Resin composition, prepreg, metal foil-clad laminate, resin composite sheet, and printed wiring board

Abstract

The present invention relates to a resin composition, a prepreg, a metal foil-clad laminate, a resin composite sheet, and a printed wiring board. Provided are: a resin composition having a low dielectric constant and dielectric loss tangent and high heat resistance; and a prepreg, a metal foil-clad laminate, a resin composite sheet, and a printed wiring board using the resin composition. The resin composition contains a polyfunctional vinyl aromatic polymer (A) and a thermosetting compound (B), and does not contain a radical polymerization initiator.

Description

[0001] This application is a divisional application of an application with an application date of February 26, 2020, an application number of 202080016923.X, and an invention title of "Resin Composition, Prepreg, Metal-Clad Laminate, Resin Composite Sheet, and Printed Circuit Board". Technical Field

[0002] The present invention relates to a resin composition, a prepreg using the same, a metal-clad laminate, a resin composite sheet, and a printed circuit board. Background Art

[0003] In recent years, the high integration and miniaturization of semiconductor elements used in electronic devices such as portable terminals and communication devices have been accelerating. Along with this, technologies capable of achieving high-density mounting of semiconductor elements are required, and printed circuit boards, which play an important role among them, also need to be improved.

[0004] On the other hand, the uses of electronic devices and the like are diversifying and continuously expanding. Affected by this, various characteristics required for printed circuit boards, metal-clad laminates used therein, prepregs, etc. are also diversified and have become stricter. Considering such demand characteristics and in order to obtain an improved printed circuit board, various materials and processing methods have been proposed. As one of them, the improvement and development of resin materials constituting prepregs can be cited.

[0005] For example, Patent Document 1 discloses a resin composition containing: a terminal vinyl compound (a) of a bifunctional phenylene ether oligomer having a polyphenylene ether skeleton, a specific maleimide compound (b), a naphthol aralkyl type cyanate ester resin (c), and a novolak type epoxy resin (d) having a modified naphthalene skeleton.

[0006] Patent Document 2 discloses a flame-retardant resin composition formed from a resin having a maleimide group at at least one end (an amino bis-maleimide resin based on N,N'-4,4'-diphenylmethane bismaleimide and a diamine), a copolymer of a brominated styrene represented by formula (c1) and a divinylbenzene represented by formula (c2).

[0007]

[0008] Prior Art Documents

[0009] Patent Documents

[0010] Patent Document 1: Japanese Patent Application Laid-Open No. 2010-138364

[0011] Patent Document 2: Japanese Patent Application Laid-Open No. 03-006293 Summary of the Invention

[0012] Problems to be Solved by the Invention

[0013] Including the above examples, various properties in printed circuit boards have been improved through their material development. However, in view of the development of technology and the expansion of applications, further performance improvement is required. Especially in recent years, materials with high heat resistance and low dielectric constant / low dielectric loss tangent are in demand.

[0014] An object of the present invention is to solve this problem, and it is to provide a resin composition having a low dielectric constant and a low dielectric loss tangent and high heat resistance, a prepreg using the same, a metal foil-clad laminate, a resin composite sheet, and a printed circuit board.

[0015] Solutions for Solving the Problems

[0016] Based on the above problems, the present inventors have studied the composition of a resin composition particularly suitable for uses such as prepregs in printed circuit boards, and as a result, it has been found that a resin composition containing a polyfunctional vinyl aromatic polymer and a thermosetting compound exhibits a low dielectric constant / low dielectric loss tangent and high heat resistance. However, it has been found that when a radical polymerization initiator is added, these properties are poor. The present invention has been completed based on this finding. Specifically, the above problems are solved by the following aspect <1>, preferably by <2> to <11>.

[0017] <1> A resin composition comprising a polyfunctional vinyl aromatic polymer (A) and a thermosetting compound (B), and not containing a radical polymerization initiator.

[0018] <2> The resin composition according to <1>, wherein the polyfunctional vinyl aromatic polymer (A) is a polymer having a structural unit represented by formula (V).

[0019]

[0020] (In the formula, Ar represents an aromatic hydrocarbon linking group. * represents the bonding position.)

[0021] <3> The resin composition according to <1> or <2>, wherein the thermosetting compound (B) has one or more functional groups selected from the group consisting of a cyanate group, a vinyl group, a maleimide group, and a nadic imide group.

[0022] <4> The resin composition according to any one of <1> to <3>, wherein the content of the thermosetting compound (B) is 5 to 95 parts by mass with respect to 100 parts by mass of the total amount of the resin components in the resin composition.

[0023] <5>The resin composition according to any one of <1> to <4>, wherein the content of the polyfunctional vinyl aromatic polymer (A) is 5 to 95 parts by mass with respect to 100 parts by mass of the total amount of the resin components in the resin composition.

[0024] <6>The resin composition according to any one of <1> to <5> further comprises a filler (C).

[0025] <7>The resin composition according to <6>, wherein the content of the filler (C) is 10 to 500 parts by mass with respect to 100 parts by mass of the total amount of the resin components in the resin composition.

[0026] <8>A prepreg formed from a base material and the resin composition according to any one of <1> to <7>.

[0027] <9>A metal foil-clad laminate comprising at least one layer formed from the prepreg according to <8> and a metal foil disposed on one or both sides of the layer formed from the prepreg.

[0028] <10>A resin composite sheet comprising a support and a layer formed from the resin composition according to any one of <1> to <7> disposed on the surface of the support.

[0029] <11>A printed circuit board comprising an insulating layer and a conductor layer disposed on the surface of the insulating layer, wherein the insulating layer comprises at least one of a layer formed from the resin composition according to any one of <1> to <7> and a layer formed from the prepreg according to <8>.

[0030] Effects of the Invention

[0031] By the present invention, a resin composition having low dielectric constant and low dielectric loss tangent and high heat resistance, and a prepreg, a metal foil-clad laminate, a resin composite sheet, and a printed circuit board using the same can be provided. Detailed Description of the Invention

[0032] Hereinafter, the content of the present invention will be described in detail according to its preferred embodiments. It should be noted that in this specification, "~" is used to mean the lower limit value and the upper limit value of the numerical values described before and after it.

[0033] The resin composition of the present embodiment is characterized by comprising a polyfunctional vinyl aromatic polymer (A) and a thermosetting compound (B), and not comprising a radical polymerization initiator.

[0034] By adopting such a configuration, a resin composition with low dielectric constant and low dissipation factor tangent and high heat resistance can be provided. Furthermore, the peel strength can also be improved. In addition, various other properties can also be enhanced. In particular, in recent years, communication and working signals tend to have higher frequencies. However, the resin composition of the present embodiment can achieve low dielectric constant / low dissipation factor tangent even in the high-frequency region and improve heat resistance.

[0035] The reason is not limited to the following, but can be considered as follows. That is, the resin composition of the present embodiment is a thermosetting resin composition in which the thermosetting groups of the polyfunctional vinyl aromatic polymer (A) and the thermosetting compound (B) are cured by heat. When such a resin composition does not contain a thermal free radical polymerization initiator, the polymerization start temperature of the polyfunctional vinyl aromatic polymer (A) is close to the polymerization start temperature of the thermosetting compound (B), and the polyfunctional vinyl aromatic polymer (A) and the thermosetting compound (B) can be sufficiently cured together. As a result, low dielectric constant / low dissipation factor tangent and high heat resistance can be achieved. In addition, by not containing a photo free radical polymerization initiator, the photocuring of the polyfunctional vinyl aromatic polymer (A) and the thermosetting compound (B) can be effectively suppressed even when not shielded from light during storage.

[0036] It should be noted that the resin composition of the present embodiment is preferably a non-photosensitive thermosetting resin composition that is not cured by light but mainly cured by heat.

[0037] <Polyfunctional vinyl aromatic polymer (A)>

[0038] The resin composition of the present embodiment contains a polyfunctional vinyl aromatic polymer (A).

[0039] The polyfunctional vinyl aromatic polymer (A) is preferably a polymer obtained by polymerizing an aromatic compound having two or more vinyl groups in the molecule. Among the aromatic compounds having two or more vinyl groups in the molecule, for example, regarding the vinyl groups, all stereoisomers are acceptable, and a mixture of these stereoisomers can also be used. More specifically, when the polyfunctional vinyl aromatic polymer (A) is an aromatic compound having two vinyl groups in the molecule, it can be an m-form, p-form, o-form, or a mixture of these stereoisomers, and any of the m-form, p-form, or a mixture of these stereoisomers is preferred.

[0040] As the monomer constituting the polyfunctional vinyl aromatic polymer (A), aromatic compounds having one or two or more vinyl groups can be mentioned (hereinafter, aromatic compounds having two or more vinyl groups are also referred to as polyfunctional vinyl aromatic compounds), and aromatic compounds having one or two vinyl groups are preferred. For example, as the polyfunctional vinyl aromatic polymer (A), polymers containing a structural unit (a) derived from an aromatic compound having two vinyl groups (also referred to as a divinyl aromatic compound) and a structural unit (b) derived from an aromatic compound having one vinyl group can be exemplified.

