Resin composition, cured product, prepreg, metal-clad laminate, resin composite sheet, printed circuit board, and semiconductor device

Abstract

Resin compositions, cured products, prepregs, metal foil laminates, resin composites, printed circuit boards, and semiconductor devices are provided. One resin composition comprises hollow silica (A) and a thermosetting resin (B), wherein the content of hollow silica (A) in the resin composition is 10 to 250 parts by weight relative to 100 parts by weight of the resin solids, and the dielectric loss tangent of the cured resin composition at a frequency of 10 GHz, as determined by the cavity resonator perturbation method, is 0.0025 or less.

Description

Technical Field

[0001] This invention relates to resin compositions, cured products, prepregs, metal foil laminates, resin composites, printed circuit boards, and semiconductor devices. Background Technology

[0002] In recent years, the integration and miniaturization of semiconductor components used in electronic and communication devices, exemplified by portable terminals, have been accelerating. This necessitates technologies capable of high-density mounting of semiconductor components, requiring improvements to the printed circuit boards, which occupy a crucial position in these devices.

[0003] On the other hand, the applications of electronic devices and the like are diversifying and continuing to expand. As a result, the required properties of printed circuit boards (PCBs), the metal foil laminates used in them, and prepregs are becoming more diverse and stringent. To improve PCBs while taking these required properties into account, various materials and processing methods have been proposed. One example is the improved development of resin materials constituting prepregs and resin composite sheets.

[0004] For example, Patent Document 1 discloses a resin composition comprising a thermosetting resin (A) and a filler (B), wherein the filler (B) comprises hollow particles (b) having 1 to 10 air bubbles inside and an average particle size of 0.01 to 10 μm.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: International Publication No. 2019 / 230661 Summary of the Invention

[0008] The problem the invention aims to solve

[0009] The cured resin composition described in Patent Document 1 has low dielectric properties and excellent appearance after curing. However, with the increasing density of semiconductor device mounting, there is a demand for resin compositions that can also be processed at higher densities on printed circuit boards.

[0010] The object of the present invention is to solve this problem and to provide: a resin composition that provides a cured product with excellent low dielectric properties (Dk and / or Df), excellent appearance after curing, and easy high-density processing; as well as cured products, prepregs, metal foil laminates, resin composites, printed circuit boards, and semiconductor devices.

[0011] Solution for solving the problem

[0012] Based on the above-mentioned issues, the inventors conducted research and found that the above-mentioned issues can be solved by adjusting the content of hollow silica and adjusting the dielectric loss tangent of the cured resin composition.

[0013] Specifically, the above-mentioned problems were solved through the following solution.

[0014] <1> A resin composition comprising hollow silica (A) and a thermosetting resin (B).

[0015] The content of hollow silica (A) in the resin composition is 10 to 250 parts by weight relative to 100 parts by weight of the resin solids.

[0016] The resin composition was impregnated into NE glass cloth at a resin composition content of 70% by volume, and dried at 155°C for 5 minutes to obtain a prepreg with a thickness of 0.1 mm. Eight pieces of the prepreg were stacked, and electrolytic copper foil with a thickness of 12 μm was placed on both sides and pressed to obtain a copper-clad laminate. The copper foil on both sides was removed from the copper-clad laminate by etching to obtain a sample with a thickness of 0.8 mm. The dielectric loss tangent of the 0.8 mm thick sample at a frequency of 10 GHz, measured by the cavity resonator perturbation method according to JIS C218:2007, was 0.0025 or less.

[0017] <2> according to <1> The resin composition wherein the relative permittivity of the 0.8 mm thick sample, as determined by the cavity resonator perturbation method at a frequency of 10 GHz according to JIS C218:2007, is 3.0 or less.

[0018] <3> according to <1> The resin composition is impregnated into NE glass cloth at a resin composition content of 70% by volume, and dried at 155°C for 5 minutes to obtain a prepreg with a thickness of 0.1 mm. Electrolytic copper foil with a thickness of 12 μm is disposed on both sides of the prepreg and pressed to obtain a copper-clad laminate. The copper foil on both sides is removed from the copper-clad laminate by etching, and the sample is cut (reduced) into a sample of 4.5 mm × 10 mm × 0.1 mm. When the sample is heated from 30°C to 340°C at a heating rate of 10°C per minute, the thermal expansion coefficient in the planar direction at 60°C to 120°C is less than 10 ppm / °C.

[0019] <4> according to <1> The resin composition, wherein,

[0020] The 0.8 mm thick sample, according to JIS C218:2007, has a relative permittivity of 3.0 or less at a frequency of 10 GHz, determined by the cavity resonator perturbation method.

[0021] The resin composition was impregnated into NE glass cloth at a resin composition content of 70% by volume, and dried at 155°C for 5 minutes to obtain a prepreg with a thickness of 0.1 mm. Electrolytic copper foil with a thickness of 12 μm was placed on both sides of the prepreg and pressed to obtain a copper-clad laminate. The copper foil on both sides was removed from the copper-clad laminate by etching, and the sample was cut (reduced) into a sample of 4.5 mm × 10 mm × 0.1 mm. When the sample was heated from 30°C to 340°C at a heating rate of 10°C per minute, the thermal expansion coefficient in the planar direction at 60°C to 120°C was less than 10 ppm / °C.

[0022] <5> according to <1> ~ <4> The resin composition of any one of the following, wherein the thermosetting resin (B) comprises an aromatic vinyl resin (D) and a maleimide compound (E).

[0023] <6> according to <1> ~ <5> The resin composition described in any one of the following statements further comprises a thermoplastic elastomer (C).

[0024] <7> according to <6> The resin composition, wherein the thermoplastic elastomer (C) comprises styrene compound units and one or more units selected from the group consisting of butadiene units, isoprene units, hydrogenated butadiene units, and hydrogenated isoprene units.

[0025] The content of styrene compound units in the thermoplastic elastomer (C) is less than 55% by mass of the total thermoplastic elastomer (C).

[0026] <8> according to <6> or <7> The resin composition wherein the content of the thermoplastic elastomer (C) in the resin composition is 5 to 30 parts by weight relative to 100 parts by weight of the resin solids.

[0027] <9> according to <5> ~ <8> The resin composition of any one of the following, wherein the aromatic vinyl resin (D) comprises one or more polymers having structural units of formula (V) and polyphenylene ether compounds having carbon-carbon unsaturated double bonds at the ends.

[0028]

[0029] (In formula (V), Ar represents an aromatic hydrocarbon linking group. * indicates a bonding position.)

[0030] <10> according to <9> The resin composition wherein the polyphenylene ether compound having carbon-carbon unsaturated double bonds at the ends comprises a polyphenylene ether compound represented by formula (OP).

[0031]

[0032] (In formula (OP), X represents an aromatic group, -(YO)) n1 - indicates a polyphenylene ether structure, n1 represents an integer from 1 to 100, and n2 represents an integer from 1 to 4. Rx is the group shown in formula (Rx-1).

[0033]

[0034] (In formula (Rx-1), R) 1 R 2 and R 3 Each group independently represents a hydrogen atom, alkyl, alkenyl, or alkynyl group. * indicates the bonding site with an oxygen atom. Mc independently represents hydrocarbon groups with 1 to 12 carbon atoms. z represents an integer from 0 to 4. r represents an integer from 0 to 6.

[0035] <11> according to <5> to <10> The resin composition according to any one of the following methods, wherein the content of the aromatic vinyl resin (D) in the resin composition is 5 to 95 parts by weight relative to 100 parts by weight of the resin solids.

[0036] <12> according to <5> ~ <11> The resin composition according to any one of the following, wherein the maleimide compound (E) comprises one or more compounds 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).

[0037]

[0038] (In formula (M1), R) M1 R M2 R M3 and R M4 Each can be used independently to represent a hydrogen atom or an organic group. R M5 and R M6 Each can be used independently to represent a hydrogen atom or an alkyl group. Ar M This indicates a divalent aromatic group. A is an alicyclic group with a 4- to 6-membered ring. R M7 and R M8 Each is an alkyl group, independently. mx is 1 or 2, lx is 0 or 1. R M9 and R M10 Each can be used independently to represent a hydrogen atom or an alkyl group. R M11 R M12 R M13 and R M14 Each can be used independently to represent a hydrogen atom or an organic group. R M15Each of these groups independently represents an alkyl group (1-10 carbon atoms), an alkoxy group (1-10 carbon atoms), an alkylthio group (1-10 carbon atoms), a cycloalkyl group (3-10 carbon atoms), an aryl group (6-10 carbon atoms), an aryloxy group (6-10 carbon atoms), an arylthio group (6-10 carbon atoms), a halogen atom, a hydroxyl group, or a mercapto group. px represents an integer from 0 to 3. nx represents an integer from 1 to 20.

[0039]

[0040] (In formula (M3), R) 55 Each of the following can be independently represented: an alkyl group with 1 to 8 carbon atoms, or a phenyl group; n5 represents an integer greater than 1 and less than 10.

[0041]

[0042] (In formula (M5), R) 58 Each of the following independently represents a hydrogen atom, an alkyl group or a phenyl group having 1 to 8 carbon atoms, and R. 59 Each can be used independently to represent a hydrogen atom or a methyl group, and n6 represents an integer greater than or equal to 1.

[0043] <13> according to <1> ~ <12> The resin composition described in any one of the following statements, wherein,

[0044] The 0.8 mm thick sample, according to JIS C218:2007, has a relative permittivity of 3.0 or less at a frequency of 10 GHz, determined by the cavity resonator perturbation method.

[0045] The resin composition was impregnated into NE glass cloth at a resin composition content of 70% by volume, and dried at 155°C for 5 minutes to obtain a prepreg with a thickness of 0.1 mm. Electrolytic copper foil with a thickness of 12 μm was deposited on both sides of the prepreg and pressed to obtain a copper-clad laminate. The copper foil on both sides was removed from the copper-clad laminate by etching, and the sample was cut and reduced to a size of 4.5 mm × 10 mm × 0.1 mm. When the sample was heated at a rate of 10°C per minute from 30°C to 340°C, the thermal expansion coefficient in the planar direction at 60°C to 120°C was less than 10 ppm / °C.

[0046] The thermosetting resin (B) comprises an aromatic vinyl resin (D) and a maleimide compound (E).

[0047] The resin composition further comprises a thermoplastic elastomer (C).

[0048] The thermoplastic elastomer (C) comprises styrene compound units and one or more units selected from the group consisting of butadiene units, isoprene units, hydrogenated butadiene units, and hydrogenated isoprene units.

[0049] The content of styrene compound units in the thermoplastic elastomer (C) is less than 55% by mass of the total thermoplastic elastomer (C).

[0050] The content of the thermoplastic elastomer (C) in the resin composition is 5 to 30 parts by weight relative to 100 parts by weight of the resin solids.

[0051] The aromatic vinyl resin (D) comprises one or more polymers selected from those having structural units shown in formula (V) and polyphenylene ether compounds having carbon-carbon unsaturated double bonds at the ends.

[0052] The polyphenylene ether compound having a carbon-carbon unsaturated double bond at the end includes the polyphenylene ether compound represented by formula (OP).

[0053] The content of the aromatic vinyl resin (D) in the resin composition is 5 to 95 parts by weight relative to 100 parts by weight of the resin solids.

[0054] The maleimide compound (E) comprises one or more compounds selected from the group consisting of the compound shown in formula (M1), the compound shown in formula (M3), and the compound shown in formula (M5).

[0055]

[0056] (In formula (V), Ar represents an aromatic hydrocarbon linking group. * indicates a bonding position.)

[0057]

[0058] (In formula (OP), X represents an aromatic group, -(YO)) n1 - indicates a polyphenylene ether structure, n1 represents an integer from 1 to 100, and n2 represents an integer from 1 to 4. Rx is the group shown in formula (Rx-1).

[0059]

[0060] (In formula (Rx-1), R) 1 R 2 and R 3 Each group independently represents a hydrogen atom, alkyl, alkenyl, or alkynyl group. * indicates the bonding site with an oxygen atom. Mc independently represents hydrocarbon groups with 1 to 12 carbon atoms. z represents an integer from 0 to 4. r represents an integer from 0 to 6.

[0061]

[0062] (In formula (M1), R) M1 RM2 R M3 and R M4 Each can be used independently to represent a hydrogen atom or an organic group. R M5 and R M6 Each can be used independently to represent a hydrogen atom or an alkyl group. Ar M This indicates a divalent aromatic group. A is an alicyclic group with a 4- to 6-membered ring. R M7 and R M8 Each is an alkyl group, independently. mx is 1 or 2, lx is 0 or 1. R M9 and R M10 Each can be used independently to represent a hydrogen atom or an alkyl group. R M11 R M12 R M13 and R M14 Each can be used independently to represent a hydrogen atom or an organic group. R M15 Each of these groups independently represents an alkyl group (1-10 carbon atoms), an alkoxy group (1-10 carbon atoms), an alkylthio group (1-10 carbon atoms), a cycloalkyl group (3-10 carbon atoms), an aryl group (6-10 carbon atoms), an aryloxy group (6-10 carbon atoms), an arylthio group (6-10 carbon atoms), a halogen atom, a hydroxyl group, or a mercapto group. px represents an integer from 0 to 3. nx represents an integer from 1 to 20.

[0063]

[0064] (In formula (M3), R) 55 Each of the following can be independently represented: an alkyl group with 1 to 8 carbon atoms, or a phenyl group; n5 represents an integer greater than 1 and less than 10.

[0065]

[0066] (In formula (M5), R) 58 Each of the following independently represents a hydrogen atom, an alkyl group or a phenyl group having 1 to 8 carbon atoms, and R. 59 Each can be used independently to represent a hydrogen atom or a methyl group, and n6 represents an integer greater than or equal to 1.

[0067] <14> according to <1> ~ <13> The resin composition described in any one of the following examples further comprises a flame retardant.

[0068] <15> according to <14> The resin composition wherein the flame retardant comprises a phosphorus-based flame retardant.

[0069] <16> A solidified substance, which is <1> ~ <15> The cured product of the resin composition described in any one of the above statements.

[0070] <17> A prepreg comprising a substrate and <1> ~ <15> The resin composition described in any one of the above statements is formed.

[0071] <18> A metal foil laminate comprising at least one sheet <17> The prepreg and the metal foil disposed on one or both sides of the prepreg.

[0072] <19> A resin composite sheet comprising a support and a substrate disposed on the surface of the support. <1> ~ <15> The layer formed by the resin composition described in any one of the above statements.

[0073] <20> A printed circuit board includes an insulating layer and a conductor layer disposed on the surface of the insulating layer, the insulating layer comprising... <1> ~ <15> The layer formed by the resin composition described in any one of the above statements.

[0074] <21> A semiconductor device comprising <20> The printed circuit board mentioned above.

[0075] The effects of the invention

[0076] Resin compositions that can provide cured products with excellent low dielectric properties (Dk and / or Df), excellent appearance after curing, and ease of high-density processing, as well as cured products, prepregs, metal foil laminates, resin composites, printed circuit boards, and semiconductor devices. Detailed Implementation

[0077] Hereinafter, a method for implementing the present invention (hereinafter referred to as "this embodiment") will be described in detail. It should be noted that the following embodiment is an example for illustrating the present invention, and the present invention is not limited to this embodiment.

[0078] It should be noted that in this specification, "~" is used to encompass the values ​​listed before and after it as the lower and upper limits.

[0079] Unless otherwise specified, all physical property values ​​and characteristic values ​​in this manual are set at 23°C.

[0080] In this specification, the description of groups (atomic groups) includes both unsubstituted and substituted groups (atomic groups). For example, "alkyl" includes not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (substituted alkyl groups). In this specification, the description of unsubstituted and unsubstituted groups is preferably unsubstituted.

[0081] In this specification, (meth)allyl means either or both of allyl and methallyl, "(meth)acrylate" means either or both of acrylate and methacrylate, "(meth)acrylic acid" means either or both of acrylic acid and methacrylic acid, and "(meth)acryloyl" means either or both of acryloyl and methacryloyl.

[0082] In this specification, the term "process" is not only used for independent processes, but also for processes that cannot be clearly distinguished from other processes, as long as the desired effect of the process can be achieved.

[0083] Unless otherwise specified, the measurement methods described in the standards shown in this instruction manual may vary depending on the year, and are based on the standards as of January 1, 2023.

[0084] In this specification, the solid resin component refers to the components other than hollow silica (A), filler materials (solid silica, porous silica, other filler materials) and solvents. Its main purpose is to include thermosetting resin (B), as well as other components that need to be mixed, and resin additive components (curing accelerators, flame retardants, and other additives).

[0085] In this specification, relative permittivity and permittivity are used with the same meaning.

[0086] The resin composition of this embodiment is characterized in that it comprises hollow silica (A) and thermosetting resin (B), wherein the content of hollow silica in the resin composition is 10 to 250 parts by mass relative to 100 parts by mass of the resin solids. The resin composition is impregnated into NE glass cloth at a content of 70% by volume, and heated and dried at 155°C for 5 minutes to obtain a prepreg with a thickness of 0.1 mm. Eight sheets of the prepreg are stacked, and electrolytic copper foil with a thickness of 12 μm is placed on both sides and pressed to obtain a copper-clad laminate. The copper foil on both sides is removed from the copper-clad laminate by etching to obtain a sample with a thickness of 0.8 mm. The dielectric loss tangent of the 0.8 mm thick sample at a frequency of 10 GHz, measured by the cavity resonator perturbation method according to JIS C218:2007, is 0.0025 or less.

[0087] By configuring it in this way, a resin composition can be obtained that provides excellent low dielectric properties (Dk and / or Df) of the cured product, excellent appearance after curing, and is easy to process with high density.

[0088] In this embodiment, the dielectric constant of the cured product is lower by using hollow silica (A). This is because, in this embodiment, hollow silica is more likely to exist in the cured product as particles containing air-filled spaces or vacuum spaces. Moreover, gases such as air and vacuum spaces have low dielectric constants, thus reducing the dielectric constant of the cured resin composition.

[0089] In addition, in this embodiment, by adjusting the content of hollow silica (A), the appearance of the obtained cured product can be improved.

[0090] Furthermore, the resin composition of this embodiment facilitates high-density processing of printed circuit boards by using hollow silica (A). This is presumably because hollow silica (A) acts similarly to a lubricant in the cured product, making it easier to integrate and process using the drill bit's positioning in high-density processing.

[0091] The following is a detailed description of this embodiment.

[0092] <Hollow Silica (A)>

[0093] The resin composition of this embodiment contains hollow silica (A). By including hollow silica (A), the low dielectric properties (Dk and / or Df) of the resulting cured product are improved. Consequently, the machinability of the drill bit is also improved.

[0094] Hollow silica (A) consists of particles having one or more, typically fewer than ten, spaces within an inorganic shell, usually one to three spaces. These spaces are typically vacuum-filled or air-filled. By including unfilled silica spaces within the silica particles, the low dielectric properties (Dk and / or Df) of the resulting cured product are improved. It should be noted that hollow silica differs from mesoporous silica and porous silica.

[0095] Hollow silica (A) refers to silica as the main component, which may also contain inorganic oxides such as alumina, zirconium oxide, and titanium oxide in addition to silica. The silica content in hollow silica particles (A) is preferably 70% by mass or more, more preferably 80% by mass, further preferably 90% by mass or more, even more preferably 95% by mass or more, and may also be less than 100% by mass.

[0096] From the viewpoint of improving the appearance of the cured product, the volume average particle size (D50) of the hollow silica (A) is preferably in the range of 0.1 to 10 μm. The lower limit of the volume average particle size is more preferably 0.5 μm or more, further preferably 1.0 μm or more, even more preferably 1.5 μm or more, and may also be 1.8 μm or more or 2.0 μm or more. The upper limit of the volume average particle size is more preferably 5.0 μm or less, further preferably 4.7 μm or less, and even more preferably 4.5 μm or less. The volume average particle size (D50) of the hollow silica (A) can be measured by laser diffraction / scattering, specifically by the method described in the examples. Furthermore, in this embodiment, the content of particles with a particle size exceeding 8.0 μm in the hollow silica (A) is preferably 10% by volume or less, more preferably 5% by volume or less, and even more preferably 1% by volume or less.

[0097] From the viewpoint of low dielectric properties and particle strength, the porosity of hollow silica (A) is preferably 5 to 80% by volume. The lower limit of porosity is more preferably 8% by volume or more, and even more preferably 10% by volume or more. The upper limit of porosity is more preferably 50% by volume or less, even more preferably 35% by volume or less, even more preferably 25% by volume or less, and even more preferably 20% by volume or less. With such porosity, excellent low dielectric properties (low dielectric constant and / or low dielectric loss tangent) are achieved, and particle strength can be maintained at a specified level or higher, effectively suppressing particle breakage. The porosity of hollow silica (A) can be calculated from the particle density, specifically, it can be determined by the method described in the examples.

[0098] Furthermore, regarding hollow silica (A), the substances described in paragraphs 0008 to 0047 of Japanese Patent No. 7320692 and paragraphs 0012 to 0021 of International Publication No. 2022 / 145350 may also be used, and their contents are incorporated into this specification.

[0099] The content of hollow silica (A) in the resin composition of this embodiment is 10 parts by mass or more, preferably 20 parts by mass or more, more preferably 30 parts by mass or more, further preferably 50 parts by mass or more, even more preferably 75 parts by mass or more, even more preferably 80 parts by mass or more, and also preferably 250 parts by mass or less, preferably 230 parts by mass or less, more preferably 210 parts by mass or less, even more preferably 190 parts by mass or less, even more preferably 150 parts by mass or less, and even more preferably 130 parts by mass or less, relative to 100 parts by mass of the resin solids. By making the content of hollow silica (A) at or above the above-mentioned lower limit value, there is a tendency to further improve the low thermal expansion, low dielectric properties, heat resistance, and drill bit machinability. In addition, by making the content of hollow silica (A) at or below the above-mentioned upper limit value, there is a tendency to further improve the appearance and formability after curing.

[0100] The resin composition of this embodiment may contain only one type of hollow silica (A), or it may contain two or more types. When it contains two or more types, the total amount is preferably within the range described above.

[0101] The resin composition of this embodiment may contain solid silica (excluding the silica in the hollow silica space mentioned above), or it may not contain it. Preferably, the resin composition of this embodiment is substantially free of solid silica. "Substantially free" means that the content of solid silica in the resin composition is less than 10% by mass of the content of hollow silica in the resin composition, preferably less than 5% by mass, more preferably less than 3% by mass, and even more preferably less than 1% by mass.

[0102] The resin composition of this embodiment may or may not contain porous silica. Preferably, the resin composition of this embodiment is substantially free of porous silica. "Substantially free" means that the content of porous silica in the resin composition is less than 10% by mass of the content of hollow silica in the resin composition, preferably less than 5% by mass, more preferably less than 3% by mass, and even more preferably less than 1% by mass.

[0103] <Thermosetting Resins (B)>

[0104] The resin composition of this embodiment comprises a thermosetting resin (B).

[0105] The type of thermosetting resin (B) is not particularly limited, but preferably includes at least one selected from the group consisting of aromatic vinyl resins (D), maleimide compounds (E), cyanate compounds, (meth)allyl compounds, (meth)acrylate compounds, epoxy compounds, phenolic compounds, oxetane resins, benzoxazine compounds, arylcyclobutene compounds, perfluorovinyl ether resins, polyimide compounds, and compounds having vinylidene groups. More preferably, it includes at least one selected from the group consisting of aromatic vinyl resins (D), maleimide compounds (E), and cyanate compounds. More preferably, it includes both aromatic vinyl resins (D) and maleimide compounds (E).

