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

Abstract

Provided are a resin composition, a cured product, a prepreg, a metal foil-clad laminate, a resin composite sheet, and a printed wiring board. A resin composition containing a polymaleimide compound (A) and a compound (B) containing two or more polymerizable carbon-carbon unsaturated double bonds, the polymaleimide compound (A) has, as reaction raw materials (1), an aromatic amine compound (a1) having one to three alkyl groups in the aromatic ring, an aromatic divinyl compound (a2) having two vinyl groups, and maleic anhydride.

Description

Technical Field

[0001] The present invention relates to a resin composition, a cured product, a prepreg, a metal foil-clad laminate, a resin composite sheet, and a printed circuit board. Background Art

[0002] In recent years, the high integration and miniaturization of semiconductors used in communication devices, communication machines, personal computers, etc. have been advancing. Along with this, the various properties required for semiconductor packaging laminates (such as metal foil-clad laminates, etc.) used in printed circuit boards among them have become increasingly strict. As the main required performances, for example, there can be mentioned: peel strength, low water absorption, chemical resistance, desmear resistance, flame resistance, low dielectric properties (low dielectric constant and / or low dielectric loss tangent), low thermal expansion, heat resistance, etc.

[0003] In order to obtain a printed circuit board with improved various properties, studies have been made on resin compositions used as materials for printed circuit boards. For example, Patent Document 1 discloses a resin composition for a printed circuit board, which contains: a bifunctional vinylbenzyl compound (a) containing a specified polyphenylene ether skeleton, a specified maleimide compound (b), a specified cyanate ester resin (c), and a specified epoxy resin (d).

[0004] In addition, Patent Document 2 discloses a resin composition containing a specified cyanate ester compound (A), a specified polymaleimide compound (B), and a filler (C) as constituent components.

[0005] Furthermore, Patent Document 3 discloses a resin composition containing: a specified polymaleimide compound (A), a modified polyphenylene ether (B) end-modified with a substituent containing a carbon-carbon unsaturated double bond, and a filler.

[0006] Prior Art Documents

[0007] Patent Documents

[0008] Patent Document 1: Japanese Unexamined Patent Application Publication No. 2010-138364

[0009] Patent Document 2: International Publication No. 2016 / 072404

[0010] Patent Document 3: International Publication No. 2019 / 138992 Summary of the Invention

[0011] Problems to be Solved by the Invention

[0012] As described above, resin compositions for various printed circuit boards have been studied. Moreover, with recent technological innovations and expanding demands, there is a need for a new resin composition that can provide a cured product with low dielectric properties.

[0013] An object of the present invention is to solve this problem, and another object is to provide: a new resin composition that can provide a cured product with low dielectric properties, as well as a cured product, a prepreg, a metal-clad laminate, a resin composite sheet, and a printed circuit board.

[0014] Means for Solving the Problems

[0015] The present inventors conducted research based on the above problems and found that a new resin composition capable of providing a cured product with low dielectric properties can be obtained by using a specified maleimide compound and a compound containing two or more polymerizable carbon-carbon unsaturated double bonds in combination.

[0016] Specifically, the above problems were solved by the following means.

[0017] <1> A resin composition comprising: a polymaleimide compound (A) and a compound (B) containing two or more polymerizable carbon-carbon unsaturated double bonds, wherein the polymaleimide compound (A) is obtained using an aromatic amine compound (a1) having one or more and three or less alkyl groups in the aromatic ring, an aromatic divinyl compound (a2) having two vinyl groups, and maleic anhydride as reaction raw materials (1).

[0018] <2> The resin composition according to <1>, wherein when the resin solid content in the resin composition is set to 100 parts by mass, the content of the polymaleimide compound (A) is 1 to 90 parts by mass.

[0019] <3> The resin composition according to <1> or <2>, wherein when the resin solid content in the resin composition is set to 100 parts by mass, the content of the compound (B) containing two or more polymerizable carbon-carbon unsaturated double bonds is 1 to 90 parts by mass.

[0020] <4> The resin composition according to any one of <1> to <3>, further containing one or more other resin components (C) selected from the group consisting of maleimide compounds other than the aforementioned polymaleimide compound (A), epoxy compounds, phenolic compounds, oxetane resins, benzoxazine compounds, cyanate ester compounds, and thermoplastic elastomers.

[0021] <5> The resin composition according to any one of <1> to <4>, further comprising a filler (D).

[0022] <6>The resin composition according to <5>, wherein the filler (D) includes one or more selected from the group consisting of silica, aluminum hydroxide, aluminum nitride, boron nitride, forsterite, titanium oxide, barium titanate, strontium titanate, and calcium titanate.

[0023] <7>The resin composition according to <5> or <6>, wherein the content of the filler (D) in the resin composition is 1 to 1600 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition.

[0024] <8>The resin composition according to any one of <1> to <7>, wherein the compound (B) containing two or more polymerizable carbon-carbon unsaturated double bonds includes at least one selected from the group consisting of compounds containing a vinyl aryl group, compounds containing a (meth)acryloyl group, and compounds containing a (meth)allyl group.

[0025] <9>The resin composition according to any one of <1> to <8>, further including 0.5 to 30 parts by mass of a monomer or oligomer having an ethylenic unsaturated group relative to 100 parts by mass of the resin solid content in the resin composition.

[0026] <10>The resin composition according to any one of <1> to <9>, further including a flame retardant, and the flame retardant includes a phosphorus-based flame retardant.

[0027] <11>The resin composition according to <1>, wherein when the resin solid content in the resin composition is set to 100 parts by mass, the content of the polymaleimide compound (A) is 1 to 90 parts by mass.

[0028] When the resin solid content in the resin composition is set to 100 parts by mass, the content of the compound (B) containing two or more polymerizable carbon-carbon unsaturated double bonds is 1 to 90 parts by mass.

[0029] The resin composition further includes a filler (D).

[0030] The filler (D) includes one or more selected from the group consisting of silica, aluminum hydroxide, aluminum nitride, boron nitride, forsterite, titanium oxide, barium titanate, strontium titanate, and calcium titanate.

[0031] The content of the filler (D) in the resin composition is 1 to 1600 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition.

[0032] The above compound (B) containing two or more polymerizable carbon-carbon unsaturated double bonds contains at least one selected from the group consisting of compounds containing a vinylaryl group, compounds containing a (meth)acryloyl group, and compounds containing a (meth)allyl group.

[0033] <12>The resin composition according to any one of <1> to <11>, wherein the polyimide compound (A) is obtained from an intermediate amine compound (C) in which the above aromatic amine compounds (a1) are connected to each other by the above aromatic divinyl compound (a2) and the above maleic anhydride as reaction raw materials (3).

[0034] <13>The resin composition according to <12>, wherein the amine equivalent of the above intermediate amine compound (C) is in the range of 172 to 400 g / equivalent.

[0035] <14>The resin composition according to any one of <1> to <13>, wherein the above reaction raw material (1) further contains an aromatic monovinyl compound (a3) having one vinyl group.

[0036] <15>The resin composition according to any one of <1> to <14>, wherein the polyimide compound (A) has a structural unit represented by the following formula (1).

[0037]

[0038] (In the above formula (1), R 1 each independently represents an alkyl group having 1 to 10 carbon atoms, R 2 each independently represents: an alkyl group having 1 to 10 carbon atoms, an alkoxy group or an alkylthio group; an aryl group, an aryloxy group or an arylthio group having 6 to 10 carbon atoms; a cycloalkyl group having 3 to 10 carbon atoms; a halogen atom; a hydroxyl group; or a mercapto group,

[0039] R 3 、R 4 、R 5 and R 6 each independently represents a hydrogen atom or a methyl group, and one of R 3 and R 4 is a hydrogen atom and the other is a methyl group, and one of R 5 and R 6 is a hydrogen atom and the other is a methyl group,

[0040] X 1 represents a substituent represented by the following formula (x),

[0041]

[0042] (In the formula (x), R 7 and R8 each independently represents a hydrogen atom or a methyl group, and R 7 and R 8 one of them is a hydrogen atom and the other is a methyl group, and R 9 each independently represents: an alkyl group, an alkoxy group or an alkylthio group having 1 to 10 carbon atoms; an aryl group, an aryloxy group or an arylthio group having 6 to 10 carbon atoms; a cycloalkyl group having 3 to 10 carbon atoms; a halogen atom; a hydroxyl group; or a mercapto group, and t represents an integer of 0 to 4.)

[0043] r is the average value of the number of substitutions of X 1 in each benzene ring to which X 1 is bonded, represents a number of 0 to 4, p represents an integer of 1 to 3, q represents an integer of 0 to 4, and k represents an integer of 1 to 100.)

[0044] <16>The resin composition according to any one of <1> to <15> is used for a printed circuit board.)

[0045] <17>A cured product of the resin composition according to any one of <1> to <16>.)

[0046] <18>A prepreg formed of a base material and the resin composition according to any one of <1> to <16>.)

[0047] <19>A metal foil-clad laminate comprising: at least one sheet of the prepreg according to <18>, and a metal foil disposed on one side or both sides of the prepreg.)

[0048] <20>A resin composite sheet comprising: a support, and a layer formed of the resin composition according to any one of <1> to <16> disposed on the surface of the support.)

[0049] <21>A printed circuit board comprising an insulating layer and a conductor layer disposed on the surface of the insulating layer, and the insulating layer comprises a layer formed of the resin composition according to any one of <1> to <16>.)

[0050] Effects of the Invention

[0051] According to the present invention, there can be provided: a novel resin composition capable of providing a cured product having low dielectric properties, and a cured product, a prepreg, a metal foil-clad laminate, a resin composite sheet, and a printed circuit board.) Detailed Embodiments

[0052] Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as "the present embodiment") will be described in detail. It should be noted that the following present embodiment is an illustration for explaining the present invention, and the present invention is not limited to the present embodiment.)

[0053] It should be noted that in this specification, "~" is used to mean the numerical values before and after it as the lower limit value and the upper limit value.

[0054] In this specification, unless otherwise specified, all physical property values and characteristic values are the values at 23°C.

[0055] In the description of groups (atomic groups) in this specification, the expressions without indicating substitution and non-substitution include groups (atomic groups) without substituents and also include groups (atomic groups) with substituents. For example, "alkyl" includes not only alkyl without substituents (unsubstituted alkyl) but also alkyl with substituents (substituted alkyl). The same applies to "vinyl", which includes not only vinyl without substituents (unsubstituted vinyl) but also vinyl with substituents (substituted vinyl). In this specification, the expressions without indicating substitution and non-substitution are preferably unsubstituted.

[0056] In this specification, (meth)allyl represents both allyl and methallyl or either one of them, and is preferably allyl. (Meth)acryloyl represents both acryloyl and methacryloyl or either one of them, and is preferably methacryloyl.

[0057] In this specification, the relative dielectric constant represents the ratio of the dielectric constant to the vacuum dielectric constant of the substance. In addition, in this specification, the relative dielectric constant is sometimes simply referred to as "dielectric constant".

[0058] It should be noted that "parts by mass" in this specification represents the relative amount of components, and "mass%" represents the absolute amount of components.

[0059] In this specification, the resin solid content refers to the components other than the filler and the solvent, and means including the polyimide compound (A) and the compound (B) containing two or more polymerizable carbon-carbon unsaturated double bonds, as well as other resin components (C) compounded as required, monomers or oligomers having an ethylenic unsaturated group, silane coupling agents and other components (additives such as dispersants, flame retardants, etc.).

[0060] When the measurement methods and the like described in the standards shown in this specification vary according to the year, and there is no special description, the standards based on the time of January 1, 2022 are adopted.

[0061] The polyimide compound (A) contains a compound having one or more maleimide groups, and preferably contains a compound having two or more maleimide groups.

[0062] The resin composition of the present embodiment is characterized by containing: a polyimide compound (A), and a compound (B) containing two or more polymerizable carbon-carbon unsaturated double bonds, wherein the polyimide compound (A) uses an aromatic amine compound (a1) having one or more and three or less alkyl groups in the aromatic ring, an aromatic divinyl compound (a2) having two vinyl groups, and maleic anhydride as reaction raw materials (1). By adopting such a configuration, a novel resin composition capable of providing a cured product with low dielectric properties can be obtained.

[0063] <Polyimide compound (A)>

[0064] The resin composition of the present embodiment contains a polyimide compound (A) using an aromatic amine compound (a1) having one or more and three or less alkyl groups on the aromatic ring, an aromatic divinyl compound (a2) having two vinyl groups, and maleic anhydride as reaction raw materials (1). By containing the polyimide compound (A), a cured product with excellent low dielectric properties can be provided. In particular, for example, compared with when using the compound shown in (M1-3) described later, a resin composition with excellent low dielectric properties (especially low dielectric loss tangent) can be obtained.

[0065] The polyimide compound (A) of the present embodiment is a compound using an aromatic amine compound (a1) having one or more and three or less alkyl groups (hereinafter also referred to as "aromatic amine compound (a1)"), an aromatic divinyl compound (a2) having two vinyl groups (hereinafter also referred to as aromatic divinyl compound (a2)), and maleic anhydride as reaction raw materials (1). Thereby, the dimensional change rate during curing is small (or excellent dimensional stability is exhibited), and a low moisture absorption rate and low dielectric loss tangent property of the cured product can be achieved at a high level.

[0066] In the present embodiment, the reaction raw materials (1) may further contain an aromatic monovinyl compound (a3) having one vinyl group (hereinafter also referred to as "aromatic monovinyl compound (a3)"). In addition, the polyimide compound (A) of the present embodiment is preferably a polyimide compound using an intermediate amine compound (C) crosslinked by aromatic amine compounds (a1) having one or more and three or less alkyl groups with each other via an aromatic divinyl compound (a2) having two vinyl groups and maleic anhydride as reaction raw materials (3). Furthermore, the intermediate amine compound (C) is preferably a compound using an aromatic amine compound (a1) having one or more and three or less alkyl groups, an aromatic divinyl compound (a2) having two vinyl groups, and an aromatic monovinyl compound (a3) having one vinyl group added as needed as reaction raw materials (2).

[0067] In other words, the intermediate amine compound (C) in the present embodiment preferably has the following structure: a structural unit of an aromatic amine compound (a1) having an aromatic ring bonded with an amino group (including a substituted amino group in which a hydrogen atom of the amino group is further substituted with an alkyl group having 1 to 6 carbon atoms) and having 1 or more and 3 or less alkyl groups on the aforementioned aromatic ring and a structural unit of an aromatic divinyl compound (a2) having 2 vinyl groups are connected by a chemical bond, and, if necessary, a structural unit of an aromatic monovinyl compound (a3) is chemically bonded to the aforementioned aromatic ring in the structural unit of the aforementioned aromatic amine compound (a1). Further, the polyimide compound (A) in the present embodiment has a structure in which the amino group (including -NH 2 and the substituted amino group) bonded to the aromatic ring of the aforementioned intermediate amine compound (C) is replaced with an N-substituted maleimide ring.

[0068] Therefore, the "polyimide compound (A)" in the present embodiment and the "intermediate amine compound (C)" which is a precursor of the "polyimide compound (A)" are polymer compounds that are different in that the amino group (including -NH 2 and the substituted amino group) bonded to the aromatic ring is replaced with an N-substituted maleimide ring.

[0069] It should be noted that the structural unit of the aromatic amine compound (a1) refers to a group formed by removing 2 hydrogen atoms from the aromatic ring of the aromatic amine compound (a1). For example, when the aromatic amine compound (a1) is represented by the following formula (a), the group formed by removing 2 hydrogen atoms from the benzene ring of the formula (a) is referred to as the structural unit of the aromatic amine compound (a1). Further, the structural unit of the aromatic divinyl compound (a2) refers to a group formed by breaking the unsaturated bonds of the 2 vinyl groups of the aromatic divinyl compound (a2).

[0070] In the present embodiment, since an aromatic amine compound (a1) having a specific aromatic ring structure is used as a reaction raw material, it is easy to control the reaction site with the aromatic divinyl compound (a2) described later. Therefore, it is easy to obtain a polyimide compound (A) having a uniform chemical structure or chain length. As a result, a polyimide compound (A) exhibiting a low moisture absorption rate and a low dielectric loss tangent during curing can be provided.

[0071] <<Preferred embodiments of the polyimide compound (A)>>

[0072] The polyimide compound (A) in the present embodiment preferably has a structural unit represented by the following formula (1).

[0073]

[0074] (In the above formula (1), R1 Each independently represents an alkyl group, R 2 each independently represents an alkyl group, alkoxy group or alkylthio group having 1 to 10 carbon atoms; an aryl group, aryloxy group or arylthio group having 6 to 10 carbon atoms; a cycloalkyl group having 3 to 10 carbon atoms; a halogen atom; a hydroxyl group; or a mercapto group,

[0075] R 3 , R 4 , R 5 and R 6 Each independently represents a hydrogen atom or a methyl group, and R 3 and R 4 One of them is a hydrogen atom and the other is a methyl group. 5 and R 6 One of them is a hydrogen atom and the other is a methyl group.

[0076] X 1 represents a substituent represented by the following formula (x),

[0077]

[0078] (In formula (x), R 7 and R 8 Each independently represents a hydrogen atom or a methyl group, and R 7 and R 8 One of them is a hydrogen atom and the other is a methyl group. 9 Each independently represents: an alkyl group, an alkoxy group or an alkylthio group having 1 to 10 carbon atoms; an aryl group, an aryloxy group or an arylthio group having 6 to 10 carbon atoms; a cycloalkyl group having 3 to 10 carbon atoms; a halogen atom; a hydroxyl group; or a mercapto group, and t represents an integer of 0 to 4. It should be noted that * in formula (1) represents a bond with other atoms)

[0079] r is the number of X per bond 1 X in the benzene ring 1 The average value of the number of substitutions is represented by , p represents an integer from 1 to 3, q ​​represents an integer from 0 to 4, and k represents an integer from 1 to 100. )

[0080] In the above formula (1), when p is an integer greater than 2, a plurality of R 1 When q is an integer greater than 2, a plurality of R 2 When t is an integer greater than 2, a plurality of R 9 They are optionally the same as or different from each other.

[0081] In the above formula (1), R 1Preferably, each independently represents an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, still more preferably an alkyl group having 1 to 3 carbon atoms, and may also be an alkyl group having 1 to 2 carbon atoms. In addition, when p is an integer of 2 or more, a plurality of R's present 1 are optionally the same as or different from each other. As the preferred R in formula (1) 1 , it is methyl, ethyl or n-propyl, and may also be methyl and / or ethyl. It should be noted that the benzene ring to which R in formula (1) 1 is bonded may be the benzene ring of the aromatic amine compound (a1).

[0082] In the above formula (1), p preferably represents 1 or 2, and more preferably 1. By making p = 1, there is a tendency to increase the molecular weight distribution of the obtained polyimide compound (A) and to reduce the moisture absorption rate and the dimensional change rate of the obtained cured product.

[0083] It should be noted that in the benzene ring to which R in formula (1) is bonded 1 , it is preferred that R is bonded at least at one of the 2nd, 3rd, 4th, 5th or 6th position relative to the maleimide group 1 , more preferably R is bonded at least at one of the 2nd, 3rd, 4th or 6th position 1 , still more preferably R is bonded at least at one of the 2nd or 6th position 1 . By bonding R at least at one of the 2nd or 6th position relative to the maleimide group 1 , there is a tendency to have excellent low dielectric properties (low dielectric constant and / or low dielectric loss tangent). When p = 2, it is preferred that R is bonded at the 2nd and 6th positions, or the 2nd and 3rd positions relative to the maleimide group 1 . As a specific example, for example, a mode in which methyl groups are bonded at the 2nd and 6th positions relative to the maleimide group can be cited. In addition, when p = 1, it is preferred that R is bonded at the 2nd position relative to the maleimide group 1 . As a specific example, for example, a mode in which an ethyl group is bonded at the 2nd position relative to the maleimide group can be cited.

[0084] In the above formula (1), R 2 preferably each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms; an aryl group having 6 to 10 carbon atoms; a cycloalkyl group having 3 to 10 carbon atoms; a halogen atom; or a hydroxyl group, more preferably represents an alkyl group having 1 to 10 carbon atoms, still more preferably represents an alkyl group having 1 to 6 carbon atoms. In addition, when q is an integer of 2 or more, a plurality of R's present 2 are optionally the same as or different from each other. As the preferred R in formula (1) 2 , it is methyl, ethyl or n-propyl. It should be noted that R in formula (1) 2The benzene ring to be bonded may be the benzene ring of the aromatic divinyl compound (a2). Further, in the above formula (1), q preferably represents 0, 1, or 2.

[0085] In the above formula (1), R 3 and R 4 One of them is a hydrogen atom and the other is a methyl group, and R 5 and R 6 One of them is a hydrogen atom and the other is a methyl group. Thus, the reactivity of the unsaturated bond possessed by the polymaleimide compound (A) itself can be maintained at a high level. R in the above formula (1) 3 , R 4 , R 5 and R 6 If the proportion of the alkyl group increases, due to steric hindrance, a tendency for the reactivity of the unsaturated bond possessed by the polymaleimide compound (A) itself to decrease may be observed. Therefore, if R 3 , R 4 , R 5 and R 6 are all alkyl groups, the reactivity of the unsaturated bond possessed by the polymaleimide compound (A) itself decreases, and a cured product cannot be efficiently formed, which may result in deterioration of the dimensional change rate and the like.

[0086] In the above formula (1), X 1 is represented by the above formula (x), and in this formula (x), preferably R 7 represents a hydrogen atom, and R 8 represents a methyl group. Further, in the above formula (x), R 9 preferably each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms; an aryl group having 6 to 10 carbon atoms; a cycloalkyl group having 3 to 10 carbon atoms; a halogen atom; or a hydroxyl group, more preferably represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, further preferably represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms, still further preferably represents an alkyl group having 1 to 10 carbon atoms, and even further preferably represents an alkyl group having 1 to 6 carbon atoms. Further, in the above formula (x), t represents an integer of 0 to 4, preferably represents an integer of 0 to 3, more preferably represents an integer of 0 to 2. It should be noted that when t is an integer of 2 or more, multiple R 9 may be the same or different from each other.

[0087] In the above formula (1), r refers to the average value of the substitution number of X 1 in each benzene ring bonded with X 1 , and is a number in the range of 0 to 4, further preferably a number in the range of 0 to 3, and may also be a number in the range of 0 to 2.

[0088] In the above formula (1), k represents the number of repeating units, which is an integer of 1 to 100, preferably an integer of 1 to 90, more preferably an integer of 1 to 80, and may also be an integer of 1 to 50 or an integer of 1 to 20.

[0089] In the polyimide compound (A) of the present embodiment, relative to the total amount (100% by mass) of the polyimide compound (A), it preferably contains 10% by mass or less of an indane skeleton (or a structural unit having an indane skeleton), preferably contains 5% by mass or less, more preferably contains 3% by mass or less, still more preferably contains 2% by mass or less, and particularly preferably contains 0.9% by mass or less.

[0090] The structural unit having an indane skeleton is preferably represented by the following formula (3).

[0091]

[0092] (In the above formula (3), R 31 , R 32 and R 33 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R 34 each independently represent an alkyl group, an alkoxy group or an alkylthio group having 1 to 10 carbon atoms; an aryl group, an aryloxy group or an arylthio group having 6 to 10 carbon atoms; a cycloalkyl group having 3 to 10 carbon atoms; a halogen atom; a hydroxyl group; or a mercapto group, and q 3 represents an integer of 0 to 3. When q 3 is an integer of 2 or more, a plurality of existing R 34 are optionally the same or different from each other. In addition, * represents a bond with other atoms)

[0093] In the above formula (3), R 34 are preferably each independently an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms. In addition, in the above formula (3), R 31 , R 32 and R 33 are preferably a hydrogen atom or a methyl group.

[0094] Hereinafter, an aromatic amine compound (a1) having 1 or more and 3 or less alkyl groups, an aromatic divinyl compound (a2) having 2 vinyl groups, an aromatic monovinyl compound (a3) having 1 vinyl group which may be an optional component, and maleic anhydride, which are constituent components of the reaction raw material (1) of the polyimide compound (A), will be described, and then other preferred embodiments of the polyimide compound (A) and a method for producing the polyimide compound (A) will be described.

[0095] <<Aromatic amine compound (a1)>>

[0096] The aromatic amine compound (a1) in the present embodiment has an aromatic ring bonded with an amino group (-NH 2 or a substituted amino group), and one or more and three or less alkyl groups are bonded to the aforementioned aromatic ring. Therefore, the aromatic amine compound (a1) can be an amine-based compound. In addition, the aromatic ring forming the central structure of the aromatic amine compound (a1) is preferably a monocyclic ring, including an aromatic hydrocarbon ring and an aromatic heterocyclic ring. As the aromatic hydrocarbon ring, a benzene ring is preferred. As the aromatic heterocyclic ring, for example, a heterohexacyclic ring such as a pyran ring or a pyridine ring can be cited. In addition, the aromatic amine compound (a1) in the present embodiment more preferably has an aromatic ring bonded with -NH 2 without a substituted amino group, and one or more and three or less alkyl groups are bonded to the aforementioned aromatic ring.

[0097] In the aromatic amine compound (a1) of the present embodiment, as the alkyl group substituting one or more and three or less hydrogen atoms of the aromatic ring of the substituted aromatic amine compound (a1), an alkyl group having 1 to 10 carbon atoms can be cited, preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and also an alkyl group having 1 to 2 carbon atoms. The aforementioned alkyl group can be any of a linear type, a branched type, or a cyclic type. For example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, etc. can be cited. The smaller the molecular weight of the aforementioned alkyl group, the more remarkable the effect (low dimensional change rate) exerted by the present invention. In addition, the higher the molecular weight of the aforementioned alkyl group, the more remarkable the effect (low moisture absorption) exerted by the present invention.

[0098] Regarding the upper limit of the number of alkyl groups bonded to the aromatic ring having an amino group (including -NH 2 and a substituted amino group) in the aromatic amine compound (a1), from the viewpoint that the aforementioned aromatic ring has an amino group (including -NH 2 and a substituted amino group) and two connecting bonds are used for polymerization, it can be the number obtained by subtracting 3 from the number of ring-forming atoms that can be substituted in the aforementioned aromatic ring in the unsubstituted state. For example, when the aforementioned aromatic ring is a benzene ring, the number of the aforementioned alkyl groups is 3 or less.

[0099] In addition, by setting the number of alkyl groups substituted on the aromatic ring of the aromatic amine compound (a1) to 2 or more, it becomes easy to control the reaction site with the aromatic divinyl compound (a2) described later, and thus it is easy to obtain a polyimide compound (A) with a uniform chemical structure or chain length. As a result, in the cured product of the polyimide compound (A), low moisture absorption and excellent high-frequency electrical properties are easily exhibited.

[0100] Taking the case where the aromatic ring of the aromatic amine compound (a1) in the present embodiment is a benzene ring as an example, the preferred mode of the aromatic amine compound (a1) will be described.

[0101] In the present embodiment, among the carbon atoms in the benzene ring constituting the aromatic amine compound (a1), it is preferable that one or more carbon atoms having the largest HOMO electron density (Hückel coefficient) are unsubstituted (or substituted with a hydrogen atom).

[0102] Thereby, it is easy to control the ArS of the cationoid reagent formed from the aromatic divinyl compound (a2) described later E reaction and molecular design. More specifically, when the carbon atom having the largest HOMO electron density (Hückel coefficient) among the carbon atoms in the benzene ring constituting the aromatic amine compound (a1) is unsubstituted, the carbocation of the aromatic divinyl compound (a2) as the cationoid reagent easily reacts with the carbon atom having the largest HOMO electron density. Therefore, by controlling the number and position of the alkyl groups bonded to the carbon atoms of the benzene ring, etc., the bonding site or the number of bonds with the aromatic divinyl compound (a2) can be adjusted. Therefore, it is presumed that it is easy to design the chemical structure or molecular chain length of the resulting polyimide compound (A).

[0103] For example, when the aromatic amine compound (a1) has an aniline skeleton containing one benzene ring and one amino group, it is preferable that at least one carbon atom among the 2-position, 4-position, and 6-position of the aniline nucleus is substituted with a hydrogen atom. Thereby, the cationoid reagent formed from the aromatic divinyl compound (a2) described later easily attacks at least one carbon atom among the 2-position, 4-position, and 6-position, which are the ortho-position and para-position with high electron density of the aniline nucleus. In particular, if an aromatic amine compound (a1) having an aniline nucleus substituted with an alkyl group at a specific position is used, the bonding site with the aromatic divinyl compound (a2) can be roughly controlled, and thus it is easy to obtain a polyimide compound (A) with a uniform chemical structure or chain length. For example, it is considered that if 2,6-dialkylaniline is used as the aromatic amine compound (a1), a large amount of the polyimide compound (A) bonded to the aromatic divinyl compound (a2) at the 4-position can be obtained.

[0104] As a specific example of the aromatic amine compound (a1) of the present embodiment, for example, dimethylaniline (2,3-dimethylaniline, 2,4-dimethylaniline, 2,6-dimethylaniline, 3,4-dimethylaniline or 3,5-dimethylaniline), diethylaniline (2,3-diethylaniline, 2,4-diethylaniline, 2,6-diethylaniline, 3,4-diethylaniline or 3,5-diethylaniline), diisopropylaniline (2,3-diisopropylaniline, 2,4-diisopropylaniline, 2,6-diisopropylaniline, 3,4-diisopropylaniline or 3,5-diisopropylaniline), ethylmethylaniline (for example, ethylmethylaniline in which any one of the 2,3-position, 2,4-position, 2,6-position, 3,4-position or 3,5-position is methyl and the other is ethyl), cyclobutylaniline, cyclopentylaniline, cyclohexylaniline, o-, m- or p-toluidine, o-, m- or p-ethylaniline, o-, m- or p-isopropylaniline, o-, m- or p-propylaniline, o-, m- or p-butylaniline, methylisopropylaniline (for example, methylisopropylaniline in which any one of the 2,3-position, 2,4-position, 2,6-position, 3,4-position or 3,5-position is methyl and the other is isopropyl), or ethylbutylaniline (for example, ethylbutylaniline in which any one of the 2,3-position, 2,4-position, 2,6-position, 3,4-position or 3,5-position is ethyl and the other is butyl) etc. can be used. In addition, the aforementioned butyl includes n-butyl, tert-butyl and sec-butyl. It should be noted that the aromatic amine compound (a1) in the present embodiment can be used alone or in combination of two or more.