[0041] The divinyl aromatic compound forming the structural unit (a) is preferably a compound having a hydrocarbon aromatic ring, and examples thereof include divinylbenzene, diallylbenzene, bis(vinyl oxy)benzene, bis(1-methylvinyl)benzene, divinylnaphthalene, divinylanthracene, divinylbiphenyl, divinylphenanthrene, bis(4-allyloxyphenyl)fluorene, etc. Among them, divinylbenzene is particularly preferred. The mode of the structural unit derived from the divinyl aromatic compound in the polymer can be: (a-1) a mode in which only one vinyl group undergoes a polymerization reaction and the other vinyl group remains unreacted and directly remains; and (a-2) a mode in which both undergo a polymerization reaction. In the present embodiment, a mode (a-1) in which one vinyl group remains unreacted is preferably included. It should be noted that within the scope of exerting the effects of the present invention, the polyfunctional vinyl aromatic compound (preferably the divinyl aromatic compound) may also have an arbitrary substituent Z (examples thereof include an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxyl group, an amino group, a carboxyl group, a halogen atom, etc.).

[0042] The structural unit (a) derived from the above polyfunctional vinyl aromatic compound (preferably the divinyl aromatic compound) preferably contains a structural unit represented by the following formula (V).

[0043]

[0044] In formula (V), Ar represents an aromatic hydrocarbon linking group. As a specific example, the following L 1 can be cited. The * in the formula represents the bonding position.

[0045] The aromatic hydrocarbon linking group may be a group formed only by an aromatic hydrocarbon optionally having a substituent, or a group formed by a combination of an aromatic hydrocarbon optionally having a substituent and other linking groups, and a group formed only by an aromatic hydrocarbon optionally having a substituent is preferred. It should be noted that among the substituents optionally possessed by the aromatic hydrocarbon, the above-mentioned substituent Z can be cited. In addition, the above aromatic hydrocarbon preferably does not have a substituent.

[0046] The aromatic hydrocarbon linking group is usually a divalent linking group.

[0047] Specifically, among the aromatic hydrocarbon linking groups, examples include a phenylene group, a naphthalenediyl group, an anthracenediyl group, a phenanthrenediyl group, a biphenyldiyl group, and a fluorenediyl group, which may optionally have a substituent, and among them, a phenylene group which may optionally have a substituent is preferred. Among the substituents, the above-mentioned substituent Z can be exemplified, but the above-mentioned groups such as the phenylene group preferably do not have a substituent.

[0048] The structural unit (a) derived from a polyfunctional vinyl aromatic compound (preferably a divinyl aromatic compound) more preferably contains at least one of the structural unit represented by the following formula (V1), the structural unit represented by the following formula (V2), and the structural unit represented by the following formula (V3). It should be noted that * in the following formula represents the bonding position.

[0049]

[0050] In formulas (V1) to (V3), L 1 is an aromatic hydrocarbon linking group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and further preferably 6 to 10 carbon atoms). Specifically, examples include a phenylene group, a naphthalenediyl group, an anthracenediyl group, a phenanthrenediyl group, a biphenyldiyl group, and a fluorenediyl group, which may optionally have a substituent, and among them, a phenylene group which may optionally have a substituent is preferred. Among the substituents, the above-mentioned substituent Z can be exemplified, but the above-mentioned groups such as the phenylene group preferably do not have a substituent.

[0051] As described above, the polyfunctional vinyl aromatic polymer (A) can be a homopolymer of the structural unit (a) or a copolymer with the structural unit (b) or the like. When the polyfunctional vinyl aromatic polymer (A) is a copolymer, the copolymerization ratio is preferably 5 mol% or more, more preferably 10 mol% or more, and further preferably 15 mol% or more for the structural unit (a). As the upper limit value, it is practical to be 90 mol% or less.

[0052] When the polyfunctional vinyl aromatic polymer (A) is a copolymer containing the structural unit (b) derived from a monovinyl aromatic compound, examples of the monovinyl aromatic compound include vinyl aromatic compounds such as styrene, vinylnaphthalene, and vinylbiphenyl; nuclear alkyl-substituted vinyl aromatic compounds such as o-methylstyrene, m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene, o-ethylvinylbenzene, m-ethylvinylbenzene, p-ethylvinylbenzene, methylvinylbiphenyl, and ethylvinylbiphenyl. The monovinyl aromatic compounds exemplified here may also appropriately have the above-mentioned substituent Z. In addition, one of these monovinyl aromatic compounds can be used, or two or more can be used.

[0053] The structural unit (b) derived from a monovinyl aromatic compound preferably has the structural unit represented by the following formula (V4).

[0054]

[0055] In formula (V4), L 2 is an aromatic hydrocarbon linking group, and as a preferred specific example, the above-mentioned L 1 can be cited as an example.

[0056] R V1 is a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms (preferably an alkyl group). When R V1 is a hydrocarbon group, its carbon number is preferably 1 to 6, more preferably 1 to 3. R V1 and L 2 may also have the above-mentioned substituent Z.

[0057] When the polyfunctional vinyl aromatic polymer (A) is a copolymer containing the structural unit (b), the copolymerization ratio of the structural unit (b) is preferably 10 mol% or more, more preferably 15 mol% or more. As the upper limit value, it is preferably 98 mol% or less, more preferably 90 mol% or less, and further preferably 85 mol% or less.

[0058] The polyfunctional vinyl aromatic polymer (A) may also have other structural units. As other structural units, for example, a structural unit (c) derived from a cycloolefin compound, etc. can be cited. As the cycloolefin compound, a hydrocarbon having a double bond in the ring structure can be cited. Specifically, in addition to monocyclic cyclic olefins such as cyclobutene, cyclopentene, cyclohexene, and cyclooctene, compounds having a norbornene ring structure such as norbornene and dicyclopentadiene, and cycloolefin compounds formed by condensation of aromatic rings such as indene and acenaphthylene can also be cited. As an example of the norbornene compound, those described in paragraphs 0037 to 0043 of Japanese Patent Laid-Open No. 2018-39995 can be cited, and the content thereof is incorporated into this specification. It should be noted that the cycloolefin compounds exemplified here may also have the above-mentioned substituent Z.

[0059] When the polyfunctional vinyl aromatic polymer (A) is a copolymer containing the structural unit (c), the copolymerization ratio of the structural unit (c) is preferably 10 mol% or more, more preferably 20 mol% or more, and further preferably 30 mol% or more. As the upper limit value, it is preferably 90 mol% or less, more preferably 80 mol% or less, further preferably 70 mol% or less, can be 50 mol% or less, and can also be 30 mol% or less.

[0060] The polyfunctional vinyl aromatic polymer (A) may further incorporate a structural unit (d) derived from a different polymerizable compound (hereinafter also referred to as other polymerizable compounds). Examples of other polymerizable compounds (monomers) include, for example, compounds containing three vinyl groups. Specifically, 1,3,5-trivinylbenzene, 1,3,5-trivinylnaphthalene, 1,2,4-trivinylcyclohexane can be cited. Alternatively, ethylene glycol diacrylate, butadiene, etc. can be cited. The copolymerization ratio of the structural unit (d) derived from other polymerizable compounds is preferably 30 mol% or less, more preferably 20 mol% or less, and further preferably 10 mol% or less.

[0061] As an embodiment of the polyfunctional vinyl aromatic polymer (A), a polymer in which the structural unit (a) is essential and contains at least one of the structural units (b) to (d) can be exemplified. Furthermore, a form in which the total of the structural units (a) to (d) accounts for 95 mol% or more, and further 98 mol% or more of all the structural units can be exemplified.

[0062] As another embodiment of the polyfunctional vinyl aromatic polymer (A), with the structural unit (a) being essential, among all the structural units except the terminals, the structural units containing an aromatic ring are preferably 90 mol% or more, more preferably 95 mol% or more, and may be 100 mol%.

[0063] When calculating the mol% in all the structural units, one structural unit is assumed to be derived from one molecule of the monomer constituting the polyfunctional vinyl aromatic polymer (A).

[0064] The production method of the polyfunctional vinyl aromatic polymer (A) is not particularly limited, and a usual method can be adopted. For example, in the presence of a Lewis acid catalyst, a monomer containing a divinyl aromatic compound (if necessary, a monovinyl aromatic compound, a cycloolefin compound, etc. coexist) is polymerized. As the Lewis acid catalyst, a metal fluoride or its complex can be used.

[0065] The structure of the chain end of the polyfunctional vinyl aromatic polymer (A) is not particularly limited. For the group derived from the above divinyl aromatic compound, a structure represented by the following formula (E1) can be cited. It should be noted that L in the formula (E1) 1 is the same as defined in the above formula (V1). * represents the bonding position.

[0066] *-CH=CH-L 1 -CH=CH2 (E1)

[0067] When the group derived from the monovinyl aromatic compound is the chain end, a structure represented by the following formula (E2) can be cited. L and R in the formula 2 andV1 They have the same meanings as those respectively defined by the aforementioned formula (V4). * represents the bonding position.

[0068] * -CH=CH-L 2 -R V1 (E2)

[0069] The molecular weight of the polyfunctional vinyl aromatic polymer (A) is preferably 300 or more, more preferably 500 or more, and still more preferably 1000 or more in terms of the number average molecular weight Mn. As the upper limit, it is preferably 100,000 or less, more preferably 10,000 or less, still more preferably 5000 or less, and still more preferably 4000 or less. The monodispersity (Mw / Mn) represented by the ratio of the weight average molecular weight Mw to the number average molecular weight Mn is preferably 100 or less, more preferably 50 or less, and still more preferably 20 or less. As the lower limit value, it is actually 1.1 or more. The polyfunctional vinyl aromatic polymer (A) is preferably soluble in toluene, xylene, tetrahydrofuran, dichloroethane or chloroform.