[0106] The content of thermosetting resin (B) in the resin composition of this embodiment is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, further preferably 30 parts by mass or more, even more preferably 40 parts by mass or more, even more preferably 50 parts by mass or more, and preferably 90 parts by mass or less, more preferably 80 parts by mass or less, and even more preferably 70 parts by mass or less, relative to 100 parts by mass of the resin solids. By setting the content of thermosetting resin (B) to the aforementioned lower limit or above, there is a tendency to further improve the heat resistance. In addition, by setting the content of thermosetting resin (B) to the aforementioned upper limit or below, there is a tendency to further improve the low thermal expansion property.

[0107] The resin composition in this embodiment may contain only one thermosetting resin (B), or it may contain two or more. When it contains two or more, the total amount is preferably within the range described above.

[0108] The first embodiment of the thermosetting resin (B) comprises an aromatic vinyl resin (D) and a maleimide compound (E). In the first embodiment of the thermosetting resin (B), the content of the maleimide compound (E) relative to 100 parts by weight of the aromatic vinyl resin (D) is preferably 50 parts by weight or more, more preferably 80 parts by weight or more, further preferably 100 parts by weight or more, even more preferably 120 parts by weight or more, and preferably 200 parts by weight or less, more preferably 180 parts by weight or less.

[0109] A second embodiment of the thermosetting resin (B) further includes a cyanate ester compound in the first embodiment. In the second embodiment of the thermosetting resin (B), the content of the cyanate ester compound relative to 100 parts by weight of the aromatic vinyl resin (D) is preferably 1 part by weight or more, more preferably 5 parts by weight or more, and preferably 50 parts by weight or less, more preferably 30 parts by weight or less. By setting the content of the cyanate ester compound to the aforementioned lower limit or above, the heat resistance of the obtained resin tends to be further improved. By setting the content of the cyanate ester compound to the aforementioned upper limit or below, the low dielectric properties (Dk and / or Df) of the obtained cured product tend to be further improved.

[0110] <<Aromatic Vinyl Resins (D)>>

[0111] Aromatic vinyl resins (D) are compounds having vinyl aryl groups and are compounds that are cured by heat. By using aromatic vinyl resins (D) and thermoplastic elastomers (C) (especially styrene-based elastomers) in combination, their compatibility is improved, and the coefficient of thermal expansion of the resulting cured product can be further reduced.

[0112] Specifically, as an aromatic vinyl resin (D), it preferably comprises one or more of the group consisting of polymers having structural units as shown in formula (V) and polyphenylene ether compounds having carbon-carbon unsaturated double bonds at the ends, and more preferably includes polyphenylene ether compounds having carbon-carbon unsaturated double bonds at the ends.

[0113] When the resin composition of this embodiment contains aromatic vinyl resin (D), its content relative to 100 parts by weight of the resin solids is preferably 5 parts by weight or more, more preferably 10 parts by weight or more, further preferably 15 parts by weight or more, and even more preferably 20 parts by weight or more. Depending on the application, it is even more preferably 30 parts by weight or more. It is also preferably 95 parts by weight or less, more preferably 80 parts by weight or less, and even more preferably 70 parts by weight or less. Depending on the application, it is even more preferably 55 parts by weight or less, and even more preferably 50 parts by weight or less. By setting the content of aromatic vinyl resin (D) to the aforementioned lower limit or above, there is a tendency to further improve compatibility and heat resistance. Furthermore, by setting the content of aromatic vinyl resin (D) to the aforementioned upper limit or below, there is a tendency to further improve low thermal expansion.

[0114] The resin composition of this embodiment may contain only one aromatic vinyl resin (D), or it may contain two or more. When it contains two or more, the total amount is preferably within the range described above.

[0115] <<<Polymers with the structural units shown in formula (V)>>>

[0116] The resin composition of this embodiment may contain a polymer having structural units as shown in Formula (V). By containing a polymer having structural units as shown in Formula (V), a resin composition with excellent low dielectric properties (low relative permittivity, low dielectric loss tangent) can be obtained.

[0117]

[0118] (In formula (V), Ar represents an aromatic hydrocarbon linking group. * indicates a bonding position.)

[0119] The aromatic hydrocarbon linking group can be a group formed solely of an aromatic hydrocarbon optionally having substituents, or a group formed by a combination of an aromatic hydrocarbon optionally having substituents and other linking groups, preferably a group formed solely of an aromatic hydrocarbon optionally having substituents. It should be noted that the substituents optionally present in the aromatic hydrocarbon can include substituent Z (e.g., alkyl groups with 1 to 6 carbon atoms, alkenyl groups with 2 to 6 carbon atoms, alkoxy groups with 2 to 6 carbon atoms, hydroxyl groups, amino groups, carboxyl groups, halogen atoms, etc.). Furthermore, the aforementioned aromatic hydrocarbon preferably does not have substituents.

[0120] Aromatic hydrocarbons typically have divalent linking groups.

[0121] Specifically, the aromatic hydrocarbon linking group may include, optionally, phenylene, naphthyl, anthracenediyl, phenanthrenediyl, biphenyldiyl, and fluorenediyl, with substituted groups being preferred. Substituents may include the aforementioned substituent Z, and the aforementioned phenylene and other groups are preferably unsubstituented.

[0122] Polymers having the structural units shown in formula (V) more preferably include at least one of the structural units shown in formula (V1), formula (V2), and formula (V3). It should be noted that * in the following formulas indicates a bonding position. Furthermore, hereinafter, the structural units shown in formulas (V1) to (V3) are sometimes collectively referred to as "structural unit (a)".

[0123]

[0124] In equations (V1) to (V3), L 1 The linking group is an aromatic hydrocarbon (preferably with 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10). Specifically, examples include phenylene, naphthyl, anthracenediyl, phenanthrenediyl, biphenyldiyl, and fluorenediyl, which are optionally substituents, with phenylene being the preferred option. Substituents can be exemplified by substituent Z described above, and the aforementioned phenylene and other groups are preferably unsubstituents.

[0125] The compound forming structural unit (a) is preferably a divinyl aromatic compound, such as divinylbenzene, bis(1-methylvinyl)benzene, divinylnaphthalene, divinylanthracene, divinylbiphenyl, divinylphenanthrene, etc. Divinylbenzene is particularly preferred. One of these divinyl aromatic compounds may be used, or two or more may be used as needed.

[0126] That is, the structural unit (a) is preferably a structural unit derived from a divinyl aromatic compound.

[0127] As described above, a polymer having the structural unit shown in formula (V) can be a homopolymer of the compound forming structural unit (a) or a copolymer of structural units derived from other monomers.

[0128] When the polymer having the structural unit shown in formula (V) is a copolymer, the copolymerization ratio of structural unit (a) is preferably 3 mol% or more, more preferably 5 mol% or more, even more preferably 10 mol% or more, and may also be 15 mol% or more. As an upper limit, it is preferably 90 mol% or less, more preferably 85 mol% or less, even more preferably 80 mol% or less, even more preferably 70 mol% or less, more preferably 60 mol% or less, even more preferably 50 mol% or less, even more preferably 40 mol% or less, particularly more preferably 30 mol% or less, and may further be 25 mol% or less, or 20 mol% or less.

[0129] As a structural unit derived from other monomers, an example can be given of a structural unit (b) derived from an aromatic compound having one vinyl group (monovinyl aromatic compound).

[0130] The structural unit (b) derived from a monovinyl aromatic compound is preferably the structural unit shown in the following formula (V4).

[0131]

[0132] In equation (V4), L 2 As a preferred example of an aromatic hydrocarbon linking group, the L group mentioned above can be cited. 1 Examples. * indicates the bonding location.

[0133] R V1 It is a hydrocarbon group (preferably alkyl) with 1 to 12 carbon atoms, consisting of hydrogen atoms. V1 When it is a hydrocarbon group, the number of carbon atoms is preferably 1 to 6, more preferably 1 to 3. V1 and L 2 It can have the above-mentioned substituent Z.

[0134] When the polymer having the structural unit shown in formula (V) is a copolymer containing structural unit (b) derived from a monovinyl aromatic compound, examples of monovinyl aromatic compounds include vinyl aromatic compounds such as styrene, vinylnaphthalene, and vinyl biphenyl; and nucleoalkyl-substituted vinyl aromatic compounds such as o-methylstyrene, m-methylstyrene, p-methylstyrene, o- and p-dimethylstyrene, o-ethylvinylbenzene, m-ethylvinylbenzene, p-ethylvinylbenzene, methylvinylbiphenyl, and ethylvinylbiphenyl. The monovinyl aromatic compounds illustrated herein may suitably have the aforementioned substituent Z. Furthermore, one or more of these monovinyl aromatic compounds may be used. Preferably, structural unit (b) contains a structural unit derived from at least one of the group consisting of o-ethylvinylbenzene, m-ethylvinylbenzene, and p-ethylvinylbenzene, and more preferably, in addition to containing a structural unit derived from at least one of the group consisting of o-ethylvinylbenzene, m-ethylvinylbenzene, and p-ethylvinylbenzene, it also contains a structural unit derived from styrene.

[0135] When the polymer having the structural unit shown in formula (V) is a copolymer containing structural unit (b), the copolymerization ratio of 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, or 75 mol% or more. As an upper limit, it is preferably 98 mol% or less, more preferably 90 mol% or less, and even more preferably 85 mol% or less.

[0136] Polymers having the structural units shown in formula (V) may also have other structural units besides structural units (a) and (b). Examples of other structural units include structural units (c) derived from cyclic olefin compounds. Examples of cyclic olefin compounds include hydrocarbons having double bonds within the ring structure. Specifically, in addition to monocyclic cyclic olefins such as cyclobutene, cyclopentene, cyclohexene, and cyclooctene, examples include compounds with a norbornene ring structure such as norbornene and dicyclopentadiene, and cyclic olefin compounds with fused aromatic rings such as indene and acenaphthene. Examples of norbornene compounds include those described in paragraphs 0037 to 0043 of Japanese Patent Application Publication No. 2018-039995, the contents of which are incorporated herein by reference. It should be noted that the cyclic olefin compounds illustrated herein may further have the aforementioned substituent Z.

[0137] When the polymer having the structural unit shown in formula (V) is a copolymer containing structural unit (c), the copolymerization ratio of structural unit (c) is preferably 10 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more. As an upper limit, it is preferably 90 mol% or less, more preferably 80 mol% or less, even more preferably 70 mol% or less, and can be 50 mol% or less, or 30 mol% or less.

[0138] In polymers having the structural units shown in formula (V), structural units (d) derived from different polymeric compounds (hereinafter also referred to as other polymeric compounds) may be further introduced. Examples of other polymeric compounds (monomers) include compounds containing three vinyl groups. Specifically, examples include 1,3,5-trivinylbenzene, 1,3,5-trivinylnaphthalene, and 1,2,4-trivinylcyclohexane. Alternatively, examples include ethylene glycol diacrylate, butadiene (e.g., 1,3-butadiene), and isoprene. The copolymerization ratio of structural units (d) derived from other polymeric compounds is preferably 30 mol% or less, more preferably 20 mol% or less, and even more preferably 10 mol% or less.

[0139] As one embodiment of a polymer having the structural unit shown in formula (V), a polymer that must have structural unit (a) and includes at least one of structural units (b) to (d) can be exemplified. Furthermore, an embodiment can be exemplified in which the total of structural units (a) to (d) accounts for more than 95 mol% and more than 98 mol% of all structural units.

[0140] As another embodiment of a polymer having the structural unit shown in formula (V), a polymer in which structural unit (a) is required, except for the end, preferably contains 90 mol% or more of the structural unit containing an aromatic ring, more preferably 95 mol% or more, and may also contain 100 mol% of the polymer.

[0141] It should be noted that when calculating the mole % relative to all structural units, one structural unit refers to one molecule of a monomer (e.g., divinyl aromatic compound, monovinyl aromatic compound, etc.) used in the manufacture of a polymer having the structural unit shown in formula (V).

[0142] The method for manufacturing polymers having the structural units shown in formula (V) is not particularly limited and can be carried out according to conventional methods. For example, polymerizing a raw material containing a divinyl aromatic compound (with monovinyl aromatic compounds, cycloolefin compounds, etc., coexisting as needed) in the presence of a Lewis acid catalyst can be carried out. As a Lewis acid catalyst, metal fluorides such as boron trifluoride or their complexes can be used.

[0143] The structure of the chain ends of polymers having the structural units shown in formula (V) is not particularly limited. However, for groups derived from the aforementioned divinyl aromatic compounds, structures of formula (E1) can be cited. Furthermore, L in formula (E1)... 1 Same as specified in equation (V1) above. * indicates the bonding position.

[0144] *-CH=CH-L 1 -CH=CH2(E1)

[0145] When the group derived from a monovinyl aromatic compound becomes the chain terminator, structures taking the form of the following formula (E2) can be listed. In the formula, L... 2 and R V1 These have the same meanings as defined in equation (V4) above. * indicates the bonding position.

[0146] *-CH=CH-L 2 -R V1 (E2)

[0147] The polymer having the structural unit shown in formula (V) preferably has a molecular weight of 300 or more, more preferably 500 or more, further preferably 1,000 or more, and even more preferably 1,500 or more, in terms of number average molecular weight (Mn). As an upper limit for the number average molecular weight, it is preferably 130,000 or less, more preferably 120,000 or less, further preferably 110,000 or less, and even more preferably 100,000 or less, but can be 30,000 or less, 10,000 or less, or 5,000 or less.

[0148] The molecular weight of the polymer having the structural unit shown in Formula (V), expressed as weight-average molecular weight Mw, is preferably 3,000 or more, more preferably 5,000 or more, and even more preferably 10,000 or more. By setting the weight-average molecular weight to the aforementioned lower limit or above, the cured resin composition can effectively exhibit the excellent low dielectric properties, particularly Df and the dielectric properties after moisture absorption, of the polymer having the structural unit shown in Formula (V). As the upper limit of the weight-average molecular weight Mw, it is preferably 130,000 or less, more preferably 100,000 or less, even more preferably 80,000 or less, and even more preferably 50,000 or less. By setting the weight-average molecular weight to the aforementioned upper limit or below, there is a tendency to avoid embedding defects when the prepreg or resin sheet is laminated onto the circuit forming substrate.

[0149] The monodispersity (Mw / Mn), expressed as the ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn), is preferably 100 or less, more preferably 50 or less, even more preferably 20 or less, and can be 15 or less, or 12 or less. As a lower limit, it is practically 1.1 or more, preferably 2.0 or more, more preferably 4 or more, even more preferably 5 or more, even more preferably 7 or more, and even more preferably 8 or more.

[0150] The above-mentioned Mw and Mn were measured according to the description of the embodiments described later.

[0151] When the resin composition of this embodiment contains two or more polymers having structural units shown in formula (V), it is preferable that the Mw, Mn, and Mw / Mn of the mixture satisfy the above-mentioned ranges.

[0152] The vinyl equivalent of the polymer having the structural unit shown in formula (V) is preferably 200 g / eq. or more, more preferably 230 g / eq. or more, and even more preferably 250 g / eq. or more, and can be 300 g / eq. or more or 350 g / eq. or more. Furthermore, the vinyl equivalent is preferably 1200 g / eq. or less, more preferably 1000 g / eq. or less, and can be 800 g / eq. or less, 600 g / eq. or less, 500 g / eq. or less, 400 g / eq. or less, or 350 g / eq. or less. By setting the vinyl equivalent to the aforementioned lower limit or above, there is a tendency to improve the storage stability of the resin composition and the flowability of the resin composition. Therefore, the formability is improved, and voids are less likely to occur during the formation of prepregs, etc., leading to a tendency to obtain printed circuit boards with higher reliability. On the other hand, by setting the vinyl equivalent to the aforementioned upper limit or below, there is a tendency to improve the heat resistance of the obtained cured product.

[0153] Polymers having the structural unit shown in Formula (V) preferably exhibit excellent low dielectric properties in their cured products. For example, in this embodiment, the relative permittivity (Dk) of the cured product of the polymer having the structural unit shown in Formula (V) at 10 GHz, measured by the cavity resonator perturbation method, is preferably 2.80 or less, more preferably 2.60 or less, further preferably 2.50 or less, and even more preferably 2.40 or less. Furthermore, the lower limit of the aforementioned relative permittivity is, for example, actually 1.80 or more. Additionally, the dielectric loss tangent (Df) of the cured product of the polymer having the structural unit shown in Formula (V) at 10 GHz, measured by the cavity resonator perturbation method, is preferably 0.0030 or less, more preferably 0.0020 or less, and even more preferably 0.0010 or less. Furthermore, the lower limit of the aforementioned dielectric loss tangent is, for example, actually 0.0001 or more.

[0154] The relative permittivity (Dk) and dielectric loss tangent (Df) were determined by the following method.

[0155] 4.5g of resin powder was spread into a stainless steel mold with a height of 100mm×30mm×1.0mm, placed in a vacuum press (made by Kitagawa Seiki Co., Ltd.), and held at 200℃, 220℃ and 240℃ for 1.5 hours. The mold was then pressed under a surface pressure of 1.9MPa to produce a cured board.

[0156] After the cured plate was reduced to a width of 1.0 mm, it was dried at 120°C for 60 minutes. Then, the relative permittivity (Dk) and dielectric loss tangent (Df) of the dried plate were measured at 10 GHz using a perturbation method cavity resonator. The measurement temperature was set to 23°C.

[0157] In this specification, for polymers having the structural units shown in formula (V), refer to the compounds and their synthesis reaction conditions described in paragraphs 0029 to 0058 of International Publication No. 2017 / 115813, the compounds and their synthesis reaction conditions described in paragraphs 0013 to 0058 of Japanese Patent Application Publication No. 2018-039995, and the compounds described in paragraphs 0008 to 0043 of Japanese Patent Application Publication No. 2018-168347. The following compounds and their synthesis reaction conditions, as well as those described in paragraphs 0014 to 0042 of Japanese Patent Application Publication No. 2006-070136, paragraphs 0014 to 0061 of Japanese Patent Application Publication No. 2006-089683, and paragraphs 0008 to 0036 of Japanese Patent Application Publication No. 2008-248001, are incorporated herein by reference.

[0158] When the resin composition of this embodiment contains a polymer having the structural unit shown in formula (V), the lower limit of its content relative to 100 parts by mass of the resin solids in the resin composition is preferably 1 part by mass or more, more preferably 10 parts by mass or more, and even more preferably 20 parts by mass or more, and can be 30 parts by mass or more, 40 parts by mass or more, 50 parts by mass or more, or 60 parts by mass or more. By making the content of the polymer having the structural unit shown in formula (V) at or above the above-mentioned lower limit, there is a tendency to effectively achieve low dielectric properties, especially low relative permittivity. In addition, the upper limit of the content of the polymer having the structural unit shown in formula (V) relative to 100 parts by mass of the resin solids in the resin composition is preferably 90 parts by mass or less, more preferably 80 parts by mass or less, and can also be 70 parts by mass or less, 60 parts by mass or less, or 50 parts by mass or less. By making the content of the polymer having the structural unit shown in formula (V) at or below the above-mentioned upper limit, there is a tendency to improve the peel strength and low water absorption of the metal foil.

[0159] The resin composition of this embodiment may contain only one polymer having the structural unit shown in formula (V), or it may contain two or more. When it contains two or more, the total amount is preferably within the range described above.

[0160] Furthermore, the resin composition in this embodiment can also be formulated to substantially not contain polymers having the structural units shown in formula (V). "Substantially not" means that the content of polymers having the structural units shown in formula (V) is less than 1 part by mass relative to 100 parts by mass of the resin solids in the resin composition, preferably less than 0.1 parts by mass, and more preferably less than 0.01 parts by mass.

[0161] <<<Polyphenylene ether compounds with carbon-carbon unsaturated double bonds at the ends>>>

[0162] The resin composition of this embodiment preferably contains a polyphenylene ether compound having carbon-carbon unsaturated double bonds at the ends, and more preferably contains a polyphenylene ether compound having two or more carbon-carbon unsaturated double bonds at the ends.

[0163] Polyphenylene ether compounds containing two or more carbon-carbon unsaturated double bonds at the ends are preferably polyphenylene ether compounds having two or more groups (preferably vinyl benzyl) at the ends as shown in the following formula (Rx-1). By using these polyphenylene ether compounds, there is a tendency to more effectively improve the low dielectric properties (Dk and / or Df) and low water absorption of printed circuit boards, etc.

[0164] The following is a detailed explanation of their features.

[0165] Examples of polyphenylene ether compounds having carbon-carbon unsaturated double bonds at the ends include compounds having a phenylene ether skeleton as shown in the following formula (X1).

[0166]

[0167] (In formula (X1), R) 24 R 25 R 26 and R 27 (The same or different can be selected to represent alkyl, aryl, halogen, or hydrogen atoms with 6 or fewer carbon atoms.)

[0168] Polyphenylene ether compounds having carbon-carbon unsaturated double bonds at the ends may further include repeating units shown in formula (X2) and / or repeating units shown in formula (X3).

[0169]

[0170] (In formula (X2), R) 28 R 29R 30 R 34 and R 35 The same or different can be used to indicate alkyl or phenyl groups with 6 or fewer carbon atoms. R 31 R 32 and R 33 (Optional, either the same or different, consisting of alkyl or phenyl groups with 6 or fewer hydrogen atoms.)

[0171]

[0172] (In formula (X3), R) 36 R 37 R 38 R 39 R 40 R 41 R 42 and R 43 (The following can be selected, either the same or different, and can be an alkyl or phenyl group with 6 or fewer carbon atoms, containing hydrogen atoms. -A- can be a straight-chain, branched, or cyclic divalent hydrocarbon group with 20 or fewer carbon atoms.)

[0173] Polyphenylene ether compounds having carbon-carbon unsaturated double bonds at the ends are preferably modified polyphenylene ether compounds whose ends are partially or completely functionalized with olefinic unsaturated groups (hereinafter, sometimes referred to as "modified polyphenylene ether compound (g)"), more preferably modified polyphenylene ether compounds having two or more vinyl benzyl groups at the ends. By using such modified polyphenylene ether compounds (g), the dielectric loss tangent (Df) of the cured resin composition can be further reduced, and the low water absorption and peel strength can be improved. These modified polyphenylene ether compounds (g) can be used alone or in combination of two or more.

[0174] Examples of modified polyphenylene ether compounds (g) include polyphenylene ether compounds represented by formula (OP).

[0175]

[0176] (In formula (OP), X represents an aromatic group, -(YO)) n1 - indicates a polyphenylene ether structure, n1 represents an integer from 1 to 100, and n2 represents an integer from 1 to 4. Rx is the group shown in formula (Rx-1).

[0177]

[0178] (In formula (Rx-1), R) 1 R 2 and R 3Each group independently represents a hydrogen atom, alkyl, alkenyl, or alkynyl group. * indicates the bonding site with an oxygen atom. Mc independently represents hydrocarbon groups with 1 to 12 carbon atoms. z represents an integer from 0 to 4. r represents an integer from 0 to 6.

