Compound, resin composition, prepreg, resin film, metal-clad laminate, printed wiring board, and semiconductor package

Abstract

To provide a compound which is usable for preparing a cured product that suppresses deterioration of dielectric characteristics by moisture absorption, and a resin composition, a prepreg, a resin film, a metal-clad laminate, a printed wiring board and a semiconductor package which use the same.SOLUTION: A compound contains an indene ring, a vinylbenzyl group, and an aromatic ring-containing group which has 6 or more carbon atoms and has no polymerizable carbon-carbon double bond, wherein the vinylbenzyl group and the aromatic ring-containing group are directly bonded to the indene ring, respectively.SELECTED DRAWING: None

Description

[Technical field]

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

[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, such as mobile communication devices such as smartphones, base station equipment, network infrastructure devices such as servers, routers, and large servers, large computers, personal computers, industrial computers, etc. They are also used in electronic devices installed in home appliances, automobiles, etc. In particular, with the spread of 5G, there is an increasing demand for electronic communication devices to process huge amounts of data at high speeds.

[0003] When electronic devices process huge amounts of data at high speed, circuit board materials with low transmission loss in the high frequency range are required. Resins with low dielectric constants and low dielectric dissipation factors are used for circuit board materials, providing circuit boards with low transmission loss, but recent developments in communication technology have created a demand for the development of resins with even lower dielectric constants and dielectric dissipation factors.

[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 having excellent low dielectric constant, low dielectric tangent, high heat resistance, and low water absorption. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2003-277440 A Summary of the Invention [Problem to be solved by the invention]

[0006] An object of the present disclosure is to provide a compound that can be used to produce a cured product in which deterioration of dielectric properties due to moisture absorption is suppressed, as well as a resin composition, a prepreg, a resin film, a metal-clad laminate, a printed wiring board, and a semiconductor package each using the compound. [Means for solving the problem]

[0007] Examples of embodiments are listed below. The present invention is not limited to the following embodiments. <1> An indene ring, A vinylbenzyl group, an aromatic ring-containing group having 6 or more carbon atoms and no polymerizable carbon-carbon double bond; The compound, wherein the vinylbenzyl group and the aromatic ring-containing group are each directly bonded to the indene ring. <2> A compound represented by the following formula (1): [ka] (In formula (1), R 1 ~R 4 R each independently represents a hydrogen atom or a monovalent substituent. 1 , R 2 and R 3 At least one of R is a vinylbenzyl group; 1 , R 2 and R 3 At least one of the four R is an aromatic ring-containing group having 6 or more carbon atoms and no polymerizable carbon-carbon double bond. 4 may all be different from each other, and the four R 4 Two or more of them may be the same.) <3> The aromatic ring-containing group is an aryl group that is unsubstituted or has a substituent that does not have a polymerizable carbon-carbon double bond, or an arylalkyl group that is unsubstituted or has a substituent that does not have a polymerizable carbon-carbon double bond. <1> or <2> The compound according to claim 1, <4> the aromatic ring-containing group is an unsubstituted benzyl group or a benzyl group having a substituent that does not have a polymerizable carbon-carbon double bond; <3> The compound according to claim 1, <5> <1> ~ <4> A resin composition comprising the compound according to any one of claims 1 to 7. <6> <5> A prepreg comprising the resin composition according to any one of claims 1 to 5 or a semi-cured product of the resin composition. <7> <5> A resin film comprising the resin composition according to any one of claims 1 to 5 or a semi-cured product of the resin composition. <8> <5> A metal-clad laminate comprising a cured product of the resin composition according to claim 1 and a metal foil. <9> <5> A printed wiring board comprising a cured product of the resin composition according to claim 1. <10> <9> A semiconductor package comprising the printed wiring board according to claim 1 and a semiconductor element. <11> A semiconductor element and a device for sealing the semiconductor element <5> and a cured product of the resin composition according to claim 1. <12> <5> A printed wiring board comprising at least one of a surface protective film and an interlayer insulating film formed from the resin composition according to claim 1. Effect of the Invention

[0008] The present disclosure makes it possible to provide a compound that can be used to produce a cured product in which deterioration of dielectric properties due to moisture absorption is suppressed, as well as a resin composition, a prepreg, a resin film, a metal-clad laminate, a printed wiring board, and a semiconductor package using the compound. [Brief description of the drawings]

[0009] [Figure 1] FIG. 1 is an NMR spectrum of compound 1. [Diagram 2] FIG. 2 is an NMR spectrum of compound 2. [Diagram 3] FIG. 3 is an NMR spectrum of compound 3. [Figure 4] FIG. 4 is an NMR spectrum of compound 4. [Diagram 5] FIG. 5 is an NMR spectrum of compound 5. [Figure 6] FIG. 6 is an NMR spectrum of compound 6. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] Hereinafter, the embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments.

[0011] In the present disclosure, a numerical range indicated using "~" indicates a range including the numerical values ​​described before and after "~" as the minimum and maximum values, respectively. In the numerical ranges described in stages in the present disclosure, the upper limit or lower limit of a certain numerical range may be replaced with the upper limit or lower limit of another numerical range. In addition, the upper limit or lower limit of a numerical range described in the present disclosure may be replaced with a value shown in the examples. In the present disclosure, unless otherwise specified, each component may contain one or more corresponding substances. In the present disclosure, when a plurality of substances corresponding to each component are present in the resin composition, the content of each component in the resin composition means the total amount of the plurality of substances present in the resin composition, unless otherwise specified.

[0012] In this disclosure, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values ​​measured by the following procedure. The weight average molecular weight and number average molecular weight are calculated from a calibration curve using standard polystyrene by gel permeation chromatography (GPC). The calibration curve is approximated by a third order equation using standard polystyrene: TSKstandard POLYSTYRENE (Type: A-2500, A-5000, F-20, F-80) (manufactured by Tosoh Corporation, trade name). The GPC conditions are as follows.

[0013] Equipment: High-speed GPC equipment "HLC-8320GPC" (Tosoh Corporation, product name) Detector: Ultraviolet absorption detector "UV-8320" (Tosoh Corporation, product name) Columns: Guard column; TSKgel guardcolumn Super(HZ)-M+, column; TSKgel SuperMultipore HZ-M (2 columns), reference column; TSKgel SuperH-RC (2 columns) (all products of Tosoh Corporation) Column size: 4.6 x 20 mm (guard column), 4.6 x 150 mm (column), 6.0 x 150 mm (reference column) Eluent: Tetrahydrofuran Sample concentration: 10mg / 1mL Injection volume: 20μL or 2μL Flow rate: 0.35mL / min Measurement temperature: 40℃

[0014] [Compound] The compound according to one embodiment of the present disclosure is a compound that includes an indene ring, a vinylbenzyl group, and an aromatic ring-containing group having 6 or more carbon atoms and no polymerizable carbon-carbon double bond (hereinafter, also referred to as "aromatic ring-containing group X"). The vinylbenzyl group and the aromatic ring-containing group X are each directly bonded to the indene ring. Hereinafter, this compound may be referred to as "compound A".