[0070] Regarding the polyfunctional vinyl aromatic polymer (A) in this specification, reference can be made to the compounds and their synthesis reaction conditions described in paragraphs 0029 to 0058 of International Publication No. 2017 / 115813, the compounds and their synthesis reaction conditions described in paragraphs 0013 to 0058 of Japanese Patent Application Laid-Open No. 2018-039995, the compounds and their synthesis reaction conditions described in paragraphs 0008 to 0043 of Japanese Patent Application Laid-Open No. 2018-168347, the compounds and their synthesis reaction conditions described in paragraphs 0014 to 0042 of Japanese Patent Application Laid-Open No. 2006-070136, the compounds and their synthesis reaction conditions described in paragraphs 0014 to 0061 of Japanese Patent Application Laid-Open No. 2006-089683, and the compounds and their synthesis reaction conditions described in paragraphs 0008 to 0036 of Japanese Patent Application Laid-Open No. 2008-248001, and they are incorporated into this specification.

[0071] When the total amount of the resin components in the resin composition is 100 parts by mass, the content of the polyfunctional vinyl aromatic polymer (A) is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 15 parts by mass or more, even more preferably 20 parts by mass or more, and further may be 30 parts by mass or more, 40 parts by mass or more, 50 parts by mass or more, 60 parts by mass or more. By setting the content of the polyfunctional vinyl aromatic polymer (A) to the above lower limit value or more, a low dielectric constant can be achieved particularly effectively. On the other hand, when the total amount of the resin components in the resin composition is 100 parts by mass, the upper limit value of the content of the polyfunctional vinyl aromatic polymer (A) is preferably 95 parts by mass or less, more preferably 90 parts by mass or less, still more preferably 85 parts by mass or less, even more preferably 80 parts by mass or less.

[0072] The polyfunctional vinyl aromatic polymer (A) in the resin composition may contain only 1 type or may contain 2 or more types. When 2 or more types are contained, the total amount is preferably in the above range.

[0073] It should be noted that the resin components include the polyfunctional vinyl aromatic polymer (A) and the thermosetting compound (B), and also include other resin components described later.

[0074] <Thermosetting compound (B)>

[0075] The resin composition of the present embodiment contains a thermosetting compound (B). In this specification, the thermosetting compound (B) means a thermosetting compound other than the polyfunctional vinyl aromatic polymer (A). As the thermosetting compound (B), a compound having one or more functional groups selected from the group consisting of a cyanate group, a vinyl group (wherein, excluding the group that becomes a polyfunctional vinyl aromatic polymer, a maleimide group, and a nadic imide group. A vinylphenyl group is preferred.), a maleimide group, and a nadic imide group is preferred, and a cyanate ester compound (B1) having a cyanate group, a modified polyphenylene ether compound (B2) having a vinyl group (preferably a vinylphenyl group), a maleimide compound (B3) having a maleimide group, and a nadic imide compound (B4) having a nadic imide group are more preferred, and a cyanate ester compound (B1) having a cyanate group, a modified polyphenylene ether compound (B2) having a vinyl group (preferably a vinylphenyl group), and a maleimide compound (B3) having a maleimide group are still more preferred.

[0076] <<Cyanate ester compound (B1)>>

[0077] The cyanate ester compound is a general term for compounds having a cyanato group. The cyanate ester compound (B1) used in the present invention preferably has one or more cyanato groups in one molecule, more preferably two or more. In addition, the upper limit of the number of cyanato groups in one molecule of the cyanate ester compound (B1) is preferably 12 or less, more preferably 10 or less. In addition, the cyanato group of the above cyanate ester compound (B1) is preferably a cyanato group directly bonded to an aromatic ring.

[0078] Examples of the cyanate ester compound (B1) include at least one selected from the group consisting of naphthol aralkyl type cyanate ester compounds (naphthol aralkyl type cyanates), naphthylene ether type cyanate ester compounds, phenol novolak type cyanate ester compounds, biphenyl aralkyl type cyanate ester compounds, bisphenol A type cyanate ester compounds, diallyl bisphenol A type cyanate ester compounds, bisphenol M type cyanate ester compounds, xylene resin type cyanate ester compounds, triphenol methane type cyanate ester compounds, and adamantane skeleton type cyanate ester compounds. Among these, at least one selected from the group consisting of naphthol aralkyl type cyanate ester compounds, naphthylene ether type cyanate ester compounds, and xylene resin type cyanate ester compounds is preferred, and naphthol aralkyl type cyanate ester compounds are more preferred. These cyanate ester compounds can be prepared by known methods or commercially available products can be used.

[0079] As the cyanate ester compound (B1), a naphthol aralkyl type cyanate ester compound represented by the following formula (S1) can be cited. The naphthol aralkyl type cyanate ester compound represented by the formula (S1) is obtained by condensing a naphthol aralkyl resin, and the naphthol aralkyl resin is obtained by the reaction of naphthols such as α-naphthol or β-naphthol with p-xylene glycol, α,α'-dimethoxy-p-xylene, 1,4-bis(2-hydroxy-2-propyl)benzene, etc. Its production method is not particularly limited, and it can be produced by any existing method in cyanate ester synthesis.

[0080]

[0081] In the formula (S1), R C1 ~R C4 each independently represents a hydrogen atom or a methyl group. n C is a number from 1 to 10. Compounds having two or more different n C may also be included.

[0082] Regarding the cyanate ester compound (B1), paragraphs 0024 and 0025 of Japanese Patent Application Laid-Open No. 2010-138364 can be referred to, and the content thereof is incorporated into this specification.

[0083] <<Modified polyphenylene ether compound (B2)>>

[0084] The thermosetting compound (B) is preferably a modified polyphenylene ether compound (B2) whose ends are modified with a substituent containing a vinyl group (preferably vinylphenyl). The modified polyphenylene ether compound (B2) used in the present invention preferably has 1 or more vinyl groups in 1 molecule, more preferably 2 or more. In addition, the upper limit of the number of vinyl groups in 1 molecule of the modified polyphenylene ether compound (B2) is preferably 5 or less, more preferably 3 or less.

[0085] The modified polyphenylene ether compound (B2) is, for example, a modified product in which all or part of the ends of the polyphenylene ether are end-modified with a vinyl group or vinylphenyl. The "polyphenylene ether" in this specification refers to a compound having a polyphenylene ether skeleton represented by the following formula (X1).

[0086]

[0087] In formula (X1), R 24 , R 25 , R 26 , and R 27 may be the same or different and represent an alkyl group having 6 or less carbon atoms, an aryl group, a halogen atom, or a hydrogen atom. * Represents the bonding position.

[0088] The modified polyphenylene ether may further contain a repeating unit represented by formula (X2) or formula (X3).

[0089]

[0090] In formula (X2), R 28 , R 29 , R 30 , R 34 , R 35 may be the same or different and are an alkyl group having 6 or less carbon atoms or a phenyl group. R 31 , R 32 , R 33 may be the same or different and are a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. * Represents the bonding position.

[0091]

[0092] In formula (X3), R 36 , R 37 , R 38 , R 39 , R 40 , R 41 , R 42 , R 43 may be the same or different and are a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. A is a linear, branched, or cyclic divalent hydrocarbon having 1 or more and 20 or less carbon atoms. * Represents the bonding position.

[0093] As the modified polyphenylene ether compound (B2), modified polyphenylene ethers in which part or all of them are functionalized with an ethylenically unsaturated group such as vinylbenzyl, an epoxy group, an amino group, a hydroxyl group, a mercapto group, a carboxyl group, or a silyl group can also be used. One of these or a combination of two or more thereof can also be used. Examples of the polyphenylene ether having a hydroxyl group at the terminal include SA90 manufactured by SABIC INNOVATIVE PLASTICS CO., LTD.

[0094] The method for producing the modified polyphenylene ether compound (B2) is not particularly limited as long as the effects of the present invention can be obtained. For example, the modified polyphenylene ether compound functionalized with vinylbenzyl can be produced by dissolving a difunctional phenylene ether oligomer and vinylbenzyl chloride in a solvent, adding a base under heating and stirring to cause a reaction, and then solidifying the resin. The modified polyphenylene ether compound functionalized with a carboxyl group can be produced, for example, by melt-kneading an unsaturated carboxylic acid and a derivative functionalized therewith in the polyphenylene ether in the presence or absence of a radical initiator and causing a reaction. Alternatively, it can be produced by dissolving the polyphenylene ether and the unsaturated carboxylic acid and its functional derivative in an organic solvent in the presence or absence of a radical initiator and causing a reaction in solution.

[0095] The modified polyphenylene ether compound (B2) preferably contains a modified polyphenylene ether having at least one (preferably both ends) ethylenically unsaturated group (hereinafter sometimes referred to as "modified polyphenylene ether (g)"). Examples of the ethylenically unsaturated group include alkenyl groups such as vinyl, allyl, acryloyl, methacryloyl, propenyl, butenyl, hexenyl, and octenyl, cycloalkenyl groups such as cyclopentenyl and cyclohexenyl, and alkenylaryl groups such as vinylphenyl, vinylbenzyl, and vinylnaphthyl. The two ethylenically unsaturated groups at both ends may be the same functional group or different functional groups.