[0179] The aromatic group X shown above may or may not have substituents on the benzene ring, but it is preferred to have substituents. When substituents are present, the substituent Z shown above can be exemplified. It is preferably at least one selected from the group consisting of alkyl, aryl, and halogen atoms having 6 or fewer carbon atoms, more preferably an alkyl group having 3 or fewer carbon atoms, and even more preferably a methyl group.

[0180] Furthermore, the polyphenylene ether structure shown above (YO)n1- may or may not have substituents on the benzene ring, but it is preferable to have substituents. When substituents are present, the substituent Z described above can be cited as an example, preferably an alkyl or phenyl group with 6 or fewer carbon atoms, more preferably an alkyl group with 3 or fewer carbon atoms, and even more preferably a methyl group.

[0181] When n1 and / or n2 are integers of 2 or more, the n1 structural units (YO) and / or n2 structural units can be the same or different. n2 is preferably 2 or more, and more preferably 2.

[0182] In equation (Rx-1), R 1 R 2 and R 3 Each can be independently represented by a hydrogen atom, alkyl group, alkenyl group, or alkynyl group.

[0183] R 1 Preferably, it is a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.

[0184] R 2 and R 3 Hydrogen atoms or alkyl groups are preferred individually, hydrogen atoms or methyl groups are more preferred, and hydrogen atoms are even more preferred.

[0185] As R 1 R 2 and R 3 The alkyl, alkenyl, or alkynyl groups preferably have 5 or fewer carbon atoms, more preferably 3 or fewer.

[0186] In formula (Rx-1), r represents an integer from 0 to 6, which can be an integer greater than or equal to 1. In addition, it is preferably an integer less than or equal to 5, more preferably an integer less than or equal to 4, further preferably an integer less than or equal to 3, even more preferably 1 or 2, and even more preferably 1.

[0187] In formula (Rx-1), Mc independently represents a hydrocarbon group with 1 to 12 carbon atoms, preferably a hydrocarbon group with 1 to 10 carbon atoms, more preferably a straight-chain or branched alkyl group with 1 to 10 carbon atoms, further preferably methyl, ethyl, isopropyl, isobutyl, tert-butyl, pentyl, octyl or nonyl, and even more preferably methyl, ethyl, isopropyl, isobutyl or tert-butyl.

[0188] In formula (Rx-1), z represents an integer from 0 to 4, preferably an integer from 0 to 3, more preferably an integer from 0 to 2, even more preferably 0 or 1, and even more preferably 0.

[0189] A specific example of the group represented by formula (Rx-1) is vinylbenzyl.

[0190] Examples of modified polyphenylene ether compounds (g) include compounds represented by formula (OP-1).

[0191]

[0192] (In formula (OP-1), X represents an aromatic group, -(YO)n2- represents a polyphenylene ether structure, R 1 R 2 and R 3 Each group independently represents a hydrogen atom, alkyl group, alkenyl group, or alkynyl group; n1 represents an integer from 0 to 6; n2 represents an integer from 1 to 100; and n3 represents an integer from 1 to 4.

[0193] The aromatic group X shown above may or may not have substituents on the benzene ring, but it is preferred to have substituents. When substituents are present, the substituent Z shown above can be exemplified. It is preferably at least one selected from the group consisting of alkyl, aryl, and halogen atoms having 6 or fewer carbon atoms, more preferably an alkyl group having 3 or fewer carbon atoms, and even more preferably a methyl group.

[0194] Furthermore, the polyphenylene ether structure shown above (YO)n2- may or may not have substituents on the benzene ring, but it is preferable to have substituents. When substituents are present, the substituent Z described above can be exemplified, preferably an alkyl or phenyl group with 6 or fewer carbon atoms, more preferably an alkyl group with 3 or fewer carbon atoms, and even more preferably a methyl group.

[0195] When n2 and / or n3 are integers of 2 or more, the n2 structural units (YO) and / or n3 structural units can be the same or different. n3 is preferably 2 or more, and more preferably 2.

[0196] The modified polyphenylene ether compound (g) in this embodiment is preferably the compound shown in formula (OP-2).

[0197]

[0198] Here, -(OXO)- is preferably represented by (OP-3) and / or formula (OP-4).

[0199]

[0200] (In formula (OP-3), R) 4 R 5 R 6 R 9 R 10 and R 11 Choose either the same or different, which are alkyl or phenyl groups having 6 or fewer carbon atoms. R 7 and R 9 (Optional, either the same or different, consisting of alkyl or phenyl groups with 6 or fewer hydrogen atoms.)

[0201]

[0202] (In equation (OP-4), R) 12 R 13 R 14 R 15 R 16 R 17 R 18 and R 19 (The following can be selected, either the same or different, and can be an alkyl or phenyl group with 6 or fewer carbon atoms, containing hydrogen atoms. -A- can be a straight-chain, branched, or cyclic divalent hydrocarbon group with 20 or fewer carbon atoms.)

[0203] In addition, -(YO)- is preferably represented by formula (OP-5).

[0204]

[0205] (In formula (OP-5), R) 20 R 21 Choose either the same or different, which are alkyl or phenyl groups having 6 or fewer carbon atoms. R 22 R 23 (Optional, either the same or different, consisting of alkyl or phenyl groups with 6 or fewer hydrogen atoms.)

[0206] Especially through R 20 and R 21 Each of the resin molecules has one or more methyl and / or cyclohexyl groups, which increases the rigidity of the resin molecules. Molecules with high rigidity have lower mobility compared to molecules with low rigidity, resulting in a longer relaxation time during dielectric relaxation and excellent low dielectric properties (Dk and / or Df, especially Dk), making them preferred.

[0207] An example of formula (OP-5) is the following structure.

[0208]

[0209] Regarding the polyphenylene ether compound having the above structure, reference can be made to the description in Japanese Patent Application Laid-Open No. 2019-194312, and its content is incorporated into this specification.

[0210] In Formula (OP-2), 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. a and b are each independently preferably an integer of 0 to 50, more preferably an integer of 1 to 30, and preferably an integer of 1 to 10. When a and / or b is an integer of 2 or more, two or more -(Y-O)- may be independently arranged in one structure, or may be block or randomly arranged in two or more structures.

[0211] In addition, when a compound represented by Formula (OP-2) is included in multiple types, the average value of a is preferably 1 < a < 10, and the average value of b is preferably 1 < b < 10.

[0212] 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) group, 1,3-phenylenebis(1-methylethylidene) group, cyclohexylidene, phenylmethylene, naphthylmethylene, 1-phenylethylidene group, etc., but are not limited thereto.

[0213] In the compound represented by the above Formula (OP-2), it is preferred that R 4 、R 5 、R 6 、R 9 、R 10 、R 11 、R 12 、R 13 、R 14 、R 15 、R 16 、R 17 、R 18 、R 19 、R 20 and R 21 are alkyl groups having 3 or fewer carbon atoms, and R 7 、R 8 、R 22 and R 23The polyphenylene ether compound is an alkyl group having 3 or fewer hydrogen atoms or carbon atoms. Particularly preferred are the -(OXO)- shown in formula (OP-3) or formula (OP-4) which are formulas (OP-9), (OP-10) and / or (OP-11), and the -(YO)- shown in formula (OP-5) which are formulas (OP-12) or (OP-13). When a and / or b are integers of 2 or more, the two or more -(YO)- are independently arranged in a structure consisting of two or more formulas (OP-12) and / or formula (OP-13), or they may be arranged in a block or random arrangement of formulas (OP-12) and (OP-13).

[0214]

[0215]

[0216] (In formula (OP-10), R) 44 R 45 R 46 and R 47 The atom can be either the same or different, and can be either hydrogen or methyl. -B- is a straight-chain, branched, or cyclic divalent hydrocarbon group with 20 or fewer carbon atoms.

[0217] -B- can be given as a specific example that is the same as the specific example of -A- in equation (OP-4).

[0218]

[0219] In formula (OP-11), -B- is a straight-chain, branched, or cyclic divalent hydrocarbon group with 20 or fewer carbon atoms.

[0220] -B- can be given as a specific example that is the same as the specific example of -A- in equation (OP-4).

[0221]

[0222]

[0223] The modified polyphenylene ether compound (g) is further preferably the compound shown in formula (OP-15).

[0224]

[0225] (In equation (OP-15), a and b independently represent integers from 0 to 100, and at least one of a and b is an integer from 1 to 100.)

[0226] In equation (OP-15), a and b have the same meaning as a and b in equation (OP-2), and the preferred range is also the same.

[0227] Alternatively, the polyphenylene ether compound used in this embodiment may also be a compound represented by formula (OP-16).

[0228]

[0229] (In equation (OP-16), x independently represents an integer from 0 to 100, and at least one of the two x's is an integer from 1 to 100.)

[0230] Polyphenylene ether compounds with carbon-carbon unsaturated double bonds at the ends can be manufactured by known methods or commercially available products can be used. Examples of commercially available modified polyphenylene ether compounds with vinyl benzyl ends include "OPE-2St1200" and "OPE-2St2200" manufactured by Mitsubishi Gas Chemical Co., Ltd. Alternatively, a modified polyphenylene ether compound with vinyl benzyl ends can be obtained by modifying a hydroxyl-terminated polyphenylene ether compound such as "SA90" manufactured by SABIC Innovative Plastics to vinyl benzyl using a vinyl benzyl chloride or similar substance.

[0231] Furthermore, details of polyphenylene ether compounds with carbon-carbon unsaturated double bonds at the ends can be found in Japanese Patent Application Publication No. 2006-028111, Japanese Patent Application Publication No. 2018-131519, International Publication No. 2019-138992, and International Publication No. 2022-054303, which are incorporated herein by reference.

[0232] The number-average molecular weight (details as described in the examples below) of polyphenylene ether compounds (preferably modified polyphenylene ether compounds (g)) with terminal carbon-carbon unsaturated double bonds, converted to polystyrene by GPC (gel permeation chromatography), is preferably 500 or more and 3,000 or less. By setting the number-average molecular weight to 500 or more, there is a tendency to further suppress stickiness when the resin composition of this embodiment is formed into a coating film. Furthermore, by setting the number-average molecular weight to 3,000 or less, there is a tendency to further improve solubility in solvents.

[0233] Furthermore, the weight-average molecular weight (according to the method described in the examples below) of the GPC-based polystyrene compound having carbon-carbon unsaturated double bonds at the ends (preferably a modified polyphenylene ether compound (g)) is preferably 800 or more and 10,000 or less, more preferably 800 or more and 5,000 or less. By setting the weight-average molecular weight to the aforementioned lower limit or above, there is a tendency for the relative permittivity (Dk) and dielectric loss tangent (Df) of the cured resin composition to become lower, and by setting it to the aforementioned upper limit or below, there is a tendency for the solubility, low viscosity, and formability of the resin composition in solvents when producing varnishes, etc., as described below below.

[0234] Furthermore, in polyphenylene ether compounds (preferably modified polyphenylene ether compounds (g)) having carbon-carbon unsaturated double bonds at their ends, the equivalent amount of carbon-carbon unsaturated double bonds at the ends is preferably 400 to 5000 g relative to each carbon-carbon unsaturated double bond, more preferably 400 to 2500 g. By making the equivalent amount of carbon-carbon unsaturated double bonds at the ends above the aforementioned lower limit, there is a tendency for the relative dielectric constant (Dk) and dielectric loss tangent (Df) of the cured resin composition to become lower, and by making it below the aforementioned upper limit, there is a tendency for the solubility, low viscosity, and formability of the resin composition in solvents to be further improved.

[0235] The functional group equivalent (carbon-carbon unsaturated double bond equivalent) of polyphenylene ether compounds with carbon-carbon unsaturated double bonds at the ends is obtained by measuring the double bond amount using an infrared spectrophotometer, and then calculated from its reciprocal.

[0236] The double bond equivalent [g / eq.] is calculated as follows.

[0237] Weigh and record the weight of the polyphenylene ether compound powder. Place the powder in a volumetric flask and dilute to the specified volume with carbon disulfide to prepare the test sample. Place the sample solution in the measurement cell and set it in an infrared spectrophotometer (FT / IR-4600, manufactured by Nippon Spectrophotometer Co., Ltd.). Then, perform infrared spectrophotometric determination of the sample solution. In the case of vinyl groups in the polyphenylene ether compound, record 905 cm⁻¹. -1 Peak areas in the nearby spectrum. With the carbon-carbon unsaturated double bond being methacrylonitrile, a peak area of ​​1640 cm⁻¹ is recorded. -1 The peak area of ​​the nearby spectrum. The double bond concentration [mol / L] is calculated from this area value and the standard curve as the measured value.

[0238] Next, the double bond equivalent is calculated using the following formula.

[0239] Double bond equivalent [g / eq.] = Weight of powder in the sample [g] / Double bond concentration [mol / L] × Volume of sample solution [L]

[0240] The functional group equivalent of thermosetting compounds other than polyphenylene ether compounds with carbon-carbon unsaturated double bonds at the ends can also be determined using the method described above. However, for compounds (monomers) that can be expressed as a single molecular weight, it is preferred to calculate the functional group equivalent by (theoretical molecular weight ÷ number of functional groups). In cases where two or more other thermosetting compounds are included, the functional group equivalent of the other thermosetting compounds is set as the sum (weighted average) of the values ​​obtained by multiplying the functional group equivalent of each other thermosetting compound by its mass fraction.

[0241] When the resin composition of this embodiment contains a polyphenylene ether compound having carbon-carbon unsaturated double bonds at the ends, the lower limit of its content relative to 100 parts by mass of the resin solids in the resin composition is preferably 1 part by mass or more, more preferably 5 parts by mass or more, further preferably 10 parts by mass or more, even more preferably 15 parts by mass or more, even more preferably 20 parts by mass or more, and can be 30 parts by mass or more, or 35 parts by mass or more, depending on the application, etc. By making the content of the polyphenylene ether compound having carbon-carbon unsaturated double bonds at the ends at the aforementioned lower limit, there is a tendency to further improve the formability of the resin composition, the heat resistance of the obtained cured product, the low water absorption, and the low dielectric properties (Dk and / or Df). In addition, the upper limit of the content of the polyphenylene ether compound having carbon-carbon unsaturated double bonds at the ends relative to 100 parts by mass of the resin solids in the resin composition is preferably 90 parts by mass or less, more preferably 80 parts by mass or less, and can also be 70 parts by mass or less, 60 parts by mass or less, or 50 parts by mass or less. By keeping the content of polyphenylene ether compound below the aforementioned upper limit, there is a tendency to obtain cured products with improved low dielectric properties (especially low dielectric loss tangent) and chemical resistance.

[0242] The resin composition in this embodiment may contain only one polyphenylene ether compound having a carbon-carbon unsaturated double bond at the end, or it may contain two or more. When containing two or more compounds, the total amount is preferably within the range described above.

[0243] <<<Other Aromatic Vinyl Resins (D)>>>

[0244] In addition to the above, for aromatic vinyl resins (D), 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 contents of which are incorporated herein by reference.

[0245] <<Maleimide Compound (E)>>

[0246] The resin composition of this embodiment preferably contains a maleimide compound (E).

[0247] In this embodiment, the maleimide compound (E) is preferably a compound having one or more (preferably two or more, more preferably two to twelve, further preferably two to six, even more preferably two to four, even more preferably two or three, even more preferably two) maleimide groups in one molecule.

[0248] More specifically, the maleimide compound (E) preferably comprises one or more compounds selected from the group consisting of compounds shown in formulas (M0) to (M7), more preferably comprises one or more compounds selected from the group consisting of compounds shown in formula (M0), formula (M1), formula (M3), formula (M4), and formula (M5), and even more preferably comprises one or more compounds selected from the group consisting of compounds shown in formula (M0), formula (M1), formula (M3), and formula (M5). From the viewpoint of low dielectric properties (Dk and / or Df), it is further preferred to include the compound shown in formula (M1).

[0249]

[0250] (In formula (M0), R) 51 Each of the following independently represents a hydrogen atom, an alkyl group or a phenyl group having 1 to 8 carbon atoms, and R. 52 Each can be used independently to represent a hydrogen atom or a methyl group, and n1 represents an integer greater than or equal to 1.

[0251] R 51 The atom is preferably a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, or phenyl, more preferably one of a hydrogen atom and a methyl atom, and even more preferably a hydrogen atom.

[0252] R 52 Methyl is preferred.

[0253] n1 is preferably an integer from 1 to 10, more preferably an integer from 1 to 5, even more preferably an integer from 1 to 3, even more preferably 1 or 2, and even more preferably 1.

[0254] The compound represented by formula (M0) can be a single compound or a mixture of two or more compounds. Examples of mixtures include mixtures of compounds with different n1 values, and R... 51 and / or R 52This includes mixtures of compounds with different types of substituents, mixtures of compounds with different bonding positions (meta, para, or ortho) of the maleimide group and oxygen atom relative to the benzene ring, and mixtures of compounds combining two or more of the above-mentioned different positions. The same applies to the compounds shown in formulas (M1) to (M7) below.

[0255]

[0256] (In formula (M1), R) M1 R M2 R M3 and R M4 Each can be used independently to represent a hydrogen atom or an organic group. R M5 and R M6 Each can be used independently to represent a hydrogen atom or an alkyl group. Ar M This indicates a divalent aromatic group. A is an alicyclic group with a 4- to 6-membered ring. R M7 and R M8 Each is an alkyl group, independently. mx is 1 or 2, lx is 0 or 1. R M9 and R M10 Each can be used independently to represent a hydrogen atom or an alkyl group. R M11 R M12 R M13 and R M14 Each can be used independently to represent a hydrogen atom or an organic group. R M15 Each of these groups independently represents an alkyl group (1-10 carbon atoms), an alkoxy group (1-10 carbon atoms), an alkylthio group (1-10 carbon atoms), a cycloalkyl group (3-10 carbon atoms), an aryl group (6-10 carbon atoms), an aryloxy group (6-10 carbon atoms), an arylthio group (6-10 carbon atoms), a halogen atom, a hydroxyl group, or a mercapto group. px represents an integer from 0 to 3. nx represents an integer from 1 to 20.

[0257] R in the formula M1 R M2 R M3 and R M4 Each can be represented independently as a hydrogen atom or an organic group. The organic group here is preferably an alkyl group, more preferably an alkyl group with 1 to 12 carbon atoms, even more preferably an alkyl group with 1 to 6 carbon atoms, and even more preferably methyl, ethyl, propyl, or butyl, with methyl being particularly preferred. R M1 and R M3 Each is preferably an alkyl group, R. M2 and R M4 Hydrogen atoms are preferred.

[0258] R M5 and R M6Each of the hydrogen atoms or alkyl groups is represented independently, 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, and even more preferably methyl, ethyl, propyl, or butyl, with methyl being particularly preferred.

[0259] Ar M The aromatic group representing the divalent group is preferably phenylene, naphthyl, phenanthrene, or anthracene, more preferably phenylene, and even more preferably m-phenylene. Ar M It may have substituents, with alkyl groups being preferred, more preferably alkyl groups having 1 to 12 carbon atoms, further preferably alkyl groups having 1 to 6 carbon atoms, and even more preferably methyl, ethyl, propyl, or butyl, with methyl being particularly preferred. However, Ar M Preferably unsubstituted.

[0260] A is a 4- to 6-membered alicyclic group, more preferably a 5-membered alicyclic group (preferably a group that forms an inden ring together with the benzene ring). By making A a 5-membered alicyclic group that forms an inden ring together with the benzene ring, there is a tendency to further improve the low dielectric properties (Dk and / or Df) of the obtained cured product. R M7 and R M8 Each of the components 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 a methyl group.

[0261] mx is 1 or 2, preferably 2.

[0262] lx is 0 or 1, preferably 1.

[0263] R M9 and R M10 Each of the above can be used to represent a hydrogen atom or an alkyl group, more 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, and even more preferably methyl, ethyl, propyl, or butyl, with methyl being particularly preferred.

[0264] R M11 R M12 R M13 and R M14 Each can be represented independently as a hydrogen atom or an organic group. The organic group here is preferably an alkyl group, more preferably an alkyl group with 1 to 12 carbon atoms, even more preferably an alkyl group with 1 to 6 carbon atoms, and even more preferably methyl, ethyl, propyl, or butyl, with methyl being particularly preferred. R M12 and R M13 Each is preferably an alkyl group, R. M11 and R M14 Hydrogen atoms are preferred.

[0265] R M15Each of the following can be independently represented: alkyl group with 1 to 10 carbon atoms, alkoxy group with 1 to 10 carbon atoms, alkylthio group with 1 to 10 carbon atoms, cycloalkyl group with 3 to 10 carbon atoms, aryl group with 6 to 10 carbon atoms, aryloxy group with 6 to 10 carbon atoms, arylthio group with 6 to 10 carbon atoms, halogen atom, hydroxyl group or mercapto group, preferably alkyl group with 1 to 4 carbon atoms, cycloalkyl group with 3 to 6 carbon atoms or aryl group with 6 to 10 carbon atoms.

[0266] px represents an integer from 0 to 3, preferably an integer from 0 to 2, more preferably 0 or 1, and even more preferably 0.

[0267] nx represents an integer from 1 to 20. nx can also be an integer less than 10.

[0268] It should be noted that the resin composition of this embodiment may contain only one compound represented by formula (M1) and at least two compounds with different nx values, or it may contain two or more compounds. When two or more compounds are contained, in order to produce a low melting point (low softening point), low melt viscosity, and excellent workability, the average value (average number of repeating units) n of nx in the compound represented by 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 even 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, even more preferably 6.0 or less, and may also be 5.0 or less. The same applies to formulas (M1-1) and the like described later.

[0269] The compound represented by formula (M1) is preferably the compound represented by the following formula (M1-1).

[0270]

[0271] (In formula (M1-1), R) M21 R M22 R M23 and R M24 Each can be used independently to represent a hydrogen atom or an organic group. R M25 and R M26 Each can be used independently to represent a hydrogen atom or an alkyl group. R M27 R M28 R M29 and R M30 Each can be used independently to represent a hydrogen atom or an organic group. R M31 and R M32 Each can be used independently to represent a hydrogen atom or an alkyl group. R M33 R M34 R M35 and R M36 Each can be used independently to represent a hydrogen atom or an organic group. R M37 RM38 and R M39 Each can be used independently to represent a hydrogen atom or an alkyl group. nx represents an integer greater than 1 and less than 20.

[0272] R in the formula M21 R M22 R M23 and R M24 Each can be independently represented by a hydrogen atom or an organic group. The organic group here is preferably an alkyl group, more preferably an alkyl group with 1 to 12 carbon atoms, even more preferably an alkyl group with 1 to 6 carbon atoms, and even more preferably methyl, ethyl, propyl, or butyl, with methyl being particularly preferred. R M21 and R M23 Preferably alkyl, R M22 and R M24 Hydrogen atoms are preferred.

[0273] R M25 and R M26 Each of the hydrogen atoms or alkyl groups is represented independently, 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, and even more preferably methyl, ethyl, propyl, or butyl, with methyl being particularly preferred.

[0274] R M27 R M28 R M29 and R M30 Each can be represented independently as 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 with 1 to 12 carbon atoms, even more preferably an alkyl group with 1 to 6 carbon atoms, and even more preferably methyl, ethyl, propyl, or butyl, with methyl being particularly preferred.

[0275] R M31 and R M32 Each of the hydrogen atoms or alkyl groups is represented independently, 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, and even more preferably methyl, ethyl, propyl, or butyl, with methyl being particularly preferred.