[0015] Since the vinylbenzyl group has a relatively low polarity, it can contribute to excellent dielectric properties. On the other hand, the inventors have found that the dielectric properties of a cured product obtained by using a compound having an indene ring and a vinylbenzyl group may deteriorate due to moisture absorption. The inventors have found that the deterioration of the dielectric properties of the cured product obtained by introducing an aromatic ring-containing group having 6 or more carbon atoms and no polymerizable carbon-carbon double bond into the compound together with the indene ring and the vinylbenzyl group can be suppressed by the moisture absorption. Although not bound by a particular theory, it is believed that this is because the bulky structure of the aromatic ring-containing group X, which is an aromatic ring-containing group having 6 or more carbon atoms, makes it difficult for water molecules to approach. In addition, materials used in electronic devices are generally required to have a low thermal expansion coefficient, but compound A can exhibit a good thermal expansion coefficient. Without being bound by a specific theory, it is speculated that the control of molecular motion by interactions between aromatic rings, such as π-π interactions, can contribute to low thermal expansion.

[0016] Compound A may have an indene ring, and one or more vinylbenzyl groups and one or more aromatic ring-containing groups X each bonded to the indene ring. Compound A has one or more vinylbenzyl groups in one molecule, and by promoting the reaction of the vinylbenzyl groups by heating or the like, a cured product can be obtained. Compound A may have two or more vinylbenzyl groups. Compound A may have two or more aromatic ring-containing groups X. Compound A may have 1 to 2 vinylbenzyl groups and 1 to 2 aromatic ring-containing groups X. Compound A may have a total of 2 or 3 vinylbenzyl groups and aromatic ring-containing groups X. Compound A may, for example, be a hydrocarbon compound.

[0017] In the compound A, the vinylbenzyl group may further have a substituent. For example, the vinylbenzyl group is represented by the following formula (2).

[0018] [ka]

[0019] In formula (2), four R 5 R each independently represents a hydrogen atom or a monovalent substituent. 5 The monovalent substituent represented by R may be, for example, a halogen atom or a monovalent organic group. 5 The monovalent organic group represented by the formula (I) may be, for example, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a thioalkoxy group having 1 to 5 carbon atoms, or an aryl group having 6 to 20 carbon atoms. The halogen atom may be a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. 5may all be different from each other, or two or more of them may be the same. For example, four R 5 may all be hydrogen atoms. In formula (2), * represents a bonding site to the indene ring.

[0020] R 5 The alkyl group having 1 to 5 carbon atoms represented by the formula (I) may be a linear or branched alkyl group, and examples thereof 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, and a neopentyl group. R 5 The alkoxy group having 1 to 5 carbon atoms represented by the formula (I) is, for example, a group represented by RO-, where R may be the above-mentioned alkyl group having 1 to 5 carbon atoms. R 5 The thioalkoxy group having 1 to 5 carbon atoms represented by the following formula (I) is, for example, a group represented by RS-, where R may be the above-mentioned alkyl group having 1 to 5 carbon atoms. R 5 The aryl group having 6 to 20 carbon atoms represented by the formula (I) may be an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon, and examples thereof include a phenyl group, a biphenyl-yl group, a terphenyl-yl group, a naphthalene-yl group, an anthracene-yl group, a tetracenyl group, a fluorene-yl group, a phenanthrene-yl group, and derivatives thereof (excluding a vinylbenzyl group and its derivatives).

[0021] R 5 The monovalent organic group represented by the formula (I) may be a non-aromatic organic group and may have 1 to 5, 1 to 4, 1 to 3, or 1 to 2 carbon atoms. 5 may be a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a thioalkoxy group having 1 to 5 carbon atoms, or may be a hydrogen atom, a halogen atom, or an alkyl group having 1 to 5 carbon atoms. 5may be a hydrogen atom, a halogen atom, or an alkyl group having 1 to 5 carbon atoms, may be a hydrogen atom, or an alkyl group having 1 to 5, 1 to 4, 1 to 3, or 1 to 2 carbon atoms, or may be a hydrogen atom, a methyl group, or an ethyl group.

[0022] In the compound A, the vinylbenzyl group may be any of o-vinylbenzyl group, m-vinylbenzyl group and p-vinylbenzyl group. When two or more vinylbenzyl groups are contained in one molecule of the compound A, the structural isomers of the two or more vinylbenzyl groups may be the same or different from each other. From the viewpoint of dielectric properties, it is preferable that at least one p-vinylbenzyl group is contained in one molecule of the vinylbenzyl compound.

[0023] In one molecule of compound A, the content of p-vinylbenzyl groups may be 10 to 100 mass %, 20 to 80 mass %, 30 to 70 mass %, or 40 to 60 mass % based on the total mass of all vinylbenzyl groups.

[0024] The vinylbenzyl group may be, for example, a monovalent group that can be directly bonded to the 1st, 2nd or 3rd carbon atom of the indene ring. For example, one vinylbenzyl group may be bonded only to any one of the 1st, 2nd or 3rd carbon atoms of the indene ring. For example, two vinylbenzyl groups may be directly bonded to the 1st carbon atom of the indene ring. For example, one vinylbenzyl group may be directly bonded to each of the 1st, 2nd or 3rd carbon atoms of the indene ring. In either case, an aromatic ring-containing group X may be further bonded to at least one of the substitutable positions among the 1st, 2nd and 3rd carbon atoms of the indene ring. In the indene ring, the 1st to 7th positions are as shown below.

[0025] [ka]

[0026] The aromatic ring-containing group (aromatic ring-containing group X) having 6 or more carbon atoms and having no polymerizable carbon-carbon double bond may be a monovalent group. The aromatic ring in the aromatic ring-containing group X may be either a carbon ring or a heterocycle, but may be a carbon ring from the viewpoint of dielectric properties. From the viewpoint of dielectric properties, the aromatic ring-containing group X is preferably a monovalent hydrocarbon group containing a carbon ring. The aromatic ring-containing group X may contain any of a monocyclic ring, a condensed ring, or a polycyclic ring in which two or more selected from a monocyclic ring and a condensed ring are bonded via a single bond, but from the viewpoint of curability, the number of rings is preferably 3 or less, and may be 2 or less, or 1. When the number of rings of the aromatic ring-containing group X is 3 or less, the reactivity of the vinylbenzyl group tends to be more effectively exhibited. For example, the aromatic ring-containing group X preferably has 3 or less carbon rings, and may be 2 or less, or 1. For example, the aromatic ring-containing group X may be a group containing a benzene ring, a biphenyl structure, a terphenyl structure, a naphthalene ring, a fluorene ring, a phenanthrene ring, or the like.

[0027] From the viewpoint of curability, the number of carbon atoms in the aromatic ring-containing group X may be 20 or less, 15 or less, 12 or less, or 10 or less. From the viewpoint of curability, the number of carbon atoms in the aromatic ring-containing group X may be 6 or more, 7 or more, or 8 or more. The number of carbon atoms in the aromatic ring-containing group X may be, for example, 6 to 20, 7 to 15, 8 to 12, or 8 to 10.

[0028] The aromatic ring-containing group X may be, for example, an aryl group that is unsubstituted or has a substituent that does not have a polymerizable carbon-carbon double bond, or an arylalkyl group that is unsubstituted or has a substituent that does not have a polymerizable carbon-carbon double bond, etc. From the viewpoint of being relatively similar to a vinylbenzyl group in which a vinyl group is bonded to a benzyl group and therefore easier synthesis of compound A, an arylalkyl group that is unsubstituted or has a substituent that does not have a polymerizable carbon-carbon double bond is preferred.