[0096] Examples of the modified polyphenylene ether (g) include the structure represented by formula (1).

[0097]

[0098] In formula (1), X a represents an aromatic group, (Y a -O)m represents a polyphenylene ether moiety, R 1 , R 2 , R 3 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, or an alkynyl group, m represents a number from 1 to 100, n represents a number from 1 to 6, and q represents a number from 1 to 4. Preferably, R 1 , R 2 , R 3is a hydrogen atom. Preferably, m is a number of 1 or more and 50 or less, more preferably a number of 1 or more and 30 or less. Preferably, n is a number of 1 or more and 4 or less, more preferably n is 1 or 2, and even more preferably n is 1. Additionally, preferably, q is a number of 1 or more and 3 or less, more preferably q is 1 or 2, and even more preferably q is 2.

[0099] It may also contain two or more compounds with different m, n, and q respectively.

[0100] The modified polyphenylene ether (g) is preferably represented by formula (2).

[0101]

[0102] At least one of a and b in formula (2) is not 0, and represents a number from 0 to 100. a and b are preferably numbers of 1 or more and 50 or less, more preferably numbers of 1 or more and 30 or less.

[0103] Here, -(O-X-O)- is preferably represented by formula (3) or formula (4). It may also contain two or more compounds with different a and b.

[0104]

[0105] In formula (3), R 4 , R 5 , R 6 , R 10 , R 11 may be the same or different, and is an alkyl group or a phenyl group having 6 or less carbon atoms. R 7 , R 8 , R 9 may be the same or different, and is a hydrogen atom, an alkyl group or a phenyl group having 6 or less carbon atoms. * indicates the bonding position.

[0106]

[0107] In formula (4), R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 may be the same or different, and is a hydrogen atom, an alkyl group or a phenyl group having 6 or less carbon atoms. A 1 is a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms. * indicates the bonding position.

[0108] In addition, -(Y-O)- in formula (2) is preferably represented by formula (5).

[0109]

[0110] In formula (5), R 22 , R 23 R may be the same or different and is a hydrogen atom, an alkyl group with a carbon number of 6 or less, or a phenyl group. 20 , R 21 The groups may be the same or different and are an alkyl group having 6 or less carbon atoms or a phenyl group.

[0111] As A in formula (4) 1 , for example, divalent organic groups such as methylene, ethylidene, 1-methylethylidene, 1,1-propylidene, 2,2-propylidene, 1,4-phenylenebis(1-methylethylidene), 1,3-phenylenebis(1-methylethylidene), cyclohexylidene, phenylmethylene, naphthylmethylene, and 1-phenylethylidene can be mentioned, but are not limited to these.

[0112] Among the above modified polyphenylene ethers, R 4 , R 5 , R 6 , R 10 , R 11 , R 20 , R 21 is an alkyl group with a carbon number of 3 or less, R 7 , R 8 , R 9 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 22 , R 23 The polyphenylene ether is a hydrogen atom or an alkyl group with a carbon number of 3 or less, and it is particularly preferred that -(OXO)- represented by formula (3) or formula (4) is formula (9), formula (10) and / or formula (11), and -(YO)- represented by formula (5) is formula (12) or formula (13), or a structure in which formula (12) and formula (13) are randomly arranged.

[0113]

[0114] In formula (10), R 44 , R 45 , R 46 , R 47 A may be the same or different and is a hydrogen atom or a methyl group. 2 A is a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms. * is a bonding position. A in formula (10) and formula (11) 2 The following examples are given: 1Those having the same specific examples as the specific examples are used as specific examples.

[0115] The number-average molecular weight in terms of polystyrene of the modified polyphenylene ether compound (B2) based on the GPC method is preferably 500 or more and 3000 or less. When the number-average molecular weight is at least the above lower limit value, there is a tendency to further suppress stickiness when the resin composition of the present embodiment is formed into a film. When the number-average molecular weight is at most the above upper limit value, there is a tendency to further improve the solubility in a solvent.

[0116] In addition, the weight-average molecular weight in terms of polystyrene of the modified polyphenylene ether compound (B2) based on GPC is preferably 800 or more and 10000 or less, more preferably 800 or more and 5000 or less. When it is at least the above lower limit value, the dielectric constant and the loss tangent of the resin composition tend to be further reduced. When it is at most the above upper limit value, the solubility, low viscosity, and moldability in a solvent tend to be further improved.

[0117] Furthermore, the carbon-carbon unsaturated double bond equivalent at the terminal of the modified polyphenylene ether compound (B2) is preferably 400 to 5000 g per carbon-carbon unsaturated double bond, more preferably 400 g to 2500 g. When it is at least the above lower limit value, the dielectric constant and the loss tangent tend to be further reduced. When it is at most the above upper limit value, the solubility, low viscosity, and moldability in a solvent tend to be further improved.

[0118] The method for producing the modified polyphenylene ether compound (B2) is not particularly limited. For example, it can be produced by a step of obtaining a bifunctional phenylene ether oligomer by oxidative coupling of a bifunctional phenol compound and a monofunctional phenol compound (oxidative coupling step); and a step of vinylbenzyl etherifying the terminal phenolic hydroxyl group of the obtained bifunctional phenylene ether oligomer (vinylbenzyl etherification step). In addition, as such a modified polyphenylene ether compound (B2), for example, those manufactured by Mitsubishi Gas Chemical Company, Inc. (OPE-2St1200, etc.) can be used.

[0119] <<Maleimide compound (B3)>>

[0120] The maleimide compound (B3) refers to a compound having one or more maleimide groups in the molecule. The maleimide compound (B3) used in the present invention preferably has one or more maleimide groups in one molecule, more preferably two or more. In addition, the upper limit of the number of maleimide groups in one molecule of the maleimide compound (B3) is preferably 15 or less, more preferably 13 or less. Among them, bismaleimide compounds and polymaleimide compounds having two or more maleimide groups in the molecule are preferred, and 4,4'-diphenylmethane maleimide, 4,4'-diphenylether bismaleimide, m-phenylene bismaleimide, 1,6-bis(maleimide)-(2,2,4-trimethyl)hexane, and compounds containing structural units represented by any of the following formulas (31) to (34) are further preferred.

[0121]

[0122] In formula (31), R 51 , R 52 , R 53 and R 54 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group.

[0123] In formula (31), R 51 , R 52 , R 53 and R 54 are preferably each independently methyl, ethyl, phenyl, or a hydrogen atom, more preferably a hydrogen atom.

[0124] n1 is a number from 1 to 10, more preferably a number from 1 to 4. Compounds with two or more different n1 values may also be included.

[0125]

[0126] In formula (32), R 56 each independently represent methyl or ethyl, and R 57 each independently represent a hydrogen atom or methyl.

[0127] Preferably, among the four R 56 , 1 to 3 are methyl, and the remaining 3 to 1 are ethyl; more preferably, among the four R 56 , 2 are methyl and the remaining 2 are ethyl. Furthermore, for the two aromatic rings, it is more preferable that the two substituted R 56 are respectively methyl and ethyl.

[0128]

[0129] In formula (33), R 58 each independently represent a hydrogen atom, methyl, or ethyl.

[0130] R 58 Preferably methyl or ethyl, more preferably methyl.

[0131]

[0132] In formula (34), R 59 Each independently represents a hydrogen atom, methyl or ethyl.

[0133] R 59 Preferably methyl or ethyl, more preferably methyl.

[0134] The equivalent weight of the unsaturated imide group of the maleimide compound (B3) is preferably 200 g / eq or more, and further preferably 400 g / eq or less. It should be noted that when two or more maleimide compounds are included, considering the mass of each maleimide compound contained in the resin composition, the equivalent weight here is the equivalent weight of the unsaturated imide group by weighted average.

[0135] <<Nadic imide compound (B4)>>

[0136] The nadic imide compound (B4) is a compound having a nadic imide group in the molecule. The nadic imide compound (B4) used in the present invention preferably has one or more nadic imide groups in one molecule, more preferably two or more. In addition, the upper limit of the number of nadic imide groups in one molecule of the nadic imide compound (B4) is preferably 5 or less, more preferably 3 or less. More specifically, the nadic imide compound (B4) preferably has a group represented by the following formula (N1) or (N2). * represents the bonding position.

[0137]

[0138] In formula (N1) and formula (N2), R 1 Each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0139] As the nadic imide compound, a compound represented by the following formula (N3) is further preferred.

[0140]

[0141] In formula (N3), R 1 Each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R 2 Represents an alkylene group having 1 to 6 carbon atoms or a divalent linking group containing an aromatic ring. As the divalent linking group containing an aromatic ring, phenylene, biphenylene and naphthylene can be exemplified.

[0142] In addition, as the nadic imide compound (B4), reference can be made to paragraphs 0026 to 0035 of International Publication No. 2015 / 105109, and these contents are incorporated into this specification.