[0276] R M33 R M34 R M35 and R M36 Each of these can be used to independently represent a hydrogen atom or an organic group. The organic group here is preferably an alkyl group, more preferably an alkyl group with 1 to 12 carbon atoms, even more preferably an alkyl group with 1 to 6 carbon atoms, and even more preferably methyl, ethyl, propyl, or butyl, with methyl being particularly preferred.

[0277] R M33 and R M36 Preferably, hydrogen atoms, RM34 and R M35 Alkyl groups are preferred.

[0278] R M37 R M38 R M39 Each of the hydrogen atoms or alkyl groups is represented independently, 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, and even more preferably methyl, ethyl, propyl, or butyl, with methyl being particularly preferred.

[0279] nx represents an integer greater than 1 and less than 20. nx can also be an integer less than 10.

[0280] The compound represented by formula (M1-1) is preferably the compound represented by formula (M1-2) below.

[0281]

[0282] (In formula (M1-2), R) M21 R M22 R M23 and R M24 Each can be used independently to represent a hydrogen atom or an organic group. R M25 and R M26 Each can be used independently to represent a hydrogen atom or an alkyl group. R M27 R M28 R M29 and R M30 Each can be used independently to represent a hydrogen atom or an organic group. R M31 and R M32 Each can be used independently to represent a hydrogen atom or an alkyl group. R M33 R M34 R M35 and R M36 Each can be used independently to represent a hydrogen atom or an organic group. R M37 R M38 and R M39 Each can be used independently to represent a hydrogen atom or an alkyl group. nx represents an integer greater than 1 and less than 20.

[0283] In formula (M1-2), R 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 RM34 R M35 R M36 R M37 R M38 R M39 and nx are respectively related to R in equation (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 It has the same meaning as nx, and the preferred range is also the same.

[0284] The compound represented by formula (M1-1) is further preferably the compound represented by formula (M1-3) below, and more preferably the compound represented by formula (M1-4) below.

[0285]

[0286] (In formula (M1-3), nx represents an integer greater than 1 and less than 20.)

[0287] nx can be an integer less than 10.

[0288]

[0289] (In formula (M1-4), nx represents an integer greater than 1 and less than 20.)

[0290] The molecular weight of the compound represented by formula (M1) is preferably 500 or more, more preferably 600 or more, and even more preferably 700 or more. By setting it to the aforementioned lower limit or above, the low dielectric properties and low water absorption of the obtained cured product tend to be further improved. Furthermore, the molecular weight of the compound represented by formula (M1) is preferably 10,000 or less, more preferably 9,000 or less, even more preferably 7,000 or less, even more preferably 5,000 or less, and even more preferably 4,000 or less. By setting it to the aforementioned upper limit or below, the heat resistance and workability of the obtained cured product tend to be further improved.

[0291]

[0292] (In formula (M2), R) 54 Each can be used independently to represent a hydrogen atom or a methyl group, and n4 represents an integer greater than or equal to 1.

[0293] n4 is preferably an integer from 1 to 10, more preferably an integer from 1 to 5, even more preferably an integer from 1 to 3, and even more preferably 1 or 2, but can also be 1.

[0294] The compound represented by formula (M2) can be a mixture of n4 different compounds, preferably a mixture. Additionally, as described in part of the compound represented by formula (M0), it can also be a mixture of other compounds with different components.

[0295]

[0296] (In formula (M3), R) 55 Each of the following can be independently represented: an alkyl group with 1 to 8 carbon atoms, or a phenyl group; n5 represents an integer greater than 1 and less than 10.

[0297] R 55 The atom is preferably a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, or phenyl, more preferably one of a hydrogen atom and a methyl atom, and even more preferably a hydrogen atom.

[0298] n5 is preferably an integer greater than or equal to 1 and less than or equal to 5, more preferably an integer from 1 to 3, and even more preferably 1 or 2.

[0299] The compound represented by formula (M3) can be a mixture of n5 different compounds, preferably a mixture. Additionally, as described in part of the compound represented by formula (M0), it can also be a mixture of other compounds with different components.

[0300]

[0301] (In formula (M4), R) 56 Each can independently represent a hydrogen atom, a methyl group, or an ethyl group, R. 57 Each can be used independently to represent a hydrogen atom or a methyl group.

[0302]

[0303] (In formula (M5), R) 58 Each of the following independently represents a hydrogen atom, an alkyl group or a phenyl group having 1 to 8 carbon atoms, and R. 59 Each can be used independently to represent a hydrogen atom or a methyl group, and n6 represents an integer greater than or equal to 1.

[0304] R 58The atom is preferably a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, or phenyl, more preferably one of a hydrogen atom and a methyl atom, and even more preferably a hydrogen atom.

[0305] R 59 Methyl is preferred.

[0306] n6 is preferably an integer from 1 to 10, more preferably an integer from 1 to 5, even more preferably an integer from 1 to 3, and even more preferably 1 or 2, or it can be 1.

[0307] The compound represented by formula (M5) can be a mixture of n6 different compounds, preferably a mixture. Additionally, as described in part of the compound represented by formula (M0), it can also be a mixture of other compounds with different components.

[0308] Maleimide compound (M6) is a compound having the structural unit shown in formula (M6) and maleimide groups at both ends of the molecular chain.

[0309]

[0310] (In formula (M6), R) 61 R represents a straight-chain or branched alkylene group having 1 to 16 carbon atoms, or a straight-chain or branched alkenyl group having 2 to 16 carbon atoms. 62 R represents a straight-chain or branched alkylene group having 1 to 16 carbon atoms, or a straight-chain or branched alkenyl group having 2 to 16 carbon atoms. 63 Each of the following groups independently represents a straight-chain or branched alkyl group with 1 to 16 carbon atoms, or a straight-chain or branched alkenyl group with 2 to 16 carbon atoms. n independently represents an integer from 0 to 10.

[0311] For details of the maleimide compound (M6) and its manufacturing method, please refer to paragraphs 0061 to 0066 of International Publication No. 2020 / 262577, the contents of which are incorporated herein by reference.

[0312] Maleimide compound (M7) is a maleimide compound that uses an aromatic amine compound (a1) having one or more but three or fewer alkyl groups on an aromatic ring, an aromatic divinyl compound (a2) having two vinyl groups, and maleic anhydride as reactants (1).

[0313] The maleimide compound (M7) is preferably a compound represented by formula (M7).

[0314]

[0315] (In the above formula (M7), R) 1R represents alkyl groups with 1 to 10 carbon atoms, each independently. 2 Each of the following can be independently represented: alkyl, alkoxy, or alkylthio group having 1 to 10 carbon atoms; aryl, aryloxy, or arylthio group having 6 to 10 carbon atoms; cycloalkyl group having 3 to 10 carbon atoms; halogen atom; hydroxyl group; or mercapto group.

[0316] R 3 R 4 R 5 and R 6 Each can independently represent 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.

[0317] X 1 Let each of the substituents shown in the following equation (x) be represented independently, where r is the number of substituents bonded to each of X. 1 X of the benzene ring 1 The average of the substitution numbers, where 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.

[0318]

[0319] (In equation (x), R) 7 and R 8 Each can independently represent 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 of these groups independently represents an alkyl, alkoxy, or alkylthio group with 1 to 10 carbon atoms; an aryl, aryloxy, or arylthio group with 6 to 10 carbon atoms; a cycloalkyl group with 3 to 10 carbon atoms; a halogen atom; a hydroxyl group; or a mercapto group, where t represents an integer from 0 to 4.

[0320] For details regarding the maleimide compound (M7) used in this embodiment, please refer to the description in Japanese Patent No. 7160151, the contents of which are incorporated herein by reference.

[0321] Maleimide compounds (E) can be manufactured by known methods or commercially available products can be used. Examples of commercially available products include: "BMI-80" manufactured by K·I Chemical Industry Co., Ltd. as a compound of formula (M0); "NE-X-9470S" and "NE-X-9480S" manufactured by DIC Co., Ltd. as compounds of formula (M1); "BMI-2300" manufactured by Daiwa Fine Chemicals Co., Ltd. as a compound of formula (M2); "MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd. as a compound of formula (M3); and "M4" manufactured by K·IChemical Industry Co., Ltd. as a compound of formula (M4). BMI-70 manufactured by Co., Ltd., MIR-5000 manufactured by Nippon Kayaku Co., Ltd. as a compound represented by formula (M5), MIZ-001 manufactured by Nippon Kayaku Co., Ltd. as a maleimide compound (M6), and NE-X-9500 manufactured by DIC Co., Ltd. as a maleimide compound (M7).

[0322] In addition to the above, for maleimide compounds (E), reference can be made to compounds described in paragraphs 0061 to 0066 of International Publication No. 2020 / 262577 and Japanese Patent No. 7160151, the contents of which are incorporated herein by reference.

[0323] In addition, as maleimide compounds (E) other than those mentioned above, examples include compounds having two or more maleimide groups. Specifically, examples include m-phenylene bismaleimide, 2,2-bis(4-(4-maleimidephenoxy)-phenyl)propane, 4-methyl-1,3-phenylene bismaleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, 4,4'-diphenyl ether bismaleimide, 4,4'-diphenyl sulfone bismaleimide, 1,3-bis(3-maleimidephenoxy)benzene, 1,3-bis(4-maleimidephenoxy)benzene, and their prepolymers, as well as prepolymers of these maleimides and amines.

[0324] The maleimide equivalent of the maleimide compound (E) is preferably 130 g / eq. or more, more preferably 150 g / eq. or more, further preferably 170 g / eq. or more, even more preferably 180 g / eq. or more, even more preferably 200 g / eq. or more, and preferably 1000 g / eq. or less, more preferably 800 g / eq. or less, even more preferably 700 g / eq. or less, even more preferably 600 g / eq. or less, and even more preferably 500 g / eq. or less. By setting the value to the aforementioned lower limit or above, the resulting cured product tends to have superior low dielectric properties (Dk and / or Df, especially Df). Furthermore, by setting the value to the aforementioned upper limit or below, the resulting cured product tends to have superior peel strength.

[0325] When the resin composition of this embodiment contains maleimide compound (E), the lower limit of its content relative to 100 parts by weight of the resin solids in the resin composition is preferably 1 part by weight or more, more preferably 5 parts by weight or more, further preferably 10 parts by weight or more, and even more preferably 15 parts by weight or more. Depending on the application, it can be 20 parts by weight or more, 25 parts by weight or more, or 30 parts by weight or more. By making the content of maleimide compound (E) 1 part by weight or more, there is a tendency to improve the flame retardancy of the obtained cured product. In addition, the upper limit of the content of maleimide compound (E) relative to 100 parts by weight of the resin solids in the resin composition is preferably 90 parts by weight or less, more preferably 80 parts by weight or less, further preferably 70 parts by weight or less, even more preferably 60 parts by weight or less, and even more preferably 50 parts by weight or less. Depending on the application, it can be 40 parts by weight or less or 30 parts by weight or less. By making the content of maleimide compound (E) 90 parts by weight or less, there is a tendency to improve peel strength and low water absorption.

[0326] The resin composition in this embodiment may contain only one maleimide compound (E), or it may contain two or more. When it contains two or more, the total amount is preferably within the range described above.

[0327] <<Cyanate Compounds>>

[0328] The resin composition of this embodiment may contain a cyanate ester compound. The cyanate ester compound in this embodiment is not particularly limited as long as it contains one or more (preferably two or more, more preferably two to twelve, further preferably two to six, even more preferably two to four, even more preferably two or three, even more preferably two) cyanate ester groups (cyanoxy groups) within one molecule; compounds commonly used in the field of printed circuit boards can be widely used. Furthermore, the cyanate ester compound is preferably a compound in which the cyanate ester group is directly bonded to an aromatic backbone (aromatic ring).

[0329] Preferred cyanate compounds in this embodiment include, for example, at least one selected from the group consisting of phenolic varnish-type cyanate compounds, naphthol aralkyl-type cyanate compounds (naphthol aralkyl-type cyanate), naphthyl 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, bisphenol A-type cyanate compounds, and diallyl bisphenol A-type cyanate compounds. From the viewpoint of further improving the low water absorption of the obtained cured product, at least one selected from the group consisting of phenolic varnish-type cyanate compounds, naphthol aralkyl-type cyanate compounds, naphthyl ether-type cyanate compounds, xylene resin-type cyanate compounds, bisphenol M-type cyanate compounds, bisphenol A-type cyanate compounds, and diallyl bisphenol A-type cyanate compounds is more preferred; at least one selected from the group consisting of phenolic varnish-type cyanate compounds and naphthol aralkyl-type cyanate compounds is even more preferred; and naphthol aralkyl-type cyanate compounds are even more preferred.

[0330] These cyanate compounds can be prepared using known methods or commercially available products. It should be noted that cyanate compounds with naphthol aralkyl, naphthyl ether, xylene, triphenol methane, or adamantane skeletons have a higher functional group equivalent number and fewer unreacted cyanate groups; therefore, cured resin compositions using these compounds tend to have superior low water absorption. Furthermore, primarily due to the presence of aromatic or adamantane skeletons, there is a tendency for further improved plating adhesion.

[0331] As a naphthol aralkyl cyanate compound, the compound shown in the following formula (1) is more preferred.

[0332]

[0333] (In equation (1), R) 3 Each can be used independently to represent a hydrogen atom or a methyl group, and n3 represents an integer greater than or equal to 1.

[0334] In equation (1), R 3Each can be represented independently as a hydrogen atom or a methyl group, with hydrogen atom being preferred.

[0335] In formula (1), n3 is an integer of 1 or more, preferably an integer of 1 to 20, more preferably an integer of 1 to 10, and even more preferably an integer of 1 to 6.

[0336] Furthermore, there are no particular limitations on the phenolic varnish-type cyanate compound, but the compound shown in formula (VII) below is preferred.

[0337]

[0338] (In equation (VII), R) 6 Each can be used independently to represent a hydrogen atom or a methyl group, and n7 represents an integer greater than or equal to 1.

[0339] In equation (VII), R 6 Each can be represented independently as a hydrogen atom or a methyl group, with hydrogen atom being preferred.

[0340] 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 even more preferably an integer of 1 to 6.

[0341] As a bisphenol A type cyanate compound, one or more of the group consisting of prepolymers of 2,2-bis(4-cyanoxyphenyl)propane and 2,2-bis(4-cyanoxyphenyl)propane can be used.

[0342] The resin composition of this embodiment preferably contains a cyanate ester compound within a range that does not impair the effects of the present invention. When the resin composition of this embodiment contains a cyanate ester compound, the lower limit of its content relative to 100 parts by mass of the resin solids in the resin composition is preferably 0.1 parts by mass or more, more preferably 2 parts by mass or more, further preferably 3 parts by mass or more, and even more preferably 5 parts by mass or more. By making the content of the cyanate ester compound 0.1 parts by mass or more, there is a tendency for the resulting cured product to have improved heat resistance, flame resistance, chemical resistance, low dielectric properties (low relative permittivity, low dielectric loss tangent), and insulation. When the resin composition of this embodiment contains a cyanate ester compound, the upper limit of the content of the cyanate ester compound relative to 100 parts by mass of the resin solids in the resin composition is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, further preferably 20 parts by mass or less, even more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less.

[0343] The resin composition in this embodiment may contain only one cyanate ester compound, or it may contain two or more. When it contains two or more, the total amount is preferably within the range described above.

[0344] <<(Methyl)allyl compounds>>

[0345] The resin composition of this embodiment may contain a (methyl)allyl compound. Preferably, the (methyl)allyl compound contains an allyl compound.

[0346] Furthermore, the (methyl)allyl compound is preferably a compound containing two or more (methyl)allyl groups, and more preferably a compound containing two or more allyl groups.

[0347] As a (methyl)allyl compound, it preferably comprises at least one selected from the group consisting of (methyl)allyl isocyanurate compounds, tri(methyl)allyl cyanurate compounds, (methyl)allyl-substituted nadicimide compounds, (methyl)allyl compounds having a glycourea structure, and diallyl phthalate; more preferably, it comprises at least one selected from the group consisting of (methyl)allyl isocyanurate compounds, (methyl)allyl-substituted nadicimide compounds, and (methyl)allyl compounds having a glycourea structure; even more preferably, it comprises (methyl)allyl isocyanurate compounds and / or (methyl)allyl-substituted nadicimide compounds; and even more preferably, it comprises (methyl)allyl-substituted nadicimide compounds.

[0348] Examples of cyanurate tri(methyl)allyl compounds include cyanurate tri(methyl)allyl compounds (e.g., cyanurate triallyl esters with structures shown below).

[0349]

[0350] In addition, as (methyl)allyl compounds, examples of resins containing allyl groups described in International Publication No. 2022 / 210095 (such as the compounds described in Synthesis Examples 3, 4, 6, 20, and 22 of that publication) are incorporated herein by reference.

[0351] When the resin composition of this embodiment contains a (methyl)allyl compound, its molecular weight is preferably 195 or more, more preferably 300 or more, and can be 400 or more, 500 or more. By setting it to the aforementioned lower limit or above, there is a tendency to further improve low dielectric properties and heat resistance. The molecular weight of the (methyl)allyl compound is also preferably 3000 or less, more preferably 2000 or less, further preferably 1000 or less, and even more preferably 800 or less. By setting it to the aforementioned upper limit or below, there is a tendency to further improve low thermal expansion.

[0352] When the resin composition of this embodiment contains a (methyl)allyl compound, its content is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and even more preferably 5 parts by mass or more, and can be 10 parts by mass or more, relative to 100 parts by mass of the resin solids in the resin composition. By setting the content of the (methyl)allyl compound to the above-mentioned lower limit value or above, there is a tendency for excellent formability and further improved heat resistance. In addition, the upper limit value of the content of the (methyl)allyl compound relative to 100 parts by mass of the resin solids in the resin composition is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 20 parts by mass or less. By setting the content of the (methyl)allyl compound to the above-mentioned upper limit value or less, there is a tendency for further improved low thermal expansion.

[0353] The resin composition of this embodiment may contain only one (methyl)allyl compound, or it may contain two or more. When it contains two or more compounds, the total amount is preferably within the range described above.

[0354] <<<(Methyl)allyl isocyanurate compounds>>>

[0355] There are no particular limitations on (methyl)allyl isocyanurate compounds, as long as they have two or more (methyl)allyl groups and an isocyanurate ring (triazacyclohexanetrione (Nurlat) skeleton). Because (methyl)allyl isocyanurate compounds have a large number of (methyl)allyl groups that serve as crosslinking points, they tend to cure firmly with maleimide compounds (E), resulting in cured products with low dielectric properties (Dk and / or Df) and excellent heat resistance. The compound shown in formula (TA) is preferred as a (methyl)allyl isocyanurate compound.

[0356] Formula (TA)

[0357]

[0358] (In formula (TA), R A (Indicates substituent).

[0359] In formula (TA), R A The term indicates a substituent, more preferably a substituent with a formula weight of 15 to 500.

[0360] R A The first example is an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms. By using allyl compounds having 1 to 22 alkyl groups or 2 to 22 alkenyl groups, it is possible to provide resin compositions with excellent crosslinking properties and yield cured products with high toughness. Thus, even when the resin composition does not contain a substrate such as glass cloth, cracking during etching processes can be suppressed.

[0361] From the viewpoint of improving operability, the aforementioned alkyl and / or alkenyl groups preferably have 3 or more carbon atoms, more preferably 8 or more, further preferably 12 or more, and preferably 18 or less. Therefore, the resin composition exhibits better resin flowability, and the circuit filling properties, etc., are improved when using the resin composition of this embodiment to fabricate multilayer circuit boards, etc.

[0362] R A The second example is a group containing an allyl isocyanurate group. R A When containing an allyl isocyanurate group, the compound represented by formula (TA) is preferably the compound represented by formula (TA-1).

[0363] Formula (TA-1)

[0364]

[0365] (In formula (TA-1), R A2 (It is a divalent linker.)

[0366] In formula (TA-1), R A2 Preferably, it is a divalent linker with a formula weight of 54 to 250, more preferably a divalent linker with a formula weight of 54 to 250 and carbon atoms at both ends, and even more preferably an aliphatic hydrocarbon group with 2 to 20 carbon atoms (wherein, the aliphatic hydrocarbon group may include an ether group, and may also have a hydroxyl group). More specifically, R A2 Preferably, it is a group represented by any of the following formulas (i) to (iii).

[0367]

[0368] (In equations (i) to (iii), p) c1 The number of repeating units of the methylene group is an integer from 2 to 18. c2 Indicates the number of repeating units of the oxyethylidene group, which is 0 or 1. * indicates the bonding site.

[0369] The above p c1 Preferably, it is an integer from 2 to 10, more preferably an integer from 3 to 8, and even more preferably an integer from 3 to 5.

[0370] The above p c2 It can be 0 or 1, but 1 is preferred.

[0371] R A The third example is a phosphorus-based substituent.

[0372] R A2 The first example is preferred.

[0373] In this embodiment, the equivalent of the reactive group (allyl) in the compound represented by formula (TA) is preferably 1000 g / eq. or less. It is believed that if the aforementioned equivalent is 1000 g / eq. or less, a high Tg can be obtained more reliably.

[0374] Examples of alkyl groups having 1 to 22 carbon atoms include straight-chain or branched alkyl groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, and docosyl. Examples of alkenyl groups having 2 to 22 carbon atoms include allyl and decenyl.

[0375] Specific examples of compounds represented by formula (TA) include, for example, 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-docodecyl-1,3-diallyl isocyanurate, and 5-decenyl-1,3-diallyl isocyanurate. They can be used alone or in combination of two or more, and can also be used in the form of prepolymers.

[0376] The method of manufacturing the compound shown in formula (TA) is not particularly limited. For example, it can be obtained by reacting diallyl isocyanurate with an alkyl halide in an aprotic polar solvent such as N,N'-dimethylformamide in the presence of alkaline substances such as sodium hydroxide, potassium carbonate, and triethylamine at a temperature of about 60°C to 150°C.

[0377] Alternatively, commercially available products can be used as the compounds represented by formula (TA). There are no particular limitations on commercially available products; examples include L-DAIC manufactured by Shikoku Chemical Industry Co., Ltd., and P-DAIC manufactured by Shikoku Chemical Industry Co., Ltd., which has phosphorus-based substituents. As a triallyl isocyanurate, TAIC manufactured by Shin-Mitsubishi Corporation can be cited as an example. As a compound represented by formula (TA-1), DD-1 manufactured by Shikoku Chemical Industry Co., Ltd. can be cited as an example.

[0378] The molecular weight of the (methyl)allyl isocyanurate compound (preferably the compound shown in formula (TA)) is preferably 200 or more, more preferably 300 or more, and can be 400 or more, or 500 or more. By setting the aforementioned molecular weight to the aforementioned lower limit or above, there is a tendency to further improve the low dielectric properties (Dk and / or Df) and heat resistance of the obtained cured product. Furthermore, the molecular weight of the (methyl)allyl isocyanurate compound (preferably the compound shown in 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 aforementioned upper limit or below, there is a tendency to further improve the low thermal expansion properties of the obtained cured product.

[0379] When the resin composition of this embodiment contains a (methyl)allyl isocyanurate compound, its content is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and even more preferably 5 parts by mass or more, and can be 10 parts by mass or more, relative to 100 parts by mass of the resin solids in the resin composition. By setting the content of the (methyl)allyl isocyanurate compound to the aforementioned lower limit or above, there is a tendency to further improve the formability of the resin composition, the heat resistance of the obtained cured product, and the low thermal expansion. In addition, the upper limit of the content of the (methyl)allyl isocyanurate compound relative to 100 parts by mass of the resin solids in the resin composition is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and can also be 20 parts by mass or less. By setting the content of the (methyl)allyl isocyanurate compound to the aforementioned upper limit or below, there is a tendency to further improve the heat resistance and low dielectric properties (Dk and / or Df) of the obtained cured product.

