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

Abstract

Provided are: a resin composition which contains a thermosetting compound and a fluororesin filler, is capable of achieving low dielectric properties, and has excellent moisture absorption and heat resistance; a cured product; a prepreg; a metal foil-clad laminate; a resin composition containing a fluororesin filler (A) having an acidic group and / or a basic group; a thermoplastic elastomer (B) having a basic group and / or an acidic group having characteristics opposite to those of the acidic group and / or basic group of the fluororesin filler (A); and a thermosetting compound (C) compatible with the thermoplastic elastomer (B).

Description

Technical Field

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

[0002] In recent years, semiconductor elements used in electronic devices, communication devices, etc., such as portable terminals, have been increasingly integrated and miniaturized. In response, technologies that enable high-density mounting of semiconductor elements are being sought, and improvements are being sought for printed circuit boards, which occupy an important position in the semiconductor elements.

[0003] On the other hand, the use of electronic devices is becoming more diverse and expanding. Therefore, the properties required of printed circuit boards, metal foil-clad laminates, prepregs, etc. used therein are also becoming more diverse and stricter. In view of such required properties, various materials and processing methods have been proposed to obtain improved printed circuit boards. As one of them, the improvement and development of resin materials constituting prepregs and resin composite sheets can be cited.

[0004] In addition, in order to impart a low dielectric constant and / or a low dielectric loss tangent to such a resin material, it has been studied to blend a fluororesin filler (Patent Documents 1 and 2).

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Publication No. 2019-99712

[0008] Patent Document 2: Japanese Patent Application Publication No. 2016-89137 Summary of the invention

[0009] Problem that the invention aims to solve

[0010] As described above, if a fluororesin filler is added to a resin material, it tends to achieve low dielectric properties. However, the present inventors have found that although a cured product of a resin composition containing a thermosetting compound and a fluororesin filler can achieve low dielectric properties, it sometimes has poor moisture absorption and heat resistance.

[0011] In order to solve this problem, the present invention aims to provide a resin composition comprising a thermosetting compound and a fluororesin filler, which can achieve low dielectric properties and excellent moisture absorption and heat resistance, as well as a cured product, a prepreg, a metal foil-clad laminate, a resin composite sheet, a printed wiring board and a semiconductor device.

[0012] Solutions for solving problems

[0013] Based on the above problems, the present inventors have studied and found that the above problems can be solved by using a substance having an acidic group and / or a basic group as a fluororesin filler in a resin composition containing a thermosetting compound and a fluororesin filler, and using a thermoplastic elastomer having a basic group and / or an acidic group having opposite characteristics to the acidic group and / or basic group of the fluororesin filler. Specifically, the above problems were solved by the following means.

[0014] <1> A resin composition comprising: a fluororesin filler (A) having an acidic group and / or a basic group; a thermoplastic elastomer (B) having a basic group and / or an acidic group having opposite properties to the acidic group and / or basic group of the fluororesin filler (A); and a thermosetting compound (C) compatible with the thermoplastic elastomer (B).

[0015] <2> according to <1> The resin composition, wherein the fluororesin filler (A) comprises a fluororesin filler (A) having an acidic group, and the thermoplastic elastomer (B) comprises a thermoplastic elastomer (B) having a basic group.

[0016] <3> according to <1> In the resin composition, the fluororesin filler (A) comprises a fluororesin filler having a carboxyl group, and the thermoplastic elastomer (B) comprises a thermoplastic elastomer having an amino group.

[0017] <4> according to <1> The resin composition, wherein the fluororesin filler (A) comprises at least one selected from the group consisting of perfluoroalkoxy polyolefins having carboxyl groups and / or acid anhydride groups and (ethylene / tetrafluoroethylene) copolymer polyolefins having carboxyl groups and / or acid anhydride groups.

[0018] <5> according to <1> ~ <4> The resin composition described in any one of the preceding claims, wherein the thermoplastic elastomer (B) comprises a styrene monomer unit and has a number average molecular weight of 50,000 to 800,000.

[0019] <6> according to <5> In the resin composition, the thermoplastic elastomer (B) further comprises a conjugated diene monomer unit.

[0020] <7> according to <1> ~ <6> The resin composition described in any one of the preceding claims, wherein the thermosetting compound (C) comprises a thermosetting compound having an aromatic ring and a carbon-carbon unsaturated bond other than an aromatic ring.

[0021] <8> according to <1> ~ <7> The resin composition described in any one of the preceding claims, wherein the thermosetting compound (C) comprises one or more selected from the group consisting of a polymer (V) having a structural unit represented by formula (V) and a polyphenylene ether compound (P) having a carbon-carbon unsaturated double bond at a terminal.

[0022]

[0023] (In formula (V), Ar represents an aromatic hydrocarbon linking group. * represents a bonding position.)

[0024] <9> according to <1> ~ <8> The resin composition described in any one of the preceding claims, comprising 1 to 70 parts by mass of the thermoplastic elastomer (B) based on 100 parts by mass of the fluororesin filler (A).