[0105] For example, in the case of a chemical structure in which a maleimide group such as N-phenylmaleimide is directly bonded to an unsubstituted benzene ring, the state in which the benzene ring and the 5-membered ring of maleimide are arranged in the same plane is stable, so it is easy to stack and exhibits high crystallinity. Therefore, it becomes the reason for poor solvent solubility. On the other hand, in the case of the present embodiment, for example, in the case of having an alkyl group (such as a methyl group) as a substituent for the benzene ring like 2,6-dimethylaniline, due to the steric hindrance of the methyl group, the benzene ring and the five-membered ring of maleimide adopt a twisted conformation, making it difficult to stack, so the crystallinity is reduced and the solvent solubility is improved, which becomes a preferred mode. However, if the steric hindrance is too large, it is feared that the reactivity during the synthesis of maleimide may sometimes be inhibited, so for example, an aromatic amine compound (a1) having an alkyl group with 1 to 6 carbon atoms is preferably used.

[0106] The aromatic amine compound (a1) necessary for the reaction raw material (1) in the present embodiment can be represented by the following formula (a), for example.

[0107]

[0108] (In the above formula (a), R 1a each independently represents an alkyl group, pa represents an integer from 1 to 3. Multiple Rs present 1a (optionally the same or different)

[0109] In the above formula (a), the alkyl group preferably represents an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, further preferably an alkyl group having 1 to 3 carbon atoms, and may also be an alkyl group having 1 to 2 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms, the alkyl group having 1 to 3 carbon atoms, and the alkyl group having 1 to 2 carbon atoms are the same as those described above.

[0110] In the above formula (a), p a is preferably 1 or 2. It should be noted that when there are multiple Rs 1a they may be the same alkyl groups as each other, or may also be different alkyl groups.

[0111] It should be noted that in the present embodiment, the aromatic amine compound (a1) represented by the above formula (a) can be used alone or in combination of two or more.

[0112] <<Aromatic divinyl compound (a2)>>

[0113] The aromatic divinyl compound (a2) in the present embodiment has two vinyl groups (CH 2 =CH-) (also called Vinyl) as substituents on the aromatic ring and can be used without particular limitation as long as it can react with the aforementioned aromatic amine compound (a1). In addition, in the present embodiment, the reaction raw material (1) preferably contains a mixture of the aromatic divinyl compound (a2) and the aromatic monovinyl compound (a3).

[0114] Examples of the aromatic divinyl compound (a2) include divinylbenzene, divinylbiphenyl, divinylnaphthalene, and various compounds in which one or more alkyl groups having 1 to 10 carbon atoms, alkoxy groups, or alkylthio groups; aryl groups, aryloxy groups, or arylthio groups having 6 to 10 carbon atoms; cycloalkyl groups having 3 to 10 carbon atoms; halogen atoms; hydroxyl groups; or mercapto groups are substituted on their aromatic rings. The preferred mode of the substituent is the same as that of R in the above formula (1). 2 The aforementioned alkyl group can be either linear or branched. Among them, from the viewpoint of showing the effect of high heat resistance, the carbon number of the aforementioned alkyl group or alkoxy group is preferably 1 to 4. Specific examples of the aforementioned alkyl group include methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, isobutyl, etc. The aforementioned alkoxy group includes, for example, methoxy, ethoxy, propoxy, butoxy, etc. The aforementioned halogen atom includes fluorine atom, chlorine atom, bromine atom, etc.

[0115] The aromatic divinyl compound (a2) as the reaction raw material (1) of the polymaleimide compound (A) in the present embodiment is preferably represented by the following formula (b1).

[0116]

[0117] (In the above formula (b1), R 2b each independently represents an alkyl group, an alkoxy group or an alkylthio group having 1 to 10 carbon atoms; an aryl group, an aryloxy group or an arylthio group having 6 to 10 carbon atoms; a cycloalkyl group having 3 to 10 carbon atoms; a halogen atom; a hydroxyl group; or a mercapto group, and q 1b represents an integer of 0 to 4. It should be noted that when q 1b is an integer of 2 or more, multiple R's present 2b are optionally the same or different from each other)

[0118] R in the above formula (b1) 2b can correspond to R in formula (1) 2 . Therefore, R in the above formula (b1) 2b is the same as R in formula (1) 2 , and preferably each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms; an aryl group having 6 to 10 carbon atoms; a cycloalkyl group having 3 to 10 carbon atoms; a halogen atom; or a hydroxyl group, more preferably represents an alkyl group having 1 to 10 carbon atoms, and further preferably represents an alkyl group having 1 to 6 carbon atoms.

[0119] In the above formula (b1), q 1b is preferably an integer of 0 to 2. It should be noted that when q 1b is an integer of 2 or more, multiple R's present b1 can be the same group as each other, or can also be different groups.

[0120] Specific examples of the aromatic divinyl compound (a2) in the present embodiment include, for example, compounds such as divinylbenzenes including 1,2-divinylbenzene, 1,3-divinylbenzene, 1,4-divinylbenzene, 2,5-dimethyl-1,4-divinylbenzene, 2,5-diethyl-1,4-divinylbenzene, cis,cis,β,β’-diethoxy-m,m-divinylbenzene, 1,4-divinyl-2,5-dibutylbenzene, 1,4-divinyl-2,5-dihexylbenzene, 1,4-divinyl-2,5-dimethoxybenzene and their derivatives, and divinylnaphthalenes including 1,3-divinylnaphthalene, 1,4-divinylnaphthalene, 1,5-divinylnaphthalene, 1,6-divinylnaphthalene, 1,7-divinylnaphthalene, 2,3-divinylnaphthalene, 2,6-divinylnaphthalene, 2,7-divinylnaphthalene, 3,4-divinylnaphthalene, 1,8-divinylnaphthalene, 1,5-dimethoxy-4,8-divinylnaphthalene and their derivatives, but are not limited thereto.

[0121] It should be noted that the aromatic divinyl compound (a2) in the present embodiment can be used alone or in combination of two or more.

[0122] In particular, from the viewpoint of fluidity, as the aromatic divinyl compound (a2), divinylbenzene and compounds having substituents on the aromatic ring thereof are preferred, and divinylbenzene is more preferred. In addition, in the present embodiment, the substitution position of the vinyl group of divinylbenzene is not particularly limited, and the meta-isomer is preferably the main component. The content of the meta-isomer in divinylbenzene is preferably 40% by mass or more, more preferably 50% by mass or more, based on the total amount of divinylbenzene.

[0123] In the present embodiment, relative to the total amount (100% by mass) of the polymaleimide compound (A), it is preferred to contain 10 to 90% by mass of the structural unit of the aromatic divinyl compound (a2), and more preferably 20 to 90% by mass. The structural unit of the aromatic divinyl compound (a2) refers to a group obtained by removing two hydrogen atoms (a total of four hydrogen atoms) from each of the two vinyl groups of the aromatic divinyl compound (a2).

[0124] <<Aromatic monovinyl compound (a3)>>

[0125] In addition to using the aromatic amine compound (a1), aromatic divinyl compound (a2), and maleic anhydride, other compounds can be further used as reaction raw materials for the polyimide compound (A) in the present embodiment. Examples of such other compounds include aromatic monovinyl compounds (a3) having one vinyl group. That is, in the present embodiment, it is preferable to use an aromatic amine compound (a1), an aromatic divinyl compound (a2), an aromatic monovinyl compound (a3), and maleic anhydride as reaction raw materials (1). The polyimide compound (A) in the present embodiment uses an aromatic monovinyl compound (a3) in addition to using an aromatic amine compound (a1), an aromatic divinyl compound (a2), and maleic anhydride as its reaction raw materials. Thus, the cured product of the finally obtained polyimide compound (A) is excellent in terms of low dielectric loss tangent, and is therefore preferable.

[0126] In addition, the aromatic monovinyl compound (a3) also generates a carbocation in the same manner as the aromatic divinyl compound (a2), and thus easily reacts with the carbon atom having the largest HOMO electron density (Hückel coefficient) among the carbon atoms in the aromatic hydrocarbon ring constituting the aromatic amine compound (a1).

[0127] Examples of the aromatic monovinyl compound (a3) in the present embodiment include vinylbenzene (styrene), vinylbiphenyl, vinylnaphthalene, and those having one or more substituents selected from alkyl groups, alkoxy groups, or alkylthio groups having 1 to 10 carbon atoms; aryl groups, aryloxy groups, or arylthio groups having 6 to 10 carbon atoms; cycloalkyl groups having 3 to 10 carbon atoms; halogen atoms; hydroxyl groups; or mercapto groups on their aromatic rings. The above alkyl groups can be either linear or branched, and may have an unsaturated bond in their structures. Among them, when low hygroscopicity is emphasized, the aforementioned alkyl group or the aforementioned alkoxy group is preferably having 1 to 4 carbon atoms. Specific examples of the aforementioned alkyl group include methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, isobutyl, etc. The aforementioned alkoxy group includes, for example, methoxy, ethoxy, propoxy, butoxy, etc. The aforementioned halogen atom includes fluorine atom, chlorine atom, bromine atom, etc.

[0128] In the present embodiment, the aromatic monovinyl compound (a3) that can be a reaction raw material (1) of the polyimide compound (A) can be represented by the following formula (b2).

[0129]

[0130] (In the above formula (b2), R 9b each independently represents an alkyl group, an alkoxy group, or an alkylthio group having 1 to 10 carbon atoms; an aryl group, an aryloxy group, or an arylthio group having 6 to 10 carbon atoms; a cycloalkyl group having 3 to 10 carbon atoms; a halogen atom; a hydroxyl group; or a mercapto group, and t1b represents an integer from 0 to 5. It should be noted that when t 1b is an integer of 2 or more, multiple Rs present b2 are optionally the same as or different from each other)

[0131] R in the above formula (b2) 9b can correspond to R in formula (x) 9 . Therefore, R in the above formula (b1) 9b and R in formula (x) 9 Similarly, each preferably independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms; an aryl group having 6 to 10 carbon atoms; a cycloalkyl group having 3 to 10 carbon atoms; a halogen atom; or a hydroxyl group, more preferably represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, further preferably represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms, still further preferably represents an alkyl group having 1 to 10 carbon atoms, and even more preferably represents an alkyl group having 1 to 6 carbon atoms.

[0132] In the above formula (b1), t 1b is preferably 1 to 4. It should be noted that when t 1b is 2 or more, multiple Rs present 9b can be the same group as each other, or can also be different groups.

[0133] As a specific example of the aromatic monovinyl compound (a3) of the present embodiment, for example, vinylbenzene compounds such as compounds containing styrene, fluorostyrene, vinylbenzyl chloride, alkylvinylbenzenes (o-, m-, p-methylstyrene, o-, m-, p-ethylvinylbenzene), o-, m-, p-(chloromethyl)styrene and their derivatives can be cited; biphenyl compounds such as compounds containing 4-vinylbiphenyl, 4-vinyl-p-terphenyl and their derivatives; and vinylnaphthalene compounds such as compounds containing 1-vinylnaphthalene, 2-vinylnaphthalene and their derivatives, but are not limited to these.

[0134] In particular, from the viewpoint of raw material acquisition, alkylvinylbenzenes and compounds having substituents on their aromatic rings are preferred, and ethylvinylbenzene is more preferred.

[0135] In addition, the substitution positions of the vinyl group and the ethyl group of ethylvinylbenzene are not particularly limited, and the meta-isomer is preferably the main component. The content of the meta-isomer in ethylvinylbenzene is more preferably 40% by mass or more, and further preferably 50% by mass or more, relative to the total amount of ethylvinylbenzene.

[0136] When using the aromatic monovinyl compound (a3) as the reaction raw material (1) of the polyimide compound (A) in the present embodiment, the molar ratio ((a2) / (a3)) of the aromatic monovinyl compound (a3) in the aforementioned reaction raw material (1) to the aromatic divinyl compound (a2) is preferably from 99 / 1 to 50 / 50, more preferably from 98 / 2 to 70 / 30.

[0137] In the present embodiment, relative to the total amount (100% by mass) of the polyimide compound (A), it is preferable to contain 0 to 40% by mass of the structural unit of the aromatic monovinyl compound (a3), and more preferably to contain 0 to 30% by mass. The structural unit of the aromatic monovinyl compound (a3) refers to a group obtained by removing two hydrogen atoms from one vinyl group of the aromatic monovinyl compound (a3).

[0138] As the reaction raw material containing the aromatic divinyl compound (a2) and the aromatic monovinyl compound (a3), commercially available products can be used. For example, "DVB-810 (a mixture of divinylbenzene / ethylstyrene (divinylbenzene / ethylstyrene = 81 / 19 (mol%)))" and "DVB-570 (a mixture of divinylbenzene / ethylstyrene (divinylbenzene / ethylstyrene = 57 / 43 (mol%)))" manufactured by Nippon Steel Chemical & Materials Co., Ltd. can be cited.

[0139] <<Maleic anhydride>>

[0140] In the present embodiment, maleic anhydride is an essential component of the reaction raw material (1) of the polyimide compound (A). As described in the item of the manufacturing method of the polyimide compound (A) described later, it is used for the reaction of maleimidizing the amino group (including -NH 2 and substituted amino group) derived from the aromatic amine compound (a1).

[0141] <<Preferred mode of the polyimide compound (A)>>

[0142] In the present embodiment, the polyimide compound (A) is preferably represented by the following formula (2).

[0143]

[0144] (In the above formula (2), R 1 each independently represents an alkyl group, R 2 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms; an aryl group having 6 to 10 carbon atoms; a cycloalkyl group having 3 to 10 carbon atoms; a halogen atom; or a hydroxyl group, R 3 , R 4 , R 5 and R 6Each independently represents a hydrogen atom or a methyl group, and R 3 and R 4 One of them is a hydrogen atom and the other is a methyl group, R 5 and R 6 One of them is a hydrogen atom and the other is a methyl group,

[0145] X 1 represents a substituent represented by the following formula (x),

[0146]

[0147] (In formula (x), R 7 and R 8 Each independently represents a hydrogen atom or a methyl group, and R 7 and R 8 One of them is a hydrogen atom and the other is a methyl group, R 9 Each independently represents: an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms; an aryl group having 6 to 10 carbon atoms; a cycloalkyl group having 3 to 10 carbon atoms; a halogen atom; or a hydroxyl group, and t represents an integer of 0 to 4.)

[0148] M 21 represents a hydrogen atom or a group represented by the following formula (i), M 22 represents a hydrogen atom, a group represented by the following formula (ii) or a group represented by the following formula (iii),

[0149]

[0150] (In the above formula (i), R 9 Each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms; an aryl group having 6 to 10 carbon atoms; a cycloalkyl group having 3 to 10 carbon atoms; a halogen atom; or a hydroxyl group, R 7 and R 8 Each independently represents a hydrogen atom or a methyl group, and R 7 and R 8 One of them is a hydrogen atom and the other is a methyl group, t represents an integer of 0 to 4, and * represents a bond to other atoms. It should be noted that when t is an integer of 2 or more, multiple R 9 may be the same or different from each other.)

[0151]

[0152] (In the above formula (ii), R 1ii represents an alkyl group, and p ii represents an integer of 0 to 4. It should be noted that when p ii is an integer of 2 or more, multiple R 1iiare each independently selected from the same or different groups. In the above formula (iii), R 1iii represents an alkyl group, and R 9 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, or a hydroxyl group. R 7 and R 8 each independently represent a hydrogen atom or a methyl group, and one of R 7 and R 8 is a hydrogen atom and the other is a methyl group. p iii represents an integer from 0 to 3, t represents an integer from 0 to 4, and r 1iii represents the average value of the number of substituents in each benzene ring bonded to X 1 , represents a number from 1 to 4, and * represents a bond to another atom. It should be noted that when p iii is an integer of 2 or more, the multiple R 1iii are each independently selected from the same or different groups. When t is an integer of 2 or more, the multiple R 9 are each independently selected from the same or different groups. r is the average value of the number of X 1 substituents in each benzene ring bonded to X 1 , represents a number from 0 to 4, p represents an integer from 1 to 3, q represents an integer from 0 to 4, and k represents an integer from 1 to 100.)

[0153] In the above formula (2), when p is an integer of 2 or more, the multiple R 1 are each independently selected from the same or different groups. When q is an integer of 2 or more, the multiple R 2 are each independently selected from the same or different groups. When t is an integer of 2 or more, the multiple R 9 are each independently selected from the same or different groups)

[0154] It should be noted that the preferred embodiments of R 1 to R 9 , X 1 , p, q, r, t, and k in the above formula (2) are the same as those in the above formula (1). Furthermore, the above formula (i) corresponds to the above formula (x), R 1ii in the above formula (ii) corresponds to R 1 in the above formula (1), and R 1iii in the above formula (iii) corresponds to R 1 in the above formula (1).

[0155] Hereinafter, the preferred embodiments of the polyimide compound (A) of the present embodiment will be described. As the polyimide compound (A) of the present embodiment, for example, the following first to third embodiments can be cited. In the following embodiments, a preferred example of the aromatic divinyl compound (a2) is divinylbenzene, and a preferred example of the aromatic vinyl compound (a3) is ethylvinylbenzene. A preferred example of the arylmaleimide structural unit is a structural unit derived from 2-ethylaniline and maleic anhydride.

[0156] The first embodiment of the polyimide compound (A) includes: a compound in which the molar ratio of the total of the structural units derived from the aromatic divinyl compound (a2) and / or the aromatic vinyl compound (a3) to the arylmaleimide structural unit is n:n+1.

[0157] Examples of the compound in which the molar ratio of the total of the structural units derived from the aromatic divinyl compound (a2) and / or the aromatic vinyl compound (a3) to the arylmaleimide structural unit is n:n+1 include the following compounds:

[0158] Aryl maleimide structural unit - structural unit derived from aromatic divinyl compound (a2) - aryl maleimide structural unit;

[0159] Aryl maleimide structural unit - structural unit derived from aromatic divinyl compound (a2) - aryl maleimide structural unit - structural unit derived from aromatic divinyl compound (a2) - aryl maleimide structural unit.

[0160] The second embodiment of the polyimide compound (A) includes: a compound in which the molar ratio of the total of the structural units derived from the aromatic divinyl compound (a2) and / or the aromatic monovinyl compound (a3) to the arylmaleimide structural unit is n:n.

[0161] Examples of the compound in which the molar ratio of the total of the structural units derived from the aromatic divinyl compound (a2) and / or the aromatic monovinyl compound (a3) to the arylmaleimide structural unit is n:n include the following compounds:

[0162] Aryl maleimide structural unit - structural unit derived from aromatic monovinyl compound (a3);

[0163] Aryl maleimide structural unit - structural unit derived from aromatic divinyl compound (a2) - aryl maleimide structural unit - structural unit derived from aromatic monovinyl compound (a3).

[0164] The third embodiment of the polyimide compound (A) includes a compound in which the total molar ratio of the structural unit derived from the aromatic divinyl compound (a2) and the structural unit derived from the aromatic monovinyl compound (a3) to the arylimide structural unit is n + 1:n.

[0165] Examples of the compound in which the total molar ratio of the structural unit derived from the aromatic divinyl compound (a2) and the structural unit derived from the aromatic monovinyl compound (a3) to the arylimide structural unit is n + 1:n include the following compounds:

[0166] Structural unit derived from aromatic monovinyl compound (a3) - arylimide structural unit - structural unit derived from aromatic monovinyl compound (a3);

[0167] Aromatic monovinyl compound (a3) - arylimide structural unit - structural unit derived from aromatic divinyl compound (a2) - arylimide structural unit - aromatic monovinyl compound (a3) unit.

[0168] The polyimide compound (A) of the present embodiment preferably contains compounds corresponding to at least two of the compounds of the above first to third embodiments, more preferably contains at least a compound corresponding to the first embodiment, and contains a compound corresponding to the second embodiment and / or a compound corresponding to the third embodiment, and still more preferably contains all of the compounds corresponding to the first to third embodiments.

[0169] It should be noted that it is speculated that the aromatic monovinyl compound (a3) easily functions as a capping agent for the arylimide structural unit.

[0170] In the following embodiments, the case where each aromatic ring is a benzene ring will be described as an example. The following chemical structural formulas are used to illustratively explain the present disclosure, and the scope of the present disclosure is not limited to the following chemical structural formulas.

[0171] In the present embodiment, the number average molecular weight (Mn) of the polyimide compound (A) is preferably 350 or more, more preferably 400 or more, and preferably 2,000 or less, more preferably 1,500 or less. In addition, the weight average molecular weight (Mw) of the polyimide compound (A) is preferably 400 or more, more preferably 450 or more, may be 1000 or more, and preferably 500,000 or less, more preferably 400,000 or less, and may also be 100,000 or less, 10,000 or less. By setting it to be above the aforementioned lower limit value, the moisture absorption rate and dimensional change rate of the obtained cured product can be reduced. Furthermore, there is a tendency that the heat resistance and chemical resistance are also improved.

[0172] In the present embodiment, from the aspect of excellent low dielectric constant and low dielectric loss tangent, the molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the polyimide compound (A) calculated by gel permeation chromatography (GPC) is preferably 1.001 or more, more preferably 1.01 or more, and preferably 500 or less, more preferably 400 or less. It should be noted that according to the GPC chromatogram obtained by GPC measurement, when the molecular weight distribution covers a wide range and there are many high molecular weight components, the proportion of high molecular weight components contributing to flexibility increases. Therefore, compared with the cured product using conventional maleimide, a cured product with suppressed brittleness, excellent flexibility and softness can be obtained, which is a preferred mode. Furthermore, by setting it to be not less than the lower limit value of the above-mentioned molecular weight distribution, the moisture absorption rate and dimensional change rate of the obtained cured product can be reduced. Furthermore, there is a tendency that the heat resistance and chemical resistance are also improved.

[0173] It should be noted that the number average molecular weight (Mn), weight average molecular weight (Mw) and molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the polyimide compound (A) in the present embodiment are measured according to the description in paragraph 0072 of Japanese Patent No. 7160151, and this description is incorporated into the present specification.

[0174] <<Manufacturing method of polyimide compound (A)>>

[0175] Hereinafter, the manufacturing method of the polyimide compound (A) of the present disclosure will be described.

[0176] The manufacturing method of the polyimide compound (A) in the present embodiment is not particularly limited, as long as an aromatic amine compound (a1), an aromatic divinyl compound (a2) and maleic anhydride are used as reaction raw materials (1), or it has the structural unit shown in the above formula (1), it can be manufactured in any way. As an example of the manufacturing method of the polyimide compound (A) of the present disclosure, for example, a manufacturing method including the following steps (1) and (2) can be cited.

[0177] Step (1): A step of reacting an aromatic amine compound (a1) with an aromatic divinyl compound (a2) as reaction raw materials (2) to obtain the intermediate amine compound (C) in the present embodiment;

[0178] Step (2): A step of reacting the intermediate amine compound (C) obtained in the above step (1) with maleic anhydride as reaction raw materials (3) to obtain the polyimide compound (A) of the present disclosure.

[0179] Specifically, the method for manufacturing the polyimide compound (A) in the present embodiment preferably includes: a step (1) (also referred to as a crosslinking step) of reacting an aromatic amine compound (a1) with an aromatic divinyl compound (a2) under a solid acid catalyst; and a step (2) (also referred to as a condensation step) of condensing the intermediate amine compound (C) generated through the above step (1) with maleic anhydride.

[0180] The following will sequentially describe each step of the method for manufacturing the polyimide compound (A) of the present disclosure.

[0181] <<<Step (1): Manufacturing step of intermediate amine compound (C)>>>

[0182] Hereinafter, the manufacturing step of the intermediate amine compound (C) in the present embodiment will be described.

[0183] The step (1) in the present embodiment is not particularly limited. For example, it is a step of reacting the above aromatic amine compound (a1), the above aromatic divinyl compound (a2) (such as divinylbenzene), and other compounds such as an aromatic monovinyl compound (a3) (such as ethyl vinylbenzene) as needed in the presence of an acid catalyst. Thereby, the intermediate amine compound (C) can be generated.

[0184] Regarding the mixing ratio of the aforementioned aromatic amine compound (a1) and the aforementioned aromatic divinyl compound (a2), considering the formability and physical property balance of curability during the manufacture of the resulting cured product, based on 1 mole of the aforementioned aromatic amine compound (a1), the molar ratio of the aforementioned aromatic divinyl compound (a2) is preferably 0.1 to 10 moles, more preferably 0.2 to 3 moles. Additionally, when the aforementioned aromatic monovinyl compound (a3) is used in combination, based on 1 mole of the aforementioned aromatic amine compound (a1), the total molar ratio of the aforementioned aromatic divinyl compound (a2) and the aforementioned aromatic monovinyl compound (a3) is preferably 0.1 to 10 moles, more preferably 0.2 to 3 moles.

[0185] In addition, as a specific method for carrying out the above reaction, it is usually the following method: all raw materials are charged together and reacted directly at a specified temperature, or the aromatic amine compound (a1) and an acid catalyst are charged, and while maintaining the specified temperature, the aromatic divinyl compound (a2), other compounds (such as aromatic monovinyl compound (a3)), etc. are added dropwise while reacting. At this time, the dropping time is usually 0.1 to 12 hours, preferably 6 hours or less. After the reaction, when a solvent is used, if necessary, the solvent and unreacted substances can be distilled off to obtain the aforementioned intermediate amine compound (C), and in the case of not using a solvent, the aforementioned intermediate amine compound (C) as the target product can be obtained by distilling off unreacted substances.

[0186] Among the acid catalysts used in the step (1) of the present embodiment, for example, inorganic acids such as phosphoric acid, hydrochloric acid, and sulfuric acid, organic acids such as oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid, and fluoromethanesulfonic acid, solid acids such as activated clay, acid clay, silica-alumina, zeolite, and strongly acidic ion exchange resin, and heteropoly hydrochloric acid can be cited. From the viewpoint of operability, it is also preferable to be able to simply remove the solid acid of the catalyst by filtration after the reaction. When using other acids, it is preferable to carry out neutralization with a base and washing with water after the reaction.

[0187] Regarding the compounding amount of the aforementioned acid catalyst, relative to the total amount of 100 parts by mass of the charged raw materials (aromatic divinyl compound (a2) or a mixture of aromatic divinyl compound (a2) and aromatic monovinyl compound (a3), and aromatic amine compound (a1)), the acid catalyst is compounded in a range of 1 to 100 parts by mass. From the aspects of operability and economy, it is preferably 1 to 60 parts by mass. The reaction temperature is usually in the range of 100 to 270 °C. In order to suppress the generation of isomeric structures and avoid side reactions such as thermal decomposition, it is preferably 100 to 220 °C.

[0188] In the step (1) of the present embodiment, as the reaction time of the mixture of the aromatic divinyl compound (a2) or the mixture of the aromatic divinyl compound (a2) and the aromatic monovinyl compound (a3) and the aromatic amine compound (a1), that is, the crosslinking reaction time, since the reaction is not completely carried out in a short time, and if it is a long time, side reactions such as thermal decomposition reaction of the product will occur. Therefore, under the aforementioned reaction temperature conditions, it is usually in the range of 1 to 48 hours in total, preferably in the range of 1 to 30 hours in total.

[0189] In the method for producing the intermediate amine compound (C) in the present embodiment, aniline or its derivative also serves as a solvent. Therefore, it is not necessary to use other solvents, but solvents can also be used. For example, in the case of reacting using divinylbenzene as a raw material, the following method can be adopted: using a solvent capable of azeotropic dehydration such as toluene, xylene, or chlorobenzene, azeotropically dehydrating the water contained in the catalyst or the like as needed, and then distilling off the solvent and carrying out the reaction within the range of the above reaction temperature.

[0190] The intermediate amine compound (C) obtained through the above step (1) is preferably represented by the following formula (4), for example.

[0191]

[0192] (In the above formula (4), R 1 each independently represents an alkyl group, and R 2 each independently represents an alkyl group, an alkoxy group, or an alkylthio group having 1 to 10 carbon atoms; an aryl group, an aryloxy group, or an arylthio group having 6 to 10 carbon atoms; a cycloalkyl group having 3 to 10 carbon atoms; a halogen atom; a hydroxyl group; or a mercapto group.

[0193] R 3 , R 4 , R 5 and R 6 each independently represents a hydrogen atom or a methyl group, and one of R 3 and R 4 is a hydrogen atom and the other is a methyl group, and one of R 5 and R 6 is a hydrogen atom and the other is a methyl group.

[0194] X 1 represents a substituent represented by the following formula (x).

[0195]

[0196] (In the formula (x), R 7 and R 8 each independently represents a hydrogen atom or a methyl group, and one of R 7 and R 8 is a hydrogen atom and the other is a methyl group, and R 9 each independently represents: an alkyl group, an alkoxy group, or an alkylthio group having 1 to 10 carbon atoms; an aryl group, an aryloxy group, or an arylthio group having 6 to 10 carbon atoms; a cycloalkyl group having 3 to 10 carbon atoms; a halogen atom; a hydroxyl group; or a mercapto group, and t represents an integer from 0 to 4.)

[0197] r is the number of X 1 bonded to each benzene ring having X 1The average value of the number of substitutions, representing a number from 0 to 4, p represents an integer from 1 to 3, q represents an integer from 0 to 4, and k represents an integer from 1 to 100.)

[0198] In addition, in the above formula (4), when p is an integer of 2 or more, multiple Rs 1 are optionally the same as or different from each other. When q is an integer of 2 or more, multiple Rs 2 are optionally the same as or different from each other. When t is an integer of 2 or more, multiple Rs 9 are optionally the same as or different from each other.)

[0199] It should be noted that R in the above formula (4) 1 ~R 9 , X 1 , p, q, r, t and k are preferably the same as those in the above formula (1). In addition, as another preferred embodiment of the intermediate amine compound (C) obtained by the above step (1), there can be mentioned a structure in which the N-substituted maleimide group in the above formula (2), which is also a preferred embodiment of the polymaleimide compound (A), is replaced with an amino group (including -NH 2 and substituted amino groups).

[0200] In the present embodiment, the amine equivalent of the intermediate amine compound (C) is preferably 172 to 400 g / equivalent, more preferably 172 to 350 g / equivalent.)

[0201] It should be noted that the measurement of the amine equivalent of the intermediate amine compound (C) in this specification uses the value measured by the method of neutralization titration as specified in JIS K 0070 (1992).

[0202] <<<Step (2): Maleimidation>>>[[]]

[0203] Step (2) in the present embodiment is a step of reacting the intermediate amine compound (C) obtained in step (1) with maleic anhydride. The amino group (including -NH 2 and substituted amino groups) of the intermediate amine compound (C) can form a chemical structure in which the aforementioned amino group is substituted with an N-substituted maleimide ring through a maleimidation reaction, and thus the polymaleimide compound (A) of the present disclosure can be obtained.)

[0204] In the present embodiment, after the intermediate amine compound (C) represented by the above formula (4) obtained through step (1) is put into a reactor and dissolved in an appropriate solvent, it is reacted with maleic anhydride in the presence of a catalyst. Then, after the reaction, unreacted maleic anhydride or other impurities are removed by washing with water, etc., and the solvent is removed by reduced pressure, whereby the target polymaleimide compound (A) can be obtained. In addition, if necessary, a dehydrating agent can also be used during the reaction.)

