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

Abstract

To provide a compound and a resin that exhibit reduced temporal variation in dielectric characteristics in a cured product, as well as a curable composition, a prepreg, a resin film, a metal-clad laminate, a printed wiring board, and a semiconductor package using the same.SOLUTION: A compound comprises an indene ring, a vinylbenzyl group, and an arylalkyl group, where the aryl group in the arylalkyl group has a polycyclic aromatic hydrocarbon structure comprising two or more condensed rings, and where the vinylbenzyl group and the arylalkyl group are each directly attached to the indene ring.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to a compound, a resin, a curable 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 and a resin that exhibit minimal change over time in the dielectric properties of the cured product, as well as a curable composition, a prepreg, a resin film, a metal-clad laminate, a printed wiring board, and a semiconductor package that use the compound and a resin. [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, and an arylalkyl group, the aryl group in the arylalkyl group has a polycyclic aromatic hydrocarbon structure containing two or more condensed rings, A compound in which the vinylbenzyl group and the arylalkyl group are each directly bonded to the indene ring. <2> A compound represented by the following formula (1):

[0008] [ka]

[0009] (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 arylalkyl group, and the aryl group in the arylalkyl group has a polycyclic aromatic hydrocarbon structure containing two or more condensed rings. 4 may all be different from each other, and the four R 4 Two or more of them may be the same.) <3> the aryl group in the arylalkyl group is at least one selected from the group consisting of a naphthyl group which may have a substituent, an anthryl group which may have a substituent, and a phenanthryl group which may have a substituent; <1> or <2> The compound according to claim 1, <4> The resin contains two or more compounds represented by the following formula (2) each having a different structure, and R 1 , R 2 and R 3 At least one of R 1 , R 2 and R 3 At least one of the above is an arylalkyl group, and the aryl group in the arylalkyl group has a polycyclic aromatic hydrocarbon structure containing two or more condensed rings.

[0010] [ka]

[0011] (In formula (2), R 1 ~R 4 Each of R independently represents a hydrogen atom or a monovalent substituent. 4 may all be different from each other, and the four R 4 Two or more of them may be the same.) <5> the molar ratio of the vinylbenzyl group to the arylalkyl group present in the resin is within a range of 1:0.1 to 1:2; <4> The resin described in <6> the aryl group in the arylalkyl group is at least one selected from the group consisting of a naphthyl group which may have a substituent, an anthryl group which may have a substituent, and a phenanthryl group which may have a substituent; <4> or <5> The resin described in <7> <1> ~ <3> or <4> ~ <6> A curable composition comprising the resin according to any one of claims 1 to 5. <8> <7> A prepreg comprising the curable composition according to claim 1 or a semi-cured product of the curable composition. <9> <7> A resin film comprising the curable composition according to any one of claims 1 to 5 or a semi-cured product of the curable composition. <10> <7> A metal-clad laminate comprising a cured product of the curable composition according to claim 1 and a metal foil. <11> <7> A printed wiring board comprising a cured product of the curable composition according to claim 1. <12> <11> A semiconductor package comprising the printed wiring board according to claim 1 and a semiconductor element. <13> A semiconductor element and a device for sealing the semiconductor element <7> and a cured product of the curable composition according to claim 1. <14> <7> A printed wiring board comprising at least one of a surface protective film and an interlayer insulating film formed from the curable composition according to claim 1. Effect of the Invention

[0012] The present disclosure makes it possible to provide compounds and resins in which the dielectric properties of the cured product change little over time, as well as curable compositions, prepregs, resin films, metal-clad laminates, printed wiring boards, and semiconductor packages using the same. [Brief description of the drawings]

[0013] [Figure 1] FIG. 1 is a 1H-NMR spectrum of the reaction mixture when Resin B was produced in Example 1. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] Hereinafter, the embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments.

[0015] 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.

[0016] In the present disclosure, unless otherwise specified, each component may contain one or more corresponding substances.

[0017] In the present disclosure, when a plurality of substances corresponding to each component are present in the curable composition, the content of each component in the curable composition means the total amount of the plurality of substances present in the curable composition, unless otherwise specified.

[0018] 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.

[0019] 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.

[0020] 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℃ [Compound] The compound according to one embodiment of the present disclosure is a compound that includes an indene ring, a vinylbenzyl group, and an arylalkyl group, in which the aryl group in the arylalkyl group has a polycyclic aromatic hydrocarbon structure containing two or more condensed rings, and the vinylbenzyl group and the arylalkyl group are each directly bonded to the indene ring. Hereinafter, this compound may be referred to as "compound A".