[0025] <10> according to <1> ~ <9> The resin composition described in any one of the preceding claims, wherein the content of the fluororesin filler (A) is 10 to 300 parts by mass based on 100 parts by mass of the resin solid content.

[0026] <11> according to <1> ~ <10> The resin composition described in any one of the above, wherein the content of the thermoplastic elastomer (B) is 1 to 90 parts by mass based on 100 parts by mass of the resin solid content.

[0027] <12> according to <1> ~ <11> The resin composition described in any one of the preceding claims, wherein the content of the thermosetting compound (C) is 1 to 90 parts by mass based on 100 parts by mass of the resin solid content.

[0028] <13> according to <1> ~ <12> The resin composition described above further comprises one or more other thermosetting compounds (D), wherein the other thermosetting compounds (D) are selected from the group consisting of maleimide compounds, epoxy compounds, phenol compounds, oxetane resins, benzoxazine compounds and cyanate compounds.

[0029] <14> according to <13> The resin composition, wherein the maleimide compound comprises one or more selected from the group consisting of a compound represented by formula (M0), a compound represented by formula (M1), a compound represented by formula (M3) and a compound represented by formula (M5).

[0030]

[0031] (In formula (M0), R 51 Each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a phenyl group, and R 52 Each independently represents a hydrogen atom or a methyl group, and n1 represents an integer greater than 1.)

[0032]

[0033] (In formula (M1), R M1 , R M2 , R M3 and R M4 Each independently represents a hydrogen atom or an organic group. M5 and R M6 Each independently represents a hydrogen atom or an alkyl group. M represents a divalent aromatic group. A is a 4- to 6-membered alicyclic group. M7 and R M8 Each is independently an alkyl group. mx is 1 or 2, and lx is 0 or 1. M9 and R M10 Each independently represents a hydrogen atom or an alkyl group. M11 , R M12 , R M13 , and R M14 Each independently represents a hydrogen atom or an organic group. M15 Each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a halogen atom, a hydroxyl group or a mercapto group. px represents an integer of 0 to 3. nx represents an integer of 1 to 20.)

[0034]

[0035] (In formula (M3), R 55 Each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group, and n5 represents an integer of 1 to 10.

[0036]

[0037] (In formula (M5), R 58 Each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a phenyl group, and R 59 Each independently represents a hydrogen atom or a methyl group, and n6 represents an integer greater than 1.)

[0038] <15> according to <1> ~ <14> The resin composition described above further comprises a flame retardant (F).

[0039] <16> according to <15> In the resin composition, the flame retardant (F) comprises a phosphorus-based flame retardant.

[0040] <17> according to <1> ~ <16> The resin composition described in any one of the preceding claims, further comprising a filler (G) other than the fluororesin filler (A).

[0041] <18> according to <17> The resin composition, wherein the filler (G) comprises at least one selected from the group consisting of silica, aluminum hydroxide, aluminum nitride, boron nitride and forsterite.

[0042] <19> according to <17> or <18> The resin composition described above, wherein the content of the filler (G) is 10 to 1000 parts by mass based on 100 parts by mass of the resin solid content.

[0043] <20> according to <17> ~ <19> The resin composition described in any one of the preceding claims, wherein the content of the filler (G) is 50 to 500 parts by mass based on 100 parts by mass of the fluororesin filler (A).

[0044] <21> according to <1> ~ <20> The resin composition according to any one of the preceding claims, wherein the fluororesin filler (A) comprises at least one selected from the group consisting of perfluoroalkoxy polyolefins having carboxyl groups and / or acid anhydride groups and (ethylene / tetrafluoroethylene) copolymer polyolefins having carboxyl groups and / or acid anhydride groups,

[0045] The thermoplastic elastomer (B) comprises a styrene monomer unit and has a number average molecular weight of 50,000 or more and 800,000 or less,

[0046] The aforementioned thermoplastic elastomer (B) further comprises a conjugated diene monomer unit,

[0047] The thermosetting compound (C) comprises one or more selected from the group consisting of a polymer (V) having a structural unit represented by formula (V) and a polyphenylene ether compound (P) having a carbon-carbon unsaturated double bond at a terminal.

[0048] The resin composition comprises 1 to 70 parts by mass of the thermoplastic elastomer (B) based on 100 parts by mass of the fluororesin filler (A).

[0049] The content of the fluororesin filler (A) is 10 to 300 parts by mass based on 100 parts by mass of the resin solid content.

[0050] The content of the thermoplastic elastomer (B) is 1 to 90 parts by mass based on 100 parts by mass of the resin solid content.

[0051] The content of the thermosetting compound (C) is 1 to 90 parts by mass based on 100 parts by mass of the resin solid content.