[0029] The aryl group is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon. Examples of the aryl group in the aromatic ring-containing group X include a phenyl group, a biphenyl-yl group, a terphenyl-yl group, a naphthalene-yl group, an anthracene-yl group, a tetracenyl group, a fluorene-yl group, and a phenanthrene-yl group.

[0030] The arylalkyl group is a group in which at least one hydrogen atom of an alkyl group is substituted with an aryl group. In the arylalkyl group in the aromatic ring-containing group X, the alkyl group may be, for example, an alkyl group having 1 to 5 carbon atoms, more specifically, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, etc. In the arylalkyl group in the aromatic ring-containing group X, the aryl group may be, for example, the aryl group described above. The number of carbon atoms of the unsubstituted monovalent arylalkyl group may be, for example, 7 to 20, 7 to 15, 8 to 12, or 8 to 10. Examples of the arylalkyl group include a benzyl group, a phenethyl group, a naphthylmethyl group, and a naphthylethyl group. A benzyl group is preferable from the viewpoint of being relatively similar to a vinylbenzyl group and therefore easier synthesis of the compound A.

[0031] In the aromatic ring-containing group X, when the aryl group or arylalkyl group has a substituent, the substituent preferably does not have a carbon-carbon double bond. Examples of such a substituent include a halogen atom, a monovalent organic group having no carbon-carbon double bond, and the like. The halogen atom may be a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. The monovalent organic group having no carbon-carbon double bond may be, for example, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a thioalkoxy group having 1 to 5 carbon atoms, or an aryl group having 6 to 20 carbon atoms. Examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an isopropyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.

[0032] The aromatic ring-containing group X may be a group containing or not containing a heteroatom. The aromatic ring-containing group X may be, for example, a monovalent group not containing a heteroatom. Examples of the aromatic ring-containing group X include a methylbenzyl group, an ethylbenzyl group, a butylbenzyl group, a dimethylbenzyl group, and a trimethylbenzyl group.

[0033] In compound A, the aromatic ring-containing group X may be, for example, a monovalent organic group represented by the following formula (3).

[0034] [ka]

[0035] In formula (3), five R 6 are each independently a hydrogen atom or a substituent. The substituent may be, for example, a halogen atom or a monovalent organic group. 6 The halogen atom and the monovalent organic group represented by the formula (2) are R 5 The five R 6 may all be different from each other, or two or more of them may be the same. For example, five R 6 In another example, all five R 6 Of these, four may be hydrogen atoms and one may be an alkyl group having 1 to 5 carbon atoms; 6 Four of R may be hydrogen atoms and one may be a methyl or ethyl group, or five R 6 Of these, four may be hydrogen atoms and one may be a methyl group. For example, five R 6 When four of the groups are hydrogen atoms and one is an alkyl group, the alkyl group may be bonded to any of the o-, m-, and p-positions, but is preferably bonded to the p-position.

[0036] The aromatic ring-containing group X may be, for example, an o-methylbenzyl group, an m-methylbenzyl group, or a p-methylbenzyl group. The aromatic ring-containing group X may be, for example, a p-methylbenzyl group.

[0037] When compound A contains two or more aromatic ring-containing groups X, the two or more aromatic ring-containing groups X may be the same or different.

[0038] The aromatic ring-containing group X may be, for example, a monovalent group that can be directly bonded to the 1st, 2nd or 3rd carbon atom on the indene ring. For example, one aromatic ring-containing group X may be bonded only to any one of the 1st, 2nd or 3rd carbon atoms of the indene ring. For example, two aromatic ring-containing groups X may be directly bonded to the 1st carbon atom of the indene ring. For example, one aromatic ring-containing group X may be directly bonded to each of two of the 1st, 2nd or 3rd carbon atoms of the indene ring. In either case, a vinylbenzyl group may be further bonded to at least one of the substitutable positions of the 1st, 2nd or 3rd carbon atoms of the indene ring.

[0039] In compound A, the carbon atom of the indene ring may further have a monovalent substituent other than a vinylbenzyl group and an aromatic ring-containing group X. Compound A may have a monovalent substituent other than a vinylbenzyl group and an aromatic ring-containing group X on one or more of the carbon atoms at the 4-position, 5-position, 6-position and 7-position of the indene ring, for example.

[0040] Examples of the monovalent substituent other than the vinylbenzyl group and the aromatic ring-containing group X include a halogen atom and a monovalent organic group. The halogen atom may be a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. Examples of the monovalent organic group include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a thioalkoxy group having 1 to 5 carbon atoms, or an aryl group having 6 to 20 carbon atoms. Examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an isopropyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.

[0041] Compound A may be, for example, a compound that does not have monovalent substituents on the carbon atoms at positions 4, 5, 6 and 7 of the indene ring. Compound A may be, for example, a compound that does not have a monovalent substituent other than a vinylbenzyl group and an aromatic ring-containing group X on a carbon atom of an indene ring.

[0042] Compound A may have a structure in which, for example, one vinylbenzyl group is directly bonded to the 1st, 2nd or 3rd carbon atom of an indene ring, one aromatic ring-containing group X is directly bonded to the 1st, 2nd or 3rd carbon atom of an indene ring, and the other carbon atoms constituting the indene ring do not have a substituent. Materials used for metal-clad laminates, prepregs and the like used in electronic devices are preferably those capable of improving the adhesive strength with metal foil, and such a structure makes it easier to obtain superior adhesive strength with metal foil.

[0043] It is possible to provide an oligomer or prepolymer having a low degree of polymerization obtained by polymerizing a compound having a vinylbenzyl group and an aromatic ring-containing group X introduced into an indene ring using compound A. Both the oligomer and the prepolymer preferably contain a certain amount of unreacted vinylbenzyl groups and are in a state in which a curing reaction is initiated by heating or the like.

[0044] An example of compound A is a compound represented by the following formula (1).

[0045] [ka]

[0046] In formula (1), R 1 ~R 4 R each independently represents a hydrogen atom or a monovalent substituent. 1 , R 2 and R 3 At least one of R is a vinylbenzyl group; 1 , R 2 and R 3 At least one of the four R is an aromatic ring-containing group X. 4 may all be different from each other, and the four R 4 Two or more of may be identical to each other. The vinylbenzyl group and the aromatic ring-containing group X are as described above.

[0047] R 1 , R 2 and R 3 The monovalent substituent represented by the formula (I) may be a halogen atom, a monovalent organic group, or the like. The halogen atom may be a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. The monovalent organic group may be, for example, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a thioalkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 20 carbon atoms, a vinylbenzyl group, or an aromatic ring-containing group X. The alkyl group having 1 to 5 carbon atoms may be, for example, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an isopropyl group, an isobutyl group, a sec-butyl group, or a tert-butyl group.

[0048] R 4 The monovalent substituent represented by the formula (I) may be, for example, a halogen atom or a monovalent organic group. The halogen atom may be a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. The monovalent organic group may be, for example, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a thioalkoxy group having 1 to 5 carbon atoms, or an aryl group having 6 to 20 carbon atoms. Examples of the alkyl group having 1 to 5 carbon atoms include R 1 , R 2 , R 3 The above-mentioned items can be mentioned.