[0205] Examples of the organic solvent used in step (2) of the present embodiment include ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, cyclohexanone, and acetophenone; aprotic solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, acetonitrile, and sulfolane; cyclic ethers such as dioxane and tetrahydrofuran; esters such as ethyl acetate and butyl acetate; aromatic solvents such as benzene, toluene, and xylene. In addition, they can be used alone or in combination.

[0206] In step (2) of the present embodiment, the preferred method is as follows: as the mixing ratio of the intermediate amine compound (C) and maleic anhydride, it is preferred to mix the equivalent ratio of maleic anhydride relative to the amino equivalent of the intermediate amine compound (C) within the range of 1 to 5, and more preferably to charge it at an equivalent ratio of 1 to 3. The reaction is carried out in an organic solvent having a mass ratio of 0.1 to 10, preferably 0.2 to 5, based on the total amount of the intermediate amine compound (C) and maleic anhydride.

[0207] Examples of the catalyst that can be used in step (2) of the present embodiment include inorganic salts such as acetates, chlorides, bromides, sulfates, and nitrates of nickel, cobalt, sodium, calcium, iron, lithium, and manganese; inorganic acids such as phosphoric acid, hydrochloric acid, and sulfuric acid; organic acids such as oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid, and fluoromethanesulfonic acid; solid acids such as activated clay, acid clay, silica alumina, zeolite, and strongly acidic ion exchange resin; heteropolyhydrochloric acid, etc. Toluene sulfonic acid is particularly preferably used.

[0208] Examples of the dehydrating agent used in step (2) of the present embodiment include lower aliphatic carboxylic anhydrides such as acetic anhydride, propionic anhydride, and butyric anhydride; oxides such as phosphorus pentoxide, calcium oxide, and barium oxide; inorganic acids such as sulfuric acid; porous ceramics such as molecular sieves, etc. Acetic anhydride can be preferably used.

[0209] There is no particular limitation on the usage amounts of the catalyst and dehydrating agent used in step (2) of the present embodiment. Generally, per 1 equivalent of the amino group (-NH 2 ) of the intermediate amine compound (C), the catalyst can be used in an amount of 0.0001 to 1.0 mol, preferably 0.01 to 0.3 mol, and the dehydrating agent can be used in an amount of 1 to 3 mol, preferably 1 to 1.5 mol.

[0210] In step (2) of this embodiment, as the reaction conditions for maleimidation, the above-mentioned intermediate amine compound (C) and maleic anhydride can be added and reacted within a temperature range of 10 to 100 °C, preferably 0 to 60 °C, for 0.5 to 12 hours, preferably 1 to 4 hours. Then, the aforementioned catalyst is added and reacted within a temperature range of 90 to 130 °C, preferably 105 to 120 °C, for 1 to 24 hours, preferably 1 to 10 hours.

[0211] The polymaleimide compound (A) of this embodiment (preferably a maleimide compound having a structural unit represented by formula (1), more preferably a maleimide compound having a structural unit represented by formula (2)) can also be a commercially available product. For example, "NE-X-9500" manufactured by DIC Corporation can be cited.

[0212] In addition, the polymaleimide compound (A) used in this embodiment preferably has excellent low dielectric properties in its cured product.

[0213] For example, the dielectric constant (Dk) at a frequency of 10 GHz measured by the cavity resonator perturbation method of the cured product of the polymaleimide compound (A) used in this embodiment is preferably 3.0 or less, more preferably 2.8 or less, and further preferably 2.6 or less. In addition, the lower limit value of the aforementioned dielectric constant is, for example, preferably 2.0 or more in practice. In addition, the dielectric loss tangent (Df) at a frequency of 10 GHz measured by the cavity resonator perturbation method of the cured product of the polymaleimide compound (A) used in this embodiment is preferably 0.010 or less, more preferably 0.007 or less. In addition, the lower limit value of the aforementioned dielectric loss tangent is, for example, preferably 0.0001 or more in practice. The relative dielectric constant and dielectric loss tangent can be measured, for example, according to the methods (curing conditions, measurement conditions) described in the examples.

[0214] In addition, the polymaleimide compound (A) used in this embodiment preferably has high heat resistance in its cured product. The cured product of the polymaleimide compound (A) used in this embodiment preferably has a glass transition temperature measured by dynamic viscoelasticity measurement according to JIS C6481 of 180 °C or higher, more preferably 200 °C or higher, and further preferably 230 °C or higher. By setting it to the above-mentioned lower limit value or higher, a cured product with more excellent heat resistance can be obtained. In addition, the upper limit value of the aforementioned glass transition temperature is, for example, preferably 400 °C or less in practice.

[0215] In addition, for details of the polymaleimide compound (A) used in this embodiment, reference can be made to the description in Japanese Patent No. 7160151, the content of which is incorporated into this specification.

[0216] In addition, in the description of the polyimide compound (A), "alkyl" can be any of linear, branched or cyclic, and examples thereof include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, 1,2-dimethylpropyl, n-hexyl, isohexyl, (n)heptyl, (n)octyl, (n)nonyl, (n)decyl, (n)undecyl, (n)dodecyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl or cyclononyl.

[0217] Furthermore, in the description of the polyimide compound (A), examples of "cycloalkyl" include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, norbornyl or adamantyl, etc.

[0218] In the description of the polyimide compound (A), examples of "alkylthio" include methylthio, ethylthio, propylthio, butylthio, octylthio or 2-ethylhexylthio.

[0219] In the description of the polyimide compound (A), examples of "alkenyl" include ethynyl, 1-propynyl, 2-propynyl, 2-butynyl, pentynyl, hexynyl, vinyl, allyl or isopropenyl, etc.

[0220] In the description of the polyimide compound (A), examples of "alkoxy" include methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentyloxy, hexyloxy, 2-ethylhexyloxy, octyloxy or nonyloxy, etc.

[0221] In the description of the polyimide compound (A), examples of "aryl" include phenyl, 1-naphthyl or 2-naphthyl, etc.

[0222] In addition, in the resin composition of the present embodiment, the content of the polyimide compound (A) is preferably 1 part by mass or more, more preferably 5 parts by mass or more, still more preferably 10 parts by mass or more, even more preferably 18 parts by mass or more, and depending on the use, etc., it may also be 20 parts by mass or more, 30 parts by mass or more, 35 parts by mass or more, 40 parts by mass or more, 50 parts by mass or more, 60 parts by mass or more, 65 parts by mass or more, 71 parts by mass or more, based on 100 parts by mass of the resin solid content in the resin composition. By making the content of the polyimide compound (A) be the above lower limit value or more, there is a tendency for the low dielectric properties (low dielectric constant and / or low dielectric loss tangent) to be further improved. In addition, the upper limit value of the content of the polyimide compound (A) is preferably 90 parts by mass or less, more preferably 88 parts by mass or less, still more preferably 86 parts by mass or less, even more preferably 84 parts by mass or less, even more preferably 82 parts by mass or less, and depending on the use, etc., it may also be 80 parts by mass or less, 70 parts by mass or less, 65 parts by mass or less, 50 parts by mass or less, 40 parts by mass or less. By making the content of the polyimide compound (A) be the above upper limit value or less, there is a tendency for the low water absorption, chemical resistance, and desmear resistance to be further improved.

[0223] The resin composition of the present embodiment may contain only one type of polyimide compound (A), or may contain two or more types. In the case of containing two or more types, the total amount is preferably within the above range.

[0224] <Compound (B) containing two or more polymerizable carbon-carbon unsaturated double bonds>

[0225] The resin composition of the present embodiment contains a compound (B) containing two or more polymerizable carbon-carbon unsaturated double bonds (hereinafter, sometimes simply referred to as "compound (B) containing two or more carbon-carbon unsaturated double bonds" in this specification). In the present embodiment, by using the polyimide compound (A) and the compound (B) containing two or more carbon-carbon unsaturated double bonds in combination, compared with the case of using a conventional maleimide compound and a compound (B) containing two or more carbon-carbon unsaturated double bonds in combination, more excellent low dielectric properties can be achieved. The compound (B) containing two or more carbon-carbon unsaturated double bonds is usually a thermosetting compound.

[0226] As the compound (B) containing two or more carbon-carbon unsaturated double bonds used in the present embodiment, compounds containing two or more carbon-carbon unsaturated double bonds that are commonly used in printed circuit boards can be widely used.

[0227] Specifically, the upper limit of the number of carbon-carbon unsaturated double bonds in the compound (B) having two or more carbon-carbon unsaturated double bonds used in the present embodiment is preferably 2000 or less, may be 10 or less, further may be 5 or less, and particularly may be 2. By setting it below the aforementioned upper limit, there is a tendency for the moisture absorption heat resistance to be further improved.

[0228] In addition, the cured product of the compound (B) having two or more carbon-carbon unsaturated double bonds used in the present embodiment preferably has excellent low dielectric properties. For example, the dielectric constant (Dk) at a frequency of 10 GHz measured by the cavity resonator perturbation method of the cured product of the compound (B) having two or more carbon-carbon unsaturated double bonds used in the present embodiment is preferably 3.0 or less, more preferably 2.6 or less. In addition, the lower limit value of the aforementioned dielectric constant is, for example, 2.0 or more in practice. In addition, the dielectric loss tangent (Df) at a frequency of 10 GHz measured by the cavity resonator perturbation method of the cured product of the compound (B) having two or more carbon-carbon unsaturated double bonds used in the present embodiment is preferably 0.010 or less, more preferably 0.007 or less. In addition, the lower limit value of the aforementioned dielectric loss tangent is, for example, 0.0001 or more in practice. The dielectric constant and the dielectric loss tangent can be measured, for example, according to the methods (curing conditions, measurement conditions) described in the examples.

[0229] In addition, the cured product of the compound (B) having two or more carbon-carbon unsaturated double bonds used in the present embodiment preferably has high heat resistance. The cured product of the compound (B) having two or more carbon-carbon unsaturated double bonds used in the present embodiment preferably has a glass transition temperature measured by dynamic viscoelasticity measurement according to JIS C6481 of 100 °C or higher, more preferably 130 °C or higher, further preferably 150 °C or higher, still further preferably 180 °C or higher, and still further preferably 200 °C or higher. By setting it above the aforementioned lower limit value, a cured product with excellent heat resistance can be obtained. In addition, the upper limit value of the aforementioned glass transition temperature is, for example, 400 °C or lower in practice.

[0230] The number-average molecular weight Mn in terms of polystyrene of the compound (B) containing two or more carbon-carbon unsaturated double bonds based on the GPC method is preferably 195 or more, more preferably 400 or more, further preferably 500 or more, still more preferably 800 or more, and furthermore, it may be 1000 or more, 1200 or more, 1500 or more, 1800 or more. By setting the aforementioned number-average molecular weight to be not less than the above lower limit value, there is a tendency for the low dielectric property to be further improved. In addition, the number-average molecular weight Mn of the compound (B) containing two or more carbon-carbon unsaturated double bonds is preferably 130,000 or less, more preferably 120,000 or less, further preferably 100,000 or less, and may also be 50,000 or less, 10,000 or less, 7000 or less, 5000 or less, 3500 or less, 3000 or less, 2500 or less. By setting the aforementioned number-average molecular weight to be not more than the above upper limit value, a resin composition with good moldability can be obtained.

[0231] The weight-average molecular weight Mw in terms of polystyrene of the compound (B) containing two or more carbon-carbon unsaturated double bonds is preferably 195 or more, more preferably 400 or more, further preferably 500 or more, still more preferably 800 or more, and may also be 1,000 or more, 1200 or more, 1500 or more, 1800 or more. By setting it to be not less than the above lower limit value, there is a tendency for the low dielectric property to be further improved. In addition, the weight-average molecular weight of the compound (B) containing two or more carbon-carbon unsaturated double bonds is preferably 160,000 or less, more preferably 150,000 or less, further preferably 140,000 or less, still more preferably 130,000 or less, still more preferably 100,000 or less, and may also be 80,000 or less, 50,000 or less, 10,000 or less. By setting it to be not more than the above upper limit value, there is a tendency for the heat resistance to be further improved.

[0232] The carbon-carbon unsaturated double bonds contained in the compound (B) containing two or more carbon-carbon unsaturated double bonds used in the present embodiment are polymerizable unsaturated groups, and are usually carbon-carbon unsaturated double bonds that react with a certain reactive functional group.

[0233] In addition, the compound (B) containing two or more carbon-carbon unsaturated double bonds preferably contains carbon-carbon unsaturated double bonds at the ends, and more preferably contains two or more carbon-carbon unsaturated double bonds at the ends.

[0234] Specifically, the compound (B) having two or more carbon-carbon unsaturated double bonds used in the present embodiment preferably contains at least one selected from the group consisting of a compound containing a vinyl aryl group, a compound containing a (meth)acryloyl group, and a compound containing a (meth)allyl group, more preferably contains at least one selected from the group consisting of a compound containing a vinyl aryl group and a compound containing a (meth)allyl group, still more preferably is a compound containing a vinyl aryl group, even more preferably is a compound containing a vinylphenyl group, and even more preferably is a compound containing a vinylbenzyl group.

[0235] In addition, the compound containing a (meth)acryloyl group is preferably a compound containing a methacrylate group, and the compound containing a (meth)allyl group is preferably a compound containing an allyl group.

[0236] The resin composition of the present embodiment may also have a constitution that substantially does not contain a compound containing an allyl group. Substantially not containing means that the content of the compound containing an allyl group is less than 1 part by mass, preferably less than 0.1 part by mass, based on 100 parts by mass in total of the other resin components (C).

[0237] In particular, the resin composition of the present embodiment may also have a constitution that substantially does not contain diallylbisphenol and its derivatives. Substantially not containing means that the content of diallylbisphenol and its derivatives is less than 1 part by mass, preferably less than 0.1 part by mass, based on 100 parts by mass in total of the other resin components (C).

[0238] More specifically, one embodiment of the compound (B) having two or more carbon-carbon unsaturated double bonds used in the present embodiment is a polyphenylene ether compound having two or more carbon-carbon unsaturated double bonds, and particularly preferably a polyphenylene ether compound having a vinyl aryl group and / or a polyphenylene ether compound having a (meth)acryloyl group, and more preferably a polyphenylene ether compound having a vinyl aryl group.

[0239] In addition, another embodiment of the compound (B) having two or more carbon-carbon unsaturated double bonds used in the present embodiment is a polymer having a structural unit represented by the formula (V).

[0240]

[0241] (In the formula (V), Ar represents an aromatic hydrocarbon linking group. * represents the bonding position.)

[0242] In addition, another embodiment of the compound (B) having two or more carbon-carbon unsaturated double bonds used in the present embodiment is a compound containing a (meth)allyl group, preferably an allyl-substituted nadic imide compound.

[0243] Details of these preferred embodiments are described later.

[0244] The compound (B) having two or more carbon-carbon unsaturated double bonds used in this embodiment may also contain a structural unit derived from maleic anhydride. Details of such a resin can be referred to the description in International Publication No. 2017 / 209108, the content of which is incorporated into this specification.

[0245] Furthermore, the aforementioned compound (B) having two or more carbon-carbon unsaturated double bonds may also contain a structural unit derived from a compound having an acid group and an acid anhydride group.

[0246] The compound (B) having two or more carbon-carbon unsaturated double bonds used in this embodiment may also be a compound having an indane skeleton with a carbon-carbon unsaturated double bond at the terminal. As such compounds, reference can be made to the descriptions in paragraphs 0011 to 0025 of International Publication No. 2023 / 176766, paragraphs 0012 to 0033 of International Publication No. 2023 / 176764, paragraphs 0012 to 0033 of International Publication No. 2023 / 176763, and paragraphs 0026 to 0043 of International Publication No. 2023 / 176765, the content of which is incorporated into this specification.

[0247] In addition, in the resin composition of this embodiment, with respect to 100 parts by mass of the resin solid content in the resin composition, the content (total amount) of the compound (B) having two or more carbon-carbon unsaturated double bonds is preferably 1 part by mass or more, more preferably 5 parts by mass or more, further preferably 10 parts by mass or more, still more preferably 18 parts by mass or more, and depending on the use and the like, it may also be 20 parts by mass or more, 30 parts by mass or more, 35 parts by mass or more, 40 parts by mass or more, 50 parts by mass or more, 60 parts by mass or more, 65 parts by mass or more, 71 parts by mass or more. By setting the content of the aforementioned compound (B) to be above the above lower limit value, there is a tendency for the low water absorption, low dielectric properties (low dielectric constant and / or low dielectric loss tangent), chemical resistance, and desmear resistance to be further improved. In addition, with respect to 100 parts by mass of the resin solid content in the resin composition, the upper limit value of the content (total amount) of the compound (B) having two or more carbon-carbon unsaturated double bonds is preferably 90 parts by mass or less, more preferably 85 parts by mass or less, and depending on the use and the like, it may also be 80 parts by mass or less, 70 parts by mass or less, 65 parts by mass or less, 50 parts by mass or less, 40 parts by mass or less. By setting the content of the aforementioned compound (B) to be below the above upper limit value, there is a tendency for the heat resistance to be further improved.

[0248] The resin composition of this embodiment may contain only one kind of the compound (B) having two or more carbon-carbon unsaturated double bonds, or may contain two or more kinds. In the case of containing two or more kinds, the total amount is preferably within the above range.

[0249] In the resin composition of the present embodiment, the total amount of the polyimide compound (A) and the compound (B) containing two or more carbon-carbon unsaturated double bonds is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, still more preferably 50% by mass or more, still more preferably 60% by mass or more, still more preferably 70% by mass or more, and may also be 80% by mass or more, 90% by mass or more, 95% by mass or more of the resin solid content in the resin composition. By setting the total amount of the polyimide compound (A) and the compound (B) containing two or more carbon-carbon unsaturated double bonds to the above lower limit value or more, there is a tendency for further improvement in low water absorption, low dielectric properties (low dielectric constant and / or low dielectric loss tangent), chemical resistance, and desmear resistance. In addition, the upper limit value of the above total amount is preferably 99.9% by mass or less of the resin solid content in the resin composition. By setting the total amount of the polyimide compound (A) and the compound (B) containing two or more carbon-carbon unsaturated double bonds to the above upper limit value or less, there is a tendency for further improvement in heat resistance.

[0250] In the resin composition of the present embodiment, the mass ratio of the polyimide compound (A) to the compound (B) containing two or more carbon-carbon unsaturated double bonds is preferably 9:1 to 1:19, more preferably 9:1 to 1:9, and further preferably 9:1 to 1:7. By setting the blending ratio in this way, low dielectric properties can be maintained, and heat resistance, low thermal expansion, low water absorption, chemical resistance, and desmear resistance can be improved.

[0251] <<Polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds>>

[0252] In the resin composition of the present embodiment, the compound (B) containing two or more carbon-carbon unsaturated double bonds preferably contains a polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds. Further, it is preferable that 90% by mass or more (more preferably 95% by mass or more, further preferably 99% by mass or more) of the compound (B) containing two or more carbon-carbon unsaturated double bonds contained in the resin composition of the present embodiment is a polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds. The polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds is preferably a polyphenylene ether compound containing two or more vinylbenzyl groups.

[0253] In addition, the polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds preferably contains a carbon-carbon unsaturated double bond at the terminal, and is preferably a polyphenylene ether compound containing two or more vinylbenzyl groups at the terminal.

[0254] Examples of the polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds include compounds containing a phenylene ether skeleton represented by the following formula (X1).

[0255]

[0256] (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, or a hydrogen atom.).

[0257] The polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds may further contain a repeating unit represented by formula (X2) and / or a repeating unit represented by formula (X3):

[0258]

[0259] (In formula (X2), R 28 , R 29 , R 30 , R 34 and R 35 may be the same or different and represent an alkyl group having 6 or less carbon atoms or a phenyl group. R 31 , R 32 and 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.).

[0260]

[0261] (In formula (X3), R 36 , R 37 , R 38 , R 39 , R 40 , R 41 , R 42 and 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 divalent hydrocarbon that is linear, branched, or cyclic and has 20 or less carbon atoms.).

[0262] The polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds is preferably a modified polyphenylene ether compound (hereinafter sometimes referred to as "modified polyphenylene ether compound (g)") obtained by functionalizing a part or all of the terminals with an ethylenically unsaturated group. More preferably, it is a modified polyphenylene ether compound having two or more groups selected from the group consisting of (meth)acryloyl, maleimide, (meth)allyl, and vinylbenzyl at the terminals. Even more preferably, it is a modified polyphenylene ether compound having two or more groups selected from the group consisting of (meth)acryloyl and vinylbenzyl. From the aspect of excellent chemical resistance and desmear resistance, a modified polyphenylene ether compound having two or more vinylbenzyl groups is even more preferred. By using such a modified polyphenylene ether compound (g), the dielectric loss tangent (Df) of the cured product of the resin composition can be made smaller. These can be used alone or in combination of two or more. By using such a modified polyphenylene ether compound (g), Df can be made smaller and the peel strength can be improved. These can be used alone or in combination of two or more.

[0263] Regarding the production method of the modified polyphenylene ether compound (g), there is no particular limitation as long as the effects of the present invention can be obtained. For example, a substance functionalized with an ethylenically unsaturated group (specifically, vinylbenzyl, etc.) can be produced by dissolving a difunctional phenylene ether oligomer and vinylbenzyl chloride in a solvent, adding a base under heating and stirring to react, and then solidifying the resin. A substance functionalized with a carboxyl group can be produced, for example, by melt-kneading an unsaturated carboxylic acid and its functionalized derivative in the polyphenylene ether compound in the presence or absence of a radical initiator to react. Alternatively, it can be produced by dissolving the polyphenylene ether compound and an unsaturated carboxylic acid and its functional derivative in an organic solvent in the presence or absence of a radical initiator and reacting in the solution.

[0264] Examples of the ethylenically unsaturated group contained in the modified polyphenylene ether compound (g) include alkenyl groups such as vinyl, allyl, methallyl, acryloyl, methacryloyl, propenyl, butenyl, hexenyl, and octenyl; cyclic alkenyl groups such as cyclopentenyl and cyclohexenyl; and vinylaryl groups such as vinylphenyl and vinylnaphthyl. Preferably, it is methacryloyl and / or vinylbenzyl. From the aspect of excellent chemical resistance and desmear resistance, vinylbenzyl is more preferred. Examples of vinylbenzyl include 4-vinylbenzyl and 3-vinylbenzyl. In the modified polyphenylene ether compound (g), two or more existing ethylenically unsaturated groups may be the same functional group or different functional groups. By using such a modified polyphenylene ether compound, Df can be made smaller and the peel strength can be improved.

[0265] Examples of the modified polyphenylene ether compound (g) include the polyphenylene ether compound represented by the formula (OP).

[0266]

[0267] (In formula (OP), X represents an aromatic group, -(Y-O) n1 - represents a polyphenylene ether structure, n1 represents an integer from 1 to 100, and n2 represents an integer from 1 to 4. Rx is a group represented by formula (Rx-1) or formula (Rx-2).)

[0268]

[0269] (In formula (Rx-1) and formula (Rx-2), R 1 , R 2 and R 3 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, or an alkynyl group. * is the bonding site to the oxygen atom. Mc each independently represents a hydrocarbon group having 1 to 12 carbon atoms. z represents an integer from 0 to 4. r represents an integer from 1 to 6.)

[0270] The aromatic group represented by the aforementioned X may or may not have a substituent on the benzene ring, and preferably has a substituent. When having a substituent, the above-mentioned substituent Z can be exemplified, preferably at least one selected from the group consisting of an alkyl group having 6 or less carbon atoms, an aryl group, and a halogen atom, more preferably an alkyl group having 3 or less carbon atoms, and further preferably a methyl group.

[0271] In addition, the polyphenylene ether structure represented by the aforementioned -(Y-O)n 1 - may or may not have a substituent on the benzene ring, and preferably has a substituent. When having a substituent, the above-mentioned substituent Z can be exemplified, preferably an alkyl group having 6 or less carbon atoms or a phenyl group, more preferably an alkyl group having 3 or less carbon atoms, and further preferably a methyl group.

[0272] n 1 and / or n 2 When is an integer of 2 or more, n 1 structural units (Y-O) and / or n 2 structural units may be the same or different from each other. n 2 is preferably 2 or more, more preferably 2.

[0273] In formula (Rx-1) and formula (Rx-2), R 1 , R 2 and R 3 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, or an alkynyl group.

[0274] R 1 is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group, and further preferably a hydrogen atom.

[0275] R2 and R 3 Each is independently preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group, and still more preferably a hydrogen atom.

[0276] As R 1 、R 2 and R 3 The number of carbon atoms of the alkyl, alkenyl, or alkynyl group of

[0277] r in the formula (Rx-1) represents an integer from 0 to 6, can be an integer of 1 or more, and preferably an integer of 5 or less, more preferably an integer of 4 or less, still more preferably an integer of 3 or less, even more preferably 1 or 2, and even more preferably 1.

[0278] Mc in the formula (Rx-1) each independently represents a hydrocarbon group having 1 to 12 carbon atoms, preferably a hydrocarbon group having 1 to 10 carbon atoms, more preferably a linear or branched alkyl group having 1 to 10 carbon atoms, still more preferably methyl, ethyl, isopropyl, isobutyl, tert-butyl, pentyl, octyl, or nonyl, and even more preferably methyl, ethyl, isopropyl, isobutyl, or tert-butyl.

[0279] z in the formula (Rx-1) represents an integer from 0 to 4, preferably an integer from 0 to 3, more preferably an integer from 0 to 2, still more preferably 0 or 1, and even more preferably 0.

[0280] Specific examples of the group represented by the formula (Rx-1) are vinylbenzyl, and specific examples of the group represented by the formula (Rx-2) are (meth)acryloyl.

[0281] Rx is preferably the group represented by the formula (Rx-2).

[0282] In the resin composition of the present embodiment, as the polyphenylene ether compound having a carbon-carbon unsaturated double bond at the terminal, the compound represented by the formula (OP) is also preferred, and it includes both a polyphenylene ether compound having a group represented by the formula (Rx-1) and a polyphenylene ether-based compound containing a group represented by the formula (Rx-2).

[0283] As the modified polyphenylene ether compound (g), the compound represented by the formula (OP-1) can be cited.

[0284]

[0285] (In the formula (OP-1), X represents an aromatic group, -(Y-O)n 2 - represents a polyphenylene ether structure, R 1 、R 2 and R 3 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, or an alkynyl group, n1 An integer representing 1 to 6, n 2 An integer representing 1 to 100, n 3 An integer representing 2 to 4.)

[0286] n 2 And / or n 3 When n is an integer of 2 or more, n 2 The (Y-O) structural units and / or n 3 The structural units may be the same or different from each other. n 3 Preferably 2 or more, more preferably 2.

[0287] The modified polyphenylene ether compound (g) of the present embodiment is preferably represented by the formula (OP-2).

[0288]

[0289] Here, -(O-X-O)- is preferably as shown in the formula (OP-3) and / or the formula (OP-4).

[0290]

[0291] (In the formula (OP-3), R 4 , R 5 , R 6 , R 10 and R 11 may be the same or different and are alkyl groups or phenyl groups having 6 or less carbon atoms. R 7 , R 8 and R 9 may be the same or different and are a hydrogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group)

[0292]

[0293] (In the formula (OP-4), R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 and R 19 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 group having 20 or less carbon atoms).

[0294] In addition, -(Y-O)- is preferably as shown in the formula (OP-5).

[0295]

[0296] (In the formula (OP-5), R 20 , R21 may be the same or different and is an alkyl group having 6 or less carbon atoms or a phenyl group. R 22 , R 23 may be the same or different and is a hydrogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group).

[0297] In formula (OP-2), at least one of a and b is not 0 and represents an integer of 0 to 100, preferably an integer of 0 to 50, more preferably an integer of 1 to 30. When a and / or b is an integer of 2 or more, two or more -(Y-O)- may each independently be arranged in one structure, or may be arranged in a block or random manner of two or more structures.

[0298] Examples of -A- in formula (OP-4) include divalent organic groups such as methylene, ethylidene, 1-methylethylidene, 1,1-propylidene, 1,4-phenylenebis(1-methylethylidene), 1,3-phenylenebis(1-methylethylidene), cyclohexylidene, phenylmethylene, naphthylmethylene, 1-phenylethylidene, etc., but are not limited to these.

[0299] In the above-mentioned modified polyphenylene ether compound (g), it is preferred that R 4 , R 5 , R 6 , R 10 , R 11 , R 20 and R 21 are alkyl groups having 3 or less carbon atoms and R 7 , R 8 , R 9 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 22 and R 23 are polyphenylene ether compounds which are hydrogen atoms or alkyl groups having 3 or less carbon atoms, and in particular, it is more preferred that -(O-X-O)- represented by formula (OP-3) or formula (OP-4) is formula (OP-9), formula (OP-10) and / or formula (OP-11), and -(Y-O)- represented by formula (OP-5) is formula (OP-12) or formula (OP-13), and it is further preferred that the aforementioned (O-X-O)- is formula (OP-9) and -(Y-O)- is formula (OP-12). When a and / or b is an integer of 2 or more, two or more -(Y-O)- may each independently be a structure formed by arranging two or more of formula (OP-12) and / or formula (OP-13), or may be a structure formed by arranging formula (OP-12) and formula (OP-13) in a block or random manner.

[0300]

[0301] (In formula (OP-10), R 44 , R 45 , R 46 and R 47 may be the same or different and are a hydrogen atom or a methyl group. -B- is a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms.)

[0302] Specific examples of -B- may be the same as those of -A- in formula (OP-4).

[0303]

[0304] (In formula (OP-11), -B- is a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms.)

[0305] Specific examples of -B- may be the same as those of -A- in formula (OP-4).

[0306]

[0307] The modified polyphenylene ether compound (g) is more preferably a compound represented by formula (OP-14) and / or a compound represented by formula (OP-15), and even more preferably a compound represented by formula (OP-15).

[0308]

[0309] (In formula (OP-14), a and b each independently represent an integer of 0 to 100, and at least one of a and b is an integer of 1 to 100.)

[0310] a and b in formula (OP-14) each independently have the same meaning as a and b in formula (OP-2), and the preferred ranges are also the same.

[0311]

[0312] (In formula (OP-15), a and b each independently represent an integer of 0 to 100, and at least one of a and b is an integer of 1 to 100.)

[0313] a and b in formula (OP-15) each independently have the same meaning as a and b in formula (OP-2), and the preferred ranges are also the same.

[0314] Polyphenylene ether compounds containing two or more carbon-carbon unsaturated double bonds can be produced by known methods or commercially available products can be used. As commercially available products, for example, as a modified polyphenylene ether compound with a methacryloyl group at the end, "SA9000" manufactured by SABIC Innovative Plastics can be cited. In addition, as a modified polyphenylene ether compound with a vinylbenzyl group at the end, "OPE-2St1200" and "OPE-2st2200" manufactured by Mitsubishi Gas Chemical can be cited. In addition, as a modified polyphenylene ether compound with a vinylbenzyl group at the end, a compound obtained by modifying a polyphenylene ether compound with a hydroxyl group at the end such as "SA90" manufactured by SABIC Innovative Plastics with vinylbenzyl chloride or the like to vinylbenzyl can also be used.