[0052] The resin composition further comprises one or more other thermosetting compounds (D), wherein the other thermosetting compounds (D) are selected from the group consisting of maleimide compounds, epoxy compounds, phenol compounds, oxetane resins, benzoxazine compounds and cyanate compounds,

[0053] The maleimide compound includes one or more selected from the group consisting of a compound represented by formula (M0), a compound represented by formula (M1), a compound represented by formula (M3) and a compound represented by formula (M5),

[0054] The resin composition further comprises a flame retardant (F),

[0055] The flame retardant (F) includes a phosphorus-based flame retardant,

[0056] The resin composition further comprises other filler (G) in addition to the aforementioned fluororesin filler (A),

[0057] The filler (G) comprises at least one selected from the group consisting of silicon dioxide, aluminum hydroxide, aluminum nitride, boron nitride and forsterite,

[0058] The content of the filler (G) is 10 to 1000 parts by mass based on 100 parts by mass of the resin solid content.

[0059] The content of the filler (G) is 50 to 500 parts by mass based on 100 parts by mass of the fluororesin filler (A).

[0060]

[0061] (In formula (V), Ar represents an aromatic hydrocarbon linking group. * represents a bonding position.)

[0062]

[0063] (In formula (M0), R 51 Each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a phenyl group, and R 52 Each independently represents a hydrogen atom or a methyl group, and n1 represents an integer greater than 1.)

[0064]

[0065] (In formula (M1), R M1 , R M2 , R M3 and R M4 Each independently represents a hydrogen atom or an organic group. M5 and R M6 Each independently represents a hydrogen atom or an alkyl group. Mrepresents a divalent aromatic group. A is a 4- to 6-membered alicyclic group. M7 and R M8 Each is independently an alkyl group. mx is 1 or 2, and lx is 0 or 1. M9 and R M10 Each independently represents a hydrogen atom or an alkyl group. M11 , R M12 , R M13 , and R M14 Each independently represents a hydrogen atom or an organic group. M15 Each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a halogen atom, a hydroxyl group or a mercapto group. px represents an integer of 0 to 3. nx represents an integer of 1 to 20.)

[0066]

[0067] (In formula (M3), R 55 Each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group, and n5 represents an integer of 1 to 10.

[0068]

[0069] (In formula (M5), R 58 Each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a phenyl group, and R 59 Each independently represents a hydrogen atom or a methyl group, and n6 represents an integer greater than 1.)

[0070] <22> A solidified material, which is <1> ~ <21> A cured product of any one of the resin compositions.

[0071] <23> A prepreg comprising a base material and <1> ~ <21> The resin composition described in any one of the above is formed.

[0072] <24> A metal foil-clad laminate comprising <23> At least one layer formed of the prepreg, and a metal foil disposed on one or both sides of the layer formed of the prepreg.

[0073] <25> A resin composite sheet comprising a support body and a resin composite sheet disposed on the surface of the support body. <1> ~ <21> A layer formed from any one of the resin compositions.

[0074] <26> A printed circuit board comprises an insulating layer and a conductor layer arranged on the surface of the insulating layer, wherein the insulating layer comprises at least one of the following: <1> ~ <21> A layer formed of the resin composition described in any one of the above <23> The prepreg forms a layer.

[0075] <27> A semiconductor device comprising <26> The printed circuit board.

[0076] Effects of the Invention

[0077] According to the present invention, a resin composition comprising a thermosetting compound and a fluororesin filler can be provided, which can achieve excellent low dielectric properties and excellent moisture absorption heat resistance; and a cured product, a prepreg, a metal foil-clad laminate, a resin composite sheet, a printed circuit board and a semiconductor device can be provided. DETAILED DESCRIPTION

[0078] Hereinafter, a mode for implementing the present invention (hereinafter referred to as "this embodiment") will be described in detail. In addition, the following this embodiment is an example for explaining the present invention, and the present invention is not limited to this embodiment.

[0079] In addition, in this specification, "to" is used to mean that the numerical values ​​described before and after it are included as a lower limit and an upper limit.

[0080] In this specification, various physical property values ​​and characteristic values ​​are assumed to be values ​​at 23° C. unless otherwise specified.

[0081] In the description of the group (atomic group) in this specification, the description that does not indicate substitution and unsubstituted includes the group (atomic group) without substitution and also includes the group (atomic group) with substitution. For example, "alkyl" includes not only the alkyl without substitution (unsubstituted alkyl), but also includes the alkyl with substitution (substituted alkyl). In this specification, the description that does not indicate substitution and unsubstituted is preferably unsubstituted.

[0082] In this specification, the relative dielectric constant represents the ratio of the dielectric constant of a substance to the dielectric constant of a vacuum. In addition, in this specification, the relative dielectric constant may be simply referred to as "dielectric constant".

[0083] In the present specification, "(meth)acrylic acid" means both or either acrylic acid or methacrylic acid. In addition, in the present specification, "(meth)acryloyl" means both or either acryloyl or methacryloyl.