[0380] The resin composition of this embodiment may contain only one (methyl)allyl isocyanurate compound, or it may contain two or more. When it contains two or more compounds, the total amount is preferably within the range described above.

[0381] <<<(Methyl)allyl-substituted nadicimide compounds>>>

[0382] As a (methyl)allyl-substituted nadicimide compound, there is no particular limitation as long as the molecule has two or more (methyl)allyl-substituted nadicimide groups. Specific examples include compounds represented by the following formula (AN-1).

[0383]

[0384] In formula (AN-1), R1 independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R2 represents an alkylene group, phenylene group, biphenylene group, naphthylene group, or a group represented by formula (AN-2) or formula (AN-3) having 1 to 6 carbon atoms.

[0385]

[0386] (In formula (AN-2), R3 represents a group represented by methylene, isopropylidene, -C(=O)-, -O-, -S-, or -S(=O)2-.)

[0387]

[0388] (In formula (AN-3), R4 independently represents an alkylene group having 1 to 4 carbon atoms or a cycloalkylene group having 5 to 8 carbon atoms.)

[0389] In addition, the compound shown in formula (AN-1) may also be a commercially available product. There are no particular limitations on what constitutes a commercially available product; examples include the compound shown in formula (AN-4) (BANI-M (manufactured by Maruzen Petrochemical Co., Ltd.)) and the compound shown in formula (AN-5) (BANI-X (manufactured by Maruzen Petrochemical Co., Ltd.)). One or more of these compounds may be used.

[0390] Formula (AN-4)

[0391]

[0392]

[0393] The molecular weight of the (methyl)allyl-substituted nadicimide compound (preferably the compound shown in formula (AN)) is preferably 400 or more, more preferably 500 or more, and may also be 550 or more. Setting the molecular weight of the (methyl)allyl-substituted nadicimide compound to the aforementioned lower limit or higher tends to further improve low dielectric properties, low thermal expansion, and heat resistance. The molecular weight of the (methyl)allyl-substituted nadicimide compound (preferably the compound shown in formula (AN)) is also preferably 1500 or less, more preferably 1000 or less, and even more preferably 800 or less, and may be 700 or less, or 600 or less. Setting the molecular weight of the (methyl)allyl-substituted nadicimide compound to the aforementioned upper limit or lower tends to further improve formability and peel strength.

[0394] When the resin composition of this embodiment contains a (methyl)allyl-substituted nadicimide compound (preferably a 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 can be 10 parts by mass or more, relative to 100 parts by mass of the resin solids in the resin composition. By setting the content of the (methyl)allyl-substituted nadicimide compound to the aforementioned lower limit or above, there is a tendency to improve formability, low dielectric properties, low thermal expansion, and further heat resistance. In addition, the upper limit of the content of the (methyl)allyl-substituted nadicimide compound (preferably a compound represented by formula (AN)) relative to 100 parts by mass of the resin solids in the resin composition is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 25 parts by mass or less, and can also be 20 parts by mass or less. By setting the content of the (methyl)allyl-substituted nadicimide compound to the aforementioned upper limit or less, there is a tendency to further improve formability and peel strength.

[0395] The resin composition of this embodiment may contain only one (methyl)allyl-substituted nadicimide compound, or it may contain two or more. When two or more compounds are contained, the total amount is preferably within the range described above.

[0396] <<<Methyl)allylic compounds with a glycourea structure>>>

[0397] As for (methyl)allyl compounds with a glycourea structure, there are no particular limitations as long as the compound contains a glycourea structure and two or more (methyl)allyl groups. When a (methyl)allyl compound with a glycourea structure is compounded into a resin composition, the number of (methyl)allyl groups can be increased, i.e., the number of crosslinking points can be increased. Therefore, similar to (methyl)allyl isocyanurate compounds, when firmly cured with maleimide compounds (E), there is a tendency to obtain cured products with low dielectric properties (Dk and / or Df) and excellent heat resistance.

[0398] In this embodiment, the (methyl)allyl compound having a glycourea structure is preferably a compound represented by formula (GU).

[0399] Formula (GU)

[0400]

[0401] (In formula (GU), R) 1 Each can be a hydrogen atom or a substituent, R. 1 At least two of them are groups containing (methyl)allyl groups. R 2 Each can be represented independently by a hydrogen atom, alkyl group, or aryl group.

[0402] In formula (GU), R1 The preferred components are hydrogen atoms, alkyl groups having 1 to 5 carbon atoms, or alkenyl groups having 2 to 5 carbon atoms, preferably alkenyl groups having 2 to 5 carbon atoms, more preferably (methyl)allyl, and even more preferably allyl.

[0403] In formula (GU), R 1 Preferably, 3 or 4 of the groups are (methyl)allyl groups, more preferably 4 of the groups are (methyl)allyl groups.

[0404] In formula (GU), R 2 The preferred components are hydrogen atoms, alkyl groups having 1 to 4 carbon atoms, or phenyl groups, and more preferably hydrogen atoms or methyl groups.

[0405] As a specific example of a compound represented by formula (GU), 1,3,4,6-tetraallylglycourea (in formula (GU), R...) can be cited. 1 All are allyl, R 2 (A compound consisting entirely of hydrogen atoms).

[0406] (Methyl)allyl compounds having a glycourea structure can also be used commercially available products. As commercially available products, there are no particular limitations; for example, TA-G manufactured by Shikoku Chemical Industry Co., Ltd. can be cited.

[0407] The molecular weight of the (methyl)allyl compound having a glycourea structure (preferred to be the compound shown in formula (GU)) is preferably 195 or more, more preferably 220 or more, and even more preferably 250 or more, and can be 300 or more, or 400 or more. By setting the molecular weight of the (methyl)allyl compound having a glycourea structure to the aforementioned lower limit or above, there is a tendency to further improve the heat resistance and low thermal expansion of the obtained cured product. The molecular weight of the (methyl)allyl compound having a glycourea structure (preferred to be the compound shown in formula (GU)) is also preferably 1500 or less, more preferably 1000 or less, and even more preferably 800 or less, and can be 700 or less, or 600 or less. By setting the molecular weight of the (methyl)allyl compound having a glycourea structure to the aforementioned upper limit or below, there is a tendency to further improve the low dielectric properties (Dk and / or Df) and heat resistance of the obtained cured product.

[0408] When the resin composition of this embodiment contains a (methyl)allyl compound having a glycourea structure (preferred to be a 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 can be 10 parts by mass or more, relative to 100 parts by mass of the resin solids in the resin composition. By setting the content of the (methyl)allyl compound having a glycourea structure to the aforementioned lower limit or above, there is a tendency to further improve the formability of the resin composition and the heat resistance and low thermal expansion of the obtained cured product. In addition, the upper limit of the content of the (methyl)allyl compound having a glycourea structure (preferred to be a compound represented by formula (GU)) relative to 100 parts by mass of the resin solids in the resin composition 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 can also be 20 parts by mass or less. By setting the content of the (methyl)allyl compound having a glycourea structure to the aforementioned upper limit or less, there is a tendency to further improve the low dielectric properties (Dk and / or Df) of the obtained cured product.

[0409] The resin composition of this embodiment may contain only one (methyl)allyl compound having a glycourea structure, or it may contain two or more. When two or more compounds are contained, the total amount is preferably within the range described above.

[0410] <<<(Meth)acrylate compounds>>>

[0411] The resin composition of this embodiment may contain (meth)acrylate compounds.

[0412] The (meth)acrylate compound used in this embodiment can be a monofunctional (meth)acrylate compound containing one (meth)acryloyloxy group per molecule, or a polyfunctional (meth)acrylate compound containing two or more (meth)acryloyloxy groups per molecule. In this embodiment, a polyfunctional (meth)acrylate compound is preferred.

[0413] The polyfunctional (meth)acrylate compound used in this embodiment is preferably a compound having 3 to 5 (meth)acryloyloxy groups, more preferably a compound having 3 or 4 (meth)acryloyloxy groups, and even more preferably a compound having 3 (meth)acryloyloxy groups. The (meth)acrylate compound is preferably a compound having methacryloyloxy groups.

[0414] Polyfunctional (meth)acrylate compounds, due to the large number of (meth)acrylate groups that serve as crosslinking points, can be firmly cured with aromatic vinyl resins (D) and maleimide compounds (E), resulting in cured products with low dielectric properties (Dk and / or Df) and excellent heat resistance. The compound shown in formula (MA) is preferred as a polyfunctional (meth)acrylate compound.

[0415] Formula (MA)

[0416]

[0417] (In formula (MA), R) 1 R represents a hydrogen atom or substituent. 2 Each can be used independently to represent a hydrogen atom or a methyl group.

[0418] In formula (MA), R 1 The substituent represents a hydrogen atom or a substituent, more preferably a substituent with a formula weight of 15 to 500, even more preferably a substituent with a formula weight of 15 to 300, even more preferably a substituent with a formula weight of 15 to 100, and even more preferably a substituent with a formula weight of 15 to 50.

[0419] R 1 Preferably, the compound is a hydrocarbon group or (meth)acryloyloxy group, more preferably a hydrocarbon group having 22 or fewer carbon atoms, and even more 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 with excellent crosslinking properties and high toughness can be provided. Therefore, even when the resin composition does not contain a substrate such as glass cloth, cracking during etching processes can be suppressed.

[0420] From the viewpoint of improving operability, the number of carbon atoms in the aforementioned alkyl and / or alkenyl groups is preferably 2 or more, but can be 8 or more, further can be 12 or more, or can be 18 or less. Therefore, the resin composition exhibits better resin flowability, and the circuit filling properties, etc., are improved when using the resin composition of this embodiment to fabricate multilayer circuit boards, etc.

[0421] In this embodiment, the (meth)acryloyl equivalent of the compound represented by formula (MA) is preferably 1000 g / eq. or less. If the aforementioned equivalent is 1000 g / eq. or less, there is a tendency to obtain a higher Tg more reliably. The lower limit of the (meth)acryloyl equivalent is, for example, 99 g / eq. or more.

[0422] As for the alkyl group having 1 to 22 carbon atoms, straight-chain alkyl groups having 1 to 22 carbon atoms or branched alkyl groups having 3 to 22 carbon atoms are preferred, and examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl, etc. Furthermore, as for the alkenyl group having 2 to 22 carbon atoms, alkenyl groups having 2 to 15 carbon atoms are preferred, and examples include allyl, decenyl, etc.

[0423] Specific examples of compounds represented by formula (MA) include trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, pentaerythritol tetra(meth)acrylate, etc. They can be used alone or in combination of two or more, and can also be used in the form of prepolymers.

[0424] Alternatively, commercially available products can be used as the compound represented by formula (MA). There are no particular limitations on what constitutes a commercially available product; for example, "NK Ester TMPT" manufactured by Shin-Nakamura Chemical Industry Co., Ltd. can be cited as an example of a trimethylolpropane trimethacrylate.

[0425] 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, or 500 or more. By setting the aforementioned molecular weight to the aforementioned lower limit or above, there is a tendency to further improve the low dielectric properties (Dk and / or Df) and heat resistance of the obtained cured product. In addition, the molecular weight of the (meth)acrylate compound (preferably the compound shown in formula (MA)) is preferably 3000 or less, more preferably 2000 or less, more preferably 1000 or less, and even more preferably 800 or less. By setting the aforementioned molecular weight to the aforementioned upper limit or below, there is a tendency to further improve the low thermal expansion properties of the obtained cured product.

[0426] (Meth)acrylate compounds can be (meth)acrylate compounds having a polyphenylene structure, such as polyphenylene ether compounds represented by formula (OP-M).

[0427]

[0428] (In formula (OP-M), X represents an aromatic group, -(YO) n1 - indicates a polyphenylene ether structure, n1 represents an integer from 1 to 100, and n2 represents an integer from 2 to 4. Rx is the group shown in formula (Rx-2).

[0429]

[0430] (In formula (Rx-2), R) 1 R 2 and R3 Each group independently represents a hydrogen atom, alkyl group, alkenyl group, or alkynyl group. * indicates the bonding site with an oxygen atom.

[0431] In the formula (OP-M), X and -(YO) n1 -, n1, and n2 are the same as X and -(YO) in formula (OP) of the above-mentioned polyphenylene ether compound having a carbon-carbon unsaturated double bond at the end. n1 - n1 and n2 have the same meaning and the same preferred range.

[0432] In equation (Rx-2), R 1 R 2 and R 3 Each can be independently represented by a hydrogen atom, alkyl group, alkenyl group, or alkynyl group.

[0433] R 1 Preferably, it is a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.

[0434] R 2 and R 3 Hydrogen atoms or alkyl groups are preferred individually, hydrogen atoms or methyl groups are more preferred, and hydrogen atoms are even more preferred.

[0435] As R 1 R 2 and R 3 The alkyl, alkenyl, or alkynyl groups preferably have 5 or fewer carbon atoms, more preferably 3 or fewer.

[0436] The (meth)acrylate compound having a polyphenylene structure is more preferably the compound shown in formula (OP-14).

[0437]

[0438] (In equation (OP-14), a and b independently represent integers from 0 to 100, and at least one of a and b is an integer from 1 to 100.)

[0439] (Meth)acrylate compounds having a polyphenylene structure can be manufactured by known methods or commercially available products can be used. An example of a commercially available product is "SA9000" manufactured by SABIC Innovative Plastics.

[0440] Regarding (meth)acrylate compounds, in addition to the above, reference may be made to resins having (meth)acryloyl groups as described in International Publication No. 2022 / 210095 (e.g., the compounds described in Synthesis Examples 5 and 21 of that publication), resins having (meth)acryloyl groups as described in Japanese Patent No. 6962507 (e.g., the compounds described in Examples 1 to 9), and compounds described in paragraph 0049 of Japanese Patent Application Publication No. 2019-194312, the contents of which are incorporated herein by reference.

[0441] When the resin composition of this embodiment contains a (meth)acrylate compound, its content is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and even more preferably 5 parts by mass or more, and can be 10 parts by mass or more, relative to 100 parts by mass of the resin solids in the resin composition. By setting the content of the (meth)acrylate compound to the above-mentioned lower limit or above, there is a tendency to further improve the formability of the resin composition, the heat resistance of the obtained cured product, and the low thermal expansion. In addition, the upper limit of the content of the (meth)acrylate compound relative to 100 parts by mass of the resin solids in the resin composition is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and can also be 20 parts by mass or less. By setting the content of the (meth)acrylate compound to the aforementioned upper limit or less, there is a tendency to further improve the heat resistance and low dielectric properties (Dk and / or Df) of the obtained cured product.

[0442] The resin composition of this embodiment may contain only one (meth)acrylate compound, or it may contain two or more. When it contains two or more compounds, the total amount is preferably within the range described above.

[0443] <<Epoxy Compounds>>

[0444] The resin composition of this embodiment may contain an epoxy compound.

[0445] There are no particular limitations on the type of epoxy compound, as long as it is a compound or resin having one or more epoxy groups in one molecule (preferably 2 to 12, more preferably 2 to 6, further preferably 2 to 4, even more preferably 2 or 3, and even more preferably 2). It can be widely used in the field of printed circuit boards.

[0446] Examples of the aforementioned epoxy compounds include: phenolic varnish-type epoxy resins, bisphenol A phenolic varnish-type epoxy resins, glycidyl ester-type epoxy resins, aralkylphenolic varnish-type epoxy resins, biphenyl aralkyl-type epoxy resins, naphthyl ether-type epoxy resins, cresol phenolic varnish-type epoxy resins, polyfunctional phenolic epoxy resins, naphthyl-type epoxy resins, anthracene-type epoxy resins, naphthalene skeleton-modified phenolic varnish-type epoxy resins, phenolic aralkyl-type epoxy resins, naphtholic aralkyl-type epoxy resins, dicyclopentadiene-type epoxy resins, biphenyl-type epoxy resins, alicyclic epoxy resins, polyol-type epoxy resins, phosphorus-containing epoxy resins, glycidylamines, glycidyl esters, compounds obtained by epoxidizing double bonds of butadiene, etc., and compounds obtained by reacting hydroxyl-containing organosilicon resins with epichlorohydrin, etc. Using these compounds improves the formability and adhesion of the resin composition. From the viewpoint of further improving flame retardancy and heat resistance, the epoxy compound is preferably selected from one or more of the group consisting of biphenyl aryl epoxy resin, naphthalene ether epoxy resin, polyfunctional phenolic epoxy resin and naphthalene epoxy resin, and more preferably biphenyl aryl epoxy resin.

[0447] When the resin composition of this embodiment contains an epoxy compound, its content is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 2 parts by mass or more, relative to 100 parts by mass of the resin solids in the resin composition. By making the epoxy compound content 0.1 parts by mass or more, there is a tendency to improve the peel strength and toughness of the metal foil. The upper limit of the epoxy compound content relative to 100 parts by mass of the resin solids in the resin composition is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, and even more preferably 10 parts by mass or less, and may also be 8 parts by mass or less, or 5 parts by mass or less. By making the epoxy compound content 50 parts by mass or less, there is a tendency to improve the electrical properties of the resulting cured product.

[0448] The resin composition in this embodiment may contain only one epoxy compound, or it may contain two or more. When it contains two or more epoxy compounds, the total amount is preferably within the range described above.

[0449] Furthermore, the resin composition in this embodiment can also be formulated to be substantially free of epoxy compounds. "Substantially free" means that, relative to 100 parts by weight of the resin solids in the resin composition, the content of epoxy compounds is less than 0.1 parts by weight, preferably less than 0.01 parts by weight, and further less than 0.001 parts by weight. By being substantially free of epoxy compounds, there is a tendency to further improve the low dielectric properties (Dk and / or Df) of the cured product. That is, since epoxy groups are highly polar, by being free of such thermosetting compounds, there is a tendency to achieve low dielectric properties (Dk and / or Df) of the cured product.

[0450] <<Phenolic Compounds>>

[0451] The resin composition of this embodiment may contain phenolic compounds.

[0452] Phenolic compounds are not particularly limited as long as they are compounds that have one or more phenolic hydroxyl groups in one molecule (preferably 2 to 12, more preferably 2 to 6, even more preferably 2 to 4, even more preferably 2 or 3, even more preferably 2), and can be widely used in the field of printed circuit boards.

[0453] Examples of the aforementioned phenolic compounds include phenolic varnish resins, bisphenol A type phenolic varnish resins, glycidyl ester type phenolic resins, aralkyl phenolic varnish resins, biphenyl aralkyl type phenolic resins, cresol phenolic varnish resins, polyfunctional phenolic resins, naphthol resins, naphthol phenolic varnish resins, polyfunctional naphthol resins, anthracene type phenolic resins, naphthalene skeleton modified phenolic varnish resins, phenolic aralkyl type phenolic resins, naphthol aralkyl type phenolic resins, dicyclopentadiene type phenolic resins, biphenyl type phenolic resins, alicyclic phenolic resins, polyol type phenolic resins, phosphorus-containing phenolic resins, and hydroxyl-containing organosilicon resins. From the viewpoint of further improving the flame retardancy of the obtained cured product, it is preferable to select at least one from the group consisting of biphenyl aralkyl type phenolic resins, naphthol aralkyl type phenolic resins, phosphorus-containing phenolic resins, and hydroxyl-containing organosilicon resins.

[0454] In addition, as for phenolic compounds, reference can be made to paragraphs 0012 to 0025 of International Publication No. 2023 / 176765, the contents of which are incorporated herein by reference.

[0455] When the resin composition of this embodiment contains a phenolic compound, its content relative to 100 parts by weight of the resin solids in the resin composition is preferably 0.1 parts by weight or more, more preferably 1 part by weight or more, and even more preferably 2 parts by weight or more. Furthermore, it is preferably 50 parts by weight or less, more preferably 30 parts by weight or less, even more preferably 20 parts by weight or less, and even more preferably 10 parts by weight or less, and may also be 5 parts by weight or less.

[0456] The resin composition in this embodiment may contain only one phenolic compound, or it may contain two or more. When it contains two or more, the total amount is preferably within the range described above.

[0457] Furthermore, the resin composition in this embodiment can also be formulated to be substantially free of phenolic compounds. "Substantially free" means that the content of phenolic compounds is less than 0.1 parts by mass relative to 100 parts by mass of the resin solids in the resin composition.

[0458] <<Oxycyclic Butane Compounds>>

[0459] The resin composition of this embodiment may contain an oxetane compound.

[0460] Oxycyclic butane compounds are not particularly limited as long as they have one or more (preferably 2 to 12, more preferably 2 to 6, further preferably 2 to 4, even more preferably 2 or 3, and even more preferably 2) oxycyclic butyl groups, and can be widely used in the field of printed circuit boards.

[0461] Examples of oxetane compounds include oxetane, alkyloxetanes (e.g., 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, 3,3-dimethyloxetane, etc.), 3-methyl-3-methoxymethyloxetane, 3,3-bis(trifluoromethyl)oxetane, 2-chloromethyloxetane, 3,3-bis(chloromethyl)oxetane, biphenyl-type oxetane, OXT-101 (manufactured by TOAGOSEI CO.,LTD.), OXT-121 (manufactured by TOAGOSEI CO.,LTD.), etc.

[0462] The resin composition of this embodiment preferably contains an oxetane compound within a range that does not impair the effects of the present invention. When the resin composition of this embodiment contains an oxetane compound, its content relative to 100 parts by mass of the resin solids in the resin composition is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 2 parts by mass or more. By making the content of the oxetane compound 0.1 parts by mass or more, there is a tendency to improve the peel strength and toughness of the metal foil of the obtained cured product. When the resin composition of this embodiment contains an oxetane compound, the upper limit of the content of the oxetane compound relative to 100 parts by mass of the resin solids in the resin composition is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, and even more preferably 8 parts by mass or less. By making the content of the oxetane compound 50 parts by mass or less, there is a tendency to improve the electrical properties of the obtained cured product.

[0463] The resin composition in this embodiment may contain only one oxetane compound, or it may contain two or more. When it contains two or more compounds, the total amount is preferably within the range described above.

[0464] Furthermore, the resin composition in this embodiment can also be formulated to be substantially free of oxetane compounds. "Substantially free" means that the content of oxetane compounds is less than 0.1 parts by weight relative to 100 parts by weight of the resin solids in the resin composition.

[0465] <<Benzoxazine Compounds>>

[0466] The resin composition of this embodiment may contain benzoxazine compounds.

[0467] As a benzoxazine compound, there is no particular limitation as long as it is a compound having two or more (preferably 2 to 12, more preferably 2 to 6, further preferably 2 to 4, even more preferably 2 or 3, and even more preferably 2) dihydrobenzoxazine rings in one molecule, and it can be widely used in the field of printed circuit boards.

[0468] Examples of benzoxazine compounds 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.), and bisphenol S type benzoxazine BS-BXZ (manufactured by Konishi Chemical Co., Ltd.).

[0469] 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 parts by weight or more, and preferably 50 parts by weight or less, relative to 100 parts by weight of the resin solids in the resin composition.

[0470] The resin composition in this embodiment may contain only one benzoxazine compound, or it may contain two or more. When it contains two or more compounds, the total amount is preferably within the range described above.