[0143] With respect to 100 parts by mass of the total amount of the resin components in the resin composition of the present embodiment, the content of the thermosetting compound (B) is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, further preferably 15 parts by mass or more, and still more preferably 20 parts by mass or more. As the upper limit value, it is preferably 95 parts by mass or less, more preferably 80 parts by mass or less, further preferably 70 parts by mass or less.

[0144] In addition, with respect to 100 parts by mass of the polyfunctional vinyl aromatic polymer (A), it is preferably 1 part by mass or more, more preferably 10 parts by mass or more, and further preferably 20 parts by mass or more. As the upper limit value, it is preferably 1900 parts by mass or less, more preferably 900 parts by mass or less, further preferably 400 parts by mass or less, can be 120 parts by mass or less, can also be 80 parts by mass or less, and can further be 60 parts by mass or less.

[0145] The resin composition may contain only one kind of thermosetting compound (B) or may contain two or more kinds. When two or more kinds are contained, the total amount is preferably in the above range.

[0146] When the resin composition of the present embodiment does not contain the following filler (C), it is preferred that the resin component accounts for 90% by mass or more of the resin composition, more preferably 95% by mass or more, and further preferably 98% by mass or more.

[0147] When the resin composition of the present embodiment contains the filler (C), it is preferred that the resin component accounts for 15% by mass or more of the resin composition, more preferably 20% by mass or more, and further preferably 30% by mass or more. In addition, as the upper limit value, it is preferred that the resin component accounts for 90% by mass or less of the resin composition, more preferably 85% by mass or less, and further preferably 80% by mass or less.

[0148] <Free radical polymerization initiator>

[0149] The resin composition of the present embodiment does not contain a free radical polymerization initiator. Here, "does not contain" means not actively compounding, and does not include the case of inadvertently compounding impurities, etc. The case of inadvertently compounding impurities, etc. means, for example, 4 ppm or less, and further 1 ppm or less on a mass basis. In the present invention, 0 ppm is preferred.

[0150] The type of the free radical polymerization initiator is not particularly limited, and examples thereof include thermal free radical polymerization initiators and photo free radical polymerization initiators.

[0151] As a radical polymerization initiator, specifically, peroxides, azo compounds, benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, and phosphine oxide compounds can be mentioned.

[0152] Examples of peroxides include compounds having a peroxy group (-O-O-) in the molecule, preferably compounds having a tert-butylperoxy group, compounds having a cumylperoxy group, and compounds having a benzoylperoxy group. As specific examples, benzoyl peroxide (BPO), p-chlorobenzoyl peroxide, dicumyl peroxide (dicup), di-tert-butyl peroxide, diisopropyl peroxydicarbonate, 2,5-dimethyl-2,5-di-tert-butylperoxyhex-3-yne (DYBP), and 2,5-dimethyl-2,5-di-tert-butylperoxyhexane can be mentioned. As commercially available products, PERBUTYL H, PERBUTYL P, PERBUTYL PV, PERCUMYL H, PERCUMYL P, PERCUMYL D, PEROCTA H, PERHEXA 25B, etc. manufactured by NOF Corporation can be mentioned.

[0153] Azo compounds refer to compounds having an azo group (-N=N-) in the molecule. Specifically, azobisisobutyronitrile (AIBN) can be mentioned. As commercially available products, AIBN, V-70, V-65, etc. manufactured by FUJIFILM Wako Pure Chemical Corporation can be mentioned.

[0154] In addition, although not a peroxide, 2,3-dimethyl-2,3-diphenylbutane can also be mentioned as a radical polymerization initiator. As a commercially available product, Nofmer BC-90, etc. can be mentioned.

[0155] Furthermore, the radical polymerization initiator described in paragraph 0042 of International Publication No. 2013 / 047305 is also exemplified, and these contents are incorporated into this specification.

[0156] On the other hand, the resin composition of this embodiment can also be configured not to contain a cationic polymerization initiator. Furthermore, the resin composition of this embodiment can also be configured not to contain a photopolymerization initiator.

[0157] <Filler (C)>

[0158] In order to improve low dielectric constant, low dielectric loss tangent, flame resistance and low thermal expansion, the resin composition of the present embodiment preferably contains a filler (C), preferably an inorganic filler. As the filler (C) used, those known in the art can be appropriately used, and the type thereof is not particularly limited, and those commonly used in the art can be suitably used. Specifically, examples include silica-based materials such as natural silica, fused silica, synthetic silica, amorphous silica, AEROSIL, and hollow silica, white carbon, titanium white, zinc oxide, magnesium oxide, zirconium oxide, boron nitride, aggregated boron nitride, silicon nitride, aluminum nitride, barium sulfate, aluminum hydroxide, heat-treated aluminum hydroxide (a product obtained by heat-treating aluminum hydroxide to reduce a part of the crystal water), boehmite, magnesium hydroxide and other metal hydrates, molybdenum compounds such as molybdenum oxide and zinc molybdate, zinc borate, zinc stannate, alumina, clay, kaolin, talc, calcined clay, calcined kaolin, calcined talc, mica, E-glass, A-glass, NE-glass, C-glass, L-glass, D-glass, S-glass, M-glass G20, glass short fibers (including glass fine powders such as E glass, T glass, D glass, S glass, and Q glass), hollow glass, spherical glass and other inorganic fillers, and rubber powders such as styrene type, butadiene type, and acrylic type, core-shell type rubber powders, silicone resin powders, silicone rubber powders, silicone composite powders and other organic fillers.

[0159] Among these, it is preferable to select one or more kinds from the group consisting of silica, aluminum hydroxide, boehmite, magnesium oxide and magnesium hydroxide, and silica is more preferable. The silica is preferably spherical silica. The spherical silica may also be hollow silica.

[0160] By using these fillers, the properties such as the thermal expansion characteristics, dimensional stability, and flame retardancy of the resin composition are improved.

[0161] The content of the filler (C) in the resin composition of the present embodiment can be appropriately set according to the desired properties and is not particularly limited. When the total amount of the resin components in the resin composition is 100 parts by mass, it is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, further preferably 30 parts by mass or more, and may also be 50 parts by mass or more. As the upper limit value, it is preferably 500 parts by mass or less, more preferably 400 parts by mass or less, further preferably 300 parts by mass or less, still more preferably 250 parts by mass or less, and may also be 200 parts by mass or less.

[0162] One kind of the filler (C) can be used, or two or more kinds can be used. When two or more kinds are used, the total amount thereof is preferably in the above range.

[0163] <Other resin components>

[0164] The resin composition of the present embodiment may also contain other resin components in addition to the above-mentioned polyfunctional vinyl aromatic polymer (A) and thermosetting compound (B). As other resin components, one or more selected from the group consisting of epoxy resins, phenolic resins, oxetane resins, benzoxazine compounds, compounds having polymerizable unsaturated groups, elastomers, and active ester compounds can be exemplified.

[0165] In the resin composition of the present embodiment, the total content of the polyfunctional vinyl aromatic polymer (A) and the thermosetting compound (B) in the resin components is preferably 50% by mass or more, preferably 70% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, may be 95% by mass or more, may be 97% by mass or more, and may also be 98% by mass or more.

[0166] <Curing accelerator (catalyst)>

[0167] The resin composition of the present embodiment may further contain a curing accelerator. There is no particular limitation on the curing accelerator, and examples thereof include organic metal salts (such as zinc octoate, zinc naphthenate, cobalt naphthenate, copper naphthenate, iron acetylacetonate, nickel octoate, manganese octoate, etc.), phenol compounds (such as phenol, xylenol, cresol, resorcinol, catechol, octylphenol, nonylphenol, etc.), alcohols (such as 1-butanol, 2-ethylhexanol, etc.), imidazoles (such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, etc.), and derivatives such as adducts of these imidazoles with carboxylic acids or their acid anhydrides, amines (such as dicyandiamide, benzyldimethylamine, 4-methyl-N,N-dimethylbenzylamine, etc.), phosphorus compounds (such as phosphine compounds, phosphine oxide compounds, phosphonium salt compounds, diphosphine compounds, etc.), and epoxy-imidazole adduct compounds.

[0168] Preferred curing accelerators are imidazoles and organic metal salts, and more preferably imidazoles.

[0169] Regarding the content of the curing accelerator, when contained, the lower limit is preferably 0.005 parts by mass or more, more preferably 0.01 parts by mass or more, and further preferably 0.1 parts by mass or more with respect to 100 parts by mass of the total amount of the resin components in the resin composition. In addition, the upper limit of the content of the curing accelerator is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and further preferably 2 parts by mass or less with respect to 100 parts by mass of the total amount of the resin components in the resin composition.

[0170] The curing accelerator may be used alone or two or more thereof may be used in combination. When two or more are used, the total amount is within the above range.

[0171] <Solvent>

[0172] The resin composition of the present embodiment may also contain a solvent, preferably an organic solvent. In this case, the resin composition of the present embodiment is in a form (solution or varnish) in which at least a part, preferably all, of the above various resin components are dissolved or compatible in the solvent. As the solvent, there is no particular limitation as long as it is a polar organic solvent or a non-polar organic solvent capable of dissolving or compatibilizing at least a part, preferably all, of the above various resin components. As the polar organic solvent, for example, ketones (such as acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), cellosolves (such as propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc.), esters (such as ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl methoxypropionate, methyl hydroxyisobutyrate, etc.), amides (such as dimethoxyacetamide, dimethylformamide, etc.) can be mentioned. As the non-polar organic solvent, aromatic hydrocarbons (such as toluene, xylene, etc.) can be mentioned.