[0084] As the example of substituent in this specification, preferably halogen atom, cyano group, nitro, hydroxyl, alkyl, alkoxyl group, aryl, aryloxy group, heterocyclic group, heterocyclic group, alkenyl group, alkylthio group, arylthio group, acyl group or amino group, more preferably halogen atom, alkyl, alkoxyl group, aryl, aryloxy group, alkenyl group or acyl group, further preferably alkyl, aryl, aryloxy group or alkenyl group, more preferably alkyl. The formula weight of these substituents is preferably more than 15, and preferably less than 200. For formula weight, for example, if it is methyl (-CH3), it is 15. These substituents may also have further substituents, but preferably no substituents.

[0085] Although the standards exemplified in this specification may differ in measurement methods and the like depending on the year, unless otherwise specified, the standards are based on January 1, 2022.

[0086] In the present specification, the resin solid content refers to the components other than the fluororesin filler (A), the filler (G) other than the fluororesin filler (A), and the solvent, and includes the thermoplastic elastomer (B) and the thermosetting compound (C), and other thermosetting compounds (D) and other resin additive components (such as the flame retardant (F)) that are blended as needed.

[0087] The resin composition of the present embodiment is characterized by comprising a fluororesin filler (A) having an acidic group and / or a basic group (sometimes referred to simply as "fluororesin filler (A)" in the present specification); a thermoplastic elastomer (B) having a basic group and / or an acidic group having opposite characteristics to the acidic group and / or basic group possessed by the fluororesin filler (A) (sometimes referred to simply as "thermoplastic elastomer (B)" in the present specification); and a thermosetting compound (C) compatible with the thermoplastic elastomer (B) (sometimes referred to simply as "thermosetting compound (C)" in the present specification).

[0088] By setting it as such a structure, it is possible to provide a resin composition which contains a thermosetting compound and a fluororesin filler, can achieve low dielectric characteristics, and is excellent in moisture absorption heat resistance.

[0089] As mentioned above, if a fluororesin filler is mixed with a thermosetting compound, low dielectric properties can be achieved. However, after research, the inventors speculated that the dispersibility of the fluororesin filler in the thermosetting compound is low. In particular, it is speculated that when a resin composition containing a thermosetting compound and a fluororesin filler is made into a cured product, the fluororesin filler will aggregate and form voids in areas where the proportion of the fluororesin filler is small. It is speculated that if a cured product having such a void portion is subjected to a wet heat treatment, water will penetrate into the void portion, and delamination will occur in a laminate having such a cured product.

[0090] In the present embodiment, it is inferred that by using a fluororesin filler (A) having an acidic group and / or a basic group and a thermoplastic elastomer (B) having a basic group and / or an acidic group having opposite characteristics to the acidic group and / or the basic group possessed by the fluororesin filler (A), the acidic group and / or the basic group possessed by the fluororesin filler (A) and the groups of opposite characteristics possessed by the thermoplastic elastomer (B) can interact with each other. Moreover, it is inferred that by using a thermosetting compound (C) compatible with the thermoplastic elastomer (B), the thermoplastic elastomer (B) can be appropriately dispersed in the thermosetting compound (C), and as a result, the fluororesin filler (A) can also be dispersed in the thermosetting compound (C). Moreover, it is inferred that by making the resin composition such a structure, the fluororesin filler (A) can also maintain a good dispersion state in its cured product, and a cured product with excellent low dielectric properties and hygroscopic heat resistance can be obtained.

[0091] <Fluororesin filler (A) having an acidic group and / or a basic group>

[0092] The resin combination of the present embodiment comprises a fluororesin filler (A) having an acidic group and / or a basic group. By using a fluororesin filler, a cured product of a resin combination having excellent low dielectric properties can be obtained. In addition, by using a substance having an acidic group and / or a basic group as a fluororesin filler, it is possible to interact with the basic group and / or the acidic group possessed by the thermoplastic elastomer (B). "Interaction" herein encompasses covalent bonding, ionic bonding, etc.

[0093] The fluororesin filler (A) may consist of a fluororesin alone or may contain additives, etc. Preferably, 95% by mass or more (more preferably 97% by mass or more, and even more preferably 99% by mass or more) of the fluororesin filler (A) consists of a fluororesin having an acidic group and / or a basic group.

[0094] The fluororesin filler (A) used in the present embodiment may have only an acidic group, may have only a basic group, or may have both an acidic group and a basic group. In addition, a fluororesin filler (AA) having only an acidic group and a fluororesin filler (AB) having only a basic group may also be included. In addition, a mixture thereof may also be included. The fluororesin filler (A) preferably includes one of an acidic group and a basic group, and more preferably has an acidic group. As the acidic group, it is not particularly limited, preferably selected from one or more of the group consisting of a carboxyl group, an anhydride group, a phenolic hydroxyl group, a phosphoric acid group and a sulfonic group, more preferably a carboxyl group and / or an anhydride group, and further preferably a carboxyl group. The basic group is not particularly limited, preferably selected from one or more of the group consisting of an amino group, an imino group, a nitrile group, a pyridyl group, a quinolyl group and an amide group, more preferably an amino group.