[0049] In formula (1), R 1 , R 2 and R 3 One or two of R may be a vinylbenzyl group. 1 , R 2 and R 3 One or two of the remaining may be an aromatic ring-containing group X. 1 , R 2 and R 3 one or two of R 1 , R 2 and R 3Among the four R groups, one or two of the remaining R groups may be aromatic ring-containing groups X, and the total number of vinylbenzyl groups and aromatic ring-containing groups X may be two or three. 4 may all be hydrogen atoms.

[0050] From the viewpoint of adhesive strength with metal foil, for example, R 1 , R 2 and R 3 Any one of R is a vinylbenzyl group; 1 , R 2 and R 3 any other one of the aromatic ring-containing group X, and R 1 , R 2 and R 3 Any other one of the groups may be a hydrogen atom.

[0051] The following describes a method for synthesizing compound A. Compound A is a compound that is specified by its molecular structure, regardless of the synthesis method described below.

[0052] As a method for synthesizing compound A, for example, a method of reacting a base compound having an indene ring, a styrene having a halogenated methyl group, and a compound containing an aromatic ring substituted with a halogen or halogenated alkyl group in the presence of a basic compound can be mentioned. Examples of styrene having a halogenated methyl group include o-chloromethylstyrene, m-chloromethylstyrene, p-chloromethylstyrene, etc., which may be one or a mixture of two or more. Examples of compounds containing an aromatic ring substituted with a halogen or halogenated alkyl group include compounds containing an aromatic ring having a chloroalkyl group such as α-chloro-p-xylene, which may be one or a mixture of two or more. Examples of basic compounds include alkali metal hydroxides, alkali metal alkoxides, etc.

[0053] A phase transfer catalyst may be used in the above reaction. 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 reaction can be carried out by solution polymerization. The reaction can be carried out, for example, under heating and stirring. A polymerization inhibitor can be added to the reaction system.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 the phenol 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, bis(2,2,6,6-tetramethyl-1-piperidinyloxy-4-yl)sebacate, etc. The obtained product may be purified by a known method such as concentration, reprecipitation, washing, etc., if necessary.

[0054] The resulting compound may be a single compound or a mixture of two or more compounds. For example, a compound is synthesized in which a vinylbenzyl group is directly bonded to at least one carbon atom at the 1st, 2nd, and 3rd positions of an indene ring, and an aromatic ring-containing group is directly bonded to at least one carbon atom at the 1st, 2nd, and 3rd positions of an indene ring, but two or more isomeric compounds with different bonding sites may be included in the mixture. Also, depending on synthesis conditions, etc., two or more compounds with different numbers of bonds and bonding sites of vinylbenzyl groups and aromatic ring-containing groups X to the indene ring may be included in the mixture. Furthermore, for example, in addition to compound A, a compound in which only one of vinylbenzyl groups or aromatic ring-containing groups X is bonded to an indene ring may be included in the mixture.

[0055] When a mixture of two or more compounds is obtained in the synthesis of compound A, the weight average molecular weight (Mw) of this mixture is not particularly limited, but from the viewpoints of moldability and handleability, it is preferably 240 to 350, more preferably 250 to 340, and even more preferably 260 to 330. In addition, the number average molecular weight (Mn) of this mixture is preferably 200 to 330, more preferably 210 to 320, and even more preferably 210 to 310.

[0056] The dielectric constant (Dk) of the cured product of the compound A at 25° C. and 10 GHz may be, for example, 4.0 or less, 3.5 or less, or 3.4 or less. On the other hand, the dielectric constant (Dk) of the cured product of the compound A at 25° C. and 10 GHz may be, for example, 2.3 or more, or 2.4 or more. The dielectric constant (Dk) of the cured product of the compound A at 25° C. and 10 GHz may be, for example, 2.3 to 4.0, 2.3 to 3.5, or 2.4 to 3.4. The dielectric loss tangent (Df) of the cured product of the compound A at 25° C. and 10 GHz may be, for example, 0.0020 or less, 0.0015 or less, 0.0013 or less, 0.0010 or less, or 0.0008 or less. On the other hand, the dielectric loss tangent (Df) of the cured product of the compound A at 25° C. and 10 GHz may be, for example, 0.0001 or more, or 0.0002 or more. The dielectric loss tangent (Df) of the cured product of compound A at 25° C. and 10 GHz may be, for example, 0.0001 to 0.0020, 0.0001 to 0.0015, 0.0001 to 0.0013, 0.0002 to 0.0010, or 0.0002 to 0.0008. The thermal expansion coefficient of the cured product of compound A at 30 to 120°C may be, for example, 30 to 50 ppm / °C. When a mixture of two or more compounds is obtained by synthesizing compound A, the relative dielectric constant (Dk) at 25°C and 10 GHz, the dielectric loss tangent (Df) at 25°C and 10 GHz, and / or the thermal expansion coefficient from 30 to 120°C of a cured product of this mixture may be, for example, within the above-mentioned ranges. The sample to be measured for the dielectric constant (Dk) at 25° C. and 10 GHz, the dielectric loss tangent (Df) at 25° C. and 10 GHz, and the thermal expansion coefficient at 30 to 120° C. of the cured product of compound A is obtained by curing compound A to a C-stage state according to JIS K 6800 (1985). Specifically, the sample can be prepared, for example, by the method described in the Examples. The dielectric constant (Dk) at 25°C and 10 GHz and the dielectric loss tangent (Df) at 25°C and 10 GHz may be measured according to the measurement of the dielectric constant (Dk) and the dielectric loss tangent (Df) at 25°C and 10 GHz of the cured product of the resin composition described later. The thermal expansion coefficient of the cured product of the compound A at 30 to 120°C may be measured according to the measurement of the thermal expansion coefficient of the cured product of the resin composition described later.

[0057] Compound A can be used in a wide range of fields, including mobile communication devices such as smartphones, base station devices thereof, network infrastructure devices such as servers, routers, and large servers, various electronic devices such as large computers, personal computers, and industrial computers, and electronic devices installed in home appliances and automobiles.

[0058] [Resin composition] The resin composition of one embodiment contains the compound A described above. <Compound A> The resin composition may contain the above-mentioned compound A alone or in combination of two or more kinds.

[0059] From the viewpoint of dielectric properties and heat resistance, the compound A may be 10 mass% or more, 20 mass% or more, or 30 mass% or more with respect to the solid content of the resin composition. On the other hand, from the viewpoint of dielectric properties and heat resistance, the compound A may be 100 mass% or less, 90 mass% or less, or 80 mass% or less with respect to the solid content of the resin composition. The compound A may be, for example, 10 to 100 mass%, 20 to 90 mass%, or 30 to 80 mass% with respect to the solid content of the resin composition.

[0060] In the present disclosure, the "solid content" of a resin composition refers to components in the resin composition other than volatile substances such as water, the solvent described below, etc. The solid content is a component that remains without volatilization when the resin composition is dried, and includes those that are liquid, syrup-like, or wax-like at room temperature around 25°C, and does not necessarily mean that they are solid.

[0061] <Other ingredients> The resin composition may contain other components in addition to the compound A, if necessary. Examples of other components include thermosetting resins, fillers, elastomers, curing agents, curing accelerators, solvents, flame retardants, antioxidants, heat stabilizers, antistatic agents, UV absorbers, pigments, colorants, and lubricants. The other components may each be used alone or in combination of two or more.