[0173] One kind of solvent may be used alone, or two or more kinds may be used in combination.

[0174] <Other components>

[0175] Within the range not impairing the effects of the present invention, in addition to the above components, the resin composition of the present embodiment may also contain a flame retardant, an ultraviolet absorber, an antioxidant, a fluorescent brightening agent, a photosensitizer, a dye, a pigment, a thickener, a flow regulator, a lubricant, an antifoaming agent, a dispersant, a leveling agent, a gloss agent, a polymerization inhibitor, a silane coupling agent, etc. These additives may be used alone or two or more thereof may be used in combination.

[0176] <Physical properties of the resin composition>

[0177] When the resin composition of the present embodiment is formed into a cured product in the form of a plate with a thickness of 1.6 mm, the dielectric constant (Dk) at 10 GHz can be set to 2.6 or less, or can also be set to 2.5 or less. The lower limit value of the aforementioned dielectric constant is preferably 1.0, but is actually 2.1 or more.

[0178] In addition, when the resin composition of the present embodiment is formed into a cured product in the form of a plate with a thickness of 1.6 mm, the tangent of the dielectric loss angle (Df) at 10 GHz can be set to 0.0030 or less, or can also be set to 0.0025 or less, or can also be set to 0.0020 or less, and can further be set to 0.0015 or less. The lower limit value of the aforementioned dielectric constant is preferably 0, but is actually 0.0001 or more.

[0179] The dielectric constant and the dielectric loss tangent are measured by the method described in the following examples.

[0180] In the resin composition of the preferred embodiment of the present invention, a low coefficient of thermal expansion (CTE) can be achieved. For example, from the perspective of the CTE (ppm / °C) specified in JlSC 6481 5.19, it is preferably 75 or less, more preferably 72 or less, and still more preferably 70 or less. The lower limit value is not particularly limited, and it is practical to be 50 or more.

[0181] When the resin composition of the present embodiment is formed into a cured product in the form of a plate with a thickness of 1.6 mm, the glass transition temperature can be set to 230°C or higher, can also be set to 235°C or higher, and can further be set to 240°C or higher. The upper limit value of the aforementioned glass transition temperature is not particularly limited, and it is practical to be 400°C or lower, and further 350°C or lower.

[0182] In addition, when the resin composition of the present embodiment is formed into a cured product in the form of a plate with a thickness of 1.6 mm, the glass transition temperature is preferably 8°C or more higher than the glass transition temperature of a cured product in the form of a plate with a thickness of 1.6 mm formed from a resin composition in which a thermal free radical polymerization initiator (for example, PERBUTYL P (trade name) manufactured by NOF Corporation) equivalent to 1% by mass of the resin component contained in the resin composition is compounded, and more preferably 10°C or more higher. As the upper limit value, for example, it is 25°C or lower.

[0183] The glass transition temperature is measured by the method described in the following examples.

[0184] <Manufacturing method of resin composition>

[0185] The resin composition of the present embodiment can be manufactured by a conventional method. For example, a method of mixing a polyfunctional vinyl aromatic polymer (A) and a thermosetting compound (B) can be cited. The preferred content at this time is as described above. In addition, in the resin composition of the present embodiment, a filler (C), other resin components, and other additives can also be appropriately coexisted and kneaded, etc. The appearance can also be improved and other properties can be optimized by compounding other resin components.

[0186] An example of the resin composition of the present embodiment is a varnish containing a solvent. Another example of the resin composition of the present embodiment is a cured product in the form of a plate and a film. Furthermore, the resin composition of the present embodiment is preferably used for the uses described below.

[0187] <Uses>

[0188] The resin composition of the present embodiment can be used as a cured product. Specifically, for the resin composition of the present embodiment, as a low dielectric constant material and / or a low dissipation factor material, it can be suitably used as an insulating layer of a printed circuit board and a material for a semiconductor package. The resin composition of the present embodiment can be suitably used as a prepreg, a metal-clad laminate formed from the prepreg, a resin composite sheet, and a material constituting a printed circuit board.

[0189] For the resin composition of the present embodiment, when a layered molded product is formed using it, its thickness is preferably 5 μm or more, more preferably 10 μm or more. As an upper limit value, it is preferably 2 mm or less, more preferably 1 mm or less. It should be noted that, for example, when the resin composition of the present embodiment is impregnated into a glass cloth, etc., the thickness of the above-mentioned layered molded product means including the thickness of the glass cloth.

[0190] Molded products such as films formed from the resin composition of the present embodiment can be used for applications where a pattern is formed by exposure and development, and can also be used for applications where exposure and development are not performed. It is particularly suitable for applications where exposure and development are not performed.

[0191] <<Prepreg>>

[0192] The prepreg of the preferred embodiment is formed from a base material (prepreg base material) and the resin composition of the present embodiment. The prepreg of the present embodiment is obtained, for example, by applying the resin composition of the present embodiment to a base material (such as impregnation or coating), and then semi-curing it by heating (such as a method of drying it at 120 to 220 °C for 2 to 15 minutes, etc.). At this time, the amount of the resin composition attached to the base material, that is, the amount of the resin composition (including the filler) relative to the total amount of the semi-cured prepreg, is preferably in the range of 20 to 99% by mass.

[0193] As the base material, there is no particular limitation as long as it is a base material used in various printed circuit board materials. Examples of the material of the base material include glass fiber (e.g., E glass, D glass, L glass, S glass, T glass, Q glass, UN glass, NE glass, spherical glass, etc.), inorganic fiber other than glass (e.g., quartz, etc.), and organic fiber (e.g., polyimide, polyamide, polyester, liquid crystal polyester, etc.). There is no particular limitation on the form of the base material, and examples thereof include base materials composed of layered fibers such as woven fabric, non-woven fabric, roving, short glass fiber mat, and surface mat. A base material composed of long fibers such as glass cloth is particularly preferred. Here, long fibers refer to those having a number-average fiber length of 6 mm or more, for example. These base materials can be used alone or in combination of two or more. Among these base materials, from the viewpoint of dimensional stability, a woven fabric subjected to an ultra-open fiber treatment and a pore blocking treatment is preferred; from the viewpoint of moisture absorption and heat resistance, a glass woven fabric subjected to a surface treatment using a silane coupling agent such as an epoxy silane treatment or an amino silane treatment is preferred; from the viewpoint of electrical properties, a low-dielectric glass woven fabric formed of glass fibers such as L-glass, NE-glass, and Q-glass that exhibit low dielectric constant and low dielectric loss tangent is preferred. The thickness of the base material is not particularly limited and can be, for example, about 0.01 to 0.19 mm.

[0194] [[Metal-clad laminate]]

[0195] The metal-clad laminate of the preferred embodiment includes: at least one layer formed of the prepreg of the present embodiment, and a metal foil disposed on one or both sides of the layer formed of the prepreg. The metal-clad laminate of the present embodiment can be produced, for example, by the following method: disposing at least one sheet of the prepreg of the present embodiment (preferably overlapping 2 or more sheets), and laminating and forming by disposing a metal foil on one or both sides thereof. More specifically, it can be produced by laminating and forming by disposing a metal foil such as copper or aluminum on one or both sides of the prepreg. The number of prepreg sheets is preferably 1 to 10 sheets, more preferably 2 to 10 sheets, and further preferably 2 to 7 sheets. As the metal foil, there is no particular limitation as long as it can be used for printed circuit board materials, and examples thereof include copper foils such as rolled copper foil and electrolytic copper foil. The thickness of the copper foil is not particularly limited and can be about 1.5 to 70 μm. As the forming method, methods commonly used when forming printed circuit board laminates and multilayer boards can be cited. More specifically, using a multi-stage press, a multi-stage vacuum press, a continuous forming machine, an autoclave forming machine, etc., at a temperature of about 180 to 350 °C, a heating time of about 100 to 300 minutes, and a surface pressure of 20 to 100 kg / cm 2A method of laminating and forming in the left - right direction. Additionally, the prepreg of the present embodiment and a separately fabricated circuit board for the inner layer (also referred to as an inner - layer circuit board) can be laminated and formed in combination to fabricate a multilayer board. As a method for manufacturing a multilayer board, for example, copper foils of about 35 μm can be disposed on both sides of one sheet of the prepreg of the present embodiment. After laminating and forming by the above - mentioned forming method, an inner - layer circuit is formed, and a blackening treatment is performed on this circuit to form an inner - layer circuit board. Then, the inner - layer circuit board and one sheet of the prepreg of the present embodiment are alternately arranged one by one, and further, copper foils are disposed on the outermost layer. Laminating and forming is preferably performed under vacuum under the above - mentioned conditions to fabricate a multilayer board. The metal - clad laminate of the present embodiment can be suitably used as a printed circuit board.