[0315] In addition, for the details of the polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds, reference can be made to the descriptions in Japanese Unexamined Patent Application Publication No. 2006-028111, Japanese Unexamined Patent Application Publication No. 2018-131519, International Publication No. 2019-138992, and International Publication No. 2022-054303, and these contents are incorporated into this specification.

[0316] The number average molecular weight in terms of polystyrene obtained by the GPC (gel permeation chromatography) method of the polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds (preferably a modified polyphenylene ether compound (g)) (details are in accordance with the method described in the examples below) is preferably 500 or more and 3,000 or less. By making the number average molecular weight 500 or more, there is a tendency to further suppress stickiness when the resin composition of this embodiment is formed into a film. In addition, by making the number average molecular weight 3000 or less, there is a tendency to further improve the solubility in a solvent.

[0317] In addition, the weight average molecular weight in terms of polystyrene obtained by GPC of the polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds (preferably a modified polyphenylene ether compound (g)) (details are in accordance with the method described in the examples below) is preferably 800 or more and 10,000 or less, more preferably 800 or more and 5,000 or less. By setting it to be above the aforementioned lower limit value, there is a tendency for the relative dielectric constant (Dk) and the dielectric loss tangent (Df) of the cured product of the resin composition to become lower, and by setting it to be below the above upper limit value, there is a tendency to further improve the solubility, low viscosity property, and formability of the resin composition in a solvent when producing a varnish or the like described below.

[0318] Furthermore, the equivalent weight of the terminal carbon-carbon unsaturated double bond in the modified polyphenylene ether compound (g) is preferably 400 to 5000 g, more preferably 400 to 2500 g, per carbon-carbon unsaturated double bond. By setting it to be not less than the aforementioned lower limit value, the relative dielectric constant (Dk) and the dielectric loss tangent (Df) of the cured product of the resin composition tend to become lower. By setting it to be not more than the above upper limit value, the solubility, low viscosity, and moldability of the resin composition in a solvent tend to be further improved.

[0319] The functional group equivalent weight (equivalent weight of the carbon-carbon unsaturated double bond) in the polyphenylene ether compound having a carbon-carbon unsaturated double bond at the terminal is obtained by determining the amount of double bonds based on the measurement results of an infrared spectroscopic apparatus, and calculating the reciprocal thereof.

[0320] The double bond equivalent weight [g / eq.] is determined as follows.

[0321] Weigh the powder of the polyphenylene ether compound and record the weight. After putting the powder into a volumetric flask, dilute it to a specified amount with carbon disulfide to prepare a measurement sample. Put the sample solution into a measurement unit and set it in an infrared spectrophotometer (FT / IR-4600, manufactured by JASCO Corporation). Then, perform infrared spectroscopic measurement of the sample solution. In the case of vinyl in the polyphenylene ether compound, record the peak area of the spectrum around 905 cm -1 In the case where the carbon-carbon unsaturated double bond is a methacryloyl group, record the peak area of the spectrum around 1640 cm -1 Based on this area value and the standard curve, determine the double bond concentration [mol / L] as the measurement value.

[0322] Next, calculate the double bond equivalent weight using the following formula.

[0323] Double bond equivalent weight [g / eq.] = weight of powder in the measurement sample [g] / double bond concentration [mol / L] × volume of the measurement sample solution [L]

[0324] The functional group equivalent weights of other compounds can also be measured by imitating the above method. Among them, for compounds (monomers) that can be represented by a single molecular weight, the value obtained by (theoretical molecular weight ÷ number of functional groups) is preferably used to determine the functional group equivalent weight.

[0325] When the resin composition of the present embodiment contains a polyphenylene ether compound having two or more carbon-carbon unsaturated double bonds, the lower limit of the content of the polyphenylene ether compound having two or more carbon-carbon unsaturated double bonds is preferably 1 part by mass or more, more preferably 5 parts by mass or more, further preferably 10 parts by mass or more, still more preferably 15 parts by mass or more, still further preferably 20 parts by mass or more, and still further preferably 25 parts by mass or more, based on 100 parts by mass of the resin solid content in the resin composition. By setting the aforementioned content to the above lower limit or more, there is a tendency for the heat resistance, low water absorption, and low dielectric properties (low dielectric constant and / or low dielectric loss tangent) of the obtained cured product to be further improved. In addition, the upper limit of the content of the polyphenylene ether compound having two or more carbon-carbon unsaturated double bonds is preferably 70 parts by mass or less, more preferably 60 parts by mass or less, further preferably 50 parts by mass or less, still more preferably 40 parts by mass or less, and may also be 35 parts by mass or less, based on 100 parts by mass of the resin solid content in the resin composition. By setting the aforementioned content to the above upper limit or less, there is a tendency for the moisture heat resistance and metal foil peel strength (preferably copper foil peel strength) of the obtained cured product to be further improved.

[0326] The resin composition in the present embodiment may contain only one kind of polyphenylene ether compound having two or more carbon-carbon unsaturated double bonds, or may contain two or more kinds. In the case of containing two or more kinds, the total amount is preferably within the above range.

[0327] <<Polymer having a structural unit represented by formula (V)>>

[0328] The resin composition of the present embodiment preferably contains a polymer having a structural unit represented by formula (V). The polymer having a structural unit represented by formula (V) is a polymer having two or more carbon-carbon unsaturated double bonds, and is preferably a polymer having two or more structural units represented by formula (V). By containing a polymer having a structural unit represented by formula (V), a resin composition with more excellent low dielectric properties (low dielectric constant, low dielectric loss tangent) can be obtained.

[0329]

[0330] (In formula (V), Ar represents an aromatic hydrocarbon linking group. * represents the bonding position.)

[0331] 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 is preferably a group formed only by an aromatic hydrocarbon optionally having a substituent. It should be noted that the substituents optionally possessed by the aromatic hydrocarbon may include substituent Z (for example, 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.). In addition, the above-mentioned aromatic hydrocarbon preferably does not have a substituent.

[0332] The aromatic hydrocarbon linking group is usually a divalent linking group.

[0333] Specifically, the aromatic hydrocarbon linking group may include a phenylene group, a naphthalenediyl group, an anthracenediyl group, a phenanthrenediyl group, a biphenyldiyl group, a fluorenediyl group, each optionally having a substituent, and among them, a phenylene group optionally having a substituent is preferred. The substituents may be exemplified by the above-mentioned substituent Z, but the above-mentioned groups such as the phenylene group preferably do not have a substituent.

[0334] The structural unit represented by the formula (V) more preferably includes 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. In addition, the structural units represented by the formulas (V1) to (V3) are sometimes collectively referred to as "structural unit (a)".

[0335]

[0336] In the 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, it may include a phenylene group, a naphthalenediyl group, an anthracenediyl group, a phenanthrenediyl group, a biphenyldiyl group, a fluorenediyl group, each optionally having a substituent, and among them, a phenylene group optionally having a substituent is preferred. The substituents may be exemplified by the above-mentioned substituent Z, but the above-mentioned groups such as the phenylene group preferably do not have a substituent.

[0337] As the compound forming the structural unit (a), a divinyl aromatic compound is preferred, and examples thereof may include divinylbenzene, bis(1-methylethenyl)benzene, divinylnaphthalene, divinylanthracene, divinylbiphenyl, divinylphenanthrene, etc. Among them, divinylbenzene is particularly preferred. These divinyl aromatic compounds may be used singly or two or more thereof may be used as needed.

[0338] The polymer having the structural unit represented by the formula (V) as described above may be a homopolymer of the structural unit (a) or a copolymer with a structural unit derived from other monomers.

[0339] When the polymer having the structural unit represented by the formula (V) is a copolymer, the copolymerization ratio is preferably 5 mol% or more, more preferably 10 mol% or more, and still more preferably 15 mol% or more for the structural unit (a). As the upper limit value, it is preferably 90 mol% or less, more preferably 85 mol% or less, still more preferably 80 mol% or less, still more preferably 70 mol% or less, still more preferably 60 mol% or less, still more preferably 50 mol% or less, still more preferably 40 mol% or less, particularly preferably 30 mol% or less, and may also be 25 mol% or less.

[0340] As the structural unit derived from other monomers, a structural unit (b) derived from an aromatic compound having one vinyl group (monovinyl aromatic compound) can be exemplified.

[0341] The structural unit (b) derived from the monovinyl aromatic compound is preferably a structural unit represented by the following formula (V4).

[0342]

[0343] In the formula (V4), L 2 is an aromatic hydrocarbon linking group, and specific examples of the preferred groups can include the examples of the above L 1 .

[0344] 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, and more preferably 1 to 3. R V1 and L 2 may have the above substituent Z.

[0345] When the polymer having the structural unit represented by the formula (V) 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-dimethylstyrene, p-dimethylstyrene, o-ethylvinylbenzene, m-ethylvinylbenzene, p-ethylvinylbenzene, methylvinylbiphenyl, and ethylvinylbiphenyl. The monovinyl aromatic compounds exemplified here may appropriately have the above substituent Z. In addition, one of these monovinyl aromatic compounds can be used, or two or more thereof can be used.

[0346] When the polymer having the structural unit represented by the formula (V) 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, and further preferably 20 mol% or more, 30 mol% or more, 40 mol% or more, 50 mol% or more, 60 mol% or more, 70 mol% or more, 75 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.

[0347] The polymer having the structural unit represented by the formula (V) may also have other structural units in addition to the structural unit (a) and the structural unit (b). Examples of the other structural units include a structural unit (c) derived from a cycloolefin compound. Examples of the cycloolefin compound include hydrocarbons having a double bond in the ring structure. Specifically, monocyclic cyclic olefins such as cyclobutene, cyclopentene, cyclohexene, cyclooctene, and 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. Examples of the norbornene compound include the compounds described in paragraphs 0037 to 0043 of JP-A-2018-39995, the content of which is incorporated herein. It should be noted that the cycloolefin compounds exemplified here may further have the above-mentioned substituent Z.

[0348] When the polymer having the structural unit represented by the formula (V) 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, and further preferably 70 mol% or less, and may be 50 mol% or less, or may be 30 mol% or less.

[0349] In the polymer having the structural unit represented by the formula (V), a structural unit (d) derived from a different polymerizable compound (hereinafter, also referred to as other polymerizable compound) may be further incorporated. Examples of the other polymerizable compound (monomer) include compounds containing three vinyl groups. Specifically, 1,3,5-trivinylbenzene, 1,3,5-trivinylnaphthalene, 1,2,4-trivinylcyclohexane can be mentioned. Alternatively, ethylene glycol diacrylate, butadiene (for example, 1,3-butadiene), isoprene, etc. can be mentioned. The copolymerization ratio of the structural unit (d) derived from the other polymerizable compound is preferably 30 mol% or less, more preferably 20 mol% or less, and further preferably 10 mol% or less.

[0350] As an embodiment of the polymer having the structural unit represented by formula (V), a polymer that necessarily contains structural unit (a) and contains at least one of structural units (b) to (d) can be exemplified. Further, an embodiment in which the total of structural units (a) to (d) accounts for 95 mol% or more of all structural units, and further 98 mol% or more can be exemplified.

[0351] As another embodiment of the polymer having the structural unit represented by formula (V), it is preferably a polymer that necessarily has the structural unit (a) and in which the structural unit containing an aromatic ring in all structural units excluding the terminal is 90 mol % or more, more preferably 95 mol % or more, and may be 100 mol %.

[0352] When calculating the mol % relative to all structural units, one structural unit refers to a structural unit derived from one molecule of a monomer (e.g., a divinyl aromatic compound, a monovinyl aromatic compound, etc.) used in the production of a polymer having a structural unit represented by formula (V).

[0353] The method for producing the polymer having the structural unit shown in formula (V) is not particularly limited, and conventional methods may be used, for example, by polymerizing a raw material comprising a divinyl aromatic compound (coexisting with a monovinyl aromatic compound, a cycloolefin compound, etc. as required) in the presence of a Lewis acid catalyst. As the Lewis acid catalyst, a metal fluoride such as boron trifluoride or a complex thereof may be used.

[0354] The structure of the chain end of the polymer having the structural unit represented by formula (V) is not particularly limited, and the group derived from the divinyl aromatic compound may be a structure of the following formula (E1). 1 The same as defined in the above formula (V1). * indicates a bonding position.

[0355] *-CH=CH-L 1 -CH=CH 2 (E1)

[0356] When the group derived from a monovinyl aromatic compound is a chain terminal, a structure of the following formula (E2) can be used. 2 and R V1 They have the same meanings as defined in the above formula (V4). * represents a bonding position.

[0357] *-CH=CH-L 2 -R V1 (E2)

[0358] The molecular weight of the polymer having the structural unit represented by the formula (V) is preferably 300 or more, more preferably 500 or more, further preferably 1,000 or more, and still more preferably 1,500 or more in terms of the number average molecular weight Mn. As the upper limit of the number average molecular weight Mn, it is preferably 130,000 or less, more preferably 120,000 or less, further preferably 110,000 or less, still more preferably 100,000 or less, and may also be 30,000 or less, 10,000 or less, 5,000 or less.

[0359] The molecular weight of the polymer having the structural unit represented by the formula (V) is preferably 1,000 or more, more preferably 2,000 or more, and further preferably 3,000 or more in terms of the weight average molecular weight Mw. By setting the weight average molecular weight to the above lower limit value or more, the cured product of the resin composition can effectively exhibit the excellent low dielectric property, particularly the low dielectric property after moisture absorption, of the polymer having the structural unit represented by the formula (V). As the upper limit of the weight average molecular weight Mw, it is preferably 160,000 or less, more preferably 150,000 or less, further preferably 140,000 or less, still more preferably 130,000 or less, and may also be 80,000 or less, 50,000 or less. By setting the weight average molecular weight to the above upper limit value or less, there is a tendency that it is not easy to occur landfill defects when the prepreg or resin composite sheet is laminated on the circuit formation substrate.

[0360] 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, further preferably 20 or less, may be 15 or less, and may also be 12 or less. As the lower limit value, it is practical that it is 1.1 or more, preferably 2.0 or more, more preferably 4 or more, further preferably 5 or more, still more preferably 7 or more, and still more preferably 8 or more. The above Mw and Mn are measured according to the description in the following examples.

[0361] When the resin composition of the present embodiment contains two or more polymers having the structural unit represented by the formula (V), it is preferable that the Mw, Mn, and Mw / Mn of the mixture satisfy the above ranges.

[0362] The equivalent weight of the vinyl group of the polymer having the structural unit represented by the formula (V) is preferably 200 g / eq. or more, more preferably 230 g / eq. or more, still more preferably 250 g / eq. or more, and may also be 300 g / eq. or more, 350 g / eq. or more. In addition, the equivalent weight of the aforementioned vinyl group is preferably 1200 g / eq. or less, more preferably 1000 g / eq. or less, and may further be 800 g / eq. or less, 600 g / eq. or less, 400 g / eq. or less, 300 g / eq. or less. By setting the equivalent weight of the aforementioned vinyl group to be above the above lower limit value, the storage stability of the resin composition tends to be improved, and the fluidity of the resin composition tends to be improved. Therefore, there is a tendency for the formability to be improved, voids are less likely to be generated when forming a prepreg, and a printed circuit board with higher reliability can be obtained. On the other hand, by setting the equivalent weight of the aforementioned vinyl group to be below the above upper limit value, there is a tendency for the moisture absorption heat resistance of the obtained cured product to be improved.

[0363] In addition, the polymer having the structural unit represented by the formula (V) used in the present embodiment preferably has excellent low dielectric properties in its cured product. For example, the relative dielectric constant (Dk) at a frequency of 10 GHz measured by the cavity resonator perturbation method of the cured product of the polymer having the structural unit represented by the formula (V) used in the present embodiment is preferably 2.80 or less, more preferably 2.60 or less, still more preferably 2.50 or less, and even more preferably 2.40 or less. In addition, the lower limit value of the aforementioned relative dielectric constant is, for example, preferably 1.80 or more in practice. In addition, the dielectric loss tangent (Df) at a frequency of 10 GHz measured by the cavity resonator perturbation method of the cured product of the polymer having the structural unit represented by the formula (V) used in the present embodiment is preferably 0.0030 or less, more preferably 0.0020 or less, still more preferably 0.0010 or less. In addition, the lower limit value of the aforementioned dielectric loss tangent is, for example, preferably 0.0001 or more in practice.

[0364] The dielectric loss tangent (Df) is measured according to the method described in the examples below. The relative dielectric constant (Dk) is also measured based on the measurement method of Df in the examples.

[0365] In this specification, regarding the polymer having a structural unit represented by formula (V), reference can be made to the compounds described in paragraphs 0029 to 0058 of International Publication No. 2017 / 115813, their synthesis reaction conditions, etc., the compounds described in paragraphs 0013 to 0058 of Japanese Patent Application Laid-Open No. 2018-039995, their synthesis reaction conditions, etc., the compounds described in paragraphs 0008 to 0043 of Japanese Patent Application Laid-Open No. 2018-168347, their synthesis reaction conditions, etc., the compounds described in paragraphs 0014 to 0042 of Japanese Patent Application Laid-Open No. 2006-070136, their synthesis reaction conditions, etc., the compounds described in paragraphs 0014 to 0061 of Japanese Patent Application Laid-Open No. 2006-089683, their synthesis reaction conditions, etc., the compounds described in paragraphs 0008 to 0036 of Japanese Patent Application Laid-Open No. 2008-248001, their synthesis reaction conditions, etc., and the contents thereof are incorporated into this specification.

[0366] When the resin composition of the present embodiment contains a polymer having a structural unit represented by formula (V), when the resin solid content in the resin composition is 100 parts by mass, the lower limit value of the content of the polymer having a structural unit represented by formula (V) is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, further preferably 15 parts by mass or more, still more preferably 20 parts by mass or more, and depending on the use, etc., it may also be 25 parts by mass or more, 30 parts by mass or more, 40 parts by mass or more, 50 parts by mass or more. By setting the content of the polymer having a structural unit represented by formula (V) to the above lower limit value or more, low dielectric properties, particularly low dielectric loss tangent, can be effectively achieved. In addition, there is a tendency to have excellent low water absorption and chemical resistance (particularly alkali resistance). On the other hand, when the resin solid content in the resin composition is 100 parts by mass, the upper limit value of the content of the polymer having a structural unit represented by formula (V) is preferably 90 parts by mass or less, more preferably 80 parts by mass or less, and depending on the use, etc., it may also be 70 parts by mass or less, 60 parts by mass or less, 50 parts by mass or less, 40 parts by mass or less, 35 parts by mass or less. In addition, by setting it to the above upper limit value or less, the metal foil peel strength of the obtained cured product can be effectively improved.

[0367] The polymer having a structural unit represented by formula (V) in the resin composition may contain only 1 type, or may contain 2 or more types. When containing 2 or more types, the total amount is preferably within the above range.

[0368] <<Compound Containing (Meth)Allyl>>

[0369] The resin composition of the present embodiment preferably contains a compound containing (meth)allyl, and more preferably contains a compound containing allyl.

[0370] In addition, the compound containing (meth)allyl is preferably a compound containing two or more (meth)allyls, more preferably a compound containing two or more allyls.

[0371] As the compound containing (meth)allyl, it is preferably at least one selected from the group consisting of allyl isocyanurate compounds, allyl-substituted nadic imide compounds, allyl compounds having a glycoluril structure, and diallyl phthalate, more preferably at least one selected from the group consisting of allyl isocyanurate compounds, allyl-substituted nadic imide compounds, and allyl compounds having a glycoluril structure, and still more preferably an allyl-substituted nadic imide compound.

[0372] When the resin composition of the present embodiment contains a compound containing (meth)allyl, its molecular weight is preferably 195 or more, more preferably 300 or more, still more preferably 400 or more, and even more preferably 500 or more. By setting it to the above lower limit value or more, there is a tendency for the low dielectric property and heat resistance to be further improved. In addition, the molecular weight of the compound containing (meth)allyl is preferably 3000 or less, more preferably 2000 or less, still more preferably 1000 or less, and even more preferably 800 or less. By setting it to the above upper limit value or less, there is a tendency for the low thermal expansion property to be further improved.

[0373] When the resin composition of the present embodiment contains a compound containing (meth)allyl, its content is preferably 1 part by mass or more, more preferably 3 parts by mass or more, still more preferably 5 parts by mass or more, and may also be 10 parts by mass or more with respect to 100 parts by mass of the resin solid content in the resin composition. By setting the content of the compound containing (meth)allyl to the above lower limit value or more, there is a tendency for excellent moldability and further improvement in heat resistance. In addition, the upper limit value of the content of the compound containing (meth)allyl is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, still more preferably 20 parts by mass or less with respect to 100 parts by mass of the resin solid content in the resin composition. By setting the content of the compound containing (meth)allyl to the above upper limit value or less, there is a tendency for the low thermal expansion property to be further improved.

[0374] The resin composition of the present embodiment may contain only one kind of compound containing (meth)allyl, or may contain two or more kinds. In the case of containing two or more kinds, the total amount is preferably within the above range.

[0375] <<<Allyl isocyanurate compound>>>

[0376] As an allyl isocyanurate compound, as long as it is a compound having two or more allyl groups and having an isocyanurate ring (allophanate skeleton), there is no particular limitation, and the compound represented by the formula (TA) is preferred.

[0377] Formula (TA)

[0378]

[0379] (In formula (TA), R A represents a substituent.)

[0380] In formula (TA), R A represents a substituent, and more preferably a substituent having a molecular weight of 15 to 500.

[0381] R A The first example of R is an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms. By using an allyl compound having an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms, a resin composition capable of providing a cured product having excellent crosslinkability and high toughness can be provided. Thus, even when a substrate such as a glass cloth is not contained in the resin composition, breakage or the like during etching treatment can be suppressed.

[0382] From the viewpoint of improving operability, the number of carbon atoms of the aforementioned alkyl group and / or alkenyl group is preferably 3 or more, more preferably 8 or more, may be 12 or more, and preferably 18 or less. Thus, it is considered that the resin fluidity of the resin composition becomes good, and the circuit filling property and the like when producing a multilayer circuit board or the like using the resin composition of the present embodiment are more excellent.

[0383] R A The second example of R is a group containing an allyl isocyanurate group. When R A contains an allyl isocyanurate group, the compound represented by the formula (TA) is preferably the compound represented by the formula (TA-1).

[0384] Formula (TA-1)

[0385]

[0386] (In formula (TA-1), R A2 is a divalent linking group.)

[0387] In formula (TA-1), R A2 is preferably a divalent linking group having a molecular weight of 54 to 250, more preferably a divalent linking group having a molecular weight of 54 to 250 and having carbon atoms at both ends, and further preferably an aliphatic hydrocarbon group having 2 to 20 carbon atoms (wherein the aliphatic hydrocarbon group may contain an ether group and may also have a hydroxyl group). More specifically, R A2Preferably a group represented by any one of the following formulas (i) to (iii).

[0388]

[0389] (In the formulas (i) to (iii), p c1 represents the number of repeating units of methylene and is an integer of 2 to 18. p c2 represents the number of repeating units of oxyethylene and is 0 or 1. * is the bonding site.)

[0390] The aforementioned p c1 is preferably an integer of 2 to 10, more preferably an integer of 3 to 8, and still more preferably an integer of 3 to 5.

[0391] The aforementioned p c2 can be 0 or 1, and is preferably 1.

[0392] R A2 is preferably the first example.

[0393] In the present embodiment, the equivalent of the reactive group (allyl group) of the compound represented by the formula (TA) is desirably 1000 or less. When the aforementioned equivalent is 1000 or less, it is considered that a higher Tg can be obtained more surely.

[0394] Examples of the alkyl group having 1 to 22 carbon atoms include linear or branched alkyl groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl, etc. In addition, examples of the alkenyl group having 2 to 22 carbon atoms include allyl, decenyl, etc.

[0395] Specific examples of the compound represented by the formula (TA) include triallyl isocyanurate, 5-octyl-1,3-diallyl isocyanurate, 5-dodecyl-1,3-diallyl isocyanurate, 5-tetradecyl-1,3-diallyl isocyanurate, 5-hexadecyl-1,3-diallyl isocyanurate, 5-octadecyl-1,3-diallyl isocyanurate, 5-eicosyl-1,3-diallyl isocyanurate, 5-docosyl-1,3-diallyl isocyanurate, 5-decenyl-1,3-diallyl isocyanurate, etc. These can be used alone or in combination of two or more, and can also be used in the form of a prepolymer.

[0396] The production method of the compound represented by formula (TA) is not particularly limited. For example, it can be obtained by the following method: in an aprotic polar solvent such as N,N'-dimethylformamide, in the presence of a basic substance such as sodium hydroxide, potassium carbonate, or triethylamine, reacting diallyl isocyanurate and an alkyl halide at a temperature of about 60°C to 150°C.

[0397] In addition, the compound represented by formula (TA) can also be a commercially available product. There is no particular limitation on the commercially available product. For example, L-DAIC manufactured by Shikoku Kasei Kogyo Co., Ltd. and P-DAIC manufactured by Shikoku Kasei Kogyo Co., Ltd. having a phosphorus-based substituent can be cited. As the triallyl isocyanurate, for example, TAIC manufactured by Shinryo Corporation can be cited. As the compound represented by formula (TA-1), for example, DD-1 manufactured by Shikoku Kasei Kogyo Co., Ltd. can be cited.

[0398] The molecular weight of the allyl isocyanurate compound (preferably the compound represented by formula (TA)) is preferably 200 or more, more preferably 300 or more, further preferably 400 or more, and even more preferably 500 or more. By setting the aforementioned molecular weight to the above lower limit value or more, there is a tendency for the low dielectric property and heat resistance to be further improved. In addition, the molecular weight of the allyl isocyanurate compound (preferably the compound represented by formula (TA)) is preferably 3000 or less, more preferably 2000 or less, further preferably 1000 or less, and even more preferably 800 or less. By setting the aforementioned molecular weight to the above upper limit value or less, there is a tendency for the low thermal expansion property of the obtained cured product to be further improved.

[0399] When the resin composition of the present embodiment contains an allyl isocyanurate compound, its content is preferably 1 part by mass or more, more preferably 3 parts by mass or more, further preferably 5 parts by mass or more, and may also be 10 parts by mass or more with respect to 100 parts by mass of the resin solid content in the resin composition. By setting the content of the allyl isocyanurate compound to the above lower limit value or more, there is a tendency for the moldability of the resin composition to be excellent and the heat resistance and low water absorption of the obtained cured product to be further improved. In addition, the upper limit value of the content of the allyl isocyanurate compound is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and further preferably 20 parts by mass or less with respect to 100 parts by mass of the resin solid content in the resin composition. By setting the content of the allyl isocyanurate compound to the above upper limit value or less, there is a tendency for the low thermal expansion property of the obtained cured product to be further improved.

[0400] The resin composition of the present embodiment may contain only one kind of allyl isocyanurate or may contain two or more kinds. In the case of containing two or more kinds, the total amount is preferably within the above range.

[0401] <<<Allyl-substituted nadimide compound>>>

[0402] As the allyl-substituted nadimide compound, there is no particular limitation as long as it is a compound having two or more allyl-substituted nadimide groups in the molecule. Specific examples thereof include the compounds represented by the following formula (AN).

[0403] Formula (AN)

[0404]

[0405] (In formula (AN), 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, a phenylene group, a biphenylene group, a naphthylene group, or a group represented by formula (AN-2) or (AN-3).

[0406] Formula (AN-2)

[0407]

[0408] (In formula (AN-2), R 3 represents a methylene group, an isopropylidene group, -C(=O)-, -O-, -S-, or a group represented by -S(=O) 2 -.)

[0409] Formula (AN-3)

[0410]

[0411] (In formula (AN-3), R 4 each independently represents an alkylene group having 1 to 4 carbon atoms or a cycloalkylene group having 5 to 8 carbon atoms.)

[0412] In addition, the compounds represented by formula (AN) can also use commercially available products. There is no particular limitation for the commercially available products. For example, compounds represented by formula (AN-4) (BANI-M (manufactured by Maruzen Petrochemical Co., Ltd.)) and compounds represented by formula (AN-5) (BANI-X (manufactured by Maruzen Petrochemical Co., Ltd.)) can be cited. These can be used alone or in combination of two or more kinds.

[0413] Formula (AN-4)

[0414]

[0415] Formula (AN-5)

[0416]

[0417] The molecular weight of the allyl-substituted nadimide compound (preferably the compound represented by formula (AN)) is preferably 400 or more, more preferably 500 or more, and may also be 550 or more. By setting the molecular weight of the allyl-substituted nadimide compound to the above lower limit or more, there is a tendency for the low dielectric property, low thermal expansion property, and heat resistance to be further improved. In addition, the molecular weight of the allyl-substituted nadimide compound (preferably the compound represented by formula (AN)) is preferably 1500 or less, more preferably 1000 or less, further preferably 800 or less, and may also be 700 or less, 600 or less. By setting the molecular weight of the allyl-substituted nadimide compound to the above upper limit or less, there is a tendency for the formability and peel strength to be further improved.

[0418] When the resin composition of the present embodiment contains an allyl-substituted nadimide compound (preferably the compound represented by formula (AN)), its content is preferably 1 part by mass or more, more preferably 3 parts by mass or more, further preferably 5 parts by mass or more, and may also be 10 parts by mass or more with respect to 100 parts by mass of the resin solid content in the resin composition. By setting the content of the allyl-substituted nadimide compound to the above lower limit or more, there is a tendency for excellent formability, low dielectric property, low thermal expansion property, and heat resistance to be further improved. In addition, the upper limit of the content of the allyl-substituted nadimide compound (preferably the compound represented by formula (AN)) is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, further preferably 25 parts by mass or less, and may also be 20 parts by mass or less with respect to 100 parts by mass of the resin solid content in the resin composition. By setting the content of the allyl-substituted nadimide compound to the above upper limit or less, there is a tendency for the formability and peel strength to be further improved.

[0419] The resin composition of the present embodiment may contain only one kind of allyl-substituted nadimide compound, or may contain two or more kinds. In the case of containing two or more kinds, the total amount is preferably within the above range.

[0420] <<<Allyl compound having a glycoluril structure>>>

[0421] The allyl compound having a glycoluril structure is not particularly limited as long as it is a compound containing a glycoluril structure and two or more allyl groups, and is preferably a compound represented by formula (GU-0), more preferably a compound represented by formula (GU).

[0422] Formula (GU-0)

[0423]

[0424] (In formula (GU-0), R 1Each independently represents a hydrogen atom or a substituent, and at least two Rs 1 are groups containing (meth)allyl. )

[0425] In formula (GU-0), R 1 each independently is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkenyl group having 2 to 5 carbon atoms, preferably an alkenyl group having 2 to 5 carbon atoms, more preferably (meth)allyl, and even more preferably allyl.