[0021] Since the vinylbenzyl group has a relatively low polarity, it can contribute to excellent dielectric properties. On the other hand, the inventors of the present application have found that the dielectric property value of a cured product obtained by using a compound having an indene ring and a vinylbenzyl group may increase over time. As a result of intensive research by the inventors of the present application, it has been found that a compound having an arylalkyl group having a polycyclic aromatic hydrocarbon structure containing two or more condensed rings, together with an indene ring and a vinylbenzyl group, can suppress the increase in the dielectric property value of the cured product over time. Although not bound by a specific theory, it is believed that the presence of a relatively bulky and highly hydrophobic polycyclic aromatic hydrocarbon structure makes it difficult for water molecules to approach, thereby suppressing moisture absorption.

[0022] In addition, prepregs, which are materials used in electronic devices, are generally required to have low tackiness in order to improve workability, but Compound A can reduce the tackiness when used in prepregs. Without being bound by a particular theory, it is presumed that this is due to, for example, the relatively high crystallinity of the polycyclic aromatic hydrocarbon structure.

[0023] Compound A can have an indene ring and one or more vinylbenzyl groups and one or more arylalkyl groups each bonded to the indene ring.

[0024] Compound A has one or more vinylbenzyl groups in one molecule, and a cured product can be obtained by accelerating the reaction of the vinylbenzyl groups by heating or the like.

[0025] Compound A may have two vinylbenzyl groups. Compound A may have two arylalkyl groups. Compound A may have 1 to 2 vinylbenzyl groups and 1 to 2 arylalkyl groups. Compound A may have a total of 2 or 3 vinylbenzyl groups and arylalkyl groups.

[0026] When compound A has two vinylbenzyl groups, they may all be different from each other, or the two may be the same.

[0027] When compound A has two arylalkyl groups, they may all be different from each other, or the two may be the same.

[0028] Compound A may, for example, be a hydrocarbon compound.

[0029] In the compound A, the vinylbenzyl group may further have a substituent. For example, the vinylbenzyl group is represented by the following formula (3).

[0030] [ka]

[0031] In formula (3), 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. 5 may 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 (3), * represents a bonding site to the indene ring.

[0032] 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.

[0033] 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.

[0034] 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.

[0035] 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).

[0036] 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. 5 may 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.

[0037] 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.

[0038] 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.

[0039] 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 arylalkyl group may be further bonded to at least one of the substitutable positions among the 1st, 2nd and 3rd carbon atoms of the indene ring.

[0040] In the indene ring, the 1st to 7th positions are as shown below.

[0041] [ka]

[0042] The arylalkyl group may be a monovalent group. The aryl group in the arylalkyl group has a polycyclic aromatic hydrocarbon structure containing two or more condensed rings. The polycyclic aromatic hydrocarbon structure may contain two or more condensed rings, and the specific structure is not particularly limited, but examples thereof include a naphthalene structure, an anthracene structure, a phenanthroline structure, a tetracene structure, a chrysene structure, a pyrene structure, and a triphenylene structure. The number of condensed rings in the polycyclic aromatic hydrocarbon structure may be 2 or 3. For example, the aryl group in the arylalkyl group may be a naphthyl group which may have a substituent, an anthryl group which may have a substituent, or a phenanthryl group which may have a substituent. Among them, the naphthyl group which may have a substituent is preferable because it has an excellent balance between the solvent solubility of the compound A and the tackiness reducing effect in the cured product. When the aryl group in the arylalkyl group is a naphthyl group which may have a substituent, the bonding position of the alkyl group on the naphthyl group may be either the 1st position or the 2nd position. Among these, it is preferable that the bonding position of the alkyl group on the naphthyl group is the 1st position, in view of the availability of reaction raw materials.

[0043] The arylalkyl group may have a substituent on the aryl group. The substituent may be, for example, a halogen atom or a monovalent organic group. 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, or a thioalkoxy group having 1 to 5 carbon atoms. The number of the substituents is not particularly limited and may be 1 or 2 or more. When a plurality of substituents are present, the substituents may all be different from each other, or two or more of the substituents may be the same as each other.

[0044] The halogen atom may be a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. The alkyl group having 1 to 5 carbon atoms may be a straight-chain 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. The alkoxy group having 1 to 5 carbon atoms may be, for example, a group represented by RO-, where R is the alkyl group having 1 to 5 carbon atoms described above. The thioalkoxy group having 1 to 5 carbon atoms may be, for example, a group represented by RS-, where R is the alkyl group having 1 to 5 carbon atoms described above.