[0196] <<Printed Circuit Board>>

[0197] The printed circuit board of the preferred embodiment includes an insulating layer and a conductor layer disposed on the surface of the aforementioned insulating layer. The aforementioned insulating layer includes at least one of a layer formed of the resin composition of the present embodiment and a layer formed of the prepreg of the above - mentioned embodiment. Such a printed circuit board can be manufactured by a usual method, and its manufacturing method is not particularly limited. Hereinafter, an example of the manufacturing method of the printed circuit board is shown. First, a metal - clad laminate such as the above - mentioned copper - clad laminate is prepared. Next, an etching treatment is performed on the surface of the metal - clad laminate to form an inner - layer circuit and fabricate an inner - layer substrate. If necessary, a surface treatment for improving the bonding strength is performed on the surface of the inner - layer circuit of the inner - layer substrate, and then the required number of the above - mentioned prepregs are overlapped on the surface of its inner - layer circuit. Further, a metal foil for the outer - layer circuit is laminated on the outside thereof, and heating and pressing are performed for integral forming. In this way, a multilayer laminate is manufactured in which an insulating layer formed of a base material and a cured product of a thermosetting resin composition is formed between the inner - layer circuit and the metal foil for the outer - layer circuit. Then, after performing drilling for through - holes and via - holes on the multilayer laminate, a plated - metal coating film for conducting the inner - layer circuit and the metal foil for the outer - layer circuit is formed on the wall surface of the holes. Further, an etching treatment is performed on the metal foil for the outer - layer circuit to form an outer - layer circuit, thereby manufacturing a printed circuit board.

[0198] The printed circuit board obtained in the above - mentioned manufacturing example has an insulating layer and a conductor layer formed on the surface of the insulating layer. The insulating layer is composed of the resin composition of the present embodiment. That is, the above - mentioned prepreg of the present embodiment (for example, a prepreg formed of a base material and the resin composition of the present embodiment impregnated or coated therein), and the layer formed of the resin composition of the above - mentioned metal - clad laminate of the present embodiment are the insulating layers of the present embodiment.

[0199] <<Resin Composite Sheet>>

[0200] The resin composite sheet of the preferred embodiment includes: a support, and a layer formed of the resin composition of this embodiment disposed on the surface of the foregoing support. The resin composite sheet can be used as a film for lamination or a dry film solder resist. As a method for manufacturing the resin composite sheet, there is no particular limitation, and for example, a method of obtaining a resin composite sheet by coating (applying) a solution obtained by dissolving the above-described resin composition of this embodiment in a solvent on the support and drying it can be cited.

[0201] Examples of the support used herein include organic film substrates such as polyethylene film, polypropylene film, polycarbonate film, polyethylene terephthalate film, ethylene-tetrafluoroethylene copolymer film, and release films coated with a release agent on the surface of these films, polyimide film, etc., conductor foils such as copper foil and aluminum foil, glass plates, SUS plates, and plate-like substrates such as FRP, and there is no particular limitation.

[0202] Examples of the coating method (application method) include a method of coating a solution obtained by dissolving the resin composition in a solvent on the support using a bar coater, a die coater, a doctor blade, a Baker applicator, etc. In addition, after drying, a single-layer sheet can also be formed by peeling the support from the resin composite sheet formed by laminating the support and the resin composition or etching it. It should be noted that a solution obtained by dissolving the above-described resin composition of this embodiment in a solvent can also be supplied into a mold having a sheet-like cavity and dried, etc., so as to be formed into a sheet shape, and thus a single-layer sheet can be obtained without using a support.

[0203] In the production of the resin composite sheet of this embodiment, the drying conditions for removing the solvent are not particularly limited. If the temperature is low, the solvent is likely to remain in the resin composition. If the temperature is high, the resin composition will be cured. Therefore, it is preferably at a temperature of 20°C to 200°C for 1 to 90 minutes. In addition, in the resin composite sheet, the resin composition can also be used in an uncured state in which only the solvent is dried, and can also be set to a semi-cured (B-staged) state and used as needed. Furthermore, the thickness of the resin layer of the resin composite sheet of this embodiment can be adjusted by the concentration and coating thickness of the solution of the resin composition of this embodiment, and there is no particular limitation. Generally, from the aspect that if the coating thickness becomes thick, the solvent is likely to remain during drying, it is preferably 0.1 to 500 μm.

[0204] Examples

[0205] Hereinafter, examples are given to further specifically illustrate the present invention. The materials, amounts used, ratios, treatment contents, treatment steps, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

[0206] In this example, measurements were carried out at 23 °C unless otherwise specified.

[0207] <Example 1>

[0208] Dissolve 75 parts by mass of the following synthesized polyfunctional vinylbenzene polymer (ap), 25 parts by mass of a biphenyl aralkyl type maleimide (manufactured by Nippon Kayaku Co., Ltd., MIR-3000 (trade name)), and 0.5 part by mass of an imidazole catalyst (manufactured by Shikoku Chemicals Corporation, 2E4MZ (trade name)) in methyl ethyl ketone and mix to obtain a varnish.

[0209] (Synthesis of polyfunctional vinylbenzene polymer (ap))

[0210] Put 2.25 moles (292.9 g) of divinylbenzene, 1.32 moles (172.0 g) of ethyl vinylbenzene, 11.43 moles (1190.3 g) of styrene, and 15.0 moles (1532.0 g) of n-propyl acetate into a reactor, add 600 mmol of boron trifluoride diethyl ether complex at 70 °C, and react for 4 hours. After stopping the polymerization solution with an aqueous sodium bicarbonate solution, wash the oil layer 3 times with pure water, and carry out devolatilization under reduced pressure at 60 °C to recover the polyfunctional vinylbenzene polymer (ap). Weigh the obtained polyfunctional vinylbenzene polymer (ap), and confirm that 860.8 g of the polyfunctional vinylbenzene polymer (ap) is obtained.

[0211] The Mn of the obtained polyfunctional vinylbenzene polymer (ap) is 2060, Mw is 30700, and Mw / Mn is 14.9. By performing 13 C-NMR and 1 H-NMR analysis, resonance lines derived from each monomer unit were observed in the polyfunctional vinylbenzene polymer (ap). Based on the NMR measurement results and GC analysis results, the proportions of the structural units of the polyfunctional vinylbenzene polymer (ap) were calculated as follows.

[0212] Structural unit derived from divinylbenzene: 20.9 mol% (24.3 mass%)

[0213] Structural unit derived from ethyl vinylbenzene: 9.1 mol% (10.7 mass%)

[0214] Structural unit derived from styrene: 70.0 mol% (65.0 mass%)

[0215] In addition, the structural unit having a residual vinyl group derived from divinylbenzene is 16.7 mol% (18.5 mass%).

[0216] (Manufacture of test piece of cured plate with thickness of 1.6 mm)

[0217] The mixed resin powder was obtained by evaporating and distilling off the solvent from the resulting varnish. The mixed resin powder was filled in a mold with a side length of 100 mm and a thickness of 1.6 mm, and 12-μm copper foils (3EC-M3-VLP, manufactured by Mitsui Mining & Smelting Co., Ltd.) were arranged on both sides, and vacuum pressing was carried out at a pressure of 30 kg / cm 2 and a temperature of 220 °C for 120 minutes to obtain a cured plate with a side length of 100 mm and a thickness of 1.6 mm.

[0218] For the obtained 1.6-mm-thick cured plate, evaluations of physical properties, etc. (dielectric properties (Dk, Df), peel strength, glass transition temperature, coefficient of thermal expansion (CTE)) were carried out according to the method described below.

[0219] <Example 2>

[0220] 25 parts by mass of the biphenyl aralkyl type maleimide was set to 12.5 parts by mass, and 12.5 parts by mass of a phenylether type maleimide (manufactured by KI Kasei Co., Ltd., BMI-80 (trade name)) was added. Otherwise, a varnish was obtained in the same manner as in Example 1. From the obtained varnish, a 1.6-mm-thick cured plate was obtained in the same manner as in Example 1. For the obtained 1.6-mm-thick cured plate, evaluations of physical properties, etc. were carried out according to the method described below.

[0221] <Example 3>

[0222] 25 parts by mass of the BisM type maleimide (manufactured by KI Kasei Co., Ltd., BMI-BisM (trade name)) was used instead of 25 parts by mass of the biphenyl aralkyl type maleimide. Otherwise, a varnish was obtained in the same manner as in Example 1. From the obtained varnish, a 1.6-mm-thick cured plate was obtained in the same manner as in Example 1. For the obtained 1.6-mm-thick cured plate, evaluations of physical properties, etc. were carried out according to the method described below.

[0223] <Example 4>

[0224] 25 parts by mass of the end-modified polyphenylene ether (manufactured by Mitsubishi Gas Chemical Company, Inc., OPE-2St 1200 (trade name)) was used instead of 25 parts by mass of the biphenyl aralkyl type maleimide, and the imidazole catalyst was not used. Otherwise, a varnish was obtained in the same manner as in Example 1. From the obtained varnish, a 1.6-mm-thick cured plate was obtained in the same manner as in Example 1. For the obtained 1.6-mm-thick cured plate, evaluations of physical properties, etc. were carried out according to the method described below.

[0225] <Example 5>

[0226] Use 25 parts by mass of the following naphthol aralkyl type cyanate resin to replace 25 parts by mass of the biphenyl aralkyl type maleimide, and use 0.1 part by mass of an organometallic catalyst (manufactured by Nippon Chemical Industry Co., Ltd., Oct-Mn (trade name)) to replace 0.5 part by mass of the imidazole catalyst. Except for this, a varnish was obtained in the same manner as in Example 1. From the obtained varnish, a cured plate with a thickness of 1.6 mm was obtained in the same manner as in Example 1. For the obtained cured plate with a thickness of 1.6 mm, evaluations such as physical properties were carried out according to the method described later.