[0095] The fluororesin filler (A) preferably comprises a fluoropolyolefin having an acidic group and / or a basic group, more preferably comprises a fluoropolyolefin having an acidic group, and more preferably comprises at least one selected from the group consisting of a perfluoroalkoxypolyolefin having a carboxyl group and / or an acid anhydride group and an (ethylene / tetrafluoroethylene) copolymer polyolefin having a carboxyl group and / or an acid anhydride group.

[0096] As the fluororesin filler (A), in addition to the above, reference may be made to JP-A-2021-530608, JP-A-2006-152234, and JP-A-2004-277689. In addition, an acid-modified or alkali-modified fluororesin filler described in paragraph 0060 of JP-A-2019-99712 may be used.

[0097] The melting point of the fluororesin constituting the fluororesin filler (A) is not particularly limited, but is, for example, preferably 150° C. or higher, more preferably 180° C. or higher, further preferably 220° C. or higher, further preferably 250° C. or higher, and further preferably 280° C. or higher. The melting point of the fluororesin constituting the fluororesin filler (A) is preferably 340° C. or lower, more preferably 320° C. or lower.

[0098] The volume flow rate of the fluororesin constituting the fluororesin filler (A) (hereinafter represented by a value Q) is preferably 0.1 to 1,000 mm 3 / sec. The value Q is an index representing the melt flowability of the fluororesin, and is usually an index of the molecular weight. A large Q value tends to be associated with a low molecular weight of the fluororesin. A small Q value tends to be associated with a high molecular weight of the fluororesin. In the present embodiment, the value Q represents the extrusion speed of the fluororesin when extruded through a throttle hole with a diameter of 2.1 mm and a total length of 8 mm at a temperature 50°C higher than the melting point of the fluororesin and a load of 7 kg using a flow tester manufactured by Shimadzu Corporation. The value Q of the fluororesin is more preferably 5 mm 3 / sec or more, more preferably 10mm 3 / sec or more, more preferably 500 mm 3 / sec or less, more preferably 200 mm 3 / sec or less.

[0099] The fluororesin filler (A) used in the present embodiment is more preferably excellent in low dielectric properties. For example, the relative dielectric constant (Dk) of the fluororesin filler (A) at a frequency of 10GHz measured by the cavity resonance perturbation method is preferably 5.0 or less, more preferably 3.0 or less, and further preferably 2.0 or less. In addition, the lower limit of the relative dielectric constant is, for example, more than 1.0 and more practical. In addition, the dielectric loss tangent (Df) of the fluororesin filler (A) at a frequency of 10GHz measured by the cavity resonance perturbation method is preferably 0.002 or less, more preferably 0.001 or less. In addition, the lower limit of the dielectric loss tangent is, for example, more than 0.0001 and more practical. The relative dielectric constant (Dk) and dielectric loss tangent (Df) of the fluororesin filler (A) are values ​​at a frequency of 10GHz measured by the cavity resonance perturbation method, more specifically, a fluororesin filler (A) is loaded into a Teflon (registered trademark) tube, and the dielectric properties of the filler monomer are calculated based on the Bruggman formula.

[0100] The average particle size (D50) of the fluororesin filler (A) is not particularly limited, but is preferably 0.1 μm or more, more preferably 0.5 μm or more, and further preferably 1 μm or more. In addition, from the viewpoint of dispersibility, the average particle size (D50) of the fluororesin filler (A) is preferably 10 μm or less, more preferably 5 μm or less, and further preferably 3 μm or less.

[0101] It should be noted that the average particle size (D50) refers to the value when the volume of the smallest particles reaches 50% of the total volume, measured by a particle size distribution measuring device such as a laser diffraction / scattering method, in which a predetermined amount of powder is added to a dispersion medium. When the dispersion medium herein includes a solvent, it refers to the solvent.

[0102] The fluororesin filler (A) used in the present embodiment may be a commercially available product. For example, as the fluororesin filler (AA) having only an acidic group, EA-2000 manufactured by AGC Corporation can be cited.

[0103] In the resin composition of the present embodiment, the content of fluororesin filler (A) is preferably more than 10 mass parts relative to 100 mass parts of resin solid components, more preferably more than 20 mass parts, further preferably more than 25 mass parts, further preferably more than 30 mass parts, more preferably more than 35 mass parts, and further preferably more than 40 mass parts. By being set to more than the aforementioned lower limit, there is a tendency that dielectric properties are further improved. In addition, the upper limit of the content of fluororesin filler (A) is preferably less than 300 mass parts relative to 100 mass parts of resin solid components, more preferably less than 200 mass parts, further preferably less than 150 mass parts, further preferably less than 110 mass parts, and can also be less than 70 mass parts. By being set to less than the aforementioned upper limit, there is a tendency that moldability is further improved.

[0104] The resin composition of the present embodiment may contain only one type of fluororesin filler (A), or may contain two or more types. When containing two or more types, the total amount is preferably within the above range.