[0045] Examples of the alkyl group in the arylalkyl group include alkyl groups having 1 to 5 carbon atoms, more specifically, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, etc. Among them, methyl group or ethyl group is preferred, and methyl group is more preferred, since it results in a compound in which the dielectric properties of the cured product change less over time.

[0046] The arylalkyl group may be at least one selected from the group consisting of a naphthylmethyl group which may have a substituent, an anthrylmethyl group which may have a substituent, and a phenanthrylmethyl group which may have a substituent. Among them, the naphthylmethyl group which may have a substituent is preferable, and the unsubstituted naphthylmethyl group is more preferable, because it is excellent in balance between the solvent solubility of compound A and the tackiness reducing effect in the cured product.

[0047] The arylalkyl group 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 arylalkyl group may be bonded only to any one of the 1st, 2nd or 3rd carbon atoms of the indene ring. For example, two arylalkyl groups may be directly bonded to the 1st carbon atom of the indene ring. For example, one arylalkyl group may be directly bonded to each 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.

[0048] When compound A contains two arylalkyl groups, the two or more arylalkyl groups may be the same or different.

[0049] Compound A may further have a monovalent substituent other than a vinylbenzyl group and an arylalkyl group on a carbon atom of the indene ring. Compound A may have a monovalent substituent other than a vinylbenzyl group and an arylalkyl group on one or more of the carbon atoms at the 4-, 5-, 6-, and 7-positions of the indene ring, for example.

[0050] Examples of the monovalent substituent other than the vinylbenzyl group and the arylalkyl group 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.

[0051] 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.

[0052] Compound A may be, for example, a compound that does not have a monovalent substituent other than a vinylbenzyl group or an arylalkyl group on a carbon atom of an indene ring.

[0053] 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 arylalkyl group 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.

[0054] 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 arylalkyl group 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.

[0055] Another embodiment of the present disclosure is a compound represented by the following formula (1): This compound is a specific example of the compound A.

[0056] [ka]

[0057] (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 arylalkyl group, and the aryl group in the arylalkyl group has a polycyclic aromatic hydrocarbon structure containing two or more condensed rings.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 arylalkyl group are as defined above.

[0058] 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.

[0059] 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.

[0060] In formula (1), R 1 , R 2 and R 3 In addition, one or two of R may be a vinylbenzyl group. 1 , R 2 and R 3 In formula (1), one or two of the remaining R may be an arylalkyl group. 1 , R 2 and R3 one or two of R 1 , R 2 and R 3 In formula (1), one or two of the remaining R are arylalkyl groups, and the total number of vinylbenzyl groups and arylalkyl groups may be two or three. 4 may all be hydrogen atoms. [resin] A resin according to another embodiment of the present disclosure includes two or more compounds having different structures among compounds represented by the following formula (2), and R 1 , R 2 and R 3 At least one of R 1 , R 2 and R 3 At least one of the groups is an arylalkyl group, and the aryl group in the arylalkyl group has a polycyclic aromatic hydrocarbon structure containing two or more condensed rings. Hereinafter, this resin may be referred to as "Resin B."

[0061] [ka]

[0062] (In formula (2), R 1 ~R 4 Each of R independently represents a hydrogen atom or a monovalent substituent. 4 may all be different from each other, and the four R 4 Two or more of them may be the same.) In formula (2), R 1 , R 2 , R 3 and R 4 Specific examples of R are the same as those in the above formula (1). 4 may all be hydrogen atoms. The monovalent group may be a vinylbenzyl group or an arylalkyl group. The details of the vinylbenzyl group and the arylalkyl group are as described above. The compound represented by formula (2) is1 ~R 3 are each independently a hydrogen atom, a vinylbenzyl group, or an arylalkyl group; R 4 may all be hydrogen atoms.

[0063] In resin B, R present in the resin 1 , R 2 and R 3 At least one of R 1 , R 2 and R 3 At least one of them is an arylalkyl group. The ratio of the two present in the resin may be such that the ratio of the arylalkyl group to 1 mole of the vinylbenzyl group is 0.1 moles or more, or may be 0.3 moles or more. The ratio of the arylalkyl group to 1 mole of the vinylbenzyl group may be 2 moles or less, or may be 1 mole or less. In particular, the molar ratio of the vinylbenzyl group to the arylalkyl group present in the resin is preferably in the range of 1:0.1 to 1:2, and more preferably in the range of 1:0.3 to 1:1, in order to obtain an excellent balance between the curability of the resin and the various properties of the cured product.