[0426] In formula (GU-0), R 1 Preferably, 3 or 4 of them are groups containing (meth)allyl, and more preferably 4 of them are groups containing (meth)allyl.

[0427] In formula (GU-0), R 2 is preferably each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and more preferably a hydrogen atom or a methyl group.

[0428] Formula (GU)

[0429]

[0430] (In formula (GU), R each independently represents a hydrogen atom or a substituent, and at least two Rs are groups containing allyl.)

[0431] In formula (GU), R each independently is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkenyl group having 2 to 5 carbon atoms, preferably an alkenyl group having 2 to 5 carbon atoms, and more preferably allyl.

[0432] In formula (GU), preferably 3 or 4 of Rs are groups containing allyl, and more preferably 4 of them are groups containing allyl.

[0433] As a specific example of the compound represented by formula (GU), 1,3,4,6-tetraallyl glycoluril (a compound in which all Rs in formula (GU) are allyl) can be cited.

[0434] In addition, the compound represented by formula (GU) can also be a commercially available product. There is no particular limitation on the commercially available product. For example, TA-G manufactured by Shikoku Kasei Kogyo Co., Ltd. can be cited.

[0435] The molecular weight of the allyl compound having a glycoluril structure (preferably the compound represented by formula (GU-0), more preferably the compound represented by formula (GU)) is preferably 195 or more, more preferably 220 or more, further preferably 250 or more, and may also be 300 or more, 400 or more. By setting the molecular weight of the allyl compound having a glycoluril structure to the above lower limit value or more, there is a tendency for the low dielectric property and heat resistance to be further improved. In addition, the molecular weight of the allyl compound having a glycoluril structure (preferably the compound represented by formula (GU-0), more preferably the compound represented by formula (GU)) is preferably 1500 or less, more preferably 1000 or less, further preferably 800 or less, and may also be 700 or less, 600 or less. By setting the molecular weight of the allyl compound having a glycoluril structure to the above upper limit value or less, there is a tendency for the low thermal expansibility to be further improved.

[0436] When the resin composition of the present embodiment contains an allyl compound having a glycoluril structure (preferably the compound represented by formula (GU-0), more preferably the compound represented by formula (GU)), its content is preferably 1 part by mass or more, more preferably 3 parts by mass or more, further preferably 5 parts by mass or more, and may also be 10 parts by mass or more with respect to 100 parts by mass of the resin solid content in the resin composition. By setting the content of the allyl compound having a glycoluril structure to the above lower limit value or more, there is a tendency for the low dielectric property, heat resistance, and low water absorption to be further improved. In addition, the upper limit value of the content of the allyl compound having a glycoluril structure (preferably the compound represented by formula (GU-0), more preferably the compound represented by formula (GU)) is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, further preferably 25 parts by mass or less, and may also be 20 parts by mass or less with respect to 100 parts by mass of the resin solid content in the resin composition. By setting the content of the allyl compound having a glycoluril structure to the above upper limit value or less, there is a tendency for the low thermal expansibility to be further improved.

[0437] The resin composition of the present embodiment may contain only one kind of allyl compound having a glycoluril structure, or may contain two or more kinds. In the case of containing two or more kinds, the total amount is preferably within the above range.

[0438] <<Polyfunctional (meth)acrylate compound>>

[0439] The resin composition of the present embodiment may contain a polyfunctional (meth)acrylate compound. Among them, a compound that is a polyfunctional (meth)acrylate compound and also belongs to a polyphenylene ether compound having a carbon-carbon unsaturated double bond at the terminal shall be classified as a polyphenylene ether compound having a carbon-carbon unsaturated double bond at the terminal.

[0440] A polyfunctional (meth)acrylate compound refers to a compound containing two or more (meth)acryloyloxy groups in one molecule, preferably three or more (meth)acryloyloxy groups in one molecule.

[0441] The polyfunctional (meth)acrylate compound is preferably a compound having 3 to 5 (meth)acryloyloxy groups, more preferably a compound having 3 or 4 (meth)acryloyloxy groups, and further preferably a compound having 3 (meth)acryloyloxy groups. The polyfunctional (meth)acrylate compound is preferably a compound having a methacryloyloxy group.

[0442] In the polyfunctional (meth)acrylate compound, since the number of (meth)acrylate groups serving as crosslinking points is large, it cures firmly with a maleimide compound (A) or the like, and there is a tendency to obtain a cured product having excellent low dielectric properties (Dk and / or Df) and heat resistance. As the polyfunctional (meth)acrylate compound, a compound represented by the formula (MA) is preferred.

[0443] Formula (MA)

[0444]

[0445] (In the formula (MA), R 1 represents a hydrogen atom or a substituent, and R 2 each independently represents a hydrogen atom or a methyl group.)

[0446] In the formula (MA), R 1 represents a hydrogen atom or a substituent, more preferably a substituent having a molecular weight of 15 to 500, more preferably a substituent having a molecular weight of 15 to 300, further preferably a substituent having a molecular weight of 15 to 100, and even more preferably a substituent having a molecular weight of 15 to 50.

[0447] R 1 is preferably a hydrocarbon group or a (meth)acryloyloxy group, more preferably a hydrocarbon group having 22 or less carbon atoms, further preferably an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms. By using a compound having an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms, a resin composition capable of providing a cured product having excellent crosslinkability and high toughness can be provided. Thus, even when the resin composition does not contain a substrate such as a glass cloth, breakage or the like during etching treatment can be suppressed.

[0448] From the viewpoint of improving workability, the carbon number of the aforementioned alkyl group and / or alkenyl group is preferably 2 or more, may be 8 or more, further may be 12 or more, and may also be 18 or less. Thus, it is considered that the resin fluidity of the resin composition becomes good, and the circuit filling property and the like are more excellent when manufacturing a multilayer circuit board or the like using the resin composition of the present embodiment.

[0449] In this embodiment, the (meth)acryloyl equivalent of the compound represented by formula (MA) is preferably 1000 g / eq. or less. When the aforementioned equivalent is 1000 g / eq. or less, there is a tendency to more surely obtain a high Tg. The lower limit value of the (meth)acryloyl equivalent is, for example, 99 g / eq. or more.

[0450] As the aforementioned alkyl group having 1 to 22 carbon atoms, a linear alkyl group having 1 to 22 carbon atoms or a branched alkyl group having 3 to 22 carbon atoms is preferred, and examples thereof include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl, etc. In addition, as the aforementioned alkenyl group having 2 to 22 carbon atoms, an alkenyl group having 2 to 15 carbon atoms is preferred, and examples thereof include allyl, decenyl, etc.

[0451] Specific examples of the compound represented by formula (MA) include trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, pentaerythritol tetra(meth)acrylate, etc. These can be used alone or in combination of two or more, and can also be used in the form of a prepolymer.

[0452] In addition, commercially available products can also be used for the compound represented by formula (MA). There is no particular limitation on the commercially available products. For example, as trimethylolpropane trimethacrylate, “NK ESTERTMPT” manufactured by Shin-Nakamura Chemical Co., Ltd. can be cited.

[0453] The molecular weight of the polyfunctional (meth)acrylate compound is preferably 200 or more, more preferably 300 or more, and can be 330 or more, 400 or more, 500 or more. By setting the aforementioned molecular weight to the above lower limit value or more, there is a tendency for the low dielectric properties (Dk and / or Df) and heat resistance of the obtained cured product to be further improved. In addition, the molecular weight of the polyfunctional (meth)acrylate compound (preferably the compound represented by formula (MA)) is preferably 3000 or less, more preferably 2000 or less, further preferably 1000 or less, and still more preferably 800 or less. By setting the aforementioned molecular weight to the above upper limit value or less, there is a tendency for the low thermal expansibility of the obtained cured product to be further improved.

[0454] In addition to the above, for the polyfunctional (meth)acrylate compound, reference can be made to the resin having a (meth)acryloyl group described in International Publication No. 2022 / 210095 (for example, the compounds described in Synthesis Examples 5 and 21 of this publication) and the resin having a (meth)acryloyl group of Japanese Patent No. 6962507 (for example, the compounds described in Examples 1 to 9), and the compounds described in paragraph 0049 of Japanese Unexamined Patent Application Publication No. 2019-194312, the contents of which are incorporated into this specification.

[0455] When the resin composition of the present embodiment contains a polyfunctional (meth)acrylate compound, its content is preferably 1 part by mass or more, more preferably 3 parts by mass or more, still more preferably 5 parts by mass or more, and may also be 10 parts by mass or more with respect to 100 parts by mass of the resin solid content in the resin composition. By setting the content of the polyfunctional (meth)acrylate compound to the above lower limit value or more, the moldability of the resin composition is excellent, and the heat resistance and low thermal expansion of the obtained cured product tend to be further improved. In addition, the upper limit value of the content of the polyfunctional (meth)acrylate compound is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and may also be 20 parts by mass or less with respect to 100 parts by mass of the resin solid content in the resin composition. By setting the content of the polyfunctional (meth)acrylate compound to the above upper limit value or less, the heat resistance and low dielectric characteristics (Dk and / or Df) of the obtained cured product tend to be further improved.

[0456] The resin composition of the present embodiment may contain only one kind of polyfunctional (meth)acrylate compound, or may contain two or more kinds. In the case of containing two or more kinds, the total amount is preferably within the above range.

[0457] <Other resin component (C)>

[0458] The resin composition of the present embodiment preferably contains one or more other resin components (C) selected from the group consisting of maleimide compounds other than the aforementioned polyimide compounds (A), epoxy compounds, phenolic compounds, oxetane resins, benzoxazine compounds, cyanate ester compounds, thermoplastic elastomers, arylcyclobutene resins, polyamide resins, polyimide resins, perfluorovinyl ether resins, and petroleum resins, and more preferably contains one or more other resin components (C) selected from the group consisting of maleimide compounds other than the aforementioned polyimide compounds (A), epoxy compounds, phenolic compounds, oxetane resins, benzoxazine compounds, cyanate ester compounds, and thermoplastic elastomers. By containing such components, other desired properties required for printed circuit boards can be more effectively exhibited. The other resin component (C) is usually a thermosetting compound.

[0459] Each of the above other resin components (C) preferably has an excellent low dielectric property of its cured product. For example, the dielectric constant (Dk) at a frequency of 10 GHz measured by the cavity resonator perturbation method of the cured product of each of the other resin components (C) is preferably 4.0 or less, more preferably 3.5 or less. In addition, the lower limit value of the aforementioned dielectric constant (Dk) is, for example, 2.0 or more in practice. In addition, the tangent of the dielectric loss angle (Df) at a frequency of 10 GHz measured by the cavity resonator perturbation method of the cured product of each of the other resin components (C) is preferably 0.03 or less, more preferably 0.002 or less. In addition, the lower limit value of the aforementioned tangent of the dielectric loss angle (Df) is, for example, 0.0001 or more in practice. The dielectric constant and the tangent of the dielectric loss angle can be measured, for example, according to the methods (curing conditions, measurement conditions) described in the examples.

[0460] In addition, each of the other resin components (C) preferably has a high heat resistance of its cured product. For example, the glass transition temperature measured by dynamic viscoelasticity measurement according to JIS C6481 of the cured product of each of the other resin components (C) is preferably 150 °C or higher, more preferably 180 °C or higher, and further preferably 200 °C or higher. By setting it to the above lower limit value or higher, a cured product with more excellent heat resistance can be obtained. In addition, the upper limit value of the aforementioned glass transition temperature is, for example, 400 °C or lower in practice.

[0461] When the resin composition of the present embodiment contains the other resin component (C), its total content is preferably 1 part by mass or more, more preferably 5 parts by mass or more, further preferably 10 parts by mass or more, still more preferably 20 parts by mass or more, and may also be 30 parts by mass or more with respect to 100 parts by mass of the resin solid content in the resin composition. By setting the content of the other resin component (C) to the above lower limit value or higher, there is a tendency for the heat resistance to be further improved. In addition, the upper limit value of the total content of the other resin component (C) is preferably 70 parts by mass or less, more preferably 60 parts by mass or less, further preferably 50 parts by mass or less, and may also be 40 parts by mass or less with respect to 100 parts by mass of the resin solid content in the resin composition. By setting the content of the other resin component (C) to the above upper limit value or lower, there is a tendency for the low dielectric property to be further improved.

[0462] <<Maleimide compounds other than the polymaleimide compound (A)>>

[0463] The resin composition of the present embodiment may contain a maleimide compound other than the polymaleimide compound (A) (hereinafter sometimes referred to as "other maleimide compound").

[0464] Other maleimide compounds are not particularly limited as long as they contain more than 1 (preferably 2 to 12, more preferably 2 to 6, further preferably 2 to 4, still further preferably 2 or 3, and most preferably 2) maleimide groups in the molecule, and compounds commonly used in the field of printed circuit boards can be widely used.

[0465] In the present embodiment, other maleimide compounds preferably contain one or more selected from the group consisting of the compound represented by formula (M0), the compound represented by formula (M1), the compound represented by formula (M2), the compound represented by formula (M3), the compound represented by formula (M4), the compound represented by formula (M5), and maleimide compound (M6). More preferably, they contain one or more selected from the group consisting of the compound represented by formula (M0), the compound represented by formula (M1), the compound represented by formula (M3), the compound represented by formula (M4), the compound represented by formula (M5), and maleimide compound (M6). Further preferably, they contain one or more selected from the group consisting of the compound represented by formula (M1), the compound represented by formula (M3), the compound represented by formula (M4), and the compound represented by formula (M5). Still further preferably, they contain one or more selected from the group consisting of the compound represented by formula (M1), the compound represented by formula (M3), and the compound represented by formula (M5). Most preferably, they contain the compound represented by formula (M1) and / or the compound represented by formula (M3). If these other maleimide compounds are used in materials for printed circuit boards (such as metal-clad laminates), excellent heat resistance can be imparted.

[0466]

[0467] (In formula (M0), R 51 each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group, and R 52 each independently represents a hydrogen atom or a methyl group, and n 1 represents an integer of 1 or more.)

[0468] R 51 each independently is preferably one selected from the group consisting of a hydrogen atom, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert-butyl group, a n-pentyl group, and a phenyl group. More preferably, it is a hydrogen atom and / or a methyl group. Further preferably, it is a hydrogen atom.

[0469] R 52 is preferably a methyl group.

[0470] n 1 is preferably an integer of 1 to 10, more preferably an integer of 1 to 5, further preferably an integer of 1 to 3, still further preferably 1 or 2, and most preferably 1.

[0471] Specifically, the following compounds can be cited as preferred examples of the formula (M0).

[0472]

[0473] In the above formula, R 8 each independently represents a hydrogen atom, a methyl group or an ethyl group, preferably a methyl group.

[0474] The compounds represented by the formula (M0) can be not only a single species but also a mixture of two or more species. As examples of the mixture, a mixture of n 1 different compounds, a mixture of compounds having different types of substituents for R 51 and / or R 52 , a mixture of compounds having different bonding positions (meta, para, ortho) of the maleimide group and the oxygen atom with respect to the benzene ring, and a mixture of compounds combining two or more of the aforementioned different points, etc. Hereinafter, the same applies to the compounds represented by the formulas (M1) to (M6).

[0475]

[0476] (In the formula (M1), R M1 , R M2 , R M3 and R M4 each independently represent a hydrogen atom or an organic group. R M5 and R M6 each independently represent a hydrogen atom or an alkyl group. Ar M is a divalent aromatic group. A is a 4- to 6-membered alicyclic group. R M7 and R M8 are each independently an alkyl group. mx is 1 or 2, and lx is 0 or 1. R M9 and R M10 each independently represent a hydrogen atom or an alkyl group. R M11 , R M12 , R M13 and R M14 each independently represent a hydrogen atom or an organic group. R M15 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a halogen atom, a hydroxyl group or a mercapto group. px represents an integer of 0 to 3. nx represents an integer of 1 to 20.)

[0477] In the formula, R M1 , R M2 , R M3 and R M4Each independently represents a hydrogen atom or an organic group. The organic group here is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, still more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably methyl, ethyl, propyl, or butyl, and among them, methyl is particularly preferred. R M1 and R M3 Each independently is preferably an alkyl group, R M2 and R M4 is preferably a hydrogen atom.

[0478] R M5 and R M6 Each independently represents a hydrogen atom or an alkyl group, and is preferably an alkyl group. The alkyl group here is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, still more preferably methyl, ethyl, propyl, or butyl, and among them, methyl is particularly preferred.

[0479] Ar M represents a divalent aromatic group, preferably a phenylene group, naphthalenediyl group, phenanthrenediyl group, anthracenediyl group, more preferably a phenylene group, and still more preferably a meta-phenylene group. Ar M Optionally has a substituent, and as the substituent, an alkyl group is preferred, more preferably an alkyl group having 1 to 12 carbon atoms, still more preferably an alkyl group having 1 to 6 carbon atoms, even more preferably methyl, ethyl, propyl, or butyl, and particularly preferably methyl. However, Ar M is preferably unsubstituted.

[0480] A is an alicyclic group having 4 to 6 members in the ring, more preferably an alicyclic group having 5 members in the ring (preferably a group that forms an indane ring together with a benzene ring). R M7 and R M8 Each independently is an alkyl group, preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably methyl.

[0481] mx is 1 or 2, and is preferably 2.

[0482] lx is 0 or 1, and is preferably 1.

[0483] R M9 and R M10 Each independently represents a hydrogen atom or an alkyl group, and is preferably an alkyl group. The alkyl group here is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, still more preferably methyl, ethyl, propyl, or butyl, and among them, methyl is particularly preferred.

[0484] R M11 、R M12 、R M13 and R M14 Each independently represents a hydrogen atom or an organic group. The organic group here is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, still more preferably an alkyl group having 1 to 6 carbon atoms, even more preferably methyl, ethyl, propyl, or butyl, and among them, methyl is particularly preferred. RM12 and R M13 are each independently preferably an alkyl group, and R M11 and R M14 is preferably a hydrogen atom.

[0485] R M15 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a halogen atom, a hydroxyl group, or a mercapto group, and is preferably an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms.

[0486] px represents an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, and still more preferably 0.

[0487] nx represents an integer of 1 to 20. nx can be an integer of 10 or less.

[0488] It should be noted that the resin composition of this embodiment may contain only one compound represented by the formula (M1) and compounds having different nx values, or may contain two or more. When two or more are contained, in order to achieve a low melting point (low softening point), a low melt viscosity, and excellent workability, the average value (average number of repeating units) n of nx in the compound represented by the formula (M1) in the resin composition is preferably 0.92 or more, more preferably 0.95 or more, further preferably 1.0 or more, and still more preferably 1.1 or more. In addition, n is preferably 10.0 or less, more preferably 8.0 or less, further preferably 7.0 or less, still more preferably 6.0 or less, and may also be 5.0 or less. The same applies to the formula (M1-1) and the like described later.

[0489] The compound represented by the formula (M1) is preferably the compound represented by the following formula (M1-1).

[0490]

[0491] (In the formula (M1-1), R M21 , R M22 , R M23 and R M24 each independently represent a hydrogen atom or an organic group. R M25 and R M26 each independently represent a hydrogen atom or an alkyl group. R M27 , R M28 , R M29 and R M30 each independently represent a hydrogen atom or an organic group. R M31 and R M32Each independently represents a hydrogen atom or an alkyl group. R M33 、R M34 、R M35 and R M36 Each independently represents a hydrogen atom or an organic group. R M37 、R M38 and R M39 Each independently represents a hydrogen atom or an alkyl group. nx represents an integer of 1 or more and 20 or less. )

[0492] In the formula, R M21 、R M22 、R M23 and R M24 Each independently represents a hydrogen atom or an organic group. The organic group here is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, still more preferably an alkyl group having 1 to 6 carbon atoms, even more preferably methyl, ethyl, propyl, butyl, and particularly preferably methyl. R M21 and R M23 are preferably alkyl groups, and R M22 and R M24 are preferably hydrogen atoms.

[0493] R M25 and R M26 Each independently represents a hydrogen atom or an alkyl group, preferably an alkyl group. The alkyl group here is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, still more preferably methyl, ethyl, propyl, butyl, and among them, particularly preferably methyl.

[0494] R M27 、R M28 、R M29 and R M30 Each independently represents a hydrogen atom or an organic group, preferably a hydrogen atom. The organic group here is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, still more preferably an alkyl group having 1 to 6 carbon atoms, even more preferably methyl, ethyl, propyl, butyl, and particularly preferably methyl.

[0495] R M31 and R M32 Each independently represents a hydrogen atom or an alkyl group, preferably an alkyl group. The alkyl group here is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, still more preferably methyl, ethyl, propyl, butyl, and among them, particularly preferably methyl.

[0496] R M33 、R M34 、R M35 and R M36Each independently represents a hydrogen atom or an organic group. The organic group here is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, still more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably methyl, ethyl, propyl, or butyl, and particularly preferably methyl.

[0497] R M33 and R M36 is preferably a hydrogen atom, and R M34 and R M35 are preferably alkyl groups.

[0498] R M37 、R M38 and R M39 Each independently represents a hydrogen atom or an alkyl group, and is preferably an alkyl group. The alkyl group here is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, still more preferably methyl, ethyl, propyl, or butyl, and particularly preferably methyl.

[0499] nx represents an integer of 1 or more and 20 or less. nx can be an integer of 10 or less.

[0500] The compound represented by the formula (M1-1) is preferably the compound represented by the following formula (M1-2).

[0501]

[0502] (In the formula (M1-2), R M21 、R M22 、R M23 and R M24 Each independently represents a hydrogen atom or an organic group. R M25 and R M26 Each independently represents a hydrogen atom or an alkyl group. R M27 、R M28 、R M29 and R M30 Each independently represents a hydrogen atom or an organic group. R M31 and R M32 Each independently represents a hydrogen atom or an alkyl group. R M33 、R M34 、R M35 and R M36 Each independently represents a hydrogen atom or an organic group. R M37 、R M38 and R M39 Each independently represents a hydrogen atom or an alkyl group. nx represents an integer of 1 or more and 20 or less.)

[0503] In the formula (M1-2), R M21 、R M22 、R M23 、R M24 、RM25 , R M26 , R M27 , R M28 , R M29 , R M30 , R M31 , R M32 , R M33 , R M34 , R M35 , R M36 , R M37 , R M38 , R M39 and nx are respectively the same as R in formula (M1-1). M21 , R M22 , R M23 , R M24 , R M25 , R M26 , R M27 , R M28 , R M29 , R M30 , R M31 , R M32 , R M33 , R M34 , R M35 , R M36 , R M37 , R M38 , R M39 and nx have the same meaning and the same preferred range.

[0504] The compound represented by formula (M1-1) is preferably the compound represented by the following formula (M1-3), and more preferably the compound represented by the following formula (M1-4).

[0505]

[0506] (In formula (M1-3), nx represents an integer of 1 or more and 20 or less.)

[0507] nx can be an integer of 10 or less.

[0508]

[0509] (In formula (M1-4), nx represents an integer of 1 or more and 20 or less.)

[0510] nx can be an integer of 10 or less.

[0511] The molecular weight of the compound represented by formula (M1) is preferably 500 or more, more preferably 600 or more, and further preferably 700 or more. By setting it to be above the aforementioned lower limit value, there is a tendency for the low dielectric constant and low water absorption of the obtained cured product to be further improved. In addition, the molecular weight of the compound represented by formula (M1) is preferably 10,000 or less, more preferably 9,000 or less, further preferably 7,000 or less, still more preferably 5,000 or less, and even more preferably 4,000 or less. By setting it to be below the aforementioned upper limit value, there is a tendency for the heat resistance and processability of the obtained cured product to be further improved.

[0512] The maleimide group equivalent of the compound represented by formula (M1) is preferably 50 g / eq. or more, more preferably 100 g / eq. or more, and further preferably 200 g / eq. or more. The upper limit value of the aforementioned maleimide equivalent is preferably 2,000 g / eq. or less, more preferably 1,000 g / eq. or less, and further preferably 800 g / eq. or less. Here, the maleimide group equivalent represents the mass of the maleimide compound per 1 equivalent of the maleimide group. When the maleimide group equivalent of the compound represented by formula (M1) is within the above range, there is a tendency for the low dielectric constant, low water absorption, heat resistance, and processability of the obtained cured product to be further improved.

[0513] The molecular weight distribution Mw / Mn of the compound represented by formula (M1) calculated by gel permeation chromatography (GPC) is preferably 1.0 to 4.0, more preferably 1.1 to 3.8, further preferably 1.2 to 3.6, and still more preferably 1.3 to 3.4. When the Mw / Mn of the compound represented by formula (M1) is within the above range, there is a tendency for the low dielectric constant, low water absorption, heat resistance, and processability of the obtained cured product to be further improved.

[0514] In addition, for the details of the compound represented by formula (M1), reference can be made to the description in International Publication No. 2020-217679, the content of which is incorporated into this specification.

[0515]

[0516] (In formula (M2), R 54 each independently represents a hydrogen atom or a methyl group, and n 4 represents an integer of 1 or more.)

[0517] n 4 is preferably an integer of 1 to 10, more preferably an integer of 1 to 5, further preferably an integer of 1 to 3, still more preferably 1 or 2, and may also be 1.

[0518] The compound represented by formula (M2) may also have n 4A mixture of different compounds, preferably a mixture. Additionally, it can also be a mixture of compounds with different other parts as described in the part of the compound represented by formula (M0).

[0519]

[0520] (In formula (M3), R 55 each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group, and n 5 represents an integer of 1 or more and 10 or less.)

[0521] R 55 each independently is preferably one selected from the group consisting of a hydrogen atom, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert-butyl group, a n-pentyl group, and a phenyl group, more preferably a hydrogen atom and / or a methyl group, and still more preferably a hydrogen atom.

[0522] n 5 is preferably an integer of 1 or more and 5 or less, more preferably an integer of 1 to 3, and still more preferably 1 or 2.

[0523] The compound represented by formula (M3) can also be a mixture of compounds with different n 5 preferably a mixture. Additionally, it can also be a mixture of compounds with different other parts as described in the part of the compound represented by formula (M0).

[0524]

[0525] (In formula (M4), R 56 each independently represents a hydrogen atom, a methyl group, or an ethyl group, and R 57 each independently represents a hydrogen atom or a methyl group.)

[0526] R 56 each independently is preferably a methyl group or an ethyl group, more preferably a methyl group and an ethyl group in each of the two benzene rings present, and R 57 is preferably a methyl group.

[0527]

[0528] (In formula (M5), R 58 each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group, and R 59 each independently represents a hydrogen atom or a methyl group, and n 6 represents an integer of 1 or more.)

[0529] R 58Each is independently preferably one selected from the group consisting of a hydrogen atom, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert-butyl group, a n-pentyl group, and a phenyl group, more preferably a hydrogen atom and / or a methyl group, and still more preferably a hydrogen atom.

[0530] R 59 Preferably a methyl group.

[0531] n 6 Preferably an integer of 1 to 10, more preferably an integer of 1 to 5, still more preferably an integer of 1 to 3, even more preferably 1 or 2, and may also be 1.

[0532] The compound represented by the formula (M5) may also be a mixture of n 6 Mixtures of different compounds, preferably mixtures. In addition, as described in the part of the compound represented by the formula (M0), it may be a mixture of compounds with different other parts.

[0533] The maleimide compound can be produced by a known method or a commercially available product can be used. As commercially available products, for example, as the compound represented by the formula (M0), "BMI-80" manufactured by KI Kasei Co., Ltd. can be cited; as the compound represented by the formula (M1), "NE-X-9470S" and "NE-X-9480S" manufactured by DIC Corporation can be cited; as the compound represented by the formula (M2), "BMI-2300" manufactured by Daiwa Kasei Kogyo Co., Ltd. can be cited; as the compound represented by the formula (M3), "MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd. can be cited; as the compound represented by the formula (M4), "BMI-70" manufactured by KI Kasei Co., Ltd. can be cited; as the compound represented by the formula (M5), "MIR-5000" manufactured by Nippon Kayaku Co., Ltd. can be cited.

[0534] The maleimide compound (M6) is a compound having a structural unit represented by the formula (M6) and having maleimide groups at both ends of the molecular chain.

[0535]

[0536] (In the formula (M6), R 61 represents a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkenylene group having 2 to 16 carbon atoms. R 62 represents a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkenylene group having 2 to 16 carbon atoms. R 63 each independently represents a linear or branched alkyl group having 1 to 16 carbon atoms, or a linear or branched alkenyl group having 2 to 16 carbon atoms. n each independently represents an integer of 0 to 10.)

[0537] The weight-average molecular weight of the maleimide compound (M6) is preferably 100 or more, more preferably 300 or more, and further preferably 5000 or less, more preferably 4500 or less. By setting the weight-average molecular weight within the above range, an appropriate viscosity can be obtained, and an increase in the viscosity of the varnish can be suppressed. It should be noted that the weight-average molecular weight of the maleimide compound (M6) refers to the mass-average molecular weight in terms of polystyrene standard based on the gel permeation chromatography (GPC) method.

[0538] Next, the details of the maleimide compound (M6) will be described.

[0539] In the formula (M6) of the maleimide compound (M6), R 61 represents a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkenylene group having 2 to 16 carbon atoms. As R 61 , from the aspect of obtaining an appropriate viscosity and being able to control the increase in the viscosity of the varnish, a linear or branched alkylene group is preferred, and a linear alkylene group is more preferred.

[0540] Regarding the number of carbon atoms of the alkylene group, from the aspect of obtaining a more appropriate viscosity and being able to further control the increase in the viscosity of the varnish, 2 to 14 is preferred, and 4 to 12 is more preferred.

[0541] Examples of the linear or branched alkylene group include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, dodecylene, undecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, neopentylene, dimethylbutylene, methylhexylene, ethylhexylene, dimethylhexylene, trimethylhexylene, methylheptylene, dimethylheptylene, trimethylheptylene, tetramethylheptylene, ethylheptylene, methyloctylene, methylnonylene, methyldecylene, methyldodecylene, methylundecylene, methyltridecylene, methyltetradecylene, methylpentadecylene, and methylhexadecylene.

[0542] Regarding the number of carbon atoms of the alkenylene group, from the aspect of obtaining a more appropriate viscosity and being able to further control the increase in the viscosity of the varnish, 2 to 14 is preferred, and 4 to 12 is more preferred.

[0543] Examples of the linear or branched alkenylene group include vinylidene, 1-methylvinylidene, allylidene, propenylene, isopropenylene, 1-butenylene, 2-butenylene, 1-pentenylene, 2-pentenylene, isopentenylene, cyclopentylenylene, cyclohexylenylene, and dicyclopentadienylene, etc.

[0544] In the formula (M6), R 62represents a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkenylene group having 2 to 16 carbon atoms. As R 62 , from the aspect of obtaining an appropriate viscosity and being able to control the viscosity increase of the varnish, it is preferably a linear or branched alkylene group, more preferably a linear alkylene group.