[0105] <Thermoplastic elastomer (B) having basic groups and / or acidic groups having opposite characteristics to the acidic groups and / or basic groups possessed by the fluororesin filler (A)>

[0106] The resin composition of the present embodiment includes a thermoplastic elastomer (B) having a basic group and / or an acidic group that are opposite to the acidic group and / or the basic group possessed by the fluororesin filler (A). By using a substance having a basic group and / or an acidic group as a thermoplastic elastomer, it is possible to interact with the acidic group and / or the basic group possessed by the fluororesin filler (A). In addition, the thermoplastic elastomer (B) used in the present embodiment is compatible with the thermosetting compound (C), so that the fluororesin filler (A) can be dispersed in the thermosetting compound (C).

[0107] Here, the basic group and / or acidic group having opposite characteristics to the acidic group and / or basic group means that the fluororesin filler (A) has a basic group when it has an acidic group, and has an acidic group when it has a basic group.

[0108] In addition, in the present embodiment, when the fluororesin filler (A) contains both an acidic group and a basic group, it may contain both a thermoplastic elastomer (BB) having a basic group and a thermoplastic elastomer (BA) having an acidic group, or may contain a thermoplastic elastomer (BC) having both a basic group and an acidic group, or may contain a thermoplastic elastomer (BB) having a basic group, a thermoplastic elastomer (BA) having an acidic group, and a thermoplastic elastomer (BC) having both a basic group and an acidic group. When the fluororesin filler (A) contains both a fluororesin filler (AA) having only an acidic group and a fluororesin filler (AB) having only a basic group, it may contain both a thermoplastic elastomer (BB) having a basic group and a thermoplastic elastomer (BA) having an acidic group, or may contain a thermoplastic elastomer (BC) having both a basic group and an acidic group, or may contain a thermoplastic elastomer (BB) having a basic group, a thermoplastic elastomer (BA) having an acidic group, and a thermoplastic elastomer (BC) having both a basic group and an acidic group.

[0109] In the present embodiment, the thermoplastic elastomer (B) is preferably a thermoplastic elastomer (BB) having a basic group.

[0110] The basic group is not particularly limited, but preferably one or more selected from the group consisting of an amino group, an imino group, a nitrile group, a pyridyl group, a quinolyl group and an amide group, and more preferably an amino group. The acidic group is not particularly limited, but preferably one or more selected from the group consisting of a carboxyl group, an anhydride group, a phenolic hydroxyl group, a phosphoric acid group and a sulfonic group, and more preferably a carboxyl group and / or an anhydride group, and further preferably a carboxyl group.

[0111] The thermoplastic elastomer (B) in the present embodiment is not particularly limited as long as it is a thermoplastic elastomer having a basic group and / or an acidic group. For example, at least one selected from the group consisting of the following substances having the above-mentioned basic group and / or acidic group can be mentioned: polyisoprene, polybutadiene, styrene butadiene, butyl rubber, ethylene propylene rubber, styrene butadiene ethylene, styrene butadiene styrene, styrene isoprene styrene, styrene ethylene butylene styrene, styrene propylene styrene, styrene ethylene propylene styrene, fluororubber, silicone rubber, their hydrides, their alkyl compounds and their copolymers.

[0112] The number average molecular weight of the thermoplastic elastomer (B) used in the present embodiment is preferably 50,000 or more. By making the number average molecular weight of the thermoplastic elastomer (B) 50,000 or more, the low dielectric properties of the obtained cured product tend to be more excellent. The number average molecular weight of the thermoplastic elastomer (B) is more preferably 60,000 or more, further preferably 70,000 or more, and more preferably 80,000 or more. The upper limit of the number average molecular weight of the thermoplastic elastomer (B) is preferably 800,000 or less, more preferably 400,000 or less, further preferably 350,000 or less, and more preferably 300,000 or less. By being set to below the above-mentioned upper limit, the solubility of the thermoplastic elastomer (B) in the resin composition tends to be improved.

[0113] When the resin composition of the present embodiment contains two or more thermoplastic elastomers (B), it is preferred that the number average molecular weight of the mixture thereof satisfy the above range.

[0114] In the present embodiment, the thermoplastic elastomer (B) preferably contains a styrene monomer unit. When the thermoplastic elastomer (B) contains a styrene monomer unit, the solubility of the thermoplastic elastomer (B) in the resin composition is improved.

[0115] Thermoplastic elastomer (B) more preferably contains styrene monomer units and conjugated diene monomer units. By using thermoplastic elastomer (B) containing styrene monomer units and conjugated diene monomer units (hereinafter referred to as "thermoplastic elastomer (B1)"), the obtained cured product has more excellent low dielectric properties.

[0116] Examples of the styrene monomer include styrene, α-methylstyrene, p-methylstyrene, divinylbenzene (vinylstyrene), N,N-dimethyl-p-aminoethylstyrene, and N,N-diethyl-p-aminoethylstyrene. Among them, styrene, α-methylstyrene, and p-methylstyrene are preferred from the viewpoint of availability and productivity. Among them, styrene is particularly preferred.