[0064] In the resin B, the ratio of vinylbenzyl groups to 1 mole of indene ring structures may be 0.8 moles or more, or may be 1 mole or more. The ratio of vinylbenzyl groups to 1 mole of indene ring structures may be 2.5 moles or less, or may be 2 moles or less. In particular, the molar ratio of indene ring structures to vinylbenzyl groups is preferably in the range of 1:0.8 to 1:2.5, and more preferably in the range of 1:1 to 1:2, in order to achieve an excellent balance between the curability of the resin and the various properties of the cured product.

[0065] In the resin B, the ratio of the arylalkyl group to 1 mole of the indene ring structure may be 0.1 moles or more, or may be 0.5 moles or more. The ratio of the arylalkyl group to 1 mole of the indene ring structure may be 2 moles or less, or may be 1.2 moles or less. In particular, the molar ratio of the indene ring structure to the arylalkyl group is preferably in the range of 1:0.1 to 1:2, and more preferably in the range of 1:0.5 to 1:1.2, in order to achieve an excellent balance between the curability of the resin and the various properties of the cured product.

[0066] The following describes a method for synthesizing compound A or resin B. Compound A or resin B is a compound that is specified by its molecular structure, regardless of the synthesis method described below.

[0067] As a method for synthesizing compound A or resin B, for example, a method of reacting a base compound having an indene ring, a styrene having a halogenated methyl group, and a polycyclic aromatic hydrocarbon compound containing two or more condensed rings substituted with a 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. The polycyclic aromatic hydrocarbon compound containing two or more condensed rings substituted with a halogenated alkyl group is a reaction raw material constituting the aryl alkyl group in compound A, and examples thereof include compounds such as chloromethylnaphthalene, which may be one or a mixture of two or more. Examples of basic compounds include alkali metal hydroxides, alkali metal alkoxides, etc.

[0068] 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.

[0069] When the obtained product is a single compound, the compound can be designated as compound A. When the obtained product is a mixture of two or more compounds, the mixture can be designated as resin B. In addition, each compound can be isolated and purified from the mixture to form compound A.

[0070] The dielectric constant (Dk) of the cured product of compound A or resin B 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 compound A or resin B at 25°C and 10 GHz may be, for example, 2.3 or more, or 2.4 or more. Or the dielectric loss tangent (Df) of the cured product of compound A or resin B 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 compound A or resin B 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 or resin B 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.

[0071] The sample to be measured for the dielectric constant (Dk) at 25°C and 10 GHz and the dielectric loss tangent (Df) at 25°C and 10 GHz of the cured product of compound A or resin B is obtained by curing compound A or resin B to a C-stage state according to JIS K 6800 (1985). Specifically, the sample can be prepared 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 curable composition described later.

[0072] Compound A or Resin B 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. [Curable composition] The curable composition of one embodiment of the present disclosure is a curable composition containing the compound A or resin B described above.

[0073] In the present disclosure, the "solid content" of the curable composition refers to the components in the curable composition other than volatile substances such as water and the solvent described below. The solid content is a component that does not volatilize and remains when the curable composition is dried. In addition, it includes those that are liquid at room temperature around 25°C, and does not necessarily mean that they are solid. <Other ingredients> The curable composition may contain other components other than the compound A or resin B, as necessary. Examples of the other components include curable compounds other than the compound A or resin B, fillers, elastomers, curing accelerators, flame retardants, antioxidants, heat stabilizers, antistatic agents, ultraviolet absorbers, pigments, colorants, lubricants, solvents, etc. Each of the other components may be used alone or in combination of two or more.

[0074] The curable composition may further contain a curable compound other than the above-mentioned compound A or resin B. As the curable compound, a compound having a reactive group can be used. For example, the curable compound may be a compound having a reactive group, which is self-curable or curable in combination with a curing agent.

[0075] The curable compound is not particularly limited, and examples thereof include polymerizable unsaturated group-containing compounds, epoxy resins, phenolic resins, cyanate resins, isocyanate resins, benzoxazine resins, oxetane resins, amino resins, dicyclopentadiene resins, silicone resins, triazine resins, melamine resins, etc. Examples of the polymerizable unsaturated group-containing compounds include styrene, divinylbenzene, triallyl isocyanurate, indene skeleton-containing polymerizable compounds, various maleimide compounds, polymerizable unsaturated bond-containing polyphenylene ether compounds, unsaturated polyester resins, allyl resins, etc.

[0076] Among these, from the viewpoints of curability and dielectric properties, polymerizable unsaturated group-containing compounds, epoxy resins, and phenolic resins are preferred.

[0077] 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.

[0078] 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.

[0079] 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.

[0080] An example of a derivative of a compound having one or more N-substituted maleimide groups is an aminomaleimide compound that contains 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.

[0081] Among the maleimide compounds, compounds having two or more N-substituted maleimide groups and derivatives thereof are preferred in terms of excellent curability, and aromatic bismaleimide compounds, aromatic polymaleimide compounds, and derivatives thereof are preferred in terms of excellent heat resistance and dielectric properties of the cured product.

[0082] 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.

[0083] The ratio of compound A or resin B to the total mass of the curable components in the curable composition may be 10 mass% or more, 20 mass% or more, 30 mass% or more, or 50 mass% or more. It may be 100 mass% or less, 90 mass% or less, or 80 mass% or less. More specifically, the curable components in the curable composition refer to compound A, resin B, and thermosetting compounds other than compound A or resin B.

[0084] 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.

[0085] 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.

[0086] When the curable composition contains a filler, the amount of the filler added may be in the range of 50 to 300 parts by mass per 100 parts by mass of the curable component in the curable composition.

[0087] 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.

[0088] 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 preferable. 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-based polymerization initiator include 2,2'-azobis(2,4,4-trimethylpentane), dimethyl 2,2'-azobis(2-methylpropionate), 2,2'-azobis(N-butyl-2-methylpropionamide), 2,2'-azobis[N-(2-propenyl)-2-methylpropionamide], 1,1'-azobis(cyclohexane-1-carbonitrile), and dimethyl 1,1'-azobis(1-cyclohexanecarboxylate). , 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2-methylpropanenitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 4,4'-azobis(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl 4-cyanopentanoate), and the like. Examples of 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.

[0089] When the curable composition contains a curing accelerator, the amount of the curing accelerator added may be in the range of 0.01 to 5 parts by mass per 100 parts by mass of the curable component in the curable composition.

[0090] Examples of the flame retardant include phosphorus-based flame retardants, nitrogen-based flame retardants, silicone-based flame retardants, inorganic flame retardants, etc. When the curable composition contains a curing accelerator, the amount of the curing accelerator added may be in the range of 0.5 to 30 parts by mass per 100 parts by mass of the curable component in the curable composition.

[0091] The curable composition may be solvent-free or may contain a solvent. The solvent can adjust the viscosity of the curable composition to further improve the coatability. The solvent is preferably an organic solvent.

[0092] 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.

[0093] When the curable composition contains a solvent, the solid content of the curable 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 curable composition. <Method of producing curable composition> The method for producing the curable composition is not particularly limited. The curable 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 curable composition, an optional component can be added to compound A or resin B as necessary and mixed to obtain a curable composition. More specifically, for example, compound A or resin B can be dissolved or dispersed in a solvent, and other components can be added and mixed as necessary to obtain a curable 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. <Dielectric properties of the cured product of the curable composition> The dielectric constant (Dk) of the cured product of the curable 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 curable 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.

[0094] For example, the relative dielectric constant (Dk) of the cured product of the curable 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.

[0095] The dielectric loss tangent (Df) of the cured product of the curable 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 dielectric loss tangent (Df) of the cured product of the curable composition at 25° C. and 10 GHz is preferably as small as possible, and there is no particular restriction on the lower limit, but it may be, for example, 0.0001 or more, or 0.0002 or more, taking into consideration the balance with other physical properties.

[0096] For example, the dielectric loss tangent (Df) of the cured product of the curable 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.

[0097] 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 PNA Network Analyzer N5227A manufactured by Agilent Technologies and an SPDR manufactured by QWED can be used.

[0098] The sample to be measured for the dielectric constant (Dk) and dielectric loss tangent (Df) of the cured product of the curable composition is the cured composition that has been cured to the C-stage state according to JIS K 6800 (1985). Specifically, the sample can be prepared, for example, by the method described in the Examples. [Prepreg] According to one embodiment, a prepreg containing a curable composition or a semi-cured product of the curable composition can be provided. The prepreg can be formed, for example, by using the curable composition and a fiber substrate. The curable composition can be the above-mentioned curable composition. Details of the curable composition are as described above.

[0099] The prepreg may contain the above-described curable composition or a semi-cured product of the above-described curable composition.

[0100] In the present disclosure, one index of a semi-cured product may be the B-stage state according to JIS K 6800 (1985).

[0101] The prepreg may contain, for example, a curable composition or a semi-cured product of the curable composition and a fibrous substrate such as a sheet-like fibrous substrate. In the prepreg, the curable composition may be in an uncured state, or the curable composition may be in a partially or entirely semi-cured state.