[0062] The resin composition may further contain, in addition to the compound A, a thermosetting resin. The thermosetting resin may be a compound having a reactive group. For example, the thermosetting resin may be a compound having a reactive group, which may be self-curable or may be curable in combination with a curing agent.

[0063] The thermosetting resin is not particularly limited, and examples thereof include epoxy resins, maleimide compounds, phenolic 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.

[0064] Among these, epoxy resins, phenolic resins, and maleimide compounds are preferred from the viewpoints of thermosetting properties and dielectric properties.

[0065] The epoxy resin preferably has two or more epoxy groups in one molecule. Examples of the epoxy resin include glycidyl ether type epoxy resins, glycidyl amine type epoxy resins, and glycidyl ester type epoxy resins. Each of these types of epoxy resins can be further classified into bisphenol type epoxy resins, alicyclic epoxy resins, aliphatic chain epoxy resins, novolac type epoxy resins, stilbene type epoxy resins, naphthalene skeleton-containing epoxy resins, biphenyl type epoxy resins, xylylene type epoxy resins, and dihydroanthracene type epoxy resins.

[0066] The maleimide compound may be a compound having one or more N-substituted maleimide groups and a derivative thereof. For example, the maleimide compound may be at least one selected from the group consisting of a compound having two or more N-substituted maleimide groups and a derivative thereof.

[0067] 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.

[0068] 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]propane 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, bi 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 type maleimide compounds, etc.

[0069] Examples of derivatives of compounds having one or more N-substituted maleimide groups include aminomaleimide compounds containing a structural unit derived from the above-mentioned compound having one or more N-substituted maleimide groups and a structural unit derived from a diamine compound.

[0070] In the resin composition, the compound A may be 10% by mass or more, 20% by mass or more, or 30% by mass or more based on the total amount of the thermosetting resin. On the other hand, the compound A may be 100% by mass or less, 90% by mass or less, or 80% by mass or less based on the total amount of the thermosetting resin. The compound A may be, for example, 10 to 100% by mass, 20 to 90% by mass, or 30 to 80% by mass based on the solid content of the resin composition.

[0071] In the resin composition, the amount of the thermosetting resin containing compound A may be, for example, 50 mass % or more, 60 mass % or more, or 70 mass % or more, or 100 mass % based on the total amount of the resin composition.

[0072] The filler is preferably an inorganic filler, such as silica (SiO2), alumina (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, beryllia, clay, talc, etc. From the viewpoint of dielectric properties, silica is preferred.

[0073] 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 the volume-based particle distribution by the laser diffraction scattering method.

[0074] Examples of the elastomer include styrene-based elastomers, olefin-based elastomers, urethane-based elastomers, polyester-based elastomers, polyamide-based elastomers, acrylic-based elastomers, and silicone-based elastomers.

[0075] 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. The radical polymerization initiator is not particularly limited, and examples thereof include an azo-based polymerization initiator and an organic peroxide-based polymerization initiator. Examples of the azo polymerization initiator include 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-methylpropionate)dimethyl, 1,1'-azobis(methyl cyclohexylcarboxylate), 2,2'-azobis[N-(2-propenyl)-2-methylpropionamide], 2,2'-azobis(N-butyl-2-methylpropionamide), 4,4'-azobis(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl 4-cyanopentanoate), and 1,1'-azobis(cyclohexane-1-carbonitrile). Examples of the organic peroxide polymerization initiator include dicumyl peroxide, dibenzoyl peroxide, 2-butanone peroxide, tert-butyl perbenzoate, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, bis(tert-butylperoxyisopropyl)benzene, and tert-butyl hydroperoxide.

[0076] The resin composition may be a solvent-free resin composition or may contain a solvent. The solvent can adjust the viscosity of the resin composition to further improve the coatability. The solvent is preferably an organic solvent.

[0077] Examples of organic solvents 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.

[0078] When the resin composition contains a solvent, the solid content of the resin composition may be, for example, 30 to 95 mass %, 40 to 90 mass %, 50 to 80 mass %, or 50 to 70 mass % relative to the total mass of the resin composition.

[0079] <Method of producing resin composition> The method for producing the resin composition is not particularly limited. The resin composition according to one embodiment is not limited by the production method, and its features are as described in the present disclosure. As an example of the method for producing the resin composition, compound A and, if necessary, any optional components are added and mixed to obtain a resin composition. More specifically, for example, compound A is dissolved or dispersed in a solvent, and other components are added and mixed if necessary to obtain a resin composition. The conditions such as the mixing order, temperature, and time of each component are not particularly limited, and may be appropriately adjusted according to the type of raw material, production scale, production equipment, etc.

[0080] <Dielectric properties of the cured resin composition> The 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 3.5 or less, and even more preferably 3.4 or less. The smaller the dielectric constant (Dk) of the cured product of the resin composition at 25° C. and 10 GHz, the more preferable it is, and there is no particular restriction on the lower limit, but it may be, for example, 2.3 or more, or 2.4 or more, taking into consideration the balance with other physical properties. For example, the relative dielectric constant (Dk) of the cured product of the resin composition at 25° C. and 10 GHz may be 2.3 to 4.0, 2.3 to 3.5, or 2.4 to 3.4.

[0081] 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 0.0015 or less, even more preferably 0.0013 or less, even more preferably 0.0010 or less, and even more preferably 0.0008 or less. The smaller the dielectric loss tangent (Df) of the cured product of the resin composition at 25° C. and 10 GHz, the more preferable it is, and there is no particular restriction on the lower limit, but in consideration of the balance with other physical properties, it may be, for example, 0.0001 or more, or 0.0002 or more.

[0082] For example, the dielectric loss tangent (Df) of the cured product of the resin composition at 25° C. and 10 GHz may be 0.0001 to 0.0020, 0.0001 to 0.0015, 0.0001 to 0.0013, 0.0002 to 0.0010, or 0.0002 to 0.0008.

[0083] In the present disclosure, the dielectric constant (Dk) and dielectric loss tangent (Df) at 25° C. and 10 GHz are measured in the 10 GHz band at 25° C. in accordance with the SPDR method (split post dielectric resonator). As the measuring device, a vector network analyzer E8364B manufactured by Agilent Technologies and a 10 GHz SPDR manufactured by Vega Technology can be used. The sample to be measured for the dielectric constant (Dk) and dielectric loss tangent (Df) of the cured resin composition is the resin composition cured to the C-stage state according to JIS K 6800 (1985). Specifically, the sample can be prepared by the method described in the Examples, for example.

[0084] <Thermal expansion coefficient of the cured resin composition> The thermal expansion coefficient of the cured resin composition at 30 to 120°C may be, for example, 30 to 50 ppm / °C. In the present disclosure, the thermal expansion coefficient at 30 to 120°C is measured in accordance with the IPC (The Institute for Interconnecting and Packaging Electronic Circuits) standard. As a measuring device, a thermomechanical measuring device (TMA) (manufactured by TA Instruments Japan, Inc., product name: Q400) can be used. The sample to be measured is a resin composition cured to a C-stage state according to JIS K 6800 (1985). Specifically, for example, a sample can be prepared by the method described in the examples.

[0085] [Prepreg] According to one embodiment, a prepreg containing a resin composition or a semi-cured product of the resin composition can be provided. The prepreg can be formed, for example, by using the resin composition and a fiber substrate. The resin composition can be any of the above-mentioned resin compositions. Details of the resin composition are as described above.