[0227] (Synthesis of α-naphthol aralkyl type cyanate resin)

[0228] Dissolve 0.47 mol (in terms of OH group) of α-naphthol aralkyl resin (SN495V, OH group equivalent: 236 g / eq., manufactured by Nippon Steel Chemical Co., Ltd.; including those with 1 to 5 repeating units of naphthol aralkyl) in 500 mL of chloroform. Add 0.7 mol of triethylamine to this solution to prepare Solution 1. While maintaining the temperature at -10 °C, dropwise add Solution 1 to 300 g of a chloroform solution of 0.93 mol of cyanogen chloride introduced into the reactor over 1.5 hours. After the dropwise addition is completed, stir for 30 minutes. Then, further dropwise add a mixed solution of 0.1 mol of triethylamine and 30 g of chloroform into the reactor, and stir for 30 minutes to end the reaction. After filtering off the by-produced triethylamine hydrochloride from the reaction solution, wash the obtained filtrate with 500 mL of 0.1 N hydrochloric acid, and then repeat washing 4 times with 500 mL of water. After drying it with sodium sulfate, evaporate it at 75 °C, and then carry out vacuum degassing at 90 °C to obtain a brown solid α-naphthol aralkyl type cyanate compound shown by the formula (S1) (in the formula, R C1 ~R C4 are all hydrogen atoms, and n c is a mixture of 1 to 5.). For the α-naphthol aralkyl type cyanate compound obtained by infrared absorption spectrum analysis, the absorption of the cyanate group was confirmed at around 2264 cm -1 .

[0229]

[0230] <Reference Example 1>

[0231] Add 1 part by mass of a thermal free radical polymerization initiator (manufactured by NOF Corporation, PERBUTYL P (trade name)). Except for this, a varnish was obtained in the same manner as in Example 1. From the obtained varnish, a cured plate with a thickness of 1.6 mm was obtained in the same manner as in Example 1. For the obtained cured plate with a thickness of 1.6 mm, evaluations such as physical properties were carried out according to the method described later.

[0232] <Reference Example 2>

[0233] 1 part by mass of an additional thermal free radical polymerization initiator (manufactured by NOF Corporation, PERBUTYL P (trade name)) was added, and otherwise, a varnish was obtained in the same manner as in Example 4. Using the obtained varnish, a cured plate with a thickness of 1.6 mm was obtained in the same manner as in Example 4. The obtained cured plate with a thickness of 1.6 mm was evaluated for physical properties and the like according to the method described below.

[0234] <Reference Example 3>

[0235] 1 part by mass of an additional thermal free radical polymerization initiator (manufactured by NOF Corporation, PERBUTYL P (trade name)) was added, and otherwise, a varnish was obtained in the same manner as in Example 5. Using the obtained varnish, a cured plate with a thickness of 1.6 mm was obtained in the same manner as in Example 5. The obtained cured plate with a thickness of 1.6 mm was evaluated for physical properties and the like according to the method described below.

[0236] <Dielectric properties (Dk and Df)>

[0237] For the test piece obtained by removing the copper foil from the obtained 1.6 mm thick cured plate by etching, the relative dielectric constant (Dk) and the dielectric loss tangent (Df) at 10 GHz were measured using a perturbation method cavity resonator. The measurement temperature was set to 23°C.

[0238] The perturbation method cavity resonator used a product of Agilent technologies, inc., Agilent8722ES.

[0239] <Peel strength>

[0240] Using the cured plate obtained as described above, the copper foil peel strength (adhesive force) was measured twice according to the provisions of "Peel strength" in JIS C6481, and the average value was obtained. The measurement temperature was set to 23°C.

[0241] <Glass transition temperature>

[0242] For the glass transition temperature (Tg), according to JIS C6481 5.17.2, a test piece obtained by removing the copper foil from the obtained 1.6 mm thick cured plate by etching was measured by the DMA (Dynamic Mechanical Analysis) bending method using a dynamic viscoelastic analyzer. The glass transition temperature was evaluated from the obtained tanδ graph.

[0243] The dynamic viscoelastic analyzer used a device manufactured by TA INSTRUMENTS.

[0244] <Coefficient of thermal expansion (CTE)>

[0245] (CTE: Coefficient of linear Thermal Expansion)

[0246] For the test piece obtained by removing the copper foil of a 1.6-mm thick cured plate through etching, the coefficient of thermal expansion of the cured plate was measured by the TMA method (Thermo-Mechanical Analysis) specified in JlS C64815.19, and its value was obtained. Specifically, after removing the copper foil on both sides of the cured plate obtained above through etching, the coefficient of linear thermal expansion (ppm / °C) was measured with a thermo-mechanical analyzer (manufactured by TA INSTRUMENTS) while heating from 40°C to 340°C at 10°C per minute. ppm is the volume ratio. For other detailed content, refer to the above JIS C 64815.19.

[0247] [Table 1]

[0248]

[0249] (Notes in the table)

[0250] Dk: Relative dielectric constant at 10 GHz

[0251] Df: Tangent of dielectric loss angle at 10 GHz

[0252] Peel strength: Results of the copper foil peel test

[0253] Glass transition temperature: Glass transition temperature evaluated based on tanδ measured by the DMA method CTE: Coefficient of thermal expansion measured by the TMA method

[0254] From the results of Table 1 above, it can be seen that the resin composition combining the polyfunctional vinyl aromatic polymer (A) (polyfunctional vinylbenzene polymer (ap)) of this embodiment and the thermosetting compound (B) has excellent dielectric properties (low dielectric constant, low tangent of dielectric loss angle), and has a high glass transition temperature and a low coefficient of thermal expansion. Furthermore, the peel strength is also high.

[0255] On the other hand, when a radical polymerization initiator is contained, from the comparison between Reference Example 1 and Example 1, Reference Example 2 and Example 4, and Reference Example 3 and Example 5, it is found that the tangent of dielectric loss angle increases, the glass transition temperature decreases, and the coefficient of thermal expansion also increases. Furthermore, the peel strength is also low.

Claims

1. A resin composition comprising a polyfunctional vinyl aromatic polymer (A) and a thermosetting compound (B) other than the polyfunctional vinyl aromatic polymer (A), and not containing a radical polymerization initiator, wherein the number average molecular weight of the polyfunctional vinyl aromatic polymer (A) is 1000 or more, the polyfunctional vinyl aromatic polymer (A) has a structural unit (a) derived from a divinyl aromatic compound and a structural unit (b) derived from a monovinyl aromatic compound, the polyfunctional vinyl aromatic polymer (A) contains the structural unit (a) derived from a divinyl aromatic compound in a proportion of 5 mol% or more and 90 mol% or less, and in all the structural units except the terminals, the structural units containing an aromatic ring are 90 mol% or more, the thermosetting compound (B) is a compound having one or more functional groups selected from the group consisting of a cyanate group, a vinyl group, a maleimide group, and a nadic imide group, and the vinyl group does not contain a maleimide group or a nadic imide group, the structural unit (a) derived from a divinyl aromatic compound contains at least one of the structural unit represented by formula (V1), the structural unit represented by formula (V2), and the structural unit represented by formula (V3), the structural unit (b) derived from a monovinyl aromatic compound contains the structural unit represented by formula (V4), In formulas (V1) to (V3), L 1 is an aromatic hydrocarbon linking group, and * represents the bonding position, In formula (V4), L 2 is an aromatic hydrocarbon linking group, R V1 is a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and * represents a bonding position.

2. The resin composition according to claim 1, wherein, relative to 100 parts by mass of the total amount of the resin components in the resin composition, the total content of the polyfunctional vinyl aromatic polymer (A) and the thermosetting compound (B) is 80 parts by mass or more.

3. The resin composition according to claim 1 or 2, wherein, relative to 100 parts by mass of the total amount of the resin components in the resin composition, the content of the thermosetting compound (B) is 5 to 95 parts by mass.

4. The resin composition according to any one of claims 1 to 3, wherein, relative to 100 parts by mass of the total amount of the resin components in the resin composition, the content of the polyfunctional vinyl aromatic polymer (A) is 5 to 95 parts by mass.

5. The resin composition according to any one of claims 1 to 4, further comprising a filler (C).

6. The resin composition according to claim 5, wherein, relative to 100 parts by mass of the total amount of the resin components in the resin composition, the content of the filler (C) is 10 to 500 parts by mass.

7. A prepreg formed from a substrate and the resin composition according to any one of claims 1 to 6.

8. A metal foil-clad laminate comprising: at least one layer formed from the prepreg according to claim 7, and a metal foil disposed on one or both sides of the layer formed from the prepreg.

9. A resin composite sheet comprising: a support, and a layer formed from the resin composition according to any one of claims 1 to 6 disposed on the surface of the support.

10. A printed circuit board comprising an insulating layer and a conductor layer disposed on the surface of the insulating layer, wherein the insulating layer contains at least one of a layer formed from the resin composition according to any one of claims 1 to 6 and a layer formed from the prepreg according to claim 7.

Images