[0102] The prepreg can be obtained, for example, by coating a fiber substrate with a curable composition and drying it. For example, the prepreg can be obtained by impregnating and coating a fiber substrate with a curable composition and drying the fiber substrate impregnated with the curable composition. The drying is preferably performed at a temperature at which volatile components such as a solvent that may be contained in the curable composition are removed or higher, and may be performed at a temperature at which the thermosetting resin contained in the curable 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 curable 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.

[0103] 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.

[0104] The material of the fibers may be either inorganic or organic.

[0105] 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.

[0106] From the viewpoints of dielectric properties and heat resistance, the material of the fiber substrate is preferably inorganic fiber, and more preferably glass fiber.

[0107] The fiber base material may be appropriately selected depending on the application of the prepreg, but a sheet-like fiber base material is preferred.

[0108] 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.

[0109] 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. [Resin film] According to one embodiment, a resin film containing the curable composition or a semi-cured product of the curable composition can be provided. Details of the curable composition are as described above.

[0110] The resin film may contain the above-mentioned curable composition or a semi-cured product of the above-mentioned curable composition. In the resin film, the curable composition may be in an uncured state, but the curable 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.

[0111] The resin film can be obtained, for example, by applying a curable 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.

[0112] 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. [Metal-clad laminate] According to one embodiment, a metal-clad laminate including a cured product of the curable composition and a metal foil can be provided. The metal-clad laminate may be, for example, a metal-clad laminate including a cured product of a prepreg and a metal foil.

[0113] 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.

[0114] The details of the curable 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).

[0115] The metal-clad laminate preferably includes a resin cured product layer containing a curable 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 curable 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.

[0116] 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.

[0117] 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 curable composition according to one embodiment.

[0118] Next, a metal foil is placed on at least one surface of this laminate.

[0119] The laminate with the metal foil disposed thereon is heated and pressurized. This causes the curing reaction of the sheet-like prepreg to proceed, and a cured prepreg can be obtained. In addition, 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 5 to 50 kg / cm. 2 After the heating and pressurizing, the prepreg may be reheated to further promote curing. The reheating temperature in this case may be 100 to 300°C.

[0120] 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.

[0121] 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.

[0122] The dielectric characteristics 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.

[0123] 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.

[0124] 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.

[0125] 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.

[0126] 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.

[0127] 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 accordance with the measurement of the dielectric constant (Dk) and dielectric loss tangent (Df) of the cured product of the curable composition at 25°C and 10 GHz described above.

[0128] 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 curable composition from 30 to 120° C. described above. [Printed wiring board] According to one embodiment, a printed wiring board including a cured product of the curable 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 curable composition can be provided. Details of the curable composition are as described above.

[0129] In the printed wiring board, the cured product of the curable composition can be produced using the curable 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 the cured product of the 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.

[0130] The printed wiring board may be either a single-layer printed wiring board or a multi-layer printed wiring board. [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 curable composition and a semiconductor element can be provided. Details of the curable composition are as described above. Details of the cured product of the curable 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 curable composition may be used as an insulating material, a sealing material, or the like of the semiconductor package. For example, a semiconductor package including a semiconductor element and a cured product of the curable composition that seals the semiconductor element can be provided. EXAMPLES

[0131] 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. Measurement method for 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.

[0132] 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~5mL Injection volume: 20μL or 2μL Flow rate: 0.35mL / min Measurement temperature: 40℃ 1 How to measure H-NMR spectra CDCl3 was used as the deuterated solvent, and measurements were performed using an "ECX400" made by JEOL RESONANCE Co., Ltd. Example 1: Preparation of Resin B Containing Compound A In a reaction vessel equipped with a stirrer, a thermometer, a reflux tube, and a nitrogen inlet, 24.8 parts by mass of indene, 48.9 parts by mass of chloromethylstyrene (*1), 5.16 parts by mass of tetra-n-butylammonium bromide (manufactured by Kanto Chemical Co., Ltd.) as a phase transfer catalyst, 0.0851 parts by mass of phenothiazine as a polymerization inhibitor, and 114 parts by mass of toluene as a solvent were charged, and the mixture was heated and stirred at 40°C while blowing in nitrogen at a flow rate of 300 ml / min. Next, 71.2 parts by mass of a 48% by mass aqueous sodium hydroxide solution (manufactured by Kanto Chemical Co., Ltd.) as a basic compound was added. After stirring at 70°C for 2 hours, 30.2 parts by mass of 1-chloromethylnaphthalene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. Stirring was then continued for 5 hours at 70°C. Nitrogen was continued to be blown in during the reaction. The reaction mixture was cooled to room temperature (25°C), neutralized with a 10% aqueous hydrochloric acid solution, and washed three times with pure water. The organic phase was precipitated in methanol to obtain resin B containing compound A.