[0086] The prepreg may contain the above-mentioned resin composition or a semi-cured product of the above-mentioned resin composition. In the present disclosure, one index of a semi-cured product may be the B-stage state according to JIS K 6800 (1985). The prepreg may contain, for example, a resin composition or a semi-cured product of the resin composition and a fibrous substrate such as a sheet-like fibrous substrate. In the prepreg, the resin composition may be in an uncured state, or the resin composition may be in a partially or entirely semi-cured state.

[0087] The prepreg can be obtained, for example, by coating a fiber substrate with a resin composition and drying it. For example, the prepreg can be obtained by impregnating and coating a fiber substrate with a resin composition and drying the fiber substrate impregnated with the resin composition. The drying is preferably performed at a temperature at which volatile components such as a solvent that may be contained in the resin composition are removed or higher, and may be performed at a temperature at which the thermosetting resin contained in the resin composition is semi-cured or higher depending on the application. In addition, the drying is preferably adjusted so that the thermosetting resin contained in the resin composition is not completely cured. From this viewpoint, 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, the drying device, its scale, and the like.

[0088] The fibrous substrate may be any of woven, knitted, and nonwoven fabrics. The fibrous substrate may be provided in the form of chopped strand mat, roving, and the like. The material of the fibers may be either inorganic or organic. Examples of inorganic fibers include glass fibers and carbon fibers. Examples of glass fibers include E glass, NE glass, D glass, S glass, and Q glass. Examples of organic fibers include polyimide, polyester, and tetrafluoroethylene. The fiber substrate may be one type of these fibers alone or two or more types of these fibers in combination. From the viewpoints of dielectric properties and heat resistance, the material of the fiber substrate is preferably inorganic fiber, and more preferably glass fiber.

[0089] The fiber base material may be appropriately selected depending on the application of the prepreg, but a sheet-like fiber base material is preferred. The sheet-like fiber base material may be, for example, any of various sheet-like fiber base materials used in known laminates for electrical insulating materials. The thickness of the sheet-like fiber substrate is not particularly limited, but is preferably 0.02 to 0.5 mm, for example. The thickness is measured at five points at equal distances over the entire surface of the sheet-like fiber substrate, and the arithmetic average value of the five points is taken as the thickness.

[0090] [Resin film] According to one embodiment, a resin film containing the resin composition or a semi-cured product of the resin composition can be provided. Details of the resin composition are as described above.

[0091] The resin film may contain the above-mentioned resin composition or a semi-cured product of the above-mentioned resin composition. In the resin film, the resin composition may be in an uncured state, but the resin composition may be in a partially or entirely semi-cured state. For example, the resin film can be cured by heat treatment or the like to obtain a cured product. The resin film can be obtained, for example, by applying a resin composition to a substrate and drying it. The drying can be performed, for example, in the same manner as in the above-mentioned method for producing a prepreg. After drying the resin film on the substrate, a product may be provided as a combination of the resin film and the substrate. For example, in this method, a resin film can be provided to form an insulating layer or the like on the substrate in electronic devices or the like. In another method, after drying the resin film on the substrate, the resin film may be peeled off from the substrate to provide the resin film as a product.

[0092] The substrate may be either an inorganic substrate or an organic substrate, and examples of the substrate include a glass substrate, a metal substrate such as a metal foil or a metal plate, a plastic substrate such as a plastic plate or a plastic film, a paper substrate, or a fiber substrate as described above for the prepreg. In order to peel the resin film from the substrate, a substrate having a release layer formed on the surface may be used.

[0093] [Metal-clad laminate] According to one embodiment, a metal-clad laminate including a cured resin composition and a metal foil can be provided. The metal-clad laminate may be, for example, a metal-clad laminate including a cured prepreg and a metal foil. According to another embodiment, a metal-clad laminate formed by using a prepreg and a metal foil can be provided. The metal-clad laminate may be, for example, a metal-clad laminate including a cured prepreg and a metal foil. The details of the resin composition and the prepreg are as described above. In the present disclosure, one index of the cured product is the C-stage state according to JIS K 6800 (1985).

[0094] The metal-clad laminate preferably includes a resin cured product layer containing a resin cured product and a metal foil disposed on at least one surface of the resin cured product layer. The resin cured product layer includes a cured product of the resin composition described above, but may be the cured product of the prepreg described above. For example, in the metal-clad laminate, a metal foil is disposed on at least one surface of the cured product of the prepreg, and more preferably, a metal foil is disposed on both surfaces of the cured product of the prepreg. The metal-clad laminate may be manufactured by disposing a metal foil on at least one surface of a single sheet-like prepreg, or may be manufactured by laminating two or more sheet-like prepregs and disposing a metal foil on at least one surface of the outermost surface of the laminate. For example, the metal-clad laminate may be manufactured by laminating two or more sheet-like prepregs and disposing a metal foil on both surfaces of the laminate.

[0095] Hereinafter, a method of arranging a metal foil on a laminate of two or more sheet-like prepregs will be described as a specific example of a method for producing a metal-clad laminate.

[0096] 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 the same as each other, or may be partially or entirely different. In the laminate, at least one of the two or more sheet-like prepregs may be obtained using the resin composition according to one embodiment.

[0097] Next, a metal foil is placed on at least one surface of this laminate. The laminate with the metal foil disposed thereon is heated and pressurized. This advances the curing reaction of the sheet-like prepreg, and a cured prepreg can be obtained. Also, adjacent sheet-like prepregs can be fixed to each other. 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 1.5 to 5 MPa. After heating and pressurizing, reheating may be performed to further advance the curing of the prepreg. In this case, the reheating temperature may be 100 to 300°C. As a method for applying pressure, for example, an autoclave molding machine, a multi-stage press machine, a multi-stage vacuum press machine, a continuous molding machine, etc. can be used.

[0098] 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 is preferable to use single metals such as copper, nickel, and aluminum. By using copper as the metal foil, a copper-clad laminate can be provided.

[0099] The dielectric properties of an evaluation board obtained by removing the metal foil from the metal-clad laminate (hereinafter also referred to as a "metal foil-removed evaluation board") are preferably as follows.

[0100] The dielectric constant (Dk) of the metal foil removal evaluation substrate at 25° C. and 10 GHz is preferably 4.0 or less, more preferably 3.5 or less, and even more preferably 3.4 or less. The smaller the dielectric constant (Dk) of the metal foil removal evaluation substrate at 25° C. and 10 GHz, the more preferable it is, and there is no particular restriction on the lower limit, but it may be, for example, 2.3 or more, or 2.4 or more, taking into consideration the balance with other physical properties. For example, the relative dielectric constant (Dk) of the metal foil-removed evaluation board at 25° C. and 10 GHz may be 2.3 to 4.0, and preferably 2.3 to 3.5, or 2.4 to 3.4.

[0101] The dielectric loss tangent (Df) of the metal foil removal evaluation substrate at 25° C. and 10 GHz is preferably 0.0020 or less, more preferably 0.0015 or less, and even more preferably 0.0013 or less. The smaller the dielectric loss tangent (Df) of the metal foil removal evaluation substrate at 25° C. and 10 GHz, the more preferable it is, and there is no particular restriction on the lower limit, but in consideration of the balance with other physical properties, it may be, for example, 0.0001 or more, 0.0002 or more, or 0.0005 or more. For example, the dielectric loss tangent (Df) of the metal foil-removed evaluation board at 25° C. and 10 GHz may be 0.0001 to 0.0020, 0.0002 to 0.0015, or 0.0005 to 0.0013.