[0545] Regarding the number of carbon atoms of the alkylene group, from the aspect of obtaining a more appropriate viscosity and being able to further control the viscosity increase of the varnish, it is preferably 2 to 14, more preferably 4 to 12.

[0546] Examples of the linear or branched alkylene group include the same groups as those described for the aforementioned R 61 .

[0547] Regarding the number of carbon atoms of the alkenylene group, from the aspect of obtaining a more appropriate viscosity and being able to further control the viscosity increase of the varnish, it is preferably 2 to 14, more preferably 4 to 12.

[0548] Examples of the linear or branched alkenylene group include the same groups as those described for the aforementioned R 61 .

[0549] In formula (M6), R 61 and R 62 may be the same or different, and are preferably the same from the aspect of being able to more easily synthesize the maleimide compound (M6).

[0550] In formula (M6), each R 63 independently represents a linear or branched alkyl group having 1 to 16 carbon atoms, or a linear or branched alkenyl group having 2 to 16 carbon atoms. From the aspect of obtaining an appropriate viscosity and being able to control the viscosity increase of the varnish, each R 63 is independently preferably a linear or branched alkyl group having 1 to 16 carbon atoms, and preferably 1 to 5 of the R 63 are linear or branched alkyl groups having 1 to 16 carbon atoms, more preferably 1 to 3 are linear or branched alkyl groups having 1 to 16 carbon atoms. It should be noted that in this embodiment, the part other than the linear or branched alkyl group having 1 to 16 carbon atoms is preferably a hydrogen atom.

[0551] Regarding the number of carbon atoms of the alkyl group, from the aspect of obtaining a more appropriate viscosity and being able to further control the viscosity increase of the varnish, it is preferably 2 to 14, more preferably 4 to 12.

[0552] As a linear or branched alkyl group, examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, n-pentyl, 2-pentyl, tert-pentyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, n-hexyl, 2-hexyl, 3-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, and 2-methylpentan-3-yl.

[0553] From the viewpoint of obtaining a more suitable viscosity and being able to further control the viscosity increase of the varnish, the number of carbon atoms of the alkenyl group is preferably 2 to 14, more preferably 4 to 12.

[0554] As a linear or branched alkenyl group, examples thereof include vinyl, allyl, 4-pentenyl, isopropenyl, and isopentyl.

[0555] In the formula (M6), n each independently represents an integer of 0 to 10, preferably 1 or more, more preferably 5 or more. Further, it is preferably 9 or less, more preferably 7 or less.

[0556] The maleimide compound (M6) has maleimide groups at both ends of the molecular chain. In the present embodiment, both ends refer to the two ends in the molecular chain of the maleimide compound (M6). For example, when the structural unit shown in the formula (M6) is located at the end of the molecular chain of the maleimide compound (M6), it means that there is a maleimide group at the end of the molecular chain of R 61 or a maleimide group at the end of the molecular chain on the N atom of the maleimide ring, or maleimide groups at both ends. The maleimide compound (M6) may also have maleimide groups at positions other than both ends of the molecular chain.

[0557] In the present embodiment, the maleimide groups bonded to the maleimide compound (M6) may be the same or different, and preferably the maleimide groups at both ends of the molecular chain are the same.

[0558] As such a maleimide compound (M6), for example, a maleimide compound represented by the following formula (M6-1) can be cited. They may be used alone or in appropriate mixture of two or more.

[0559]

[0560] (In the formula (M6-1), a represents an integer of 1 to 10)

[0561] From the viewpoint of obtaining a more suitable viscosity and being able to further control the viscosity increase of the varnish, a is preferably an integer of 1 to 6.

[0562] The maleimide compound (M6) can also be a commercially available product. Examples of commercially available products include MIZ-001 manufactured by Nippon Kayaku Co., Ltd.

[0563] For the production method of the maleimide compound (M6), reference can be made to paragraphs 0061 to 0066 of International Publication No. 2020 / 262577. The content is incorporated herein.

[0564] In addition, examples of other maleimide compounds other than the above include N-phenylmaleimide, N-cyclohexylmaleimide, oligomers of phenylmethane maleimide, m-phenylene bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, 4,4'-diphenylether bismaleimide, 4,4'-diphenylsulfone bismaleimide, 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene, and their prepolymers, prepolymers of these maleimides and amines, etc.

[0565] Among them, monofunctional maleimide compounds such as N-phenylmaleimide and N-cyclohexylmaleimide tend to give a resin composition capable of providing a cured product with more excellent low dielectric properties when used in combination with a polymer having a structural unit represented by the above formula (V).

[0566] When the resin composition of the present embodiment contains other maleimide compounds (preferably the compound represented by the formula (M1)), the lower limit of the content is preferably 1 part by mass or more, more preferably 5 parts by mass or more, still more preferably 10 parts by mass or more, and may also be 20 parts by mass or more, based on 100 parts by mass of the resin solid content in the resin composition. By making the content of other maleimide compounds be the above lower limit or more, the low dielectric properties, flame resistance, low water absorption, and chemical resistance of the obtained cured product tend to be improved. In addition, the upper limit of the content of other maleimide compounds is preferably 70 parts by mass or less, more preferably 60 parts by mass or less, still more preferably 50 parts by mass or less, and may also be 40 parts by mass or less, 30 parts by mass or less, depending on the use, etc., based on 100 parts by mass of the resin solid content in the resin composition. By making the content of other maleimide compounds be the above upper limit or less, the metal foil peel strength and low water absorption tend to be improved.

[0567] The resin composition of the present embodiment may contain only one kind of other maleimide compound, or may contain two or more kinds. In the case of containing two or more kinds, the total amount is preferably within the above range.

[0568] <<Epoxy compound>>

[0569] The resin composition of the present embodiment may contain an epoxy compound.

[0570] The epoxy compound is not particularly limited as long as it is a compound or resin having one or more (preferably 2 to 12, more preferably 2 to 6, further preferably 2 to 4, still further preferably 2 or 3, and even still further preferably 2) epoxy groups in one molecule, and compounds commonly used in the field of printed circuit boards can be widely used.

[0571] Examples of the epoxy compound include bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolak type epoxy resin, bisphenol A novolak type epoxy resin, glycidyl ester type epoxy resin, aralkyl phenol novolak type epoxy resin, biphenyl aralkyl type epoxy resin, naphthylene ether type epoxy resin, cresol novolak type epoxy resin, polyfunctional phenol type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, naphthalene skeleton modified novolak type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, alicyclic epoxy resin, polyol type epoxy resin, phosphorus-containing epoxy resin, glycidylamine, glycidyl ester, a compound obtained by epoxidizing a double bond such as butadiene, and a compound obtained by reacting a hydroxyl group-containing organosilicon resin with epichlorohydrin. Among these, from the viewpoint of further improving flame retardancy and heat resistance, biphenyl aralkyl type epoxy resin, naphthylene ether type epoxy resin, polyfunctional phenol type epoxy resin, and naphthalene type epoxy resin are preferred, and biphenyl aralkyl type epoxy resin is more preferred.

[0572] The resin composition of the present embodiment preferably contains an epoxy compound within a range that does not impair the effects of the present invention. From the viewpoints of moldability and adhesion, when the resin composition of the present embodiment contains an epoxy compound, its content is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, and further preferably 2 part by mass or more with respect to 100 parts by mass of the resin solid content in the resin composition. By making the content of the epoxy compound 0.1 part by mass or more, there is a tendency to improve the metal foil peel strength and toughness. When the resin composition of the present embodiment contains an epoxy compound, the upper limit value of the content of the epoxy compound is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, further preferably 20 parts by mass or less, still further preferably 10 parts by mass or less, even still further preferably 8 parts by mass or less, and yet even still further preferably 5 parts by mass or less with respect to 100 parts by mass of the resin solid content in the resin composition. By making the content of the epoxy compound 50 parts by mass or less, there is a tendency to improve electrical properties.

[0573] The epoxy resin composition in this embodiment may contain only one type of epoxy compound, or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.

[0574] In addition, the epoxy resin composition in this embodiment may be configured to be substantially free of epoxy compounds. Substantially free means that the content of the epoxy compound is less than 0.1 part by mass relative to 100 parts by mass of the resin solid content in the resin composition.

[0575] <<Phenolic compound>>

[0576] The resin composition of this embodiment may contain a phenolic compound.

[0577] The phenolic compound is not particularly limited as long as it has one or more (preferably 2 to 12, more preferably 2 to 6, further preferably 2 to 4, still further preferably 2 or 3, and still further preferably 2) phenolic hydroxyl groups in one molecule, and compounds commonly used in the field of printed circuit boards can be widely used.

[0578] Examples of the phenolic compound include: bisphenol A phenolic resin, bisphenol E phenolic resin, bisphenol F phenolic resin, bisphenol S phenolic resin, phenol novolac resin, bisphenol A novolac type phenolic resin, glycidyl ester type phenolic resin, aralkylphenol novolac phenolic resin, biphenyl aralkyl type phenolic resin, cresol novolac type phenolic resin, polyfunctional phenolic resin, naphthol resin, naphthol novolac resin, polyfunctional naphthol resin, anthracene type phenolic resin, naphthalene skeleton modified novolac type phenolic resin, phenol aralkyl type phenolic resin, naphthol aralkyl type phenolic resin, dicyclopentadiene type phenolic resin, biphenyl type phenolic resin, alicyclic phenolic resin, polyol type phenolic resin, phosphorus-containing phenolic resin, hydroxyl group-containing silicone resin, etc. Among them, from the viewpoint of further improving the flame retardancy, it is preferably at least one selected from the group consisting of biphenyl aralkyl type phenolic resin, naphthol aralkyl type phenolic resin, phosphorus-containing phenolic resin, and hydroxyl group-containing silicone resin.

[0579] In addition, as the phenolic compound, reference can also be made to the description in paragraphs 0012 to 0025 of International Publication No. 2023 / 176765, the content of which is incorporated into this specification.

[0580] The resin composition of this embodiment preferably contains a phenolic compound within the range that does not impair the effects of the present invention. When the resin composition of this embodiment contains a phenolic compound, its content is preferably 0.1 part by mass or more and preferably 50 parts by mass or less relative to 100 parts by mass of the resin solid content in the resin composition.

[0581] The resin composition in the present embodiment may contain only one type of phenolic compound, or may contain two or more types. In the case of containing two or more types, the total amount is preferably within the above range.

[0582] In addition, the resin composition in the present embodiment may also have a constitution substantially free of phenolic compounds. Substantially free means that the content of the phenolic compound is less than 0.1 part by mass relative to 100 parts by mass of the resin solid content in the resin composition.

[0583] <<Oxetane resin>>

[0584] The resin composition of the present embodiment may contain an oxetane resin.

[0585] The oxetane resin is not particularly limited as long as it is a compound having one or more (preferably 2 to 12, more preferably 2 to 6, further preferably 2 to 4, still further preferably 2 or 3, and still further preferably 2) oxetanyl groups, and compounds commonly used in the field of printed circuit boards can be widely used.

[0586] Examples of the oxetane resin include oxetane, alkyl oxetane (such as 2-methyl oxetane, 2,2-dimethyl oxetane, 3-methyl oxetane, 3,3-dimethyl oxetane, etc.), 3-methyl-3-methoxymethyl oxetane, 3,3-bis(trifluoromethyl)perfluoroxetane, 2-chloromethyl oxetane, 3,3-bis(chloromethyl)oxetane, biphenyl-type oxetane, OXT-101 (manufactured by Toagosei Co., Ltd.), OXT-121 (manufactured by Toagosei Co., Ltd.), etc.

[0587] The resin composition of the present embodiment preferably contains an oxetane resin within a range that does not impair the effects of the present invention. When the resin composition of the present embodiment contains an oxetane resin, its content is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, and further preferably 2 part by mass or more relative to 100 parts by mass of the resin solid content in the resin composition. By making the content of the oxetane resin 0.1 part by mass or more, there is a tendency to improve the metal foil peeling strength and toughness. When the resin composition of the present embodiment contains an oxetane resin, the upper limit value of the content of the oxetane resin is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, further preferably 20 parts by mass or less, still further preferably 10 parts by mass or less, and still further preferably 8 parts by mass or less relative to 100 parts by mass of the resin solid content in the resin composition. By making the content of the oxetane resin 50 parts by mass or less, there is a tendency to improve the electrical properties.

[0588] The resin composition in this embodiment may contain only one kind of oxetane resin, or may contain two or more kinds. When two or more kinds are contained, the total amount is preferably within the above range.

[0589] In addition, the resin composition in this embodiment may also be configured to be substantially free of oxetane resin. Substantially free means that the content of the oxetane resin is less than 0.1 part by mass relative to 100 parts by mass of the resin solid content in the resin composition.

[0590] <<Benzoxazine compound>>

[0591] The resin composition of this embodiment may contain a benzoxazine compound.

[0592] As the benzoxazine compound, there is no particular limitation as long as it has two or more (preferably 2 to 12, more preferably 2 to 6, still more preferably 2 to 4, even more preferably 2 or 3, and even more preferably 2) dihydrobenzoxazine rings in one molecule, and compounds commonly used in the field of printed circuit boards can be widely used.

[0593] Examples of the benzoxazine compound include bisphenol A type benzoxazine BA-BXZ (manufactured by Konishi Chemical Co., Ltd.), bisphenol F type benzoxazine BF-BXZ (manufactured by Konishi Chemical Co., Ltd.), bisphenol S type benzoxazine BS-BXZ (manufactured by Konishi Chemical Co., Ltd.), and the like.

[0594] The resin composition of this embodiment preferably contains a benzoxazine compound within a range that does not impair the effects of the present invention. When the resin composition of this embodiment contains a benzoxazine compound, its content is preferably 0.1 part by mass or more and preferably 50 parts by mass or less relative to 100 parts by mass of the resin solid content in the resin composition.

[0595] The resin composition in this embodiment may contain only one kind of benzoxazine compound, or may contain two or more kinds. When two or more kinds are contained, the total amount is preferably within the above range.

[0596] In addition, the resin composition in this embodiment may also be configured to be substantially free of benzoxazine compound. Substantially free means that the content of the benzoxazine compound is less than 0.1 part by mass relative to 100 parts by mass of the resin solid content in the resin composition.

[0597] <<Cyanate ester compound>>

[0598] The resin composition of this embodiment may contain a cyanate ester compound.

[0599] The cyanate ester compound is not particularly limited as long as it contains one or more (preferably 2 to 12, more preferably 2 to 6, still more preferably 2 to 4, even more preferably 2 or 3, and even more preferably 2) cyanate groups (cyanoyl groups) in the molecule, and compounds commonly used in the field of printed circuit boards can be widely used.

[0600] The cyanate ester compound is preferably a cyanate ester compound that is commonly used in printed circuit boards and has two or more aromatic moieties in the molecule that are each substituted by at least one cyanoyl group.

[0601] Specifically, the lower limit of the number of cyanoyl groups in the cyanate ester compound is preferably two or more, more preferably three or more. By setting it below the above upper limit value, there is a tendency for the heat resistance to be further improved. In addition, the upper limit of the number of cyanoyl groups is preferably 100 or less, more preferably 50 or less.

[0602] In addition, the cured product of the cyanate ester compound preferably has excellent low dielectric properties. For example, the cured product of the cyanate ester compound preferably has a dielectric constant (Dk) of 4.0 or less, more preferably 3.5 or less, at a frequency of 10 GHz measured by the cavity resonator perturbation method. In addition, the lower limit value of the aforementioned dielectric constant is, for example, 2.0 or more in practice. In addition, the cured product of the cyanate ester compound (B) preferably has a dielectric loss tangent (Df) of 0.02 or less, more preferably 0.015 or less, at a frequency of 10 GHz measured by the cavity resonator perturbation method. In addition, the lower limit value of the aforementioned dielectric loss tangent is, for example, 0.0001 or more in practice. The dielectric constant and the dielectric loss tangent can be measured, for example, according to the methods (curing conditions, measurement conditions) described in the examples.

[0603] In addition, the cured product of the cyanate ester compound preferably has high heat resistance. The cured product of the cyanate ester compound preferably has a glass transition temperature of 150 °C or higher, more preferably 180 °C or higher, and still more preferably 200 °C or higher, as measured by JIS C6481 dynamic viscoelasticity measurement. By setting the glass transition temperature above the aforementioned lower limit value, a cured product with excellent heat resistance can be obtained.

[0604] The polystyrene-reduced weight-average molecular weight of the cyanate ester compound based on the GPC method is preferably 200 or more, more preferably 300 or more, and still more preferably 400 or more. By setting the weight-average molecular weight above the aforementioned lower limit value, there is a tendency for the heat resistance to be further improved. In addition, the weight-average molecular weight of the cyanate ester compound is preferably 1000 or less, more preferably 900 or less, and still more preferably 800 or less. By setting the weight-average molecular weight below the aforementioned upper limit value, there is a tendency for the formability and processability to be further improved.

[0605] Examples of the cyanate ester compound include the compound represented by formula (B1).

[0606] Formula (B1)

[0607]

[0608] (In formula (B1), Ar 1 each independently represents a phenylene group optionally having a substituent, a naphthylene group optionally having a substituent, or a biphenylene group optionally having a substituent. R 6 each independently selected from a hydrogen atom, an alkyl group having 1 to 6 carbon atoms optionally having a substituent, an aryl group having 6 to 12 carbon atoms optionally having a substituent, an alkoxy group having 1 to 4 carbon atoms optionally having a substituent, an aralkyl group optionally having a substituent formed by bonding an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 12 carbon atoms, or an alkylaryl group optionally having a substituent formed by bonding an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 12 carbon atoms. n 4 represents the number of cyano groups bonded to Ar 1 and is an integer from 1 to 3. n 5 represents the number of R 1 bonded to Ar 6 , and when Ar 1 is a phenylene group, it is 4 - n 4 , when it is a naphthylene group, it is 6 - n 4 , and when it is a biphenylene group, it is 8 - n 4 . n 6 represents the average repeat number and is an integer from 0 to 50. The compound represented by formula (B1) may also be a mixture of compounds with different n 5 and / or n 6 . Z each independently selected from a single bond, a divalent organic group having 1 to 50 carbon atoms (wherein a hydrogen atom is optionally substituted by a heteroatom), and a divalent organic group having 1 to 10 nitrogen atoms (-N-R-N-, etc.).)

[0609] The substituents in the above formula (B1) are preferably non-polar groups.

[0610] The alkyl group in R 6 of formula (B1) may have at least one of a straight-chain structure, a branched-chain structure, and a cyclic structure (such as a cycloalkyl group). In addition, the hydrogen atom in the alkyl group and the aryl group in R 6 in formula (B1) may be substituted by a halogen atom such as a fluorine atom or a chlorine atom, an alkoxy group such as a methoxy group or a phenoxy group, a cyano group, etc.

[0611] Specific examples of the alkyl group include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, 1-ethylpropyl, 2,2-dimethylpropyl, cyclopentyl, hexyl, cyclohexyl, trifluoromethyl, etc.

[0612] Specific examples of the aryl group include phenyl, xylyl, mesityl, naphthyl, phenoxyphenyl, ethylphenyl, o-, m- or p-fluorophenyl, dichlorophenyl, dicyanophenyl, trifluorophenyl, methoxyphenyl, o-, m- or p-tolyl, and the like.

[0613] Specific examples of the alkoxy group include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, and the like.

[0614] Specific examples of the divalent organic group in Z of formula (B1) include methylene, ethylene, trimethylene, cyclopentylene, cyclohexylene, trimethylcyclohexylene, biphenylmethylene, dimethylmethylene-phenylene-dimethylmethylene, fluorenediyl, phthaloyldiyl, and the like. The hydrogen atoms in the aforementioned divalent organic group may be substituted with halogen atoms such as fluorine atoms and chlorine atoms, alkoxy groups such as methoxy and phenoxy, and cyano groups. Specific examples of the divalent organic group in Z of formula (B1) having 1 to 10 nitrogen atoms include imino, polyimide group, and the like.

[0615] In addition, as Z in formula (B1), the structure represented by the following formula (B2) or the structure represented by the following formula (B3) may be mentioned.

[0616] Formula (B2)

[0617]

[0618] (In formula (B2), Ar 2 is selected from any one of phenylene, naphthylene, and biphenylene. R 7 , R 8 , R 11 and R 12 are each independently selected from any one of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an aryl group substituted with at least one of trifluoromethyl and phenolic hydroxyl group. R 9 and R 10 are each independently selected from any one of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a hydroxyl group. n7 represents an integer of 0 to 5, and the compound represented by formula (B1) may be a mixture of compounds having different n7 values.)

[0619] Formula (B3)

[0620]

[0621] (In formula (B3), Ar 3 is selected from any one of phenylene, naphthylene, and biphenylene. R 13 and R 14Each independently selected from a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a benzyl group, an alkoxy group having 1 to 4 carbon atoms, and an aryl group substituted with at least one of a hydroxyl group, a trifluoromethyl group, and a cyano group. n 8 represents an integer of 0 to 5, and the compound represented by formula (B1) may be n 8 a mixture of different compounds.)

[0622] Furthermore, as Z in formula (B1), divalent groups represented by the following formulas can be cited.

[0623]

[0624] (In the formula, n 9 represents an integer of 4 to 7. R 15 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)

[0625] As specific examples of Ar in formula (B2) 2 and Ar in formula (B3) 3 , 1,4-phenylene, 1,3-phenylene, 4,4'-biphenylene, 2,4'-biphenylene, 2,2'-biphenylene, 2,3'-biphenylene, 3,3'-biphenylene, 3,4'-biphenylene, 2,6-naphthylene, 1,5-naphthylene, 1,6-naphthylene, 1,8-naphthylene, 1,3-naphthylene, 1,4-naphthylene, etc. can be cited. R 7 to R 12、 in formula (B2) and R 13 and R 14 in formula (B3) are the same as the groups described in formula (B1).

[0626] As specific examples of the cyanate ester compound, 1,2-dicyanate benzene, 1,3-dicyanate benzene, 1,4-dicyanate benzene, 1,4-dicyanate-2-tert-butyl benzene, 1,4-dicyanate-2,4-dimethyl benzene, 1,4-dicyanate-2,3,4-trimethyl benzene, 1,3-dicyanate-2,4,6-trimethyl benzene, 1,3-dicyanate-5-methyl benzene, 2,2'-dicyanate-1,1'-binaphthalene, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 2,3-, 2,6- or 2,7-dicyanate naphthalene, 2,2'- or 4,4'-dicyanate biphenyl, 4,4'-dicyanate octafluorobiphenyl, 2,4'- or 4,4'-dicyanate diphenylmethane, bis(4-cyanate-3,5-dimethylphenyl)methane, 1,1-bis(4-cyanate phenyl)ethane, 1,1-bis(4-cyanate phenyl)propane, 2,2-bis(4-cyanate phenyl)propane, 2,2-bis(3-allyl-4-cyanate phenyl)propane, 2,2-bis(4-cyanate-3-methylphenyl)propane, 2,2-bis(2-cyanate-5-biphenyl)propane, 2,2-bis(4-cyanate phenyl)hexafluoropropane, 2,2-bis(4-cyanate-3,5-dimethylphenyl)propane, 1,1-bis(4-cyanate phenyl)butane, 1,1-bis(4-cyanate phenyl)isobutane, 1,1-bis(4-cyanate phenyl)pentane, 1,1-bis(4-cyanate phenyl)-3-methylbutane, 1,1-bis(4-cyanate phenyl)-2-methylbutane, 1,1-bis(4-cyanate phenyl)-2,2-dimethylpropane, 2,2-bis(4-cyanate phenyl)butane, 2,2-bis(4-cyanate phenyl)pentane, 2,2-bis(4-cyanate phenyl)hexane, 2,2-bis(4-cyanate phenyl)-3-methylbutane, 2,2-bis(4-cyanate phenyl)-4-methylpentane, 2,2-bis(4-cyanate phenyl)-3,3-dimethylbutane, 3,3-bis(4-cyanate phenyl)hexane, 3,3-bis(4-cyanate phenyl)heptane, 3,3-bis(4-cyanate phenyl)octane, 3,3-bis(4-cyanate phenyl)-2-methylpentane, 3,3-bis(4-cyanate phenyl)-2-methylhexane, 3,3-bis(4-cyanate phenyl)-2,2-dimethylpentane, 4,4-bis(4-cyanate phenyl)-3-methylheptane, 3,3-bis(4-cyanate phenyl)-2-methylheptane, 3,3-bis(4-cyanate phenyl)-2,2-dimethylhexane, 3,3-bis(4-cyanate phenyl)-2,4-dimethylhexane, 3,3-bis(4-cyanate phenyl)-2,2,4-trimethylpentane, 2,2-bis(4-cyanate phenyl)-1,1,1,3,3,3-hexafluoropropane, bis(4-cyanate phenyl)phenylmethane, 1,1-Bis(4-cyanophenyl)-1-phenylethane, bis(4-cyanophenyl)biphenylmethane, 1,1-bis(4-cyanophenyl)cyclopentane, 1,1-bis(4-cyanophenyl)cyclohexane, 2,2-bis(4-cyano-3-isopropylphenyl)propane, 1,1-bis(3-cyclohexyl-4-cyanophenyl)cyclohexane, bis(4-cyanophenyl)diphenylmethane, bis(4-cyanophenyl)-2,2-dichloroethane, 1,3-bis[2-(4-cyanophenyl)-2-propyl]benzene, 1,4-bis[2-(4-cyanophenyl)-2-propyl]benzene, 1,1-bis(4-cyanophenyl)-3,3,5-trimethylcyclohexane, 4-[bis(4-cyanophenyl)methyl]biphenyl, 4,4-dicyanobenzophenone, 1,3-bis(4-cyanophenyl)-2-propen-1-one, bis(4-cyanophenyl)ether, bis(4-cyanophenyl)sulfide, bis(4-cyanophenyl)sulfone, 4-cyanobenzoic acid 4-cyanophenyl ester, (4-cyanophenyl-4-cyanobenzoate), bis-(4-cyanophenyl)carbonate, 1,3-bis(4-cyanophenyl)adamantane, 1,3-bis(4-cyanophenyl)-5,7-dimethyladamantane, 3,3-bis(4-cyanophenyl)isobenzofuran-1(3H)-one (cyanate ester of phenolphthalein), 3,3-bis(4-cyano-3-methylphenyl)isobenzofuran-1(3H)-one (cyanate ester of o-cresolphthalein), 9,9-bis(4-cyanophenyl)fluorene, 9,9-bis(4-cyano-3-methylphenyl)fluorene, 9,9-bis(2-cyano-5-biphenylyl)fluorene, tris(4-cyanophenyl)methane, 1,1,1-tris(4-cyanophenyl)ethane, 1,1,3-tris(4-cyanophenyl)propane, α,α,α'-tris(4-cyanophenyl)-1-ethyl-4-isopropylbenzene, 1,1,2,2-tetrakis(4-cyanophenyl)ethane, tetrakis(4-cyanophenyl)methane, 2,4,6-tris(N-methyl-4-cyanoanilino)-1,3,5-triazine, 2,4-bis(N-methyl-4-cyanoanilino)-6-(N-methylanilino)-1,3,5-triazine, bis(N-4-cyano-2-methylphenyl)-4,4'-oxybisphthalimide, bis(N-3-cyano-4-methylphenyl)-4,4'-oxybisphthalimide, bis(N-4-cyanophenyl)-4,4'-oxybisphthalimide, bis(N-4-cyano-2-methylphenyl)-4,4'-(hexafluoroisopropylidene)bisphthalimide, tris(3,5-dimethyl-4-cyanobenzyl)isocyanurate, 2-phenyl-3,3-bis(4-cyanophenyl)phthalimidine, 2-(4-methylphenyl)-3,3-bis(4-cyanophenyl)phthalimidine, 2-phenyl-3,3 - Bis(4 - cyanato - 3 - methylphenyl)benzyl methylamide, 1 - methyl - 3,3 - bis(4 - cyanatophenyl)indolin - 2 - one, 2 - phenyl - 3,3 - bis(4 - cyanatophenyl)indolin - 2 - one, phenol novolak resin, cresol novolak resin (a substance obtained by reacting phenol, alkyl - substituted phenol, or halogen - substituted phenol with formaldehyde compounds such as formalin and paraformaldehyde in an acidic solution by a known method), triphenol novolak resin (a substance obtained by reacting hydroxybenzaldehyde with phenol in the presence of an acidic catalyst), fluorene novolak resin (a substance obtained by reacting a pentanone compound with 9,9 - bis(hydroxyaryl)fluorenes in the presence of an acidic catalyst), phenol aralkyl resin, cresol aralkyl resin, naphthol aralkyl resin, biphenyl aralkyl resin (a substance obtained by reacting a bis - halomethyl compound represented by Ar, 4 -(CH 2 Z’) 2 with a phenol compound in the presence or absence of an acidic catalyst), a bis(alkoxymethyl) compound represented by Ar 4 -(CH 2 OR) 2 , a bis(hydroxymethyl) compound represented by Ar 4 -(CH 2 OH) 2 with a phenol compound in the presence of an acidic catalyst, or a substance obtained by polycondensing an aromatic aldehyde compound, an aralkyl compound, or a phenol compound), phenol - modified xylene - formaldehyde resin (a substance obtained by reacting xylene - formaldehyde resin with a phenol compound in the presence of an acidic catalyst by a known method), modified naphthaldehyde resin (a substance obtained by reacting naphthaldehyde resin with a hydroxy - substituted aromatic compound in the presence of an acidic catalyst by a known method), phenol - modified dicyclopentadiene resin, a phenol resin having a polynaphthalene ether structure (a substance obtained by dehydrating and condensing a polyhydroxy naphthalene compound having two or more phenolic hydroxyl groups in one molecule in the presence of a basic catalyst) and other phenol resins by cyanation, etc., are not particularly limited. These cyanate compounds can be used alone or in combination of two or more.

[0627] As preferred cyanate compounds, at least one selected from the group consisting of novolak-type cyanate compounds, naphthol aralkyl-type cyanate compounds (naphthol aralkyl-type cyanates), naphthylene ether-type cyanate compounds, biphenyl aralkyl-type cyanate compounds, xylene resin-type cyanate compounds, triphenol methane-type cyanate compounds, adamantane skeleton-type cyanate compounds, bisphenol M-type cyanate compounds, and bisphenol A-type cyanate compounds can be cited. Among these, from the viewpoint of further improving low water absorption, at least one selected from the group consisting of novolak-type cyanate compounds, naphthol aralkyl-type cyanate compounds, naphthylene ether-type cyanate compounds, xylene resin-type cyanate compounds, bisphenol M-type cyanate compounds, and bisphenol A-type cyanate compounds is preferred, and at least one selected from the group consisting of novolak-type cyanate compounds, naphthol aralkyl-type cyanate compounds, naphthylene ether-type cyanate compounds, bisphenol A-type cyanate compounds, and bisphenol M-type cyanate compounds is more preferred. Further preferably, at least one selected from the group consisting of novolak-type cyanate compounds, naphthol aralkyl-type cyanate compounds, and bisphenol A-type cyanate compounds is selected. Even more preferably, it is a naphthol aralkyl-type cyanate compound and / or a bisphenol A-type cyanate compound, and even more preferably, it is a naphthol aralkyl-type cyanate compound.