[0133] In the above manufacturing process, a small amount of sample was taken from the reaction mixture after a total of 7 hours of reaction at 70°C, neutralized with a 10% aqueous hydrochloric acid solution, and the obtained organic layer was 1 The H-NMR spectrum was measured and is shown in Figure 1. 1 The progress of the desired reaction was confirmed by comparing H-NMR spectra and confirming the shift or disappearance of the peaks. Specifically, it was found that the reaction of bonding a vinylbenzyl group or a naphthylmethyl group to the 1- to 3-positions of the indene ring had occurred from the shift or disappearance of the H peak at the 1-position of indene, the shift or disappearance of the H peak at the 2- and 3-positions of indene, the shift of the methylene peaks of chloromethylstyrene and 1-chloromethylnaphthalene, and the shift of the vinyl peak of chloromethylstyrene.

[0134] (*1) Chloromethylstyrene “CMS-P”: AGC Seimi Chemical Co., Ltd., a mixture of m- and p-isomers, with m- and p-isomer content of approximately 50% by mass and p-isomer content of approximately 50% by mass. Comparative Example 1: Production of Comparative Resin (Indene Compound Having Vinylbenzyl Group) In a reaction vessel equipped with a stirrer, a thermometer, a reflux tube and a nitrogen inlet, 35.6 parts by mass of indene, 101.2 parts by mass of the above (*1) chloromethylstyrene, 7.1 parts by mass of tetra-n-butylammonium bromide (Kanto Chemical Co., Ltd.) as a phase transfer catalyst, 0.1 parts by mass of phenothiazine as a polymerization inhibitor, and 77.6 parts by mass of toluene were charged, and the mixture was heated and stirred at 40°C while blowing in nitrogen at a flow rate of 50 ml / min. Next, 46.5 parts by mass of a 48% by mass aqueous sodium hydroxide solution (Kanto Chemical Co., Ltd.) as a basic compound was dropped over 20 minutes, and the mixture was stirred at 60°C for 9 hours. The nitrogen blowing was continued during the reaction. The mixture was cooled to room temperature (25°C), neutralized with a 10% aqueous hydrochloric acid solution, and then washed twice with pure water. After distilling off the toluene under reduced pressure, the resulting viscous liquid was washed with methanol and vacuum dried to obtain a comparative resin. The weight average molecular weight (Mw) of the comparative resin measured by GPC under the above conditions was 500. Preparation and Evaluation of Curable Compositions Each component was mixed according to the amounts shown in Table 1, and stirred and mixed at 25°C to prepare a curable composition with a solid content of about 70% by mass. The solid content was adjusted by adding toluene. When the component is a solution, the amounts shown in Table 1 are expressed as mass% converted to solid content.

[0135] The obtained curable composition was subjected to various evaluation tests according to the following procedures, and the results are shown in Table 1.

[0136] Details of each component listed in Table 1 are as follows. Maleimide resin: an aromatic maleimide compound having an indane skeleton represented by the following formula:

[0137] [ka]

[0138] (In the formula, n is a number from 0.95 to 10.0.) Inorganic filler: Silica with an average particle size of 2.4 μm Flame retardant: "PQ-60" (phosphorus-based flame retardant) manufactured by Daiichi Kogyo Seiyaku Co., Ltd. Curing accelerator: Fujifilm Corporation's "VR-110" (2,2'-azobis(2,4,4-trimethylpentane) Prepreg manufacturing The curable composition was applied to an IPC standard #1078 glass cloth by impregnation, and then heated and dried at 120° C. for 10 minutes to obtain a prepreg. The content of solids derived from the curable composition in the prepreg was about 80% by mass. Manufacturing of double-sided copper-clad laminates An electrolytic copper foil ("SI-VSP-18" manufactured by Mitsui Mining & Smelting Co., Ltd.) having a thickness of 18 μm was laminated on both sides of the prepreg obtained above, with the matte side facing the prepreg side. 2 The laminate was heated and pressed at 110° C. for 60 minutes and then at 230° C. for 60 minutes under vacuum pressing conditions to obtain a double-sided copper-clad laminate. Tackiness of prepreg The surface of the prepreg obtained above was touched with a finger at room temperature and evaluated for the presence or absence of stickiness according to the following criteria.