[0102] The dielectric constant (Dk) and dielectric loss tangent (Df) of the metal foil removal evaluation board at 25°C and 10 GHz may be measured in the same manner as in the measurement of the dielectric constant (Dk) and dielectric loss tangent (Df) of the cured product of the resin composition described above at 25°C and 10 GHz.

[0103] The thermal expansion coefficient of the metal foil removal evaluation substrate from 30 to 120° C. (also simply referred to as the thermal expansion coefficient of the metal-clad laminate from 30 to 120° C.) may be, for example, 30 to 50 ppm / ° C. The thermal expansion coefficient of the metal foil removal evaluation substrate from 30 to 120° C. may be measured in accordance with the measurement of the thermal expansion coefficient of the cured product of the resin composition from 30 to 120° C. described above.

[0104] [Printed wiring board] According to one embodiment, a printed wiring board including a cured product of the resin composition can be provided. Also, according to one embodiment, a printed wiring board including at least one of a surface protective film and an interlayer insulating film formed by the resin composition can be provided. Details of the resin composition are as described above.

[0105] In the printed wiring board, the cured product of the resin composition can be produced using a resin composition, a prepreg, a resin film, a metal-clad laminate, or a combination thereof. For example, a printed wiring board can be provided by forming wiring on a cured product of a prepreg by a known method. In another example, a printed wiring board can be provided by forming wiring using a metal-clad laminate by a known method. A printed wiring board that combines these examples may be used. Details of the prepreg, the resin film, and the metal-clad laminate are as described above.

[0106] The printed wiring board may be either a single-layer printed wiring board or a multi-layer printed wiring board.

[0107] [Semiconductor package] According to one embodiment, a semiconductor package including a printed wiring board and a semiconductor element can be provided. More specifically, for example, a semiconductor package including a printed wiring board including a cured product of a resin composition and a semiconductor element can be provided. Details of the resin composition are as described above. Details of the cured product of the resin composition and the printed wiring board are also as described above. The semiconductor package can be manufactured, for example, by mounting a semiconductor element, a memory, or the like on a printed wiring board by a known method. The cured product of the resin composition may be used as an insulating material, an encapsulating material, or the like of the semiconductor package. For example, a semiconductor package including a semiconductor element and a cured product of a resin composition that encapsulates the semiconductor element can be provided. EXAMPLES

[0108] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples.

[0109] <Method of measuring weight average molecular weight (Mw) and number average molecular weight (Mn)> The weight average molecular weight and number average molecular weight were calculated from a calibration curve using standard polystyrene by gel permeation chromatography (GPC). The calibration curve was approximated by a third order equation using standard polystyrene: TSKstandard POLYSTYRENE (Type: A-2500, A-5000, F-20, F-80) (manufactured by Tosoh Corporation, trade name). The measurement conditions for GPC are shown below.

[0110] Equipment: High-speed GPC equipment HLC-8320GPC (Tosoh Corporation, product name) Detector: Ultraviolet absorption detector UV-8320 (Tosoh Corporation, product name) Columns: Guard column; TSKgel guardcolumn Super(HZ)-M+, column; TSKgel SuperMultipore HZ-M (2 columns), reference column; TSKgel SuperH-RC (2 columns) (all products of Tosoh Corporation) Column size: 4.6 x 20 mm (guard column), 4.6 x 150 mm (column), 6.0 x 150 mm (reference column) Eluent: Tetrahydrofuran Sample concentration: 10mg / 1mL Injection volume: 20μL or 2μL Flow rate: 0.35mL / min Measurement temperature: 40℃

[0111] <Production of Compounds> A 500 mL reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet was charged with the amounts of indene shown in Table 1, the following chloromethylstyrene (CMS), α-chloro-p-xylene (CPX), tetra-n-butylammonium bromide (Kanto Chemical Co., Ltd.) as a phase transfer catalyst, phenothiazine as a polymerization inhibitor, and 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.

[0112] Chloromethylstyrene "CMS-P": AGC Seimi Chemical Co., Ltd., a mixture of m- and p-forms, with m-form content of 50% by mass and p-form content of 50% by mass.

[0113] Next, the following aqueous sodium hydroxide solution in the amount shown in Table 1 was added dropwise over 20 minutes, and the mixture was stirred at 60°C for another 9 hours. Nitrogen was continuously blown in during the reaction. The mixture was cooled to room temperature (25°C) and neutralized with a 10% aqueous hydrochloric acid solution, then washed twice with pure water, and the toluene was distilled off under reduced pressure. The resulting viscous liquid was washed with methanol and then vacuum dried. In this way, compounds 1 to 7 were obtained.

[0114] Sodium hydroxide solution: an aqueous solution of sodium hydroxide with a concentration of 48% by mass, Kanto Chemical Co., Ltd.

[0115] [Table 1]

[0116] Using ECX400II manufactured by JEOL RESONANCE Co., Ltd. 1 H-NMR spectrum (0.2 Hz, CDCl3, standard substance: tetramethylsilane (TMS)) was measured. 1 From the H-NMR analysis, it was found that the reaction of bonding a vinylbenzyl group to any one of the 1-3 positions of the indene ring and a methylbenzyl group to any one of the 1-3 positions of the indene ring had occurred, specifically, the shift or disappearance of the H peak at the 1st position of indene, the shift or disappearance of the H peak at the 2nd and 3rd positions of indene, the shift of the methylene peaks of CMS and CPX, the shift of the vinyl peak of CMS, and the shift of the methyl peak of CPX. 1 H-NMR spectra are shown in Figs.

[0117] Furthermore, it was confirmed by GPC analysis that Compounds 1 to 6 were a mixture of compounds having one substituent selected from the group consisting of vinylbenzyl and methylbenzyl groups (monosubstituted compounds), compounds having two substituents (disubstituted compounds), and compounds having three substituents (trisubstituted compounds).

[0118] Table 2 shows the yield (%), the ratio (intensity ratio) of tri-, di- and mono-substituted compounds determined by GPC, the weight average molecular weight (Mw) and the number average molecular weight (Mn) for the obtained compounds 1 to 7.

[0119] [Table 2]

[0120] <Examples 1 to 6 and Comparative Example 1> Compounds 1 to 7 obtained above were used in Examples 1 to 6 and Comparative Example 1. Specifically, as shown in Table 3, compound 7 was used in Comparative Example 1, compound 1 was used in Example 1, compound 4 was used in Example 2, compound 5 was used in Example 3, compound 2 was used in Example 4, compound 6 was used in Example 5, and compound 3 was used in Example 6.

[0121] <Resin Compositions of Examples 7 to 9 and Comparative Example 2> The resin compositions of Examples 7 to 9 and Comparative Example 2 having a solid content concentration of about 60 mass% were prepared by stirring and mixing each of the components shown in Table 4 together with toluene at 25°C in the amounts shown in Table 4. In Table 1, when the component is a solution, the mass% is calculated as the solid content.