[0628] As the naphthol aralkyl-type cyanate compound, a compound represented by the formula (N1) is more preferred.

[0629] Formula (N1)

[0630]

[0631] (In the formula (N1), R 3 each independently represents a hydrogen atom or a methyl group, and n3 represents an integer of 1 or more.)

[0632] In the formula (N1), R 3 each independently represents a hydrogen atom or a methyl group, and preferably a hydrogen atom.

[0633] In the formula (N1), n3 is an integer of 1 or more, preferably an integer of 1 to 50, more preferably an integer of 1 to 20, further preferably an integer of 1 to 10, and even more preferably an integer of 1 to 6.

[0634] In addition, as the novolak-type cyanate compound, there is no particular limitation, and for example, a compound represented by the following formula (VII) is preferred.

[0635]

[0636] (In the formula (VII), R 6Each independently represents a hydrogen atom or a methyl group, and n7 represents an integer of 1 or more.)

[0637] In formula (VII), R 6 Each independently represents a hydrogen atom or a methyl group, preferably a hydrogen atom.)

[0638] In formula (VII), n7 is an integer of 1 or more, preferably an integer of 1 to 20, more preferably an integer of 1 to 10, and still more preferably an integer of 1 to 6.)

[0639] As the bisphenol A type cyanate ester compound, one or more selected from the group consisting of 2,2-bis(4-cyanatophenyl)propane and a prepolymer of 2,2-bis(4-cyanatophenyl)propane can be used.)

[0640] These cyanate ester compounds can be prepared by known methods or commercially available products can also be used. It should be noted that the functional group equivalent number of the cyanate ester compound having a naphthol aralkyl skeleton, a naphthylene ether skeleton, a xylene skeleton, a triphenol methane skeleton, or an adamantane skeleton is relatively large, and the unreacted cyanate group will be less. Therefore, the resin composition using them has a tendency to be more excellent in low water absorption. In addition, mainly due to having an aromatic skeleton or an adamantane skeleton, there is a tendency for the adhesion of the plating to be further improved.)

[0641] When the resin composition of the present embodiment contains a cyanate ester compound, the lower limit value of its content is preferably 1 part by mass or more, more preferably 5 part by mass or more, still more preferably 10 part by mass or more, and may also be 20 part by mass or more, relative to 100 parts by mass of the resin solid content in the resin composition. By making the content of the cyanate ester compound the above lower limit value or more, there is a tendency for the heat resistance, combustion resistance, chemical resistance, low dielectric constant, low dielectric loss tangent, and insulation to be improved. When the resin composition of the present embodiment contains a cyanate ester compound, the upper limit value of the content of the cyanate ester compound is preferably 70 parts by mass or less, more preferably 60 parts by mass or less, still more preferably 50 parts by mass or less, and may also be 40 parts by mass or less, 30 parts by mass or less, relative to 100 parts by mass of the resin solid content in the resin composition.)

[0642] The resin composition in the present embodiment may contain only one kind of cyanate ester compound or may contain two or more kinds. In the case of containing two or more kinds, the total amount is preferably within the above range.)

[0643] <<Thermoplastic elastomer>>

[0644] The resin composition of the present embodiment may contain a thermoplastic elastomer.)

[0645] The thermoplastic elastomer in this embodiment is not particularly limited. For example, at least one selected from the group consisting of polyisoprene, polybutadiene, styrene-butadiene, butyl rubber, ethylene-propylene rubber, styrene-butadiene-ethylene, styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-ethylene-butene-styrene, styrene-propylene-styrene, styrene-ethylene-propylene-styrene, fluororubber, silicone rubber, their hydrogenated compounds, their alkyl compounds, and their copolymers can be cited.

[0646] The number average molecular weight of the thermoplastic elastomer used in this embodiment is preferably 50,000 or more. By setting the number average molecular weight to 50,000 or more, the dielectric properties (low dielectric loss tangent property) of the obtained cured product tend to be more excellent. The number average molecular weight is preferably 60,000 or more, more preferably 70,000 or more, and further preferably 80,000 or more. The upper limit of the number average molecular weight of the thermoplastic elastomer is preferably 400,000 or less, more preferably 350,000 or less, and further preferably 300,000 or less. By setting it below the aforementioned upper limit value, the solubility of the thermoplastic elastomer component in the resin composition tends to increase.

[0647] When the resin composition of this embodiment contains two or more thermoplastic elastomers, it is preferable that the number average molecular weight of their mixture satisfies the above range.

[0648] In this embodiment, the thermoplastic elastomer is preferably a thermoplastic elastomer containing styrene monomer units and conjugated diene monomer units (hereinafter referred to as "thermoplastic elastomer (E)"). By using such a thermoplastic elastomer (E), the dielectric properties (low dielectric loss tangent property) of the obtained cured product are more excellent.

[0649] The above thermoplastic elastomer (E) contains styrene monomer units. By containing styrene monomer units, the solubility of the thermoplastic elastomer (E) in the resin composition is increased. Examples of the styrene monomer include styrene, α-methylstyrene, p-methylstyrene, divinylbenzene (vinylstyrene), N,N-dimethyl-p-aminoethylstyrene, N,N-diethyl-p-aminoethylstyrene, etc. Among these, from the viewpoints of availability and productivity, styrene, α-methylstyrene, and p-methylstyrene are preferred. Among these, styrene is particularly preferred.

[0650] The content of the styrene monomer units in the above thermoplastic elastomer (E) is preferably in the range of 10 to 50% by mass of all monomer units, more preferably in the range of 13 to 45% by mass, and further preferably in the range of 15 to 40% by mass. If the content of the styrene monomer units is 50% by mass or less, the adhesion and bonding properties to substrates and the like will become better. In addition, if it is 10% by mass or more, there is a tendency to be able to suppress excessive adhesion, and it is not easy to generate residual glue and stay marks, and the peelability between the bonding surfaces becomes good, so it is preferred.

[0651] The thermoplastic elastomer (E) may contain only one kind of styrene monomer unit, or may contain two or more kinds. When two or more kinds are contained, the total amount is preferably within the above range.

[0652] The method for measuring the content of the styrene monomer unit in the thermoplastic elastomer (E) of the present embodiment may refer to the description in International Publication No. 2017 / 126469, the content of which is incorporated into this specification. The same applies to the conjugated diene monomer unit and the like described later.

[0653] The above thermoplastic elastomer (E) contains a conjugated diene monomer unit. By containing a conjugated diene monomer unit, the solubility of the thermoplastic elastomer (E) in the resin composition is improved. As the conjugated diene monomer, there is no particular limitation as long as it is a diolefin having a pair of conjugated double bonds. Examples of the conjugated diene monomer include 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, and farnesene. Preferred are 1,3-butadiene and isoprene, and more preferred is 1,3-butadiene.

[0654] The thermoplastic elastomer (E) may contain only one kind of conjugated diene monomer unit, or may contain two or more kinds.

[0655] In the above thermoplastic elastomer (E), the mass ratio of the styrene monomer unit to the conjugated diene monomer unit is preferably in the range of styrene monomer unit / conjugated diene monomer unit = 5 / 95 to 80 / 20, more preferably in the range of 7 / 93 to 77 / 23, and further preferably in the range of 10 / 90 to 70 / 30. If the mass ratio of the styrene monomer unit to the conjugated diene monomer unit is in the range of 5 / 95 to 80 / 20, it is possible to suppress excessive adhesion and maintain high adhesive strength, and the peelability between the adhesive surfaces becomes good.

[0656] In the above thermoplastic elastomer (E), all of the conjugated diene bonds of the thermoplastic elastomer may be hydrogenated, or a part may be hydrogenated, or it may not be hydrogenated.

[0657] The above thermoplastic elastomer (E) may contain other monomer units in addition to the styrene monomer unit and the conjugated diene monomer unit, or may not contain them. Examples of other monomer units include aromatic vinyl compound units other than the styrene monomer unit.

[0658] In the above thermoplastic elastomer (E), it is preferred that the total of the styrene monomer unit and the conjugated diene monomer unit is 90% by mass or more of all monomer units, more preferably 95% by mass or more, further preferably 97% by mass or more, and even more preferably 99% by mass or more.

[0659] As described above, the thermoplastic elastomer (E) may contain only one kind of styrene monomer unit and conjugated diene monomer unit respectively, or may contain two or more kinds. In the case of containing two or more kinds, the total amount is preferably within the above range.

[0660] The thermoplastic elastomer (E) used in the present embodiment may be a block polymer or a random polymer. In addition, it may be a hydrogenated elastomer in which the conjugated diene monomer unit is hydrogenated, an unhydrogenated elastomer in which it is not hydrogenated, or a partially hydrogenated elastomer in which it is partially hydrogenated. An unhydrogenated elastomer or a partially hydrogenated elastomer is preferred.

[0661] In one embodiment of the present embodiment, the thermoplastic elastomer (E) is a hydrogenated elastomer. Here, the hydrogenated elastomer refers to, for example, an elastomer in which the double bond based on the conjugated diene monomer unit in the thermoplastic elastomer is hydrogenated, and includes elastomers with a hydrogenation rate of 80% or more in addition to the elastomer with a hydrogenation rate of 100%. The hydrogenation rate in the hydrogenated elastomer is preferably 85% or more, more preferably 90% or more, and further preferably 95% or more. In the present embodiment, the hydrogenation rate is calculated from 1 the measurement results determined by H-NMR spectroscopy.

[0662] In one embodiment of the present embodiment, the thermoplastic elastomer (E) is an unhydrogenated elastomer. Here, the unhydrogenated elastomer refers to an elastomer in which the proportion of the double bond based on the conjugated diene monomer unit in the elastomer, that is, the hydrogenation rate, is 20% or less. The hydrogenation rate is preferably 15% or less, more preferably 10% or less, and further preferably 5% or less.

[0663] On the other hand, the partially hydrogenated elastomer refers to an elastomer in which a part of the double bond based on the conjugated diene monomer unit in the thermoplastic elastomer is hydrogenated, and generally refers to an elastomer with a hydrogenation rate less than 80% and greater than 20%.

[0664] As commercially available products of the thermoplastic elastomer (E) used in the present embodiment, SEPTON (registered trademark) 2104, V9461, S8104 manufactured by Kuraray Co., Ltd., S.O.E. (registered trademark) S1606, S1613, S1609, S1605 manufactured by Asahi Kasei Corporation, H1041, H1043, P2000, MP10 of TUFTEC (registered trademark) manufactured by Asahi Kasei Corporation, DYNARON (registered trademark) 9901P, TR2250 manufactured by JSR Corporation, etc. can be exemplified.

[0665] In addition, the elastomer used in the present embodiment may also be a liquid diene. A liquid diene refers to a liquid elastomer containing conjugated diene monomer units. Examples of the conjugated diene monomer include 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, and farnesene. Preferred are 1,3-butadiene and isoprene, and more preferred is 1,3-butadiene.

[0666] Examples of the liquid diene used in the present embodiment include liquid polybutadiene, liquid polyisoprene, modified products of liquid polybutadiene, modified products of liquid polyisoprene, liquid acrylonitrile-butadiene copolymers, and liquid styrene-butadiene copolymers.

[0667] In addition, regarding the number average molecular weight of the liquid diene, there is no particular limitation as long as it is liquid at 20°C, and it is preferably 500 or more and 10,000 or less.

[0668] When the resin composition of the present embodiment contains a thermoplastic elastomer (preferably thermoplastic elastomer (E)), its content is preferably 1 part by mass or more, more preferably 5 parts by mass or more, still more preferably 8 parts by mass or more, and depending on the use, etc., it may also be 10 parts by mass or more, 12 parts by mass or more, relative to 100 parts by mass of the resin solid content in the resin composition. By setting it to the above lower limit value or more, there is a tendency for the dielectric properties (low dielectric loss tangent property), low water absorption, and chemical resistance to be further improved. In addition, the upper limit value of the content of the thermoplastic elastomer is preferably 45 parts by mass or less, more preferably 40 parts by mass or less, still more preferably 35 parts by mass or less, even more preferably 32 parts by mass or less, and even more preferably 28 parts by mass or less, relative to 100 parts by mass of the resin solid content in the resin composition. By setting it to the above upper limit value or less, there is a tendency for the heat resistance to be further improved.

[0669] The resin composition of the present embodiment may contain only one type of thermoplastic elastomer, or may contain two or more types. In the case of containing two or more types, the total amount is preferably within the above range.

[0670] In addition, for details of the arylcyclobutene resin, polyamide resin, polyimide resin, perfluoro vinyl ether resin, and petroleum resin, reference can be made to the descriptions in paragraphs 0198 to 0200 and 0232 to 0242 of International Publication No. 2023 / 176765, the content of which is incorporated into this specification.

[0671] <Filler (D)>

[0672] The resin composition of the present embodiment preferably contains a filler (D). By containing the filler (D), physical properties such as the low dielectric property (low dielectric constant property, low dielectric loss tangent property, etc.), flame retardancy, and low thermal expansibility of the resin composition and its cured product can be further improved.

[0673] In addition, the filler (D) used in the present embodiment preferably has excellent low dielectric property. For example, the relative dielectric constant (Dk) at a frequency of 10 GHz measured by the cavity resonator perturbation method of the filler (D) used in the present embodiment is preferably 8.0 or less, more preferably 6.0 or less, and further preferably 4.0 or less. In addition, the lower limit value of the relative dielectric constant is, for example, preferably 2.0 or more in practice. In addition, the dielectric loss tangent (Df) at a frequency of 10 GHz measured by the cavity resonator perturbation method of the filler (D) used in the present embodiment is preferably 0.05 or less, more preferably 0.01 or less. In addition, the lower limit value of the dielectric loss tangent is, for example, preferably 0.0001 or more in practice.

[0674] The type of the filler (D) used in the present embodiment is not particularly limited, and fillers commonly used in the technical field can be suitably used. Specifically, silica such as natural silica, fused silica, synthetic silica, amorphous silica, AEROSIL, and hollow silica can be mentioned; metal oxides such as alumina, white carbon, titanium white, titanium oxide, zinc oxide, magnesium oxide, and zirconium oxide; composite oxides such as zinc borate, zinc stannate, forsterite, barium titanate, strontium titanate, and calcium titanate; nitrides such as boron nitride, aggregated boron nitride, silicon nitride, and aluminum nitride; metal hydroxides (including hydrates) such as aluminum hydroxide, heat-treated aluminum hydroxide (a substance obtained by heat-treating aluminum hydroxide and reducing a part of the crystal water), boehmite, and magnesium hydroxide; molybdenum compounds such as molybdenum oxide and zinc molybdate; inorganic fillers such as barium sulfate, 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, and spherical glass; and organic fillers such as rubber powders of styrene type, butadiene type, and acrylic type, core-shell rubber powders, silicone resin powders, silicone rubber powders, and silicone composite powders.

[0675] In the present embodiment, the filler (D) preferably contains an inorganic filler, more preferably contains one or more selected from the group consisting of silica, aluminum hydroxide, aluminum nitride, boron nitride, forsterite, titanium oxide, barium titanate, strontium titanate, and calcium titanate. From the viewpoint of low dielectric properties, it is more preferably contains one or more selected from the group consisting of silica and aluminum hydroxide, and further preferably contains silica. By using these fillers, the properties such as heat resistance, low dielectric properties, thermal expansion characteristics, dimensional stability, and flame retardancy of the cured product of the resin composition are further improved.

[0676] The content of the filler (D) in the resin composition of the present embodiment can be appropriately set according to the desired properties and is not particularly limited. Relative to 100 parts by mass of the resin solid content in the resin composition, it is preferably 1 part by mass or more, more preferably 5 parts by mass or more, further preferably 10 parts by mass or more, still more preferably 30 parts by mass or more, still more preferably 50 parts by mass or more, still more preferably 80 parts by mass or more, still more preferably 100 parts by mass or more, and may also be 120 parts by mass or more. By setting the content of the filler (D) to the above lower limit value or more, there is a tendency for further improvement in low thermal expansibility and low dielectric loss tangent. In addition, relative to 100 parts by mass of the resin solid content in the resin composition, the upper limit value of the content of the filler (D) is preferably 1600 parts by mass or less, more preferably 1200 parts by mass or less, further preferably 800 parts by mass or less, still more preferably 500 parts by mass or less, still more preferably 300 parts by mass or less, still more preferably 200 parts by mass or less. By setting the content of the filler (D) to the above upper limit value or less, there is a tendency for further improvement in moldability.

[0677] In the resin composition of the present embodiment, as an example of a preferred embodiment, a mode in which the content of the filler (D) is 1 to 95% by mass of the components other than the solvent can be exemplified, and it is preferably 30 to 80% by mass.

[0678] The resin composition of the present embodiment may contain only one type of filler (D), or may contain two or more types. In the case of containing two or more types, the total amount is preferably within the above range.

[0679] In the resin composition of the present embodiment, when using the filler (D), especially when using an inorganic filler, a silane coupling agent can be further contained. By containing the silane coupling agent, there is a tendency for further improvement in the dispersibility of the filler (D) and the adhesive strength between the resin component, the filler (D), and the substrate described later.

[0680] As the silane coupling agent, there is no particular limitation, and examples thereof include silane coupling agents usually used in the surface treatment of inorganic substances, such as amino silane compounds (e.g., γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, etc.), epoxy silane compounds (e.g., γ-glycidoxypropyltrimethoxysilane, etc.), vinyl silane compounds (e.g., vinyltrimethoxysilane, etc.), styryl silane compounds (e.g., p-styryltrimethoxysilane, etc.), acrylic silane compounds (e.g., γ-acryloxypropyltrimethoxysilane, etc.), cationic silane compounds (e.g., N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride, etc.), phenyl silane compounds, etc. The silane coupling agent can be used alone or in combination of two or more.

[0681] In particular, as the silane coupling agent, at least one selected from the group consisting of vinyl silane compounds, acrylic silane compounds, and styryl silane compounds is used, and a compound containing a vinyl aryl group (especially a polymer having a structural unit represented by formula (V)) is used, whereby there is a tendency to further improve the low dielectric property. Further, by using at least one selected from the group consisting of vinyl silane compounds, acrylic silane compounds, and styryl silane compounds, and combining a compound containing a vinyl aryl group (especially a polymer having a structural unit represented by formula (V)) and a thermoplastic elastomer, there is a tendency to further improve the low dielectric property.

[0682] The content of the silane coupling agent is not particularly limited and can be 0.1 to 5.0 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition.

[0683] <Monomer or oligomer having an ethylenically unsaturated group>

[0684] In the resin composition of the present embodiment, in order to improve the thermosetting property and the curability based on active energy rays (e.g., photocurability based on ultraviolet rays, etc.), a monomer or oligomer having an ethylenically unsaturated group may also be used in combination. The oligomer or monomer having an ethylenically unsaturated group used in the present embodiment is not particularly limited as long as it is an oligomer or monomer having one or more ethylenically unsaturated groups in one molecule. Examples thereof include monomers or oligomers having vinyl, isopropenyl, allyl, (meth)acryloyl, vinylidene, etc., preferably monomers or oligomers having vinyl, isopropenyl, allyl, (meth)acryloyl, etc., and more preferably monomers or oligomers having vinyl.

[0685] It should be noted that in this specification, a compound that belongs to a monomer or oligomer having an ethylenically unsaturated group and also belongs to a polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds is regarded as a polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds.

[0686] More specifically, as the monomer having an ethylenically unsaturated group, a compound (F1) (compound (F1)) having a molecular weight of less than 1000 and containing one organic group having an ethylenically unsaturated bond in the molecule can be cited.

[0687] The ethylenically unsaturated bond constituting the aforementioned organic group having an ethylenically unsaturated bond does not include an ethylenically unsaturated bond contained as a part of an aromatic ring. On the other hand, it includes an ethylenically unsaturated bond contained as a part of a non-aromatic ring. Examples of the ethylenically unsaturated bond contained as a part of a non-aromatic ring include a cyclohexenyl group in the molecule. In addition, it also includes a part other than the terminal of a linear or branched organic group, that is, an ethylenically unsaturated bond contained in the linear or branched chain.

[0688] The aforementioned organic group having an ethylenically unsaturated bond is more preferably one selected from the group consisting of vinyl, isopropenyl, allyl, acryloyl, methacryloyl, and vinylidene, more preferably one selected from the group consisting of vinyl, isopropenyl, allyl, acryloyl, and methacryloyl, and further preferably vinyl.

[0689] In addition, in this specification, a compound that belongs to a monomer or oligomer having an ethylenically unsaturated group and also belongs to a silane coupling agent is regarded as a silane coupling agent.

[0690] The compound (F1) used in this embodiment is preferably composed only of atoms selected from carbon atoms, hydrogen atoms, oxygen atoms, and silicon atoms, and more preferably composed only of atoms selected from carbon atoms, hydrogen atoms, and oxygen atoms.

[0691] In addition, the compound (F1) used in this embodiment may or may not have a polar group. The compound (F1) used in this embodiment preferably does not have a polar group. Examples of the polar group include an amino group, a carboxyl group, a hydroxyl group, and a nitro group.

[0692] In this embodiment, the molecular weight of the compound (F1) is preferably 70 or more, more preferably 80 or more, and still more preferably 90 or more. By setting it to be the above lower limit value or more, there is a tendency to suppress the volatilization of the compound (F1) from the resin composition, its cured product, etc. of this embodiment. The upper limit of the molecular weight of the aforementioned compound (F1) is preferably 500 or less, more preferably 400 or less, still more preferably 300 or less, even more preferably 200 or less, and may also be 150 or less. By setting it to be the above upper limit value or less, there is a tendency for the effect of further improving the reactivity with other thermoplastic resin components to be further improved.

[0693] When the resin composition of this embodiment contains two or more kinds of the compound (F1), it is preferable that the average molecular weight value of the compound (F1) is within the above range, and more preferably the molecular weight of each compound is within the above preferable range.

[0694] In this embodiment, the boiling point of the compound (F1) is preferably 110 °C or more, more preferably 115 °C or more, and still more preferably 120 °C or more. By setting it to be the above lower limit value or more, it is possible to suppress the volatilization of the compound (F1) when the resin composition is thermally cured, and to cause the thermosetting resin (C) to react with the compound (F1). The boiling point of the aforementioned compound (F1) is preferably 300 °C or less, more preferably 250 °C or less, and still more preferably 200 °C or less. By setting it to be the above upper limit value or less, it is possible to make it less likely to remain in the cured product in the form of a residual solvent.

[0695] When the resin composition of this embodiment contains two or more kinds of the compound (F1), it is sufficient that the average value of the boiling points falls within the above range, and preferably the boiling point of each compound is within the above preferable range.

[0696] Examples of the compound (F1) include (meth)acrylate compounds, aromatic vinyl compounds (preferably styrene-based compounds), saturated fatty acid vinyl compounds, vinyl cyanide compounds, olefinically unsaturated carboxylic acids, olefinically unsaturated carboxylic anhydrides, monoalkyl esters of olefinically unsaturated dicarboxylic acids, olefinically unsaturated carboxamides, etc. Preferably, it is at least one selected from the group consisting of (meth)acrylate compounds, aromatic vinyl compounds, and saturated fatty acid vinyl compounds, and more preferably an aromatic vinyl compound.

[0697] As specific examples when the compound (F1) is an aromatic vinyl compound, styrene (e.g., 4-methylstyrene), ethyl vinylbenzene, diethyl 4-vinylbenzyl phosphonate, 4-vinylbenzyl glycidyl ether, α-methylstyrene, 4-tert-butylstyrene, divinylbenzene, 1,2-bis(4-vinylphenyl)ethane (BVPE), and vinylbenzyl ether can be mentioned. Styrene (e.g., 4-methylstyrene), ethyl vinylbenzene, diethyl 4-vinylbenzyl phosphonate, 4-vinylbenzyl glycidyl ether, α-methylstyrene, etc. can be exemplified.

[0698] In addition, as specific examples of the compound (F1), reference can be made to the descriptions in paragraphs 0046 and 0049 of Japanese Unexamined Patent Application Publication No. 2019-194312, the contents of which are incorporated into this specification.

[0699] As specific examples when the compound (F1) has a vinylene group, acenaphthylene and pyrazylene are preferred, and acenaphthylene is more preferred.

[0700] In this specification, as in the case of the imidazole compound described later, a compound that also corresponds to a compound having a vinylene group and is explicitly stated as a component other than the compound having a vinylene group (e.g., a curing accelerator) is regarded as not belonging to the compound having a vinylene group.

[0701] On the other hand, in order to improve the low dielectric constant property and the low dielectric loss tangent property, the resin composition of this embodiment preferably further contains a styrene oligomer (F2). The styrene oligomer (F2) of this embodiment is preferably polymerized from at least one selected from the group consisting of styrene, the above-mentioned styrene derivatives, and vinyltoluene. The number average molecular weight of the styrene oligomer (F2) is preferably 178 or more, and preferably 1600 or less. In addition, the styrene oligomer (F2) is preferably a compound having an average aromatic ring number of 2 to 14, the total amount of aromatic ring numbers of 2 to 14 being 50% by mass or more, a boiling point of 300°C or more, and no branched structure.

[0702] As the styrene oligomer (F2) used in this embodiment, for example, styrene polymers, vinyltoluene polymers, α-methylstyrene polymers, vinyltoluene-α-methylstyrene polymers, styrene-α-styrene polymers, etc. can be cited. As the styrene polymer, commercially available products can be used. For example, Piccolastic A5 (manufactured by Eastman Chemical Company), Piccolastic A-75 (manufactured by Eastman Chemical Company), Piccotex 75 (manufactured by Eastman Chemical Company), FTR-8100 (manufactured by Mitsui Chemicals, Inc.), FTR-8120 (manufactured by Mitsui Chemicals, Inc.) can be cited. In addition, as the vinyltoluene-α-methylstyrene polymer, Piccotex LC (manufactured by Eastman Chemical Company) can be cited. In addition, as the α-methylstyrene polymer, Kristalex 3070 (manufactured by Eastman Chemical Company), Kristalex 3085 (manufactured by Eastman Chemical Company), Kristalex (3100), Kristalex 5140 (manufactured by Eastman Chemical Company), FMR-0100 (manufactured by Mitsui Chemicals, Inc.), FMR-0150 (manufactured by Mitsui Chemicals, Inc.) can be cited. In addition, as the styrene-α-styrene polymer, FTR-2120 (manufactured by Mitsui Chemicals, Inc.) can be cited. These styrene oligomers can be used alone or in combination of two or more.

[0703] In the resin composition of this embodiment, the α-methylstyrene oligomer is preferably used because it cures thermally well, has good fillability for fine wiring, and is excellent in solder heat resistance, low relative dielectric constant, and low dielectric loss tangent.

[0704] In addition, in order to improve the low dielectric constant property and low dielectric loss tangent property, the resin composition of this embodiment preferably further contains a divinyl compound (F3) as a monomer having an ethylenically unsaturated group.

[0705] The divinyl compound is a low-molecular compound having two vinyl groups. By having two vinyl groups, a good crosslinking density that does not increase too much is achieved. As a result, the free volume of the molecules becomes large, and thus the dielectric loss tangent (Df) of the obtained cured product can be suppressed to a small value. Furthermore, it is considered that the divinyl compound (F3) is used as a substitute for a part of the polymaleimide compound (A), the compound (B) containing two or more polymerizable carbon-carbon unsaturated double bonds, and other resin components (C). Therefore, the decrease in the content of the component having a polar group itself also contributes to the decrease in the dielectric loss tangent (Df). In addition, it is considered that by making both of the two functional groups of the divinyl compound vinyl groups, the reactivity with the polymaleimide compound (A) and the compound (B) containing two or more polymerizable carbon-carbon unsaturated double bonds becomes good. As a result, there is a tendency for the heat resistance to be easily improved.

[0706] It should be noted that the divinyl compound (F3) here refers to a compound having a molecular weight lower than 195, and the lower limit value of the molecular weight is 54 in reality. Examples of the divinyl compound (F3) include divinylbenzene and 1,3-divinyltetramethylsiloxane.

[0707] In addition, for details of the monomer or oligomer having an ethylenic unsaturated group, reference can be made to paragraphs 0069 to 0087 of International Publication No. 2017 / 135168 and paragraphs 0065 to 0067 of International Publication No. 2019 / 230945, the contents of which are incorporated herein by reference.

[0708] In particular, by using a monomer or oligomer having an ethylenic unsaturated group and using an elastomer as the other resin component (C), a resin composition having excellent low dielectric properties and excellent moisture absorption heat resistance can be obtained.

[0709] In addition, in particular, by using a monomer or oligomer having an ethylenic unsaturated group and using a compound containing a vinyl aryl group (especially a polymer having a structural unit represented by the formula (V)), a resin composition having excellent low dielectric properties and excellent moisture absorption heat resistance can be obtained.

[0710] When the resin composition of the present embodiment contains a monomer or oligomer having an ethylenically unsaturated group, its content is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, further preferably 2 parts by mass or more, still more preferably 3 parts by mass or more, and further may be 5 parts by mass or more, relative to 100 parts by mass of the resin solid content in the resin composition. By setting it to the above lower limit value or more, there is a tendency for the low dielectric property to be further improved. In addition, the upper limit value of the content of the monomer or oligomer having an ethylenically unsaturated group is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, further preferably 20 parts by mass or less, still more preferably 15 parts by mass or less, and still more preferably 10 parts by mass or less, relative to 100 parts by mass of the resin solid content in the resin composition. By setting it to the above upper limit value or less, there is a tendency for the heat resistance to be further improved. In addition, there is a tendency for the low dielectric constant property, low dielectric loss tangent property, and chemical resistance to be further improved.

[0711] The resin composition of the present embodiment may contain only one kind of monomer or oligomer having an ethylenically unsaturated group, or may contain two or more kinds. In the case of containing two or more kinds, the total amount is preferably in the above range.

[0712] <Active ester compound>

[0713] The resin composition of the present embodiment may contain an active ester compound.

[0714] The active ester compound is not particularly limited, and examples thereof include compounds having two or more (preferably 2 to 12, more preferably 2 to 6, further preferably 2 to 4, still more preferably 2 or 3, and still more preferably 2) active ester groups in one molecule.

[0715] The active ester compound may be a linear, branched, or cyclic compound. Among them, from the viewpoint of further improving the heat resistance of the obtained cured product, an active ester compound obtained by reacting a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound is preferred, and an active ester compound obtained by reacting a carboxylic acid compound with one or more compounds selected from the group consisting of a phenol compound, a naphthol compound, and a thiol compound is more preferred. An aromatic compound having two or more active ester groups in one molecule obtained by reacting a carboxylic acid compound with an aromatic compound having a phenolic hydroxyl group is further preferred, and an aromatic compound having two or more active ester groups in one molecule obtained by reacting a compound having two or more carboxylic acids in one molecule with an aromatic compound having a phenolic hydroxyl group is particularly preferred.