[0471] Alternatively, the resin composition in this embodiment can also be formulated to be substantially free of benzoxazine compounds. "Substantially free" means that the content of benzoxazine compounds is less than 0.1 parts by weight per 100 parts by weight of the resin solids in the resin composition.

[0472] <<Compounds containing vinylidene>>

[0473] The resin composition of this embodiment may contain compounds having vinylidene content.

[0474] Examples of compounds having vinylidene groups include compounds containing one or more -CH=CH- groups in their molecules, with compounds containing one -CH=CH- group being preferred. Furthermore, compounds that are both vinylidene compounds and maleimide compounds (B) are designated as maleimide compounds.

[0475] Specific examples of compounds having vinylidene content include acenaphthene and pyracylene, with acenaphthene being more preferred.

[0476] In this specification, as with the imidazole compounds described later, compounds that are also compounds having vinylidene content and are explicitly stated as components other than compounds having vinylidene content (e.g., curing accelerators) are defined as compounds that do not have vinylidene content.

[0477] <Thermoplastic Elastomers (C)>

[0478] The resin composition of this embodiment preferably includes a thermoplastic elastomer (C). By including a thermoplastic elastomer (C), a cured product with excellent low dielectric properties (Dk and / or Df) and minimal warpage during reflow soldering can be obtained. In particular, by using a styrene-based elastomer and a substance with a small amount of styrene-derived structural units, compatibility with aromatic vinyl resins (D) can be improved, resulting in low dielectric properties (Dk and / or Df) of the obtained cured product, and warpage of the cured product can be reduced.

[0479] The thermoplastic elastomer (C) in this embodiment is not particularly limited, but may include, 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 hydrides, their alkyl compounds, and their copolymers.

[0480] In addition, as thermoplastic elastomers (C), examples may also include oligomers or polymers with curable vinyl functional groups described in paragraphs 0044 and 0045 of Japanese Patent Application Publication No. 2019-194312, and polybutadiene resins, and these contents are incorporated into this specification.

[0481] The number-average molecular weight of the thermoplastic elastomer (C) used in this embodiment is preferably 1,000 or more. By having a number-average molecular weight of 1,000 or more, the resulting cured product tends to have superior low dielectric properties (Dk and / or Df, particularly low dielectric loss tangent). The number-average molecular weight is preferably 1,500 or more, more preferably 2,000 or more, and depending on the application, it can be 60,000 or more, 70,000 or more, or 80,000 or more. The upper limit of the number-average molecular weight of the thermoplastic elastomer (C) is preferably 400,000 or less, more preferably 350,000 or less, and even more preferably 300,000 or less. By setting the number-average molecular weight below the aforementioned upper limit, there is a tendency to increase the solubility of the thermoplastic elastomer (C) component in the resin composition.

[0482] When the resin composition of this embodiment contains two or more thermoplastic elastomers (C), it is preferable that the number average molecular weight of their mixture satisfies the above-mentioned range.

[0483] The thermoplastic elastomer (C) used in this embodiment can be a resin containing a polybutadiene structure. Optionally, some or all of the polybutadiene structure is hydrogenated. Specific examples include Nippon Soda Corporation's B-1000, B-2000, B-3000, BI-2000, BI-3000, CRAY VALLEY Corporation's Ricon100, Ricon130, Ricon131, Ricon142, Ricon150, Ricon181, Ricon184, etc.

[0484] The thermoplastic elastomer (C) used in this embodiment can be a resin having a poly(meth)acrylate structure. Specific examples include Teisan Resin manufactured by Nagase ChemteX, and ME-2000, W-197C, KG-15, and KG-3000 manufactured by Negami Kogyo Co., Ltd.

[0485] The thermoplastic elastomer (C) used in this embodiment can be a resin having a polycarbonate structure. Sometimes, a resin having a polycarbonate structure is referred to as a "polycarbonate resin." Examples of such resins include carbonate resins without reactive groups, hydroxyl-containing carbonate resins, phenolic hydroxyl-containing carbonate resins, carboxyl-containing carbonate resins, acid anhydride-containing carbonate resins, isocyanate-containing carbonate resins, urethane-containing carbonate resins, and epoxy-containing carbonate resins. Here, "reactive group" refers to functional groups such as hydroxyl, phenolic hydroxyl, carboxyl, acid anhydride, isocyanate, urethane, and epoxy groups that can react with other components.

[0486] Specific examples of polycarbonate resins include FPC0220 and FPC2136 manufactured by Mitsubishi Gas Chemical Co., Ltd., and T6002 and T6001 (polycarbonate diol) manufactured by Asahi Kasei Corporation.

[0487] The thermoplastic elastomer (C) used in this embodiment can be a resin having a polysiloxane structure. Specific examples include SMP-2006, SMP-2003PGMEA, SMP-5005PGMEA, KR-510, and SMP-7014-3S manufactured by Shin-Etsu Chemical Industry Co., Ltd.

[0488] The thermoplastic elastomer (C) used in this embodiment can be a resin having a polyalkylene structure and / or a polyalkylene oxide structure. The polyalkylene oxide structure is preferably a polyalkylene oxide structure with 2 to 15 carbon atoms, more preferably a polyalkylene oxide structure with 3 to 10 carbon atoms, and particularly preferably a polyalkylene oxide structure with 5 to 6 carbon atoms. Specific examples of resins having a polyalkylene structure and / or a polyalkylene oxide structure include PTXG-1000 and PTXG-1800 manufactured by Asahi Kasei Corporation.

[0489] The thermoplastic elastomer (C) used in this embodiment can be a resin having a polyisoprene structure. Specific examples include KL-610 and KL613 manufactured by Kuraray.

[0490] The thermoplastic elastomer (C) used in this embodiment can be a resin having a polyisobutylene structure. Specific examples include SIBSTAR-073T (styrene-isobutylene-styrene triblock copolymer) and SIBSTAR-042D (styrene-isobutylene diblock copolymer) manufactured by Kaneka Corporation.

[0491] In this embodiment, the thermoplastic elastomer (C) is preferably a thermoplastic elastomer comprising styrene compound units and one or more thermoplastic elastomers selected from the group consisting of butadiene units, isoprene units, hydrogenated butadiene units, and hydrogenated isoprene units (hereinafter referred to as "thermoplastic elastomer (c1)"). By using such a thermoplastic elastomer (c1), the low dielectric properties (Dk and / or Df, especially low dielectric loss tangent) of the cured product are superior. Here, styrene compound units refer to structural units derived from styrene compounds, butadiene units refer to structural units derived from butadiene, and hydrogenated butadiene units refer to structural units derived from butadiene and hydrogenated. The same applies to others.

[0492] The aforementioned thermoplastic elastomer (c1) comprises styrene compound units. By including styrene compound units, the solubility of the thermoplastic elastomer (c1) in the resin composition is improved. Examples of styrene compounds include styrene, α-methylstyrene, p-methylstyrene, divinylbenzene (vinylstyrene), N,N-dimethyl-p-aminoethylstyrene, and N,N-diethyl-p-aminoethylstyrene, among which styrene, α-methylstyrene, and p-methylstyrene are preferred from the viewpoint of availability and productivity. Styrene is particularly preferred.

[0493] The content of styrene compound units in the aforementioned thermoplastic elastomer (C1) is preferably 20% by mass or more of the total thermoplastic elastomer (C), more preferably 30% by mass or more, even more preferably 35% by mass or more, and preferably 70% by mass or less, more preferably 65% ​​by mass or less, even more preferably 60% by mass or less, and even more preferably 55% by mass or less. When the content of styrene compound units is at or above the aforementioned lower limit, there is a tendency for improved compatibility and heat resistance, which is therefore preferred. In addition, by keeping the content of styrene compound units below or above the aforementioned upper limit, the low thermal expansion property is improved.

[0494] The thermoplastic elastomer (c1) may contain only one type of styrene compound unit, or it may contain two or more types. When it contains two or more types, the total amount is preferably within the range described above.

[0495] The method for determining the content of styrene compound units in the thermoplastic elastomer (c1) of this embodiment can be found in International Publication No. 2017 / 126469, the contents of which are incorporated herein by reference. The same applies to the conjugated diene unit A, etc., which will be described later.

[0496] The aforementioned thermoplastic elastomer (c1) further comprises one or more units selected from the group consisting of butadiene units, isoprene units, hydrogenated butadiene units, and hydrogenated isoprene units (hereinafter sometimes referred to as "conjugated diene unit A"). Preferably, the aforementioned thermoplastic elastomer (c1) comprises one or more units selected from the group consisting of hydrogenated butadiene units and hydrogenated isoprene units as essential components, and comprises one or more units selected from the group consisting of butadiene units and isoprene units.

[0497] In the aforementioned thermoplastic elastomer (c1), the mass ratio of styrene compound units to conjugated diene units A is preferably in the range of 5 / 95 to 75 / 25, more preferably in the range of 30 / 70 to 65 / 35, even more preferably in the range of 35 / 65 to 60 / 40, and even more preferably in the range of 35 / 65 to 55 / 45. When the mass ratio of styrene compound units to conjugated diene units A is within the above range, the compatibility and heat resistance become good.

[0498] The aforementioned thermoplastic elastomer (c1) may contain other monomer units besides the styrene compound unit and the conjugated diene unit A, or it may not contain other monomer units. Examples of other monomer units include aromatic vinyl compound units other than the styrene compound unit.

[0499] The thermoplastic elastomer (c1) preferably comprises 90% or more by mass of styrene compound units and conjugated diene units A, more preferably 95% or more by mass, even more preferably 97% or more by mass, and even more preferably 99% or more by mass, and other than 100% or less by mass.

[0500] As described above, the thermoplastic elastomer (c1) may contain only one styrene compound unit and one conjugated diene unit A, or it may contain two or more. When it contains two or more, the total amount is preferably within the range described above.

[0501] The thermoplastic elastomer (c1) used in this embodiment can be a block polymer or a random polymer. Furthermore, the conjugated diene unit A can be a hydrogenated elastomer containing hydrogenated butadiene units and / or hydrogenated isoprene units, or an unhydrogenated elastomer without hydrogenated butadiene units and / or hydrogenated isoprene units, or a partially hydrogenated elastomer containing butadiene units and / or isoprene units and containing hydrogenated butadiene units and / or hydrogenated isoprene units; preferably, it is an unhydrogenated elastomer or a partially hydrogenated elastomer.

[0502] In one embodiment of this invention, the thermoplastic elastomer (c1) is a hydrogenated elastomer. Here, the hydrogenated elastomer includes those with a hydrogenation rate of 80% or higher, in addition to those with a hydrogenation rate of 100%. The hydrogenation rate of the hydrogenated elastomer is preferably 85% or higher, more preferably 90% or higher, and even more preferably 95% or higher. The hydrogenation rate is determined by… 1 The results of H-NMR spectroscopy were calculated.

[0503] In one embodiment of this invention, the thermoplastic elastomer (c1) is an unhydrogenated elastomer. Here, an unhydrogenated elastomer refers to one in which the proportion of hydrogenated double bonds in the double bonds based on the conjugated diene unit A, i.e., the hydrogenation rate, is 20% or less. The hydrogenation rate is preferably 15% or less, more preferably 10% or less, and even more preferably 5% or less.

[0504] On the other hand, partially hydrogenated elastomers refer to elastomers in which a portion of the double bond based on the conjugated diene unit A is hydrogenated, typically referring to elastomers with a hydrogenation rate of less than 80% and greater than 20%.

[0505] The thermoplastic elastomer (c1) was subjected to a tensile test using an Autograph AGS-X puls manufactured by Shimadzu Corporation at a test speed of 10 mm / min. The elastic modulus at a strain of 0.05% to 0.25% was preferably 10 GPa or less, more preferably 6 GPa or less, and even more preferably 4 GPa or less. By setting the value to the aforementioned lower limit or above, warping of the obtained cured product can be effectively suppressed.

[0506] When the resin composition of this embodiment contains two or more thermoplastic elastomers (c1), it is preferable that the sum (weighted average) of the values ​​obtained by multiplying the elastic modulus of each thermoplastic elastomer (c1) by its mass fraction satisfies the above-mentioned range.

[0507] Thermoplastic elastomers (c1) may have reactive functional groups at the molecular ends or in the molecular chain. Examples of reactive functional groups include epoxy, hydroxyl, carboxyl, amino, amide, isocyanate, acryloyl, methacryloyl, and vinyl groups. From the viewpoint of good adhesion to metals, reactive functional groups are preferably epoxy, hydroxyl, carboxyl, amino, or amide groups. From the viewpoint of further improving heat resistance and insulation reliability, epoxy, hydroxyl, or amino groups are more preferred.

[0508] Commercially available thermoplastic elastomers (C) used in this embodiment include SEPTON (registered trademark) 2104, V9461, and S8104 manufactured by Kuraray Co., Ltd.; SOE (registered trademark) S1606, S1613, S1609, and S1605 manufactured by Asahi Kasei Corporation; H1041, H1043, P2000, and MP10 manufactured by Tuftec (registered trademark) manufactured by Asahi Kasei Corporation; and DYNARON (registered trademark) 9901P and TR2250 manufactured by ENEOS Materials Corporation.

[0509] When the resin composition of this embodiment includes thermoplastic elastomer (C), its content relative to 100 parts by mass of the resin solids in the resin composition is preferably 5 parts by mass or more, more preferably 8 parts by mass or more, and even more preferably 10 parts by mass or more. Depending on the application, it can be 12 parts by mass or more, 15 parts by mass or more, or 18 parts by mass or more. By setting it to the aforementioned lower limit or above, there is a tendency to further improve the low dielectric loss tangent. In addition, relative to 100 parts by mass of the resin solids in the resin composition, the upper limit of the content of thermoplastic elastomer (C) is preferably 30 parts by mass or less, more preferably 28 parts by mass or less, even more preferably 26 parts by mass or less, even more preferably 24 parts by mass or less, and even more preferably 22 parts by mass or less. By setting it to the aforementioned upper limit or below, there is a tendency to further improve the heat resistance.

[0510] The resin composition of this embodiment may contain only one thermoplastic elastomer (C), or it may contain two or more. When it contains two or more, the total amount is preferably within the range described above.

[0511] <Curing Accelerator>

[0512] The resin composition of this embodiment may further include a curing accelerator.

[0513] As a curing accelerator, there are no particular limitations. Examples include imidazoles such as 2-ethyl-4-methylimidazole and triphenylimidazole; organic peroxides such as benzoyl peroxide, lauroyl peroxide, acetyl peroxide, p-chlorobenzoyl peroxide, di-tert-butyldisperoxyphthalate, α,α'-di(tert-butylperoxy)diisopropylbenzene, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, and 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexyne-3; azo compounds such as azobisnitrile; N,N-dimethylbenzylamine, N,N-dimethylaniline, N,N-dimethyltoluidine, 2-N-ethylaniline ethanol, tri-n-butylamine, and pyridine. Tertiary amines such as quinoline, N-methylmorpholine, triethanolamine, triethylenediamine, tetramethylbutanediamine, and N-methylpiperidine; phenols such as phenol, xylenol, cresol, resorcinol, and catechol; high-temperature decomposition free radical generators such as 2,3-dimethyl-2,3-diphenylbutane; organometallic salts such as lead naphthenate, lead stearate, zinc naphthenate, zinc octanoate, manganese octanoate, tin oleate, dibutyltin maleate, manganese naphthenate, cobalt naphthenate, and iron acetylacetone; substances formed by dissolving these organometallic salts in hydroxyl-containing compounds such as phenol and bisphenol; inorganic metal salts such as tin chloride, zinc chloride, and aluminum chloride; organotin compounds such as dioctyltin oxide, other alkyltin, and alkyltin oxide. Preferably, the curing accelerator is at least one selected from the group consisting of imidazoles, organometallic salts, and organic peroxides, more preferably at least one selected from the group consisting of imidazoles and organic peroxides.

[0514] When the resin composition of this embodiment contains a curing accelerator, the lower limit of its content relative to 100 parts by weight of the resin solids in the resin composition is preferably 0.005 parts by weight or more, more preferably 0.01 parts by weight or more, and even more preferably 0.1 parts by weight or more. Furthermore, the upper limit of the content of the curing accelerator relative to 100 parts by weight of the resin solids in the resin composition is preferably 10 parts by weight or less, more preferably 5 parts by weight or less, even more preferably 3 parts by weight or less, even more preferably 2 parts by weight or less, even more preferably 1.5 parts by weight or less, even more preferably 1.0 parts by weight or less, even more preferably 0.8 parts by weight or less, and particularly preferably 0.7 parts by weight or less. The resin composition of this embodiment is preferred in that it allows the resin composition to be sufficiently cured even when the content of the curing accelerator is set to 0.8 parts by weight or less.

[0515] Curing accelerators can be used alone or in combination of two or more. When using two or more, the total amount shall be within the range mentioned above.

[0516] Flame retardants

[0517] The resin composition of this embodiment may contain a flame retardant. Examples of flame retardants include phosphorus-based flame retardants, halogen-based flame retardants, inorganic flame retardants, and organosilicon-based flame retardants, with phosphorus-based flame retardants being preferred.

[0518] As flame retardants, known alternatives include, for example: brominated epoxy resins, brominated polycarbonates, brominated polystyrene, brominated styrene, brominated phthalimide, tetrabromobisphenol A, pentabromobenzyl acrylate, pentabromotoluene, tribromophenol, hexabromobenzene, decabromodiphenyl ether, bis-1,2-pentabromophenylethane, chlorinated polystyrene, chlorinated paraffin, and other halogenated flame retardants; red phosphorus, tricresyl phosphate, triphenyl phosphate, cresol diphenyl phosphate, tri(dimethyl) phosphate, etc. Phosphorus-based flame retardants include phenyl esters, trialkyl phosphates, dialkyl phosphates, trichloroethyl phosphates, phosphazenes, 1,3-phenylenebis(2,6-di(xylyl)phosphate), 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, etc.; inorganic flame retardants include aluminum hydroxide, magnesium hydroxide, some boehmite, zinc borate, antimony trioxide, etc.; and organosilicon-based flame retardants include organosilicon rubber, organosilicon resin, etc.

[0519] In this embodiment, 1,3-phenylenebis(2,6-bis(di(xylyl)phosphate) does not impair the low dielectric properties (Dk and / or Df), and is therefore preferred.

[0520] When the resin composition of this embodiment contains a flame retardant, 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 even more preferably 7 parts by mass or more, relative to 100 parts by mass of the resin solids in the resin composition. Furthermore, the lower limit of the flame retardant content is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, relative to 100 parts by mass of the resin solids in the resin composition.

[0521] Flame retardants can be used alone or in combination of two or more. When using two or more, the total amount shall be within the range mentioned above.

[0522] <Active Ester Compounds>

[0523] The resin composition of this embodiment may contain an active ester compound without impairing the effects of the present invention. There are no particular limitations on the active ester compound; for example, reference can be made to paragraphs 0064-0066 of International Publication No. 2021 / 172317, the contents of which are incorporated herein by reference.

[0524] When the resin composition of this embodiment contains an active ester compound, it is preferably 1 part by mass or more, and more preferably 50 parts by mass or less, relative to 100 parts by mass of the resin solids in the resin composition.

[0525] The resin composition in this embodiment may contain only one active ester compound, or it may contain two or more. When it contains two or more, the total amount is preferably within the range described above.

[0526] Furthermore, the resin composition in this embodiment can also be formulated to be substantially free of active ester compounds. "Substantially free" means that the content of active ester compounds is less than 1 part by weight relative to 100 parts by weight of the resin solids in the resin composition, preferably less than 0.1 parts by weight, and more preferably less than 0.01 parts by weight.

[0527] <Aromatic oligomers>

[0528] The resin composition of this embodiment may contain aromatic oligomers. Aromatic oligomers refer to oligomers having structural units derived from aromatic vinyl compounds, and generally refer to compounds with a weight-average molecular weight of less than 3000. Furthermore, aromatic oligomers are typically thermoplastic oligomers. It should be noted that the aromatic oligomers in this embodiment are intended to be free of polymers having structural units shown in formula (V), thermoplastic elastomers (C), and other compounds explicitly stated above.

[0529] Examples of the aforementioned aromatic vinyl compounds include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-tert-butylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 2,4,6-trimethylstyrene, 2-ethyl-4-benzylstyrene, 4-(phenylbutyl)styrene, 1-vinylnaphthalene, 2-vinylnaphthalene, vinylanthracene, N,N-diethyl-4-aminoethylstyrene, vinylpyridine, 4-methoxystyrene, monochlorostyrene, dichlorostyrene, and divinylbenzene. These aromatic vinyl compounds can be used alone or in combination of two or more. Styrene, α-methylstyrene, and 4-methylstyrene are preferred, with α-methylstyrene being more preferred.

[0530] Aromatic oligomers may contain structural units derived from monomers other than aromatic vinyl compounds. Examples of such other monomers include (meth)acrylic acid, (meth)acrylic acid derivatives, (meth)acrylamide, (meth)acrylamide derivatives, (meth)acrylonitrile, isoprene, 1,3-butadiene, ethylene, vinyl acetate, vinyl chloride, vinylidene chloride, N-vinylindole, N-vinylphthalimide, N-vinylpyrrolidone, N-vinylcarbazole, and N-vinylcaprolactam.

[0531] The content of structural units derived from aromatic vinyl compounds in the aromatic oligomer is preferably 60% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, and even more preferably 95% by mass or more.

[0532] The weight-average molecular weight (Mw) of the aromatic oligomer is preferably 300 or more, more preferably 500 or more, even more preferably 1,000 or more, and generally less than 3,000, preferably 2,800 or less, more preferably 2,500 or less, and can be 2,000 or less. It should be noted that the weight-average molecular weight (Mw) of the aromatic oligomer is a value obtained by gel permeation chromatography converted from standard polystyrene.

[0533] Examples of aromatic oligomers include polystyrene, polyα-methylstyrene, poly4-methylstyrene, styrene / α-methylstyrene copolymers, styrene / 4-methylstyrene copolymers, α-methylstyrene / 4-methylstyrene copolymers, and styrene / α-methylstyrene / 4-methylstyrene copolymers. It should be noted that an aromatic oligomer can be used alone or in combination of two or more.

[0534] As an aromatic oligomer, it can be used in commercially available products. Commercially available aromatic oligomers include, for example: Piccolastic A5 (polystyrene, softening point 5°C, Mw350), Piccolastic A-75 (polystyrene, softening point 74°C, Mw1300), Piccotex 75 (α-methylstyrene / 4-methylstyrene copolymer, softening point 75°C, Mw1100), Piccotex LC (α-methylstyrene / 4-methylstyrene copolymer, softening point 91°C, Mw1350), Kristalex 3070 (styrene / α-methylstyrene copolymer, softening point 70°C, Mw950), Kristalex 3085 (styrene / α-methylstyrene copolymer, softening point 85°C, Mw1150), Kristalex 3100 (styrene / α-methylstyrene copolymer, softening point 100°C, Mw1500), etc., aromatic polymers manufactured by EASTMAN, and YS Resin. SX-100 (polystyrene, softening point 100℃, Mw 2500; manufactured by YASUHARA CHEMICAL CO., LTD.), FMR-0150 (styrene / aromatic hydrocarbon copolymer, softening point 145℃, Mw 2040; manufactured by Mitsui Chemicals), FTR-6100 (styrene / aliphatic hydrocarbon copolymer, softening point 95℃, Mw 1210; manufactured by Mitsui Chemicals), FTR-6110 (styrene / aliphatic hydrocarbon copolymer, softening point 110℃, Mw 1570; manufactured by Mitsui Chemicals), FTR-6125 (styrene / aliphatic hydrocarbon copolymer, softening point 145℃, Mw 204 ...0 (styrene / aliphatic hydrocarbon copolymer, softening point 145℃, Mw 2040; manufactured by Mitsui Chemicals), FTR-6120 (styrene / aliphatic hydrocarbon copolymer, softening point 14 , FTR-7100 (styrene / α-methylstyrene / aliphatic hydrocarbon copolymer, softening point 100℃, Mw1440; manufactured by Mitsui Chemicals), FTR-0100 (poly-α-methylstyrene, softening point 100℃, Mw1960; manufactured by Mitsui Chemicals), FTR-2120 (styrene / α-methylstyrene copolymer, softening point 120℃, Mw2630; manufactured by Mitsui Chemicals), etc.

[0535] In addition to the above, for details regarding aromatic oligomers, the substances equivalent to aromatic oligomers described in paragraphs 0069 to 0087 of International Publication No. 2017 / 135168 may be used, and this content is incorporated into this specification.

[0536] When the resin composition of this embodiment contains aromatic oligomers, the content of these oligomers relative to 100 parts by mass of the resin solids is preferably 1 part by mass or more, more preferably 2 parts by mass or more, even more preferably 3 parts by mass or more, and can be 4 parts by mass or more. By setting the content to the aforementioned lower limit or above, there is a tendency to further reduce the relative permittivity and dielectric loss tangent. In addition, the upper limit of the content of aromatic oligomers relative to 100 parts by mass of the resin solids is preferably 45 parts by mass or less, more preferably 30 parts by mass or less, even more preferably 15 parts by mass or less, even more preferably 10 parts by mass or less, and can also be 8 parts by mass or less. By setting the content to the aforementioned upper limit or below, there is a tendency to further improve chemical resistance.

[0537] The resin composition of this embodiment may contain only one aromatic oligomer, or it may contain two or more. When it contains two or more, the total amount is preferably within the range described above.

[0538] <Other Filling Materials>

[0539] The resin composition of this embodiment may contain filler materials other than the hollow silica (A), solid silica, and porous silica described above (sometimes referred to as other filler materials in this specification), or it may not contain any filler materials.

[0540] As other filler materials, fillers commonly used in the art can be appropriately used. Specifically, examples include: metal oxides such as alumina, titanium dioxide, titanium dioxide, 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, condensed boron nitride, silicon nitride, and aluminum nitride; metal hydroxides (including hydrates) such as aluminum hydroxide, heat-treated aluminum hydroxide (aluminum hydroxide that has undergone heat treatment to remove a portion of its water of crystallization), boehmite, and magnesium hydroxide; molybdenum compounds such as molybdenum oxide and zinc molybdate; barium sulfate, clay, kaolin, and talc. The resin composition of this embodiment preferably contains no other filler materials, such as stone, 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 micropowders such as E-glass, T-glass, D-glass, S-glass, and Q-glass), insulated glass, and spherical glass. Organic filler materials can also be included, such as styrene-type, butadiene-type, acrylic-type rubber powders, core-shell rubber powders, silicone resin powders, silicone rubber powders, and silicone composite powders. The resin composition of this embodiment preferably contains no other filler materials. "Substantially contains no other filler materials" means that the content of other filler materials in the resin composition is less than 10% by mass of the content of hollow silica in the resin composition, preferably less than 5% by mass, more preferably less than 3% by mass, and even more preferably less than 1% by mass.

[0541] <Silane Coupling Agent>

[0542] The resin composition of this embodiment may further include a silane coupling agent. By including a silane coupling agent, there is a tendency to further improve the dispersibility of hollow silica (A), the filler material added as needed, and the adhesion strength between the resin components and the hollow silica (A) and the substrate described later.

[0543] There are no particular limitations on silane coupling agents. Examples of silane coupling agents commonly used in the surface treatment of inorganic materials include aminosilane compounds (e.g., γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, etc.), epoxysilane compounds (e.g., γ-epoxypropoxypropyltrimethoxysilane, etc.), vinylsilane compounds (e.g., vinyltrimethoxysilane, etc.), styrylsilane compounds (e.g., styryltrimethoxysilane, etc.), acrylic silane compounds (e.g., γ-acryloyloxypropyltrimethoxysilane, etc.), methacrylic silane compounds (e.g., γ-methacryloyloxypropyltrimethoxysilane, etc.), cationic silane compounds (e.g., N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride, etc.), and phenylsilane compounds. Silane coupling agents can be used alone or in combination of two or more.

[0544] The content of the silane coupling agent is not particularly limited, but can be 0.1 to 5 parts by weight relative to 100 parts by weight of the resin solids.

[0545] <Dispersant>

[0546] The resin composition of this embodiment may contain a dispersant. As a dispersant, it is preferable to use a dispersant commonly used in coatings, and there is no particular limitation on its type. The dispersant is preferably a wetting dispersant of the copolymer matrix; specific examples include BYK Japan KK's DISPERBYK (registered trademark) - 110, 111, 161, 180, 2009, 2152, 2155, BYK (registered trademark) - W996, W9010, W903, W940, etc.

[0547] When the resin composition of this embodiment contains a dispersant, the lower limit of its content is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and may also be 0.3 parts by mass or more, relative to 100 parts by mass of the resin solids in the resin composition. Furthermore, the upper limit of the dispersant content is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and may also be 3 parts by mass or less, relative to 100 parts by mass of the resin solids in the resin composition.

[0548] Dispersants can be used alone or in combination of two or more. When using two or more, the total amount shall be within the range described above.

[0549] Solvent

[0550] The resin composition of this embodiment may contain a solvent, preferably an organic solvent. When containing a solvent, the resin composition of this embodiment is in a form (solution or varnish) in which at least a portion, preferably all, of the above-mentioned solid resin components are dissolved or compatible with the solvent. As a solvent, there are no particular limitations as long as it is a polar or non-polar organic solvent capable of dissolving or compatibility with at least a portion, preferably all, of the above-mentioned solid resin components. Examples of polar organic solvents include ketones (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), cellosols (e.g., propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc.), esters (e.g., ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl methoxypropionate, methyl hydroxyisobutyrate, etc.), and amides (e.g., dimethoxyacetamide, dimethylformamide, etc.). Examples of non-polar organic solvents include aromatic hydrocarbons (e.g., toluene, xylene, etc.).

[0551] Solvents may be used alone or in combination of two or more. When using two or more solvents, the total amount shall be within the range described above.

[0552] <Other Ingredients>

[0553] In addition to the components described above, the resin composition of this embodiment may also contain various polymeric compounds such as thermoplastic resins and their oligomers, petroleum resins, and various additives. Examples of additives include ultraviolet absorbers, antioxidants, photopolymerization initiators, fluorescent whitening agents, photosensitizers, dyes, pigments, thickeners, flow modifiers, lubricants, defoamers, leveling agents, gloss agents, and polymerization inhibitors. These additives may be used individually or in combination of two or more.

[0554] In the resin composition of this embodiment, the thermosetting resin (B) (preferably an aromatic vinyl resin (D) and a maleimide compound (E) and a cyanate ester compound mixed as needed), the thermoplastic elastomer (C) and the flame retardant together account for 90% or more by mass of the solid resin components, more preferably 95% or more by mass, and even more preferably 98% or more by mass.

[0555] Furthermore, in the resin composition of this embodiment, the total amount of aromatic vinyl resin (D), maleimide compound (E), thermoplastic elastomer (C) and flame retardant accounts for 90% or more by mass of the resin solids, more preferably 95% or more by mass, and even more preferably 98% or more by mass.

[0556] <Applications>

[0557] The resin composition of this embodiment is used in the form of a cured product. Specifically, the resin composition of this embodiment is suitable for use as a resin composition for electronic materials such as materials with low relative permittivity and / or low dielectric loss tangent, insulating layers for printed circuit boards, and materials for semiconductor packaging. The resin composition of this embodiment is suitable for use as a prepreg, a metal-clad laminate using prepreg, a resin composite sheet, and a material for printed circuit boards.

[0558] The resin composition of this embodiment preferably has a low relative permittivity (Dk) and dielectric loss tangent (Df) in its cured product. Specifically, it is preferable that the sample obtained by removing the metal foil from a metal foil-coated laminate formed using a prepreg made from the resin composition of this embodiment has a low relative permittivity (Dk) and dielectric loss tangent (Df).

[0559] More specifically, the resin composition is impregnated into NE glass cloth at a resin composition content of 70% by volume, and dried at 155°C for 5 minutes to obtain a prepreg with a thickness of 0.1 mm. Eight sheets of the prepreg are overlapped, and electrolytic copper foil with a thickness of 12 μm is placed on both sides and pressed to obtain a copper-clad laminate. The copper foil on both sides is removed from the copper-clad laminate by etching to obtain a sample with a thickness of 0.8 mm. The dielectric loss tangent (Df) of the 0.8 mm thick sample at a frequency of 10 GHz, measured by the cavity resonator perturbation method according to JIS C218:2007, is 0.0025 or less, preferably 0.0022 or less. There is no particular limitation on the lower limit of the dielectric loss tangent (Df), for example, it is actually 0.0001 or more.

[0560] Furthermore, the relative permittivity (Dk) of the aforementioned 0.8 mm thick sample, measured at a frequency of 10 GHz using the cavity resonator perturbation method according to JIS C218:2007, is preferably 3.0 or less. There is no specific specification for the lower limit of the relative permittivity (Dk), but in practice it is, for example, 0.01 or more.

[0561] The low dielectric properties (Dk and / or Df) described above can be achieved by using hollow silica (A) and using aromatic vinyl resin (D) and / or maleimide compound (E) as thermosetting resin (B). The aromatic vinyl resin (D) preferably comprises one or more compounds selected from the group consisting of polymers having structural units shown in formula (V) and polyphenylene ether compounds having carbon-carbon unsaturated double bonds at the ends. The maleimide compound (E) preferably comprises one or more compounds selected from the group consisting of compounds shown in formula (M1), compounds shown in formula (M3), and compounds shown in formula (M5), more preferably comprising the compound shown in formula (M1).

[0562] Furthermore, free radical curing, achieved by curing the resin composition using free radical curing, tends to cure rapidly within a specific temperature range, thus enabling the resin composition to be cured more densely, and resulting in a lower dielectric property (Dk and / or Df) in the cured product. In other words, an example of the resin composition in this embodiment is a free radical curable resin composition.

[0563] The dielectric loss tangent (Df) and relative permittivity (Dk) of the above-mentioned cured material were determined more specifically by the methods described in the embodiments described later.

[0564] In addition, the resin composition of this embodiment preferably has a low coefficient of thermal expansion when it is cured.

[0565] The resin composition of this embodiment is impregnated into NE glass cloth at a resin composition content of 70% by volume, and dried at 155°C for 5 minutes to obtain a prepreg with a thickness of 0.1 mm. Electrolytic copper foil with a thickness of 12 μm is disposed on both sides of the prepreg and pressed to obtain a copper-clad laminate. The copper foil on both sides is removed from the copper-clad laminate by etching, and the sample is cut (reduced) into a sample of 4.5 mm × 10 mm × 0.1 mm. When the sample is measured at a heating rate of 10°C per minute from 30°C to 340°C, the thermal expansion coefficient in the planar direction at 60°C to 120°C is preferably 10 ppm / °C or less, more preferably 9 ppm / °C or less, even more preferably 5 ppm / °C or less, and practically 0 ppm / °C or more.

[0566] Such low thermal expansion can be achieved by blending resins with low elastic modulus or by using styrene-based thermoplastic elastomers with a small proportion of styrene compound units.

[0567] The resin composition of this embodiment is used as a prepreg, resin composite sheet, or other layered material (including film, sheet, etc.) that serves as an insulating layer for a printed circuit board. When producing this layered material, its thickness is preferably 5 μm or more, more preferably 10 μm or more. As an upper limit for thickness, it is preferably 200 μm or less, more preferably 180 μm or less. It should be noted that the thickness of the layered material mentioned above, for example, when the resin composition of this embodiment is impregnated with glass cloth, refers to the thickness including the glass cloth.

[0568] The material formed from the resin composition of this embodiment can be used for pattern formation by exposure and development, or for applications without exposure and development. It is particularly suitable for applications without exposure and development.

[0569] <<Prepreg>>

[0570] The prepreg of this embodiment is formed from a substrate (prepreg substrate) and the resin composition of this embodiment. The prepreg of this embodiment is obtained, for example, by applying the resin composition of this embodiment to the substrate (e.g., impregnation and / or coating), and then semi-curing it by heating (e.g., drying at 120-220°C for 2-15 minutes). At this time, the amount of resin composition (including hollow silica and filler material) adhering to the substrate, i.e., the total amount of the semi-cured prepreg, is preferably in the range of 20-99% by mass, and more preferably in the range of 20-80% by mass.

[0571] There are no particular limitations on the substrate material, as long as it is used in various printed circuit board materials. Examples of substrate materials include glass fibers (such as E-glass, D-glass, L-glass, S-glass, T-glass, Q-glass, UN-glass, NE-glass, NER-glass, spherical glass, etc.), inorganic fibers other than glass (such as quartz), and organic fibers (such as polyimide, polyamide, polyester, liquid crystal polyester, polytetrafluoroethylene, etc.). There are no particular limitations on the form of the substrate, and examples include woven fabrics, non-woven fabrics, rovings, chopped strand mats, and surface-treated mats. These substrates can be used alone or in combination of two or more. Among these substrates, from the viewpoint of dimensional stability, woven fabrics with super-opening fiber treatment and mesh blocking treatment are preferred; from the viewpoint of strength and low water absorption, substrates with a thickness of 200 μm or less and a weight of 250 g / m³ are preferred. 2 From the viewpoint of moisture absorption and heat resistance, the following glass fabrics are preferably surface-treated with epoxy silane, amino silane, etc. From the viewpoint of electrical properties, low-dielectric glass cloths formed of glass fibers exhibiting low relative permittivity and low dielectric loss tangent, such as L-glass, NE-glass, NER-glass, and Q-glass, are more preferred.

[0572] Examples of substrates with low relative permittivity include those with a relative permittivity of 5.0 or less (preferably 3.0 to 4.9). Examples of substrates with low dielectric loss tangent include those with a dielectric loss tangent of 0.006 or less (preferably 0.001 to 0.005). The relative permittivity and dielectric loss tangent are set as values ​​measured using a perturbation method cavity resonator at a frequency of 10 GHz.

[0573] <<Metal Foil-Coated Laminates>>

[0574] The metal-clad laminate of this embodiment comprises at least one layer formed from the prepreg of this embodiment and metal foil disposed on one or both sides of the layer formed from the prepreg. As a method for manufacturing the metal-clad laminate of this embodiment, for example, a method can be described by disposing of at least one sheet of the prepreg of this embodiment (preferably overlapping two or more sheets) and depositing metal foil on one or both sides thereon to form a laminate. More specifically, it can be manufactured by depositing metal foil such as copper or aluminum on one or both sides of the prepreg and then laminating them. The number of prepreg sheets is preferably 1 to 10 sheets, more preferably 2 to 10 sheets, and even more preferably 2 to 9 sheets.

[0575] As for the metal foil, there are no particular limitations as long as it is used as a material for printed circuit boards; examples include rolled copper foil and electrolytic copper foil. The thickness of the metal foil (preferably copper foil) is not particularly limited and can be approximately 1.5 to 70 μm. Furthermore, when using copper foil as the metal foil, it is preferable to adjust the surface roughness Rz of the copper foil, as measured according to JIS B0601:2013, to be 0.2 to 4.0 μm. By setting the surface roughness Rz of the copper foil to 0.2 μm or more, the surface roughness of the copper foil becomes an appropriate value, and there is a tendency to further improve the peel strength of the copper foil. On the other hand, by setting the surface roughness Rz of the copper foil to 4.0 μm or less, the surface roughness of the copper foil becomes an appropriate value, and there is a tendency to further improve the dielectric loss tangent characteristics of the resulting cured product. From the viewpoint of the dielectric loss tangent characteristics of the obtained cured product and the peel strength of the copper foil, the surface roughness Rz of the copper foil is more preferably 0.5 μm or more, further preferably 0.6 μm or more, particularly preferably 0.7 μm or more, and even more preferably 3.5 μm or less, further preferably 3.0 μm or less, and particularly preferably 2.0 μm or less.

[0576] As a method for lamination forming, methods commonly used in forming laminates and multilayer boards for printed circuit boards can be cited. More specifically, methods using multi-stage presses, multi-stage vacuum presses, continuous forming machines, autoclave forming machines, etc., to perform lamination forming under conditions of approximately 180-350°C, heating time of approximately 100-300 minutes, and surface pressure of approximately 1-10 MPa can be cited. Alternatively, multilayer boards can also be manufactured by combining the prepreg of this embodiment with separately manufactured wiring boards for inner layers and laminating them. As a method for manufacturing multilayer boards, for example, copper foil of approximately 35 μm is disposed on both sides of a piece of prepreg of this embodiment, and after lamination forming using the above forming method, an inner layer circuit is formed. This circuit is then blackened to form an inner layer circuit board. Then, one inner layer circuit board and one piece of prepreg of this embodiment are alternately disposed, and copper foil is disposed on the outermost layer. Lamination forming is performed under the above conditions, preferably under vacuum, thereby manufacturing a multilayer board. The metal-clad laminate of this embodiment is suitable for use as a printed circuit board.

[0577] The peel strength of the metal-clad foil laminate of this embodiment, measured according to section 5.7 "Peel Strength" of JIS C6481, is preferably 0.30 kN / m or more, more preferably 0.35 kN / m or more, and even more preferably 0.50 kN / m or more. There is no particular limitation on the upper limit of the peel strength; for example, even 2.00 kN / m or less is sufficient to meet the required performance.

[0578] As described above, the electronic material resin composition obtained by using the resin composition of this embodiment (a resin composition containing a combination of specific components) can have the following properties after curing: low dielectric properties (low dielectric constant, low dielectric loss tangent, especially low dielectric constant), good appearance of the cured product, excellent high-density processability, and excellent properties such as moisture absorption and heat resistance, peel strength to metal foil, heat resistance, descaling resistance, crack resistance, and low thermal expansion.

[0579] Printed Circuit Boards

[0580] The printed circuit board of this embodiment is a printed circuit board comprising an insulating layer and a conductor layer disposed on the surface of the aforementioned insulating layer. The aforementioned insulating layer comprises at least one of a layer formed from the resin composition of this embodiment and a layer formed from the prepreg of this embodiment. Such a printed circuit board can be manufactured according to conventional methods, and the manufacturing method is not particularly limited. Hereinafter, an example of a method for manufacturing a printed circuit board is shown. First, a copper-clad laminate or a metal-clad laminate as described above is prepared. Next, the surface of the metal-clad laminate is etched to form inner layer circuits, thus creating an inner layer substrate. On the surface of the inner layer circuits of the inner layer substrate, a surface treatment is performed as needed to improve the adhesion strength. Then, the required number of the aforementioned prepregs are stacked on the surface of the inner layer circuits, and then metal foils for outer layer circuits are stacked on the outside of them. The substrate is then heated and pressed to integrally form the circuit. In this way, a multilayer laminate in which a substrate and an insulating layer formed from a cured resin composition are formed between the metal foils for inner and outer layer circuits is manufactured. Next, after drilling holes for through holes and vias on the multi-layered laminate, a plated metal film is formed on the wall of the hole to conduct the metal foil used for inner layer circuits and outer layer circuits. Then, the metal foil used for outer layer circuits is etched to form the outer layer circuits, thereby manufacturing a printed circuit board.

[0581] The printed circuit board obtained in the above manufacturing example has an insulating layer and a conductor layer formed on the surface of the insulating layer. The insulating layer is composed of the resin composition of this embodiment and / or its cured form. That is, the layer formed by the prepreg of this embodiment (for example, a prepreg formed from a substrate and the resin composition of this embodiment impregnated or coated thereon) and the resin composition of the metal foil laminate of this embodiment becomes the insulating layer of this embodiment.

[0582] Furthermore, this embodiment also relates to a semiconductor device including the aforementioned printed circuit board. Detailed information about the semiconductor device can be found in paragraphs 0200 to 0202 of Japanese Patent Application Publication No. 2021-021027, and this information is incorporated herein by reference.

[0583] Furthermore, the insulating layer formed from the cured resin composition of this embodiment preferably has a reduced surface roughness after the roughening treatment. Specifically, the arithmetic mean roughness Ra of the surface of the roughened insulating layer is preferably 200 nm or less, more preferably 150 nm or less, and particularly preferably 100 nm or less. The lower limit 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, in VSI mode, with a 50x lens.

[0584] The non-contact surface roughness meter used is the Veeco Instruments WYKONT3300.

[0585] <<Resin Composite Sheet>>

[0586] The resin composite sheet of this embodiment includes a support and a layer formed of the resin composition of this embodiment disposed on the surface of the support. The resin composite sheet can be used as an additive film or a dry film solder resist. There are no particular limitations on the manufacturing method of the resin composite sheet; for example, a method can be described by coating a solution obtained by dissolving the resin composition of this embodiment in a solvent onto a support and then drying it to obtain the resin composite sheet.

[0587] Examples of supports used here include, for example, polyethylene film, polypropylene film, polycarbonate film, polyethylene terephthalate film, ethylene tetrafluoroethylene copolymer film, and release films coated with release agents on the surface of these films, organic film substrates such as polyimide film, conductor foils such as copper foil and aluminum foil, glass plates, SUS (Steel Use Stainless) plates, FRP (Fiber-Reinforced Plastics) and other plate-shaped supports, without particular limitation.

[0588] As a coating method, examples include applying a solution obtained by dissolving the resin composition of this embodiment in a solvent onto a support using a bar coater, die coater, doctor blade, Baker applicator, etc. Alternatively, after drying, the support can be peeled off or etched from the resin composite sheet on which the support and resin composition are stacked, thereby producing a single-layer sheet. It should be noted that by supplying the solution obtained by dissolving the resin composition of this embodiment in a solvent to a mold having a sheet-like cavity and drying it, a single-layer sheet can also be obtained without using a support.

[0589] It should be noted that in the fabrication of the single-layer sheet or resin composite sheet in this embodiment, the drying conditions for removing the solvent are not particularly limited. If the temperature is low, the solvent is likely to remain in the resin composition; if the temperature is high, the resin composition will cure. Therefore, it is preferable to perform the drying process at a temperature of 20°C to 200°C for 1 to 90 minutes. Furthermore, the single-layer sheet or resin composite sheet can be used in an uncured state where only the solvent has been dried, or it can be used in a semi-cured (B-stage) state as needed. Moreover, the thickness of the resin layer in the single-layer sheet or resin composite sheet of this embodiment can be adjusted by the concentration of the solution of the resin composition of this embodiment used in the coating process and the coating thickness, and is not particularly limited. Generally, when the coating thickness is too thick, solvent is likely to remain during drying; therefore, a thickness of 0.1 to 500 μm is preferred.

[0590] Example

[0591] The following examples illustrate the present invention in more detail. The materials, amounts, proportions, processing contents, and processing steps shown in the following examples can be appropriately modified without departing from the spirit of the invention. Therefore, the scope of protection of the present invention is not limited to the specific examples shown below.