[0139] A: Non-sticky B: Sticky Evaluation of δDf value The copper foil on both sides of the double-sided copper-clad laminate obtained above was removed by immersing it in a copper etching solution (*2) to prepare a 100mm x 40mm test piece. The dielectric tangent value (Df0) of the obtained test piece immediately after drying at 105°C for 1 hour, and the dielectric tangent value (Df0) after drying at 105°C for 1 hour and then leaving it at an atmospheric temperature of 25±2°C and a humidity of 40±10%RH for 24 hours were measured. 24 ) and measure the difference [(Df 24 )-(Df0)] was defined as the ΔDf value. When the value for the comparative resin was taken as 100, the relative value for Resin B was 61.

[0140] The dielectric loss tangent value was measured.

[0141] (*2) Copper etchant: 10% by weight solution of ammonium persulfate (manufactured by Mitsubishi Gas Chemical Co., Ltd.) Copper foil peel strength measurement The double-sided copper-clad laminate obtained above was immersed in the copper etching solution described above (*2) and the copper foil was removed leaving a 3 mm wide strip to prepare a test specimen. Using a tensile tester (Shimadzu Corporation's "EZ Test"), the strip was peeled off in a 90° direction at a speed of 50 mm / min, and the copper foil peel strength was measured. Solder heat resistance test The double-sided copper-clad laminate obtained above was cut into 30 mm square pieces to be used as test pieces. The test pieces were floated in a solder bath at 288°C, and the appearance was observed to measure the time until blistering occurred. The test was carried out for a maximum of 1800 seconds, and if no blistering was observed by the time 1800 seconds had elapsed, it was evaluated as ">1800".

[0142] [Table 1]

[0143] As shown in Table 1, Example 1 using Resin B had a smaller ΔDf value than Comparative Example 1 using the comparative resin, indicating that the dielectric properties of the cured product changed little over time.

[0144] Furthermore, as shown in Table 1, Example 1 using Resin B maintained the same copper foil peel strength and solder resistance as Comparative Example 1, while suppressing the change over time in the dielectric properties described above, and was also shown to have excellent tackiness.

Claims

1. An indene ring, A vinylbenzyl group, and an arylalkyl group, the aryl group in the arylalkyl group has a polycyclic aromatic hydrocarbon structure containing two or more condensed rings, A compound in which the vinylbenzyl group and the arylalkyl 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 arylalkyl group, and the aryl group in the arylalkyl group has a polycyclic aromatic hydrocarbon structure containing two or more condensed rings. ４ may all be different from each other, and the four R ４ Two or more of them may be the same.)

3. 3. The compound according to claim 1, wherein the aryl group in the arylalkyl group is a naphthyl group which may have a substituent, an anthryl group which may have a substituent, or a phenanthryl group which may have a substituent.

4. The compound R present in the resin contains two or more compounds having different structures among the compounds represented by the following formula (2): １ , R ２ and R ３ At least one of R １ , R ２ and R ３ At least one of the above is an arylalkyl group, and the aryl group in the arylalkyl group has a polycyclic aromatic hydrocarbon structure containing two or more condensed rings. 【Chemistry 2】 (In formula (2), R １ ~R ４ Each of R independently represents a hydrogen atom or a monovalent substituent. ４ may all be different from each other, and the four R ４ Two or more of them may be the same.)

5. The resin of claim 4, wherein the molar ratio of said vinylbenzyl groups to said arylalkyl groups present in the resin ranges from 1:0.1 to 1:

2.

6. The resin according to claim 4, wherein the aryl group in the arylalkyl group is at least one type selected from the group consisting of a naphthyl group which may have a substituent, an anthryl group which may have a substituent, and a phenanthryl group which may have a substituent.

7. A curable composition comprising the compound according to claim 1 or 2, or the resin according to any one of claims 4 to 6.

8. A prepreg comprising the curable composition according to claim 7 or a semi-cured product of the curable composition.

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

10. A metal-clad laminate comprising the cured product of the curable composition according to claim 7 and a metal foil.

11. A printed wiring board comprising a cured product of the curable composition according to claim 7.

12. A semiconductor package comprising the printed wiring board according to claim 11 and a semiconductor element.

13. A semiconductor package comprising: a semiconductor element; and a cured product of the curable composition according to claim 7 that encapsulates the semiconductor element.

14. A printed wiring board comprising at least one of a surface protective film and an interlayer insulating film formed from the curable composition according to claim 7.

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