[0117] In the thermoplastic elastomer (B1), the content of the styrene monomer unit is preferably in the range of 10 to 50% by mass of all monomer units, more preferably in the range of 13 to 45% by mass, further preferably in the range of 15 to 40% by mass, and more preferably in the range of 20 to 35% by mass. If the content of the styrene monomer unit is 50% by mass or less, the adhesion and adhesiveness with the substrate etc. are better. In addition, if it is 10% by mass or more, it is possible to suppress excessive adhesion, and it is not easy to produce residual glue and stop marks. There is a tendency for the easy peelability of the bonding surfaces to become good, so it is preferred.

[0118] The thermoplastic elastomer (B1) may contain only one type of styrene monomer unit, or may contain two or more types. When containing two or more types, the total amount is preferably within the above range.

[0119] The method for measuring the content of the styrene monomer unit in the thermoplastic elastomer (B1) can refer to the description of International Publication No. 2017 / 126469, the contents of which are incorporated herein. The same applies to the conjugated diene monomer unit described later.

[0120] The conjugated diene monomer unit is not particularly limited as long as it is a diene having one pair of conjugated double bonds. Examples of the conjugated diene monomer include 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene and farnesene, preferably 1,3-butadiene and isoprene, more preferably 1,3-butadiene.

[0121] The thermoplastic elastomer (B1) may contain only one type of conjugated diene monomer unit, or may contain two or more types.

[0122] In the thermoplastic elastomer (B1), the mass ratio of the styrene monomer unit to the conjugated diene monomer unit is preferably in the range of styrene monomer unit / conjugated diene monomer unit = 5 / 95 to 80 / 20, more preferably in the range of 7 / 93 to 77 / 23, and further preferably in the range of 10 / 90 to 70 / 30. If the mass ratio of the styrene monomer unit to the conjugated diene monomer unit is in the range of 5 / 95 to 80 / 20, excessive adhesion can be suppressed, and the adhesive force can be maintained at a high level, and the easy peelability of the adhesive surfaces becomes good.

[0123] In the thermoplastic elastomer (B1), the conjugated diene bonds of the thermoplastic elastomer may be all hydrogenated, partially hydrogenated, or not hydrogenated.

[0124] The thermoplastic elastomer (B1) may or may not contain other monomer units in addition to the styrene monomer units and the conjugated diene monomer units. Examples of the other monomer units include aromatic vinyl compound units other than the styrene monomer units.

[0125] In the thermoplastic elastomer (B1), the total content of the styrene monomer units and the conjugated diene monomer units is preferably 90% by mass or more, more preferably 95% by mass or more, further preferably 97% by mass or more, and even more preferably 99% by mass or more of all monomer units.

[0126] In the thermoplastic elastomer (B1), the styrene monomer unit and the conjugated diene monomer unit may each contain only one kind or two or more kinds. When two or more kinds are contained, the total amount is preferably within the above range.

[0127] The thermoplastic elastomer (B1) may be a block polymer or a random polymer. In addition, the conjugated diene monomer unit may be a hydrogenated elastomer that has been hydrogenated, an unhydrogenated elastomer that has not been hydrogenated, or a partially hydrogenated partially hydrogenated elastomer.

[0128] In one embodiment of the present embodiment, the thermoplastic elastomer (B1) is a hydrogenated elastomer. Here, the hydrogenated elastomer refers to, for example, an elastomer in which the double bonds based on the conjugated diene monomer units are hydrogenated, and includes not only those with a hydrogenation rate (hydrogenation rate) of 100%, but also those with a hydrogenation rate of 80% or more. The hydrogenation rate of the hydrogenated elastomer is preferably 85% or more, more preferably 90% or more, and further preferably 95% or more. In this embodiment, the hydrogenation rate is 1 The measurement results of H-NMR spectrum measurement were calculated.

[0129] In one embodiment of the present embodiment, the thermoplastic elastomer (B1) is an unhydrogenated elastomer. Here, the unhydrogenated elastomer means an elastomer having a ratio of hydrogenated double bonds based on conjugated diene monomer units, i.e., a hydrogenation rate (hydrogenation rate) of 20% or less. The hydrogenation rate in the unhydrogenated elastomer is preferably 15% or less, more preferably 10% or less, and further preferably 5% or less.

[0130] On the other hand, the partially hydrogenated elastomer refers to an elastomer in which a part of the double bonds based on the conjugated diene monomer units in the elastomer are hydrogenated, and generally refers to an elastomer with a hydrogenation rate (hydrogenation rate) of less than 80% and more than 20%.

[0131] The thermoplastic elastomer (BA) having an acidic group used in the present embodiment can be produced, for example, by reacting an unmodified unhydrogenated, partially hydrogenated, or fully hydrogenated thermoplastic elastomer with an acid such as maleic acid or maleic anhydride. In addition, the thermoplastic elastomer having a basic group can be obtained, for example, by reacting an unmodified thermoplastic elastomer with a base such as imidazolidinone, an alkylamine (e.g., an alkylamine having 1 to 10 carbon atoms), an amino alcohol (e.g., an amino alcohol having 1 to 4 carbon atoms), or N-methyl-2-pyrrolidone when synthesizing the unmodified thermoplastic elastomer. Or it can be obtained by reacting an unmodified unhydrogenated, partially hydrogenated, or fully hydrogenated thermoplastic elastomer with an acid such as maleic acid or maleic anhydride, and then reacting it with a base such as an alkylamine (e.g., an alkylamine having 1 to 10 carbon atoms).