[0592] If the measuring instruments used in the embodiments are difficult to obtain due to production stoppages or other reasons, other instruments with equivalent performance can be used for measurement.

[0593] <Determination of weight-average molecular weight and number-average molecular weight>

[0594] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the compounds (including resins) were determined by gel permeation chromatography (GPC). A standard curve based on monodisperse polystyrene was prepared using a pump (Shimadzu Corporation LC-20AD), a differential refractive index detector (Shimadzu Corporation RID-20A), a GPC column (Showa Denko Corporation GPC KF-801, 802, 803, 804), tetrahydrofuran as solvent, at a flow rate of 1.0 mL / min and a column temperature of 40 °C.

[0595] <Determination of the average particle size (D50) of hollow silica>

[0596] The determination was performed using laser diffraction / scattering. The apparatus used was a SEISHIN ENTERPRISE Co., Ltd. Laser Micron Sizer (LMS-3000) for dry determination.

[0597] <Particle density of hollow silica>

[0598] The density was determined by the gas specific gravity bottle method. Particle density was determined using an Ultrapyc 1200e (Quantachrome Instruments). Nitrogen gas was used.

[0599] <Porosity of hollow silica>

[0600] This is calculated from the particle density mentioned above. Specifically, for porosity, let the density of silica be 2.2 g / cm³. 3 , can be calculated using the following formula (1).

[0601] Porosity (%) = [2.2 - (particle density of hollow silica)] / 2.2 × 100 … Equation (1)

[0602] <Synthetic Example 1: Synthesis of a polyphenylene ether compound (D1) with terminal carbon-carbon unsaturated double bonds>

[0603] <<Synthesis of 2-functionalized phenylene ether oligomers>>

[0604] In a longitudinally elongated reactor equipped with a stirrer, thermometer, air inlet pipe, and baffle, 0.33 g (1.5 mmol) of CuBr2 (copper bromide), 0.63 g (3.7 mmol) of N,N'-di-tert-butylethylenediamine, 6.95 g (69 mmol) of n-butyldimethylamine, 670 g of toluene, and 320 g of methanol were added and stirred at a reaction temperature of 40 °C until dissolved. To this end, 46.2 g (171 mmol) of 2,2',3,3',5,5'-hexamethyl-(1,1'-biphenyl)-4,4'-diol, 129.5 g (1,060 mmol) of 2,6-dimethylphenol, 0.33 g (1.5 mmol) of CuBr2 (copper bromide), 0.63 g (3.7 mmol) of N,N'-di-tert-butylethylenediamine, 6.95 g (69 mmol) of n-butyldimethylamine, 440 g of toluene, and 170 g of methanol were added to other containers in advance and stirred at a reaction temperature of 40 °C to dissolve them.

[0605] Then, while bubbling nitrogen and air into the mixture in the polymerization tank to adjust the mixed gas to an oxygen concentration of 8%, the mixture in the drop addition tank was added dropwise over a period of 280 minutes, and the mixture was stirred.

[0606] After the addition was complete, 700 g of water containing 7.1 g (16 mmol) of tetrasodium ethylenediaminetetraacetate was added to stop the reaction. The aqueous layer and organic layer were separated. The organic layer was washed with 1 M hydrochloric acid aqueous solution, followed by pure water. The resulting solution was concentrated to 50% by mass using an evaporator to obtain 340 g of toluene solution A of phenylene ether resin. The number-average molecular weight of polystyrene based on GPC was 985, the weight-average molecular weight of polystyrene based on GPC was 1090, and the hydroxyl equivalent was 478 g / eq.

[0607] <<Synthesis of Modified Polyphenylene Ether Compounds>>

[0608] In a reactor equipped with a stirrer, thermometer, and reflux pipe, 300 g of toluene solution A of the obtained phenylene ether resin, 57.5 g (0.38 mol) of vinyl benzyl chloride (manufactured by AGC Seimi Chemical Co., Ltd., "CMS-P"), 1200 g of dichloromethane, 5 g (0.037 mol) of benzyl dimethylamine, 70 g of pure water, and 63 g of 30.5% NaOH aqueous solution were added. The reaction was stirred at 40°C. After stirring for 24 hours, the organic layer was washed with 1M hydrochloric acid aqueous solution, followed by pure water. The resulting solution was concentrated and added dropwise to methanol for solidification. The solid was recovered by filtration and vacuum dried to obtain 178 g of polyphenylene ether compound (D1) with the compound shown in formula (OP-15) as the main component.

[0609] The number-average molecular weight of polystyrene converted from GPC is 1200, the weight-average molecular weight of polystyrene converted from GPC is 1840, the vinyl double bond equivalent is 620 g / eq., and the hydroxyl equivalent is 48500 g / eq.

[0610] <Synthetic Example 2: Synthesis of Cyanate Ester Compounds>

[0611] The naphthol aralkyl cyanate compound (SNCN) was synthesized based on the description in paragraphs 0074 to 0077 of Japanese Patent Application Publication No. 2018-035327.

[0612] Example 1

[0613] The following were used: 25 parts by mass of the polyphenylene ether compound (D1) with terminal carbon-carbon unsaturated double bonds obtained in Synthesis Example 1 above; 35 parts by mass of the maleimide compound (ma) with the structure shown below (manufactured by DIC Corporation, “NE-X-9470S”, functional group equivalent (maleimide group equivalent) of 450 g / eq., compound shown in formula (M1)); 5 parts by mass of the cyanate compound (SNCN) obtained in Synthesis Example 2 above; 15 parts by mass of the phosphorus flame retardant (PX-200, manufactured by Daihachi Chemical Industry Co., Ltd., 1,3-phenylene bis(2,6-di(dimethylyl)phosphate)); and 20 parts by mass of the thermoplastic elastomer (C1) (Dynaron9901P, ENEOS Materials). A varnish is prepared by Corporation and contains 53% by mass of styrene compound units. 40 parts by mass of hollow silica (Al) (porosity 32%, average particle size (D50) 4.0 μm) are mixed and diluted with methyl ethyl ketone to a solid content of 65% by mass. The mixing amounts of the above components are expressed as values ​​based on solid content.

[0614] Maleimide compounds (ma)

[0615]

[0616] Manufacturing of metal foil-clad laminates

[0617] The varnish obtained above was impregnated and coated onto NE glass fabric (manufactured by Nitto Boshoku Co., Ltd., N3313 S101S), and dried at 155°C for 5 minutes to obtain a prepreg (thickness 0.1 mm) with a resin composition content of 70% by volume. It should be noted that the characteristics of the NE glass fabric used are as described below.

[0618] IPC corresponding product: 3313

[0619] Density (strips / 25mm) longitudinal: 60

[0620] Density (roots / 25mm) Horizontal: 62

[0621] Thickness (mm): 0.075

[0622] mass (g / m 2 ): 83

[0623] The obtained prepreg is overlapped in layers of 1, 8, or 12 sheets, and an electrolytic copper foil (3EC-M3-VLP, manufactured by Mitsui Metals & Minerals Co., Ltd.) with a thickness of 12 μm is placed on both sides. The mixture is then subjected to a pressure of 30 kgf / cm². 2 The copper-clad laminate is obtained by vacuum pressing at 220℃ for 120 minutes to obtain a copper-clad laminate with an insulation layer thickness of 0.1mm, 0.8mm, or 1.2mm.

[0624] <Determination Methods and Evaluation Methods>

[0625] <Dielectric Properties>

[0626] For the copper-clad laminate (insulation layer thickness 0.8 mm) obtained as described above, after removing the copper foil on both sides by etching, it is cut (reduced) to 1.0 mm × 100 mm × 0.8 mm. Using the evaluation sample prepared by drying at 120 °C for 60 minutes, the relative permittivity (Dk) and dielectric loss tangent (Df) at a frequency of 10 GHz are determined by cavity resonator perturbation method according to JIS C218:2007.

[0627] The cavity resonator was manufactured by EM Labs, and the network analyzer was a Keysight Technologies P5005A. The measurement temperature was set to 23°C. The evaluation is as follows.

[0628] <<Relative Permittivity (Dk)>>

[0629] A: Below 3.0

[0630] B: Greater than 3.0

[0631] <<Dielectric Loss Tangent (Df)>>

[0632] A: Below 0.0022

[0633] B: Greater than 0.0022 and less than 0.0025

[0634] C: Greater than 0.0025

[0635] <Appearance after curing>

[0636] For the copper-clad laminate (insulation layer thickness 0.8 mm) obtained as described above, the appearance was visually evaluated after etching to remove the copper foil on both sides. The evaluation was based on a majority decision by 5 experts, as follows.

[0637] A: No cosmetic defects

[0638] B: There are defects in appearance.

[0639] <CTE(X)>

[0640] The coefficient of linear thermal expansion (CTE) is determined using the TMA (Thermo-Mechanical Analysis) method specified in JlS C 6481 5.19 as follows.

[0641] Specifically, the copper foil on both sides of the copper-clad laminate (insulation layer thickness 0.1 mm) obtained above was removed by etching. For evaluation samples cut (reduced) to 4.5 mm × 10 mm × 0.1 mm, the linear coefficient of thermal expansion (CTE(X)) in the planar direction (unit: ppm / ℃) was measured using a thermomechanical analysis apparatus (TA Instruments, TMA Q-400) at a rate of 10 °C per minute from 30 °C to 320 °C. The measurement direction was set to the warp direction of the glass cloth of the laminate. ppm is a volume ratio. For other details, refer to JIS C 6481 5.19 above. The evaluation is as follows.

[0642] S: below 5ppm / ℃

[0643] A: Greater than 5 ppm / ℃ and less than 9 ppm / ℃

[0644] B: Greater than 9 ppm / ℃ and less than 10 ppm / ℃

[0645] C: Greater than 10 ppm / ℃

[0646] <Drill bit machinability>

[0647] For the copper-clad laminate (insulation layer thickness 1.2 mm) obtained as described above, a pad, two overlapping copper-clad laminates, and a cover plate are stacked sequentially from bottom to top to create an evaluation sample. After machining the sample 5000 hits from the top under the drilling conditions described below, the offset of the hole positions on the back side of the copper-clad laminate from specified coordinates is measured using a hole analyzer (manufactured by Via Mechanics, Ltd.). All positional offsets are measured for each drill bit's machined holes, and the maximum value is calculated.

[0648] Machine tool: Via Mechanics, Ltd. ND-1 V212

[0649] Cover plate: LE-R12F3 manufactured by Mitsubishi Gas Chemical Co., Ltd.

[0650] Pad: SPB-W manufactured by Nihon Decoluxe Co., Ltd.

[0651] Drill bit: UNION TOOL Co., KCW V103VWU 0.15×3.5

[0652] The evaluation is as follows.

[0653] A: Less than 35μm

[0654] B: 35μm or larger and less than 40μm

[0655] C: Above 40μm

[0656] Example 2

[0657] In Example 1, the content of hollow silica (Al) was changed to 200 parts by mass, and otherwise the same procedure was followed.

[0658] Example 3

[0659] In Example 1, the content of hollow silica (Al) was changed to 100 parts by mass, and otherwise the same procedure was followed.

[0660] Example 4

[0661] In Example 1, the content of polyphenylene ether compound (D1) was changed to 40 parts by mass, the content of maleimide compound (ma) was changed to 15 parts by mass, 10 parts by mass of maleimide compound (mb) (biphenyl aralkyl maleimide, manufactured by Nippon Kayaku Co., Ltd., compound shown in formula (M3)) was mixed in, the cyanate ester compound (SNCN) was not mixed in, and the content of hollow silica (A1) was changed to 100 parts by mass. Otherwise, the same procedure was followed.

[0662] Comparative Example 1

[0663] In Example 1, 40 parts by weight of hollow silica (A1) were replaced with 135 parts by weight of solid silica (A2) (Admatechs Co., Ltd., SC4500SQ), and the same procedure was followed otherwise.

[0664] Comparative Example 2

[0665] In Example 1, hollow silica (Al) was not mixed in; otherwise, the same procedure was followed.

[0666] Comparative Example 3

[0667] In Example 1, the content of hollow silica (Al) was changed to 300 parts by mass, and otherwise the same procedure was followed.

[0668] Comparative Example 4

[0669] In Example 4, 100 parts by weight of hollow silica (A1) were replaced with 135 parts by weight of solid silica (A2), and otherwise the same procedure was followed.

[0670] [Table 1]

[0671]

Claims

1. A resin composition comprising hollow silica A and thermosetting resin B, The content of hollow silica A in the resin composition is 10 to 250 parts by weight relative to 100 parts by weight of the resin solids. The resin composition was impregnated into NE glass cloth at a resin composition content of 70% by volume, and dried at 155°C for 5 minutes to obtain a prepreg with a thickness of 0.1 mm. Eight pieces of the prepreg were stacked, and electrolytic copper foil with a thickness of 12 μm was placed on both sides and pressed to obtain a copper-clad laminate. The copper foil on both sides was removed from the copper-clad laminate by etching to obtain a sample with a thickness of 0.8 mm. The dielectric loss tangent of the 0.8 mm thick sample at a frequency of 10 GHz, measured by the cavity resonator perturbation method according to JIS C218:2007, was 0.0025 or less.

2. The resin composition according to claim 1, wherein, The sample with a thickness of 0.8 mm, according to JIS C218:2007, has a relative permittivity of 3.0 or less at a frequency of 10 GHz, as determined by the cavity resonator perturbation method.

3. The resin composition according to claim 1, wherein, The resin composition is impregnated into NE glass cloth at a resin composition content of 70% by volume, and dried at 155°C for 5 minutes to obtain a prepreg with a thickness of 0.1 mm. Electrolytic copper foil with a thickness of 12 μm is placed on both sides of the prepreg and pressed to obtain a copper-clad laminate. The copper foil on both sides is removed from the copper-clad laminate by etching, and the sample is cut and reduced to a size of 4.5 mm × 10 mm × 0.1 mm. When the sample is heated from 30°C to 340°C at a heating rate of 10°C per minute, the thermal expansion coefficient in the planar direction at 60°C to 120°C is less than 10 ppm / °C.

4. The resin composition according to claim 1, wherein, The 0.8 mm thick sample, according to JIS C218:2007, has a relative permittivity of 3.0 or less at a frequency of 10 GHz, determined by the cavity resonator perturbation method. The resin composition is impregnated into NE glass cloth at a resin composition content of 70% by volume, and dried at 155°C for 5 minutes to obtain a prepreg with a thickness of 0.1 mm. Electrolytic copper foil with a thickness of 12 μm is placed on both sides of the prepreg and pressed to obtain a copper-clad laminate. The copper foil on both sides is removed from the copper-clad laminate by etching, and the sample is cut and reduced to a size of 4.5 mm × 10 mm × 0.1 mm. When the sample is heated from 30°C to 340°C at a heating rate of 10°C per minute, the thermal expansion coefficient in the planar direction at 60°C to 120°C is less than 10 ppm / °C.

5. The resin composition according to any one of claims 1 to 4, wherein, The thermosetting resin B comprises an aromatic vinyl resin D and a maleimide compound E.

6. The resin composition according to any one of claims 1 to 4, further comprising thermoplastic elastomer C.

7. The resin composition according to claim 6, wherein, The thermoplastic elastomer C comprises styrene compound units and one or more units selected from the group consisting of butadiene units, isoprene units, hydrogenated butadiene units, and hydrogenated isoprene units. The content of styrene compound units in the thermoplastic elastomer C is less than 55% by mass of the total thermoplastic elastomer C.

8. The resin composition according to claim 6, wherein, The content of the thermoplastic elastomer C in the resin composition is 5 to 30 parts by weight relative to 100 parts by weight of the resin solids.

9. The resin composition according to claim 5, wherein, The aromatic vinyl resin D comprises one or more polymers selected from those having structural units shown in formula (V) and polyphenylene ether compounds having carbon-carbon unsaturated double bonds at the ends. In formula (V), Ar represents an aromatic hydrocarbon linking group, and * represents a bonding position.

10. The resin composition according to claim 9, wherein, The polyphenylene ether compound having a carbon-carbon unsaturated double bond at the end includes the polyphenylene ether compound represented by formula (OP). In formula (OP), X represents an aromatic group, and -(YO) n1 - indicates a polyphenylene ether structure, n1 represents an integer from 1 to 100, n2 represents an integer from 1 to 4, and Rx is the group shown in formula (Rx-1). In equation (Rx-1), R 1 R 2 and R 3 Each of these groups independently represents a hydrogen atom, alkyl, alkenyl, or alkynyl group, * represents the bonding site with an oxygen atom, Mc independently represents a hydrocarbon group with 1 to 12 carbon atoms, z represents an integer from 0 to 4, and r represents an integer from 0 to 6.

11. The resin composition according to claim 5, wherein, The content of the aromatic vinyl resin D in the resin composition is 5 to 95 parts by weight relative to 100 parts by weight of the resin solids.

12. The resin composition according to claim 5, wherein, The maleimide compound E comprises one or more compounds selected from the group consisting of compounds represented by formula (M1), formula (M3), and formula (M5). In formula (M1), R M1 R M2 R M3 and R M4 Each can independently represent a hydrogen atom or an organic group, R M5 and R M6 Each can be used independently to represent a hydrogen atom or an alkyl group, Ar M Indicates a divalent aromatic group, where A is an alicyclic group of a 4-6 membered ring, and R... M7 and R M8 Each is independently an alkyl group, mx is 1 or 2, lx is 0 or 1, R M9 and R M10 Each can be independently represented by a hydrogen atom or an alkyl group, R M11 R M12 R M13 and R M14 Each can independently represent a hydrogen atom or an organic group, R M15 Each of these groups independently represents an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, an alkylthio group with 1 to 10 carbon atoms, a cycloalkyl group with 3 to 10 carbon atoms, an aryl group with 6 to 10 carbon atoms, an aryloxy group with 6 to 10 carbon atoms, an arylthio group with 6 to 10 carbon atoms, a halogen atom, a hydroxyl group, or a mercapto group. px represents an integer from 0 to 3, and nx represents an integer from 1 to 20. In formula (M3), R 55 Each of these can independently represent an alkyl group or a phenyl group with 1 to 8 carbon atoms, and n5 represents an integer greater than 1 and less than 10. In formula (M5), R 58 Each of the following independently represents a hydrogen atom, an alkyl group or a phenyl group having 1 to 8 carbon atoms, and R. 59 Each can be used to independently represent a hydrogen atom or a methyl group, and n6 represents an integer greater than or equal to 1.

13. The resin composition according to claim 1, wherein, The 0.8 mm thick sample, according to JIS C218:2007, has a relative permittivity of 3.0 or less at a frequency of 10 GHz, determined by the cavity resonator perturbation method. The resin composition was impregnated into NE glass cloth at a resin composition content of 70% by volume, and dried at 155°C for 5 minutes to obtain a prepreg with a thickness of 0.1 mm. Electrolytic copper foil with a thickness of 12 μm was deposited on both sides of the prepreg and pressed to obtain a copper-clad laminate. The copper foil on both sides was removed from the copper-clad laminate by etching, and the sample was cut and reduced to a size of 4.5 mm × 10 mm × 0.1 mm. When the sample was heated at a rate of 10°C per minute from 30°C to 340°C, the thermal expansion coefficient in the planar direction at 60°C to 120°C was less than 10 ppm / °C. The thermosetting resin B comprises an aromatic vinyl resin D and a maleimide compound E. The resin composition further comprises thermoplastic elastomer C. The thermoplastic elastomer C comprises styrene compound units and one or more units selected from the group consisting of butadiene units, isoprene units, hydrogenated butadiene units, and hydrogenated isoprene units. The content of styrene compound units in the thermoplastic elastomer C is less than 55% by mass of the total thermoplastic elastomer C. The content of the thermoplastic elastomer C in the resin composition is 5 to 30 parts by weight relative to 100 parts by weight of the resin solids. The aromatic vinyl resin D comprises one or more polymers selected from those having structural units shown in formula (V) and polyphenylene ether compounds having carbon-carbon unsaturated double bonds at the ends. The polyphenylene ether compound having a carbon-carbon unsaturated double bond at the end includes the polyphenylene ether compound represented by formula (OP). The content of the aromatic vinyl resin D in the resin composition is 5 to 95 parts by weight relative to 100 parts by weight of the resin solids. The maleimide compound E comprises one or more compounds selected from the group consisting of compounds represented by formula (M1), formula (M3), and formula (M5). In formula (V), Ar represents an aromatic hydrocarbon linking group, and * indicates a bonding position. In formula (OP), X represents an aromatic group, and -(YO) n1 - indicates a polyphenylene ether structure, n1 represents an integer from 1 to 100, n2 represents an integer from 1 to 4, and Rx is the group shown in formula (Rx-1). In equation (Rx-1), R 1 R 2 and R 3 Each group independently represents a hydrogen atom, alkyl, alkenyl, or alkynyl group; * indicates the bonding site with an oxygen atom; Mc independently represents a hydrocarbon group with 1 to 12 carbon atoms; z represents an integer from 0 to 4; and r represents an integer from 0 to 6. In formula (M1), R M1 R M2 R M3 and R M4 Each can independently represent a hydrogen atom or an organic group, R M5 and R M6 Each can be used independently to represent a hydrogen atom or an alkyl group, Ar M Indicates a divalent aromatic group, where A is an alicyclic group of a 4-6 membered ring, and R... M7 and R M8 Each is independently an alkyl group, mx is 1 or 2, lx is 0 or 1, R M9 and R M10 Each can be independently represented by a hydrogen atom or an alkyl group, R M11 R M12 R M13 and R M14 Each can independently represent a hydrogen atom or an organic group, R M15 Each of these groups independently represents an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, an alkylthio group with 1 to 10 carbon atoms, a cycloalkyl group with 3 to 10 carbon atoms, an aryl group with 6 to 10 carbon atoms, an aryloxy group with 6 to 10 carbon atoms, an arylthio group with 6 to 10 carbon atoms, a halogen atom, a hydroxyl group, or a mercapto group. px represents an integer from 0 to 3, and nx represents an integer from 1 to 20. In formula (M3), R 55 Each of these can independently represent an alkyl group or a phenyl group with 1 to 8 carbon atoms, and n5 represents an integer greater than 1 and less than 10. In formula (M5), R 58 Each of the following independently represents a hydrogen atom, an alkyl group or a phenyl group having 1 to 8 carbon atoms, and R. 59 Each can be used to independently represent a hydrogen atom or a methyl group, and n6 represents an integer greater than or equal to 1.

14. The resin composition according to any one of claims 1 to 4 and 13, further comprising a flame retardant.

15. The resin composition according to claim 14, wherein, The flame retardant includes phosphorus-based flame retardants.

16. A cured product, which is a cured product of the resin composition according to any one of claims 1 to 4 and 13.

17. A prepreg formed from a substrate and a resin composition according to any one of claims 1 to 4 and 13.

18. A metal foil laminate comprising at least one prepreg as described in claim 17 and a metal foil disposed on one or both sides of the prepreg.

19. A resin composite sheet comprising a support and a layer formed of the resin composition according to any one of claims 1 to 4 and 13 disposed on the surface of the support.

20. A printed circuit board comprising an insulating layer and a conductor layer disposed on the surface of the insulating layer, the insulating layer comprising a layer formed of a resin composition according to any one of claims 1 to 4 and 13.

21. A semiconductor device comprising the printed circuit board of claim 20.

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