[0122] Details of each material listed in Tables 3 and 4 are as follows. Compounds 1 to 7: All of the compounds were prepared as described above. Maleimide compound: Aromatic maleimide compound having an indane skeleton represented by the following formula:

[0123] [ka] (In the above formula, n is a number from 0.95 to 10.0.)

[0124] <How to prepare the cured product> (Examples 1 to 6 and Comparative Example 1) In Comparative Example 1 and Examples 1 to 6, resin boards having copper foil on both sides were obtained as follows. A Teflon (registered trademark) sheet cut into a size of 0.8 mm thick x 70 mm long x 50 mm wide was placed on a low-profile copper foil (manufactured by Mitsui Mining & Smelting Co., Ltd., product name: SI-VSP-18) with a thickness of 18 μm, and powder of the compounds (compounds 1 to 7) listed in Table 3 was poured into the cut-out portion. Next, a low-profile copper foil (manufactured by Mitsui Mining & Smelting Co., Ltd., product name: SI-VSP-18) with a thickness of 18 μm was also placed on the side of the Teflon (registered trademark) sheet where the powder of the compound was poured. The two copper foils were placed in a state where the M surface (matte surface) was in contact with the powder of the compound that was poured. Next, the product was cured by vacuum heating and pressure molding under conditions of a temperature of 230° C., a pressure of 2.0 MPa, and a time of 60 minutes, to obtain a resin plate with copper foil on both sides. (Examples 7 to 9 and Comparative Example 2) For Comparative Example 2 and Examples 7 to 9, a resin plate with copper foil on both sides was obtained as follows. The resin compositions of each of the Examples and Comparative Examples obtained above (resin compositions of Examples 7 to 9 and Comparative Example 2) were applied to a PET film having a thickness of 38 μm (manufactured by Teijin Limited, product name: G2000), and then heated and dried at 140° C. for 5 minutes to produce a resin film in a B-stage state. This resin film was peeled off from the PET film and then crushed to obtain a resin powder. A resin plate with copper foil on both sides was obtained in the same manner as described above (Examples 1 to 6 and Comparative Example 1), except for using the resin powder.

[0125] <Measuring method for dielectric properties (dielectric constant (Dk) and dielectric loss tangent (Df))> The resin plate with copper foil on both sides obtained as described above was immersed in a 10 mass% solution of ammonium persulfate (manufactured by Mitsubishi Gas Chemical Co., Ltd.) which is a copper etching solution, to remove the copper foil on both sides, and a test piece of 70 mm x 50 mm was prepared. Next, the relative permittivity (Dk) and dielectric loss tangent (Df) were measured at an ambient temperature of 25°C and a 10 GHz band using a split post dielectric resonator (SPDR) for each of the test pieces immediately after drying at 105°C for 1 hour and the test piece left for 24 hours at an ambient temperature of 25°C and a humidity of 50%RH after drying at 105°C for 1 hour. The measuring instruments used were a vector network analyzer E8364B manufactured by Agilent Technologies and a 10 GHz SPDR manufactured by Vega Technology, respectively.

[0126] The results are shown in Tables 3 and 4. In Tables 3 and 4, "Dk immediately after drying" and "Df immediately after drying" indicate the dielectric constant (Dk) and dielectric loss tangent (Df) immediately after drying at 105°C for 1 hour. "Dk after 24 hr" and "Df after 24 hr" indicate the dielectric constant (Dk) and dielectric loss tangent (Df) after drying at 105°C for 1 hour and then leaving the sample at an ambient temperature of 25°C and a humidity of 50% RH for 24 hours. "ΔDf (24 hr - immediately after drying)" indicates the difference in dielectric loss tangent (Df) before and after leaving the sample at an ambient temperature of 25°C and a humidity of 50% RH for 24 hours.

[0127] <Method of measuring thermal expansion coefficient> The resin plate with copper foil on both sides obtained as described above was immersed in a 10 mass% solution of ammonium persulfate (manufactured by Mitsubishi Gas Chemical Co., Ltd.) which is a copper etching solution, to remove the copper foil on both sides and prepare a 5 mm square test piece. Next, the thermal expansion coefficient of the test piece from 3 to 120°C was measured using a thermomechanical analyzer (TMA) (manufactured by TA Instruments Japan, Inc., product name: Q400) in accordance with the IPC (The Institute for Interconnecting and Packaging Electronic Circuits) standard. More specifically, measurements were taken twice under conditions of a temperature range of 30 to 260°C, a load of 5 g, and a temperature rise rate of 10°C / min, and the thermal expansion coefficient was taken as the average thermal expansion coefficient in the temperature range of 30 to 120°C in the second measurement. The thermal expansion coefficient was the thermal expansion coefficient in the thickness direction of the resin plate. The results are shown in Tables 3 and 4.

[0128] <Method of measuring copper foil peel strength> For Comparative Example 1, Examples 1 to 3, and Example 5, the copper foil peel strength was measured as an index of adhesion to the metal foil. The resin plate with copper foil on both sides obtained as described above was etched to remove the copper foil except for a straight line portion 3 mm wide, and used as a test piece. The straight line copper foil thus formed was attached to a small tabletop tester (Shimadzu Corporation, product name "EZ-TEST") and peeled at room temperature (25°C) in a 90° direction to measure the peel strength. The pulling speed when peeling the copper foil was 50 mm / min. The results are shown in Table 3.

[0129] [Table 3]

[0130] [Table 4]

[0131] As shown in Table 3, Examples 1 to 6 in which compounds 1 to 6 were used had smaller ΔDf (24 hr-immediately after drying) values ​​than Comparative Example 1 in which compound 7 was used, indicating that deterioration of dielectric properties due to moisture absorption was suppressed. Furthermore, as shown in Table 4, in Examples 7 to 9 in which a resin composition containing compound 1, 4 or 5 was used, the ΔDf (24 hr-immediately after drying) value was smaller than that in Comparative Example 2 in which compound 7 was used, indicating that deterioration of dielectric properties due to moisture absorption was suppressed.

Claims

1. An indene ring, A vinylbenzyl group, an aromatic ring-containing group having 6 or more carbon atoms and no polymerizable carbon-carbon double bond, The compound, wherein the vinylbenzyl group and the aromatic ring-containing group are each directly bonded to the indene ring.

2. A compound represented by the following formula (1): 【Chemistry 1】 (In formula (1), R １ ~R ４ R each independently represents a hydrogen atom or a monovalent substituent. １ , R ２ and R ３ At least one of R is a vinylbenzyl group; １ , R ２ and R ３ At least one of the four R's is an aromatic ring-containing group having 6 or more carbon atoms and no polymerizable carbon-carbon double bond. ４ may all be different from each other, and the four R ４ Two or more of them may be the same.)

3. The compound according to claim 1 or 2, wherein the aromatic ring-containing group is an aryl group that is unsubstituted or has a substituent that does not have a polymerizable carbon-carbon double bond, or an arylalkyl group that is unsubstituted or has a substituent that does not have a polymerizable carbon-carbon double bond.

4. The compound according to claim 3, wherein the aromatic ring-containing group is an unsubstituted benzyl group or a benzyl group having a substituent that does not have a polymerizable carbon-carbon double bond.

5. A resin composition comprising the compound according to claim 1 or 2.

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

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

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

9. A printed wiring board comprising a cured product of the resin composition 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 resin composition according to claim 5 that encapsulates the semiconductor element.

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

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