin composition containing the polyfunctional vinylbenzyl compound according to claim 1 .

16. A semiconductor package comprising a printed wiring board containing a cured resin and a semiconductor element, The resin cured product is a cured product of a resin composition containing the polyfunctional vinylbenzyl compound according to any one of claims 1 to 8.

Images