[0716] Examples of the carboxylic acid compound include one or more selected from the group consisting of benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Among them, from the viewpoint of further improving the heat resistance of the obtained cured product, one or more selected from the group consisting of succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, and terephthalic acid are preferred, and one or more selected from the group consisting of isophthalic acid and terephthalic acid are more preferred.

[0717] Examples of the thiocarboxylic acid compound include one or more selected from thioacetic acid and thiobenzoic acid.

[0718] Examples of the phenol compound or naphthol compound include one or more selected from the group consisting of hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, pyrogallol, dicyclopentadienyl diphenol, and phenol novolac. From the viewpoint of further improving the heat resistance and solvent solubility of the obtained cured product, bisphenol A, bisphenol F, bisphenol S, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, pyrogallol, dicyclopentadienyl diphenol, and phenol novolac are preferred. More preferably, one or more selected from the group consisting of catechol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, pyrogallol, dicyclopentadienyl diphenol, and phenol novolac are selected. Further preferably, one or more selected from the group consisting of 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyl diphenol, and phenol novolac are selected. Particularly preferably, one or more selected from the group consisting of dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyl diphenol, and phenol novolac are selected (preferably one or more selected from the group consisting of dicyclopentadienyl diphenol and phenol novolac, and more preferably dicyclopentadienyl diphenol).

[0719] Examples of the thiol compound include one or more selected from the group consisting of benzenedithiol and triazinedithiol.

[0720] Further, from the viewpoint of further improving the compatibility with the epoxy compound, the active ester compound is preferably a compound having two or more carboxylic acids in one molecule and containing an aliphatic chain, and from the viewpoint of further improving the heat resistance, it is preferably a compound having an aromatic ring. As a more specific active ester compound, the active ester compounds described in JP-A-2004-277460 can be cited.

[0721] The active ester compound can be a commercially available product or can be prepared by a known method. As commercially available products, compounds containing a dicyclopentadienyl diphenol structure (for example, EXB9451, EXB9460, EXB9460S, HPC-8000-65T (all manufactured by DIC Corporation), etc.), acetylated products of phenol novolac (for example, DC808 (manufactured by Mitsubishi Chemical Corporation)), and benzoylated products of phenol novolac (for example, YLH1026, YLH1030, YLH1048 (all manufactured by Mitsubishi Chemical Corporation)) can be cited. From the viewpoint of further improving the storage stability of the varnish and the low thermal expansion property of the resin composition when cured (cured product), EXB9460S is preferred.

[0722] The active ester compound can be prepared by a known method. For example, it can be obtained by a condensation reaction of a carboxylic acid compound and a hydroxy compound. As a specific example, a method of reacting (a) a carboxylic acid compound or its halide, (b) a hydroxy compound, and (c) an aromatic monohydroxy compound in a ratio of 1 mole of the carboxyl group or acyl halide group of (a), 0.05 to 0.75 moles of the phenolic hydroxy group of (b), and 0.25 to 0.95 moles of (c) can be cited.

[0723] It is preferably included within the range not impairing the effects of the present invention. When the resin composition of the present embodiment contains an active ester compound, it is preferably 1 part by mass or more, and preferably 50 parts by mass or less, relative to 100 parts by mass of the resin solid content in the resin composition.

[0724] The resin composition in the present embodiment may contain only one kind of active ester compound or may contain two or more kinds. When two or more kinds are contained, the total amount is preferably within the above range.

[0725] Further, the resin composition in the present embodiment may be configured to substantially not contain an active ester compound. Substantially not containing means that the content of the active ester compound is less than 1 part by mass, preferably less than 0.1 part by mass, and more preferably less than 0.01 part by mass, relative to 100 parts by mass of the resin solid content in the resin composition.

[0726] <Dispersant>

[0727] The resin composition of this embodiment may also contain a dispersant. As the dispersant, a dispersant commonly used for coatings can be suitably used, and its type is not particularly limited. A wetting dispersant with a copolymer matrix is preferably used as the dispersant. Specific examples include DISPERBYK (registered trademark)-110, 111, 161, 180, 2009, 2152, 2155 manufactured by BYK Japan Co., Ltd., BYK (registered trademark)-W996, W9010, W903, W940, etc.

[0728] When the resin composition of this embodiment contains a dispersant, the lower limit of its content is preferably 0.01 part by mass or more, more preferably 0.1 part by mass or more, and may be 0.3 part by mass or more, based on 100 parts by mass of the resin solid content in the resin composition. In addition, the upper limit of the content of the dispersant is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and further preferably 3 parts by mass or less, based on 100 parts by mass of the resin solid content in the resin composition.

[0729] The dispersant can be used alone or in combination of two or more. When two or more are used, the total amount falls within the above range.

[0730] <Curing accelerator>

[0731] 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 imidazoles such as 2-ethyl-4-methylimidazole and triphenylimidazole; organic peroxides such as benzoyl peroxide, bis(1-methyl-1-phenylethyl) peroxide, di-tert-butyl peroxide, lauroyl peroxide, acetyl peroxide, p-chlorobenzoyl peroxide, di-tert-butyl diperoxyphthalate, α,α'-bis(tert-butylperoxy) diisopropylbenzene, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hex-3-yne; azo compounds such as azodinitrile (e.g., azobisisobutyronitrile); tertiary amines such as N,N-dimethylbenzylamine, N,N-dimethylaniline, N,N-dimethyltoluidine, 2-N-ethylphenylaminoethanol, tri-n-butylamine, pyridine, quinoline, N-methylmorpholine, triethanolamine, triethylenediamine, tetramethylbutanediamine, N-methylpiperidine; phenols such as phenol, xylenol, cresol, resorcinol, catechol; high-temperature decomposition type radical generators such as 2,3-dimethyl-2,3-diphenylbutane; organic metal salts such as lead naphthenate, lead stearate, zinc naphthenate, zinc octoate, manganese octoate, tin oleate, dibutyltin maleate, manganese naphthenate, cobalt naphthenate, iron acetylacetonate; substances obtained by dissolving these organic metal salts in hydroxy group-containing compounds such as phenol and bisphenol; inorganic metal salts such as tin chloride, zinc chloride, aluminum chloride; organic tin compounds such as dioctyltin oxide, other alkyltin, and alkyltin oxide, etc.

[0732] The curing accelerator is preferably at least one selected from the group consisting of imidazoles, organic peroxides, and organic metal salts, more preferably at least one selected from the group consisting of imidazoles and organic metal salts, and still more preferably imidazoles.

[0733] In addition, in the present embodiment, a configuration substantially free of polymerization initiators such as organic peroxides and azo compounds may be adopted. Substantially free means that the content of the polymerization initiator is less than 0.1 part by mass relative to 100 parts by mass of the resin solid content in the resin composition.

[0734] When the resin composition of the present embodiment contains a curing accelerator, the lower limit value of its content is preferably 0.005 part by mass or more, more preferably 0.01 part by mass or more, and still more preferably 0.1 part by mass or more relative to 100 parts by mass of the resin solid content in the resin composition. In addition, the upper limit value of the content of the curing accelerator is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, still more preferably 3 parts by mass or less, and even more preferably 32 parts by mass or less relative to 100 parts by mass of the resin solid content in the resin composition.

[0735] The curing accelerator can be used alone or in combination of two or more kinds. When two or more kinds are used, the total amount falls within the above range.

[0736] <Flame retardant>

[0737] The resin composition of the present embodiment may contain a flame retardant. Examples of the flame retardant include phosphorus-based flame retardants, halogen-based flame retardants, inorganic flame retardants, and silicone-based flame retardants, with phosphorus-based flame retardants being preferred.

[0738] As the flame retardant, known flame retardants can be used, such as halogen-based flame retardants like brominated epoxy resin, brominated polycarbonate, brominated polystyrene, brominated styrene, brominated phthalimide, tetrabromobisphenol A, pentabromobenzyl (meth)acrylate, pentabromotoluene, tribromophenol, hexabromobenzene, decabromodiphenyl ether, bis-1,2-pentabromophenyl ethane, chlorinated polystyrene, chlorinated paraffin; phosphorus-based flame retardants like red phosphorus, tricresyl phosphate, triphenyl phosphate, tolyldiphenyl phosphate, tris(dimethylphenyl) phosphate, trialkyl phosphate, dialkyl phosphate, tris(2-chloroethyl) phosphate, phosphazene, 1,3-phenylene bis(2,6-bis(dimethylphenyl) phosphate), 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide; inorganic flame retardants like aluminum hydroxide, magnesium hydroxide, partial boehmite, boehmite, zinc borate, antimony trioxide; and silicone-based flame retardants like silicone rubber, silicone resin.

[0739] In the present embodiment, among these compounds, 1,3-phenylene bis(2,6-di(dimethylphenyl)) phosphate is preferred because it does not impair the low dielectric property.

[0740] When the resin composition of the present embodiment contains a flame retardant, its content is preferably 1 part by mass or more, more preferably 5 parts by mass or more, based on 100 parts by mass of the resin solid content in the resin composition. In addition, the lower limit value of the content of the aforementioned flame retardant is preferably 25 parts by mass or less, more preferably 20 parts by mass or less.

[0741] The flame retardant can be used alone or in combination of two or more kinds. When two or more kinds are used, the total amount falls within the above range.

[0742] <Solvent>

[0743] The resin composition of the present embodiment may contain a solvent, preferably an organic solvent. When a solvent is contained, 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-mentioned various resin solid components are dissolved or compatible with 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-mentioned various resin solid components. Examples of polar organic solvents include 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.), and examples of non-polar organic solvents include aromatic hydrocarbons (such as toluene, xylene, etc.).

[0744] The solvent may be used alone or in combination of two or more. When two or more are used, the total amount is within the above range.

[0745] <Other components>

[0746] In addition to the above components, the resin composition of the present embodiment may also contain various high molecular compounds such as thermoplastic resins and their oligomers, and various additives. Examples of additives include ultraviolet absorbers, antioxidants, photoinitiators, fluorescent brighteners, photosensitizers, dyes, pigments, thickeners, flow regulators, lubricants, defoamers, leveling agents, brighteners, polymerization inhibitors, etc. These additives may be used alone or in combination of two or more.

[0747] <Use>

[0748] The resin composition of the present embodiment can be used in the form of a cured product. Specifically, the resin composition of the present embodiment can be suitably used as a resin composition for electronic materials such as an insulating layer of a printed circuit board and a material for a semiconductor package as a low relative permittivity material and / or a low dielectric loss tangent material. The resin composition of the present embodiment can be suitably used as a prepreg, a metal-clad laminate using the prepreg, a resin composite sheet, and a material for a printed circuit board.

[0749] The resin composition of the present embodiment can be used as a prepreg, a resin composite sheet, or other layered (including film-like and sheet-like) materials that form an insulating layer of a printed circuit board. When manufacturing such layered materials, the thickness is preferably 5 μm or more, more preferably 10 μm or more. As the upper limit of the thickness, it is preferably 200 μm or less, more preferably 180 μm or less. It should be noted that the thickness of the above-mentioned layered material refers to the thickness including the glass cloth, etc. in the case where the resin composition of the present embodiment is infiltrated into a glass cloth or the like.

[0750] The material 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.

[0751] <<Prepreg>>

[0752] The prepreg of the present embodiment is formed from a base material (prepreg base material) and the resin composition of the present embodiment. The prepreg of the present embodiment can be obtained, for example, by applying (such as infiltrating and / or coating) the resin composition of the present embodiment to the base material and then semi-curing it by heating (such as a method of drying at 120 to 220 °C for 2 to 15 minutes). At this time, the adhesion amount of the resin composition to the base material, that is, the amount of the resin composition relative to the total amount of the semi-cured prepreg (including the filler (D)) is preferably in the range of 20 to 99% by mass, more preferably in the range of 20 to 80% by mass.

[0753] The base material is not particularly limited as long as it is a base material for various printed circuit board materials. Examples of the material of the base material include glass fibers (such as E-glass, D-glass, L-glass, S-glass, T-glass, Q-glass, UN-glass, NE-glass, spherical glass, etc.), inorganic fibers other than glass (such as quartz, etc.), and organic fibers (such as polyimide, polyamide, polyester, liquid crystal polyester, polytetrafluoroethylene, etc.). The form of the base material is not particularly limited, and examples include woven fabric, non-woven fabric, roving, chopped glass mat, surface mat, etc. 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 that has been subjected to an ultra-fibrillation treatment and a caulking treatment is preferred. From the viewpoints of strength and low water absorption, the base material is preferably a glass woven fabric with a thickness of 200 μm or less and a mass of 250 g / m 2 Hereinafter, from the viewpoint of moisture absorption and heat resistance, a glass woven fabric that has been surface-treated with a silane coupling agent such as epoxy silane or amino silane is preferred. From the viewpoint of electrical properties, a low-dielectric glass cloth formed from glass fibers such as L-glass, NE-glass, and Q-glass that exhibit a low relative dielectric constant and a low dielectric loss tangent is more preferred.

[0754] Examples of substrates with low relative permittivity include substrates having a relative permittivity of 5.0 or less (preferably 3.0 to 4.9). Examples of substrates with low tangent of dielectric loss angle include substrates having a tangent of dielectric loss angle of 0.006 or less (preferably 0.001 to 0.005). The relative permittivity and the tangent of dielectric loss angle are values measured at a frequency of 10 GHz using a perturbed cavity resonator.

[0755] <<Metal-clad laminate>>

[0756] The metal-clad laminate of the present embodiment includes: at least one layer formed from the prepreg of the present embodiment, and a metal foil disposed on one or both sides of the layer formed from the aforementioned prepreg. As a method for manufacturing the metal-clad laminate of the present embodiment, for example, the following method can be cited: arranging at least one sheet (preferably overlapping two or more sheets) of the prepreg of the present embodiment, disposing a metal foil on one or both sides thereof, and performing laminate forming. More specifically, it can be manufactured by disposing a metal foil such as copper or aluminum on one or both sides of the prepreg and performing laminate forming. As the number of prepreg sheets, it is preferably 1 to 10 sheets, more preferably 2 to 10 sheets, and further preferably 2 to 9 sheets.

[0757] The metal foil is not particularly limited as long as it is a metal foil for printed circuit board materials, and examples thereof include rolled copper foil, electrolytic copper foil, and the like. The thickness of the metal foil (preferably copper foil) is not particularly limited and can be about 1.5 to 70 μm. When using copper foil as the metal foil, as the copper foil, the roughness Rz of the copper foil surface measured in accordance with JIS B0601:2013 is preferably adjusted to 0.2 to 4.0 μm. By setting the roughness Rz of the copper foil surface to 0.2 μm or more, the roughness of the copper foil surface becomes an appropriate size, and the copper foil peel strength tends to be further improved. On the other hand, by setting the roughness Rz of the copper foil surface to 4.0 μm or less, the roughness of the copper foil surface becomes an appropriate size, and the tangent of dielectric loss angle characteristics of the obtained cured product tend to be further improved. From the viewpoints of copper foil peel strength and reduction of the tangent of dielectric loss angle, the roughness Rz of the copper foil surface is more preferably 0.5 μm or more, further preferably 0.6 μm or more, particularly preferably 0.7 μm or more, and also more preferably 3.5 μm or less, further preferably 3.0 μm or less, and particularly preferably 2.0 μm or less.

[0758] As a method for laminate forming, methods commonly used for forming printed circuit board laminates and multilayer boards can be cited. More specifically, it can be cited that a multi-stage press, a multi-stage vacuum press, a continuous forming machine, an autoclave forming machine, etc. are used 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 at about left and right or about 1 to 10 MPa. In addition, a multilayer board can also be manufactured by combining the prepreg of the present embodiment with an inner-layer circuit board manufactured separately and performing laminating and forming. As a method of manufacturing a multilayer board, for example, copper foils of about 35 μm can be disposed on both sides of one prepreg of the present embodiment, and an inner-layer circuit is formed after laminating and forming using the above-described forming method. The circuit is subjected to blackening treatment to form an inner-layer circuit board. Then, one inner-layer circuit board and the prepreg of the present embodiment are alternately disposed one by one, and copper foils are further disposed on the outermost layer. Laminating and forming is performed under the above conditions, preferably under vacuum, thereby manufacturing a multilayer board. The metal foil-clad laminate of the present embodiment can be suitably used as a printed circuit board.

[0759] In addition, the metal foil-clad laminate of the present embodiment preferably has a low relative dielectric constant (Dk) measured using a laminate from which the metal foil has been removed by etching. Specifically, for a sample obtained by removing the metal foil from the metal foil-clad laminate by etching, the relative dielectric constant (Dk) at a frequency of 10 GHz measured according to the cavity resonator perturbation method in accordance with JIS C2138:2007 is preferably 3.50 or less, more preferably 3.39 or less, further preferably 3.37 or less, still further preferably 3.35 or less, and even further preferably 3.32 or less. There is no particular limitation on the lower limit value of the aforementioned relative dielectric constant (Dk), and for example, it is preferably 0.1 or more in practice.

[0760] The measurement of the relative dielectric constant is carried out as described in the examples below.

[0761] In addition, the metal foil-clad laminate of the present embodiment preferably has a low dielectric loss tangent (Df) measured using a laminate from which the metal foil has been removed by etching. Specifically, for a sample obtained by removing the metal foil from the metal foil-clad laminate by etching, the dielectric loss tangent (Df) at a frequency of 10 GHz measured according to the cavity resonator perturbation method in accordance with JIS C2138:2007 is preferably 0.00350 or less, more preferably 0.00300 or less, further preferably 0.0029 or less, still further preferably 0.00270 or less, even further preferably 0.00255 or less, and even further preferably 0.00230 or less. There is no particular limitation on the lower limit value of the aforementioned dielectric loss tangent (Df), and for example, it is preferably 0.0001 or more in practice.

[0762] The measurement of the dielectric loss tangent is carried out as described in the examples below.

[0763] In addition, the metal foil-clad laminate of the present embodiment preferably has a large metal foil peel strength (preferably a copper foil peel strength). Specifically, the measured value obtained in accordance with JIS C6481:1996 is preferably 0.4 kN / m or more, more preferably 0.5 kN / m or more. There is no particular limitation on the upper limit value of the metal foil peel strength. For example, it is practical that it is 1.4 kN / m or less.

[0764] In addition, the metal foil-clad laminate of the present embodiment preferably has a low water absorption rate. For a sample obtained by cutting the metal foil-clad laminate into 30 mm × 30 mm, the water absorption rate calculated based on the weight change before and after treatment at 121°C and 2 atmospheres for 5 hours using a pressure cooker (PCT) tester in accordance with JIS C6481 is preferably 0.80% by mass or less, more preferably 0.75% by mass or less, further preferably 0.70% by mass or less, still more preferably 0.60% by mass or less, and even more preferably 0.50% by mass or less. In addition, regarding the lower limit value, it is ideal to be 0, and it is practical that it is 0.1% by mass or more.

[0765] The measurement of the water absorption rate is carried out as described in the examples below.

[0766] As described above, the cured product of the resin composition for electronic materials obtained using the resin composition (resin composition containing a specific component combination) of the present embodiment has excellent characteristics such as low dielectric properties (low dielectric loss tangent), moisture heat resistance, crack resistance, appearance of the cured product, and low thermal expansion.

[0767] <<Printed Circuit Board>>

[0768] The printed circuit board of the present embodiment includes an insulating layer and a conductor layer disposed on the surface of the insulating layer, and the 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 present embodiment. Such a printed circuit board can be manufactured by a conventional 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 foil-clad laminate such as the above copper-clad laminate is prepared. Next, an etching treatment is performed on the surface of the metal foil-clad laminate to form an inner layer circuit and produce an inner layer substrate. On the surface of the inner layer circuit of the inner layer substrate, a surface treatment for improving the bonding strength is performed as needed, and then the required number of the above prepregs is overlapped on the surface of the inner layer circuit. Further, a metal foil for an outer layer circuit is laminated on the outside thereof, and heating and pressing are performed to integrally form it. By such an operation, a multilayer laminate in which an insulating layer formed of a cured product of a base material and a resin composition is formed between the inner layer circuit and the metal foil for the outer layer circuit is manufactured. Then, after performing an opening process for through holes and via holes on the multilayer laminate, a metal-plated coating film that conducts the inner layer circuit and the metal foil for the outer layer circuit is formed on the wall surface of the holes, and 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.

[0769] The printed circuit board obtained in the above manufacturing example has the following structure: having an insulating layer and a conductor layer formed on the surface of the insulating layer, and the insulating layer contains the resin composition of the present embodiment and / or its cured product. That is, the layer formed of the 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 on the base material) and the resin composition of the metal foil-clad laminate of the present embodiment becomes the insulating layer of the present embodiment.

[0770] In addition, the present embodiment also relates to a semiconductor device including the above printed circuit board. For details of the semiconductor device, reference can be made to the description in paragraphs 0200 to 0202 of Japanese Patent Application Laid-Open No. 2021-021027, and these contents are incorporated into the present specification.

[0771] In addition, the insulating layer formed of the cured product of the resin composition of the present embodiment preferably reduces the surface roughness after the roughening treatment of the insulating layer. Specifically, the arithmetic mean roughness Ra of the surface of the insulating layer after the roughening treatment is preferably 200 nm or less, more preferably 150 nm or less, and particularly preferably 100 nm or less. The lower limit value of the arithmetic mean roughness Ra is not particularly limited, and for example, it can be 10 nm or more. The arithmetic mean roughness Ra of the surface of the insulating layer is measured using a non-contact surface roughness meter and is obtained by measuring in the VSI mode with a 50-fold lens.

[0772] The non-contact surface roughness meter uses WYKONT3300 manufactured by Veeco Instruments Inc.

[0773] <<Resin composite sheet>>

[0774] The resin composite sheet of the present embodiment includes: a support, and a layer formed of the resin composition of the present embodiment disposed on the surface of the support. The resin composite sheet can be used as a lamination film 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 resin composition of the present embodiment in a solvent on the support and drying it can be cited.

[0775] 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 obtained by coating a release agent on the surface of these films, polyimide film, etc., conductor foils such as copper foil and aluminum foil, glass plates, SUS (Steel Use Stainless) plates, FRP (Fiber-Reinforced Plastics) and other plate-like supports, and there is no particular limitation.

[0776] Examples of the coating method (application method) include the following method: using a bar coater, a die coater, a doctor blade, a Baker film applicator, etc., to coat a solution obtained by dissolving the resin composition of the present embodiment in a solvent on the support. In addition, after drying, the support can be peeled off or etched from the resin composite sheet formed by laminating the support and the resin composition, thereby forming a single-layer sheet. It should be noted that a single-layer sheet can also be obtained without using a support by supplying a solution obtained by dissolving the resin composition of the present embodiment in a solvent into a mold having a sheet-shaped cavity and drying it to form a sheet shape.

[0777] It should be noted that in the production of the single-layer sheet or resin composite sheet of the present embodiment, the drying conditions during solvent removal are not particularly limited. From the perspective that the solvent is likely to remain in the resin composition at low temperatures and the curing of the resin composition is promoted at high temperatures, a temperature of 20°C to 200°C for 1 to 90 minutes is preferred. In addition, the single-layer sheet or resin composite sheet can be used in an uncured state after only drying the solvent, or can be used in a semi-cured (B-staged) state as needed. Furthermore, the thickness of the resin layer in the single-layer sheet or resin composite sheet of the present embodiment can be adjusted by the concentration and coating thickness of the solution of the resin composition for coating (painting), and is not particularly limited. Generally, if the coating thickness becomes thicker, the solvent is more likely to remain during drying, so it is preferably 0.1 to 500 μm.

[0778] Examples

[0779] The following examples are given to further illustrate the present invention specifically. 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.

[0780] When the measuring equipment used in the examples is difficult to obtain due to production stoppage, etc., other equipment with equivalent performance can be used for measurement.

[0781] <Synthesis Example 1 Synthesis of Modified Polyphenylene Ether Compound>

[0782] <<Synthesis of Difunctional Phenyl Ether Oligomer>>

[0783] In a 12 L vertical reactor equipped with a stirring device, a thermometer, an air inlet tube, and a baffle, CuBr was added 29.36 g (42.1 mmol), 1.81 g (10.5 mmol) of N,N'-di-tert-butylethylenediamine, 67.77 g (671.0 mmol) of n-butyldimethylamine, and 2600 g of toluene were stirred at a reaction temperature of 40°C. While bubbling a mixed gas of nitrogen and air adjusted to an oxygen concentration of 8 vol% at a flow rate of 5.2 L / min, a mixed solution of 129.32 g (0.48 mol) of 2,2',3,3',5,5'-hexamethyl-(1,1'-biphenol)-4,4'-diol, 878.4 g (7.2 mol) of 2,6-dimethylphenol, 1.22 g (7.2 mmol) of N,N'-di-tert-butylethylenediamine, and 26.35 g (260.9 mmol) of n-butyldimethylamine, which was previously dissolved in 2300 g of methanol, was added dropwise over 230 minutes and stirred. After the addition was completed, 1500 g of water in whic...

Claims

1. A resin composition, comprising: A polyimide compound A and a compound B containing two or more polymerizable carbon-carbon unsaturated double bonds, The polyimide compound A is prepared from an aromatic amine compound a1 having one to three alkyl groups in the aromatic ring, an aromatic divinyl compound a2 having two vinyl groups, and maleic anhydride as reaction raw material 1.

2. The resin composition according to claim 1, wherein When the resin solid content in the resin composition is set to 100 parts by mass, the content of the polyimide compound A is 1 to 90 parts by mass.

3. The resin composition according to claim 1 or 2, wherein When the resin solid content in the resin composition is set to 100 parts by mass, the content of the compound B containing two or more polymerizable carbon-carbon unsaturated double bonds is 1 to 90 parts by mass.

4. The resin composition according to claim 1 or 2, further containing one or more other resin components C selected from the group consisting of maleimide compounds other than the polyimide compound A, epoxy compounds, phenolic compounds, oxetane resins, benzoxazine compounds, cyanate ester compounds, and thermoplastic elastomers.

5. The resin composition according to claim 1 or 2, further comprising a filler D.

6. The resin composition according to claim 5, wherein The filler D contains one or more selected from the group consisting of silica, aluminum hydroxide, aluminum nitride, boron nitride, forsterite, titanium oxide, barium titanate, strontium titanate, and calcium titanate.

7. The resin composition according to claim 5, wherein The content of the filler D in the resin composition is 1 to 1600 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition.

8. The resin composition according to claim 1 or 2, wherein The compound B containing two or more polymerizable carbon-carbon unsaturated double bonds contains at least one selected from the group consisting of compounds containing vinyl aryl, compounds containing (meth)acryloyl, and compounds containing (meth)allyl.

9. The resin composition according to claim 1 or 2, wherein Relative to 100 parts by mass of the resin solid content in the resin composition, it further contains 0.5 to 30 parts by mass of a monomer or oligomer having an ethylenic unsaturated group.

10. The resin composition according to claim 1 or 2, further comprising a flame retardant, and the flame retardant contains a phosphorus-based flame retardant.

11. The resin composition according to claim 1, wherein When the resin solid content in the resin composition is set to 100 parts by mass, the content of the polyimide compound A is 1 to 90 parts by mass, When the resin solid content in the resin composition is set to 100 parts by mass, the content of the compound B containing two or more polymerizable carbon-carbon unsaturated double bonds is 1 to 90 parts by mass, The resin composition further comprises a filler D, The filler D contains one or more selected from the group consisting of silica, aluminum hydroxide, aluminum nitride, boron nitride, forsterite, titanium oxide, barium titanate, strontium titanate, and calcium titanate, The content of the filler D in the resin composition is 1 to 1600 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition, The compound B containing two or more polymerizable carbon-carbon unsaturated double bonds contains at least one selected from the group consisting of compounds containing a vinyl aryl group, compounds containing a (meth)acryloyl group, and compounds containing a (meth)allyl group.

12. The resin composition according to claim 1, 2 or 11, wherein, The polyimide compound A uses the intermediate amine compound C formed by connecting the aromatic amine compounds a1 to each other through the aromatic divinyl compound a2 and the maleic anhydride as reaction raw materials 3.

13. The resin composition according to claim 12, wherein, The amine equivalent of the intermediate amine compound C is in the range of 172 to 400 g / equivalent.

14. The resin composition according to claim 1, 2 or 11, wherein, The reaction raw material 1 further contains an aromatic monovinyl compound a3 having one vinyl group.

15. The resin composition according to claim 1, 2 or 11, wherein, The polyimide compound A has a structural unit represented by the following formula (1), In the formula (1), R 1 each independently represents an alkyl group having 1 to 10 carbon atoms, R 2 each independently represents: an alkyl group having 1 to 10 carbon atoms, an alkoxy group or an alkylthio group; an aryl group, an aryloxy group or an arylthio group having 6 to 10 carbon atoms; a cycloalkyl group having 3 to 10 carbon atoms; a halogen atom; a hydroxyl group; or a mercapto group, R 3 、R 4 、R 5 and R 6 each independently represents a hydrogen atom or a methyl group, and one of R 3 and R 4 is a hydrogen atom and the other is a methyl group, one of R 5 and R 6 is a hydrogen atom and the other is a methyl group. X 1 represents a substituent represented by the following formula (x), where r is the number of X bonded to each benzene ring having X 1 in the benzene ring of 1 The average value of the number of substitutions of, represents a number from 0 to 4, p represents an integer from 1 to 3, q represents an integer from 0 to 4, and k represents an integer from 1 to 100 In formula (x), R 7 and R 8 each independently represents a hydrogen atom or a methyl group, and one of R 7 and R 8 is a hydrogen atom and the other is a methyl group, R 9 each independently represents: an alkyl group, an alkoxy group or an alkylthio group having 1 to 10 carbon atoms; an aryl group, an aryloxy group or an arylthio group having 6 to 10 carbon atoms; a cycloalkyl group having 3 to 10 carbon atoms; a halogen atom; a hydroxyl group; or a mercapto group, and t represents an integer of 0 to 4.

16. The resin composition according to claim 1, 2 or 11, which is used for a printed circuit board.

17. A cured product of the resin composition according to claim 1, 2 or 11.

18. A prepreg formed from a substrate and the resin composition according to claim 1, 2 or 11.

19. A metal foil-clad laminate comprising: at least one prepreg according to claim 18, and a metal foil disposed on one or both sides of the prepreg.

20. A resin composite sheet comprising: a support, and a layer formed from the resin composition according to claim 1, 2 or 11 disposed on the surface of the support.

21. A printed circuit board comprising an insulating layer and a conductor layer disposed on the surface of the insulating layer, The insulating layer contains a layer formed from the resin composition according to claim 1, 2 or 11.

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