[0132] The thermoplastic elastomer (B) used in this embodiment may also be a commercially available product. For example, as the thermoplastic elastomer (BA) having an acidic group, TUFTEC M1943, M1913, and M1911 manufactured by Asahi Kasei Corporation may be cited. In addition, as the thermoplastic elastomer (BB) having a basic group, TUFTEC MP10 manufactured by Asahi Kasei Corporation may be cited.

[0133] In the resin combination of the present embodiment, the content of thermoplastic elastomer (B) is preferably more than 1 mass part relative to 100 mass parts of resin solids, more preferably more than 5 mass parts, further preferably more than 7 mass parts, more preferably more than 10 mass parts, more preferably more than 12 mass parts.By being set to more than the aforementioned lower limit, low dielectric properties have a tendency to be further improved.In addition, the upper limit of the content of thermoplastic elastomer (B) is preferably less than 90 mass parts relative to 100 mass parts of resin solids, more preferably less than 70 mass parts, further preferably less than 50 mass parts, more preferably less than 30 mass parts, more preferably less than 20 mass parts.By being set to less than the aforementioned upper limit, hygroscopic heat resistance has a tendency to be further improved.

[0134] The resin composition of the present embodiment may contain only one thermoplastic elastomer (B) or two or more thereof. When containing two or more thereof, the total amount is preferably within the above range.

[0135] <Method of blending fluororesin filler (A) and thermoplastic elastomer (B)>

[0136] Next, a preferred blending mode of the fluororesin filler (A) and the thermoplastic elastomer (B) in the resin composition of the present embodiment will be described.

[0137] In this embodiment, it is preferred that the fluororesin filler (A) includes a fluororesin filler (AA) having an acidic group (preferably a carboxyl group), and the thermoplastic elastomer (B) includes a thermoplastic elastomer (BB) having a basic group (preferably an amino group).

[0138] In addition, in the resin composition of the present embodiment, the content of thermoplastic elastomer (B) is preferably more than 1 mass part relative to 100 mass parts of fluororesin filler (A), more preferably more than 5 mass parts, further preferably more than 10 mass parts, more preferably more than 15 mass parts, more preferably more than 25 mass parts. By being set to more than the aforementioned lower limit, low dielectric properties, hygroscopic heat resistance, peel strength have a tendency to be further improved. The content of thermoplastic elastomer (B) is preferably less than 70 mass parts relative to 100 mass parts of fluororesin filler (A), more preferably less than 60 mass parts, further preferably less than 51 mass parts, more preferably less than 40 mass parts, and can also be less than 35 mass parts. By being set to less than the aforementioned upper limit, hygroscopic heat resistance has a tendency to be further improved.

[0139] <Thermosetting compound (C) compatible with thermoplastic elastomer (B)>

[0140] The resin composition of the present embodiment includes a thermosetting compound (C) compatible with a thermoplastic elastomer (B). In the present embodiment, by making the thermoplastic elastomer (B) and the thermosetting compound (C) compatible, the fluororesin filler (A) that interacts with the thermoplastic elastomer (B) via an acidic group and / or a basic group can be dispersed in the thermosetting compound (C).

[0141] Here, the term "compatible" means that the thermoplastic elastomer (B) and the thermosetting compound (C) are fully mixed and do not undergo gross separation after being left to stand, which can usually be observed visually.

[0142] The thermosetting compound (C) used in this embodiment preferably includes a thermosetting compound having an aromatic ring and a carbon-carbon unsaturated bond other than an aromatic ring. Such a compound tends to be more compatible with the thermoplastic elastomer (B). In particular, when the thermoplastic elastomer (B) contains a styrene monomer unit, the compatibility tends to be improved.

[0143] In the present embodiment, the thermosetting compound (C) preferably contains one or more selected from the group consisting of a polymer (V) having a structural unit represented by formula (V) and a polyphenylene ether compound (P) having a carbon-carbon unsaturated double bond at a terminal.

[0144]

[0145] (In formula (V), Ar represents an aromatic hydrocarbon linking group. * represents a bonding position.)

[0146] <<Polyphenylene ether compound (P) having a carbon-carbon unsaturated double bond at the terminal>>

[0147] The resin composition of the present embodiment may contain a polyphenylene ether compound (P) having a carbon-carbon unsaturated double bond at a terminal.

[0148] The polyphenylene ether compound (P) having a carbon-carbon unsaturated double bond at a terminal is preferably a polyphenylene ether compound having two or more carbon-carbon unsaturated double bonds at a terminal.

[0149] In the present embodiment, more preferably, the polyphenylene ether compound comprises one or more groups selected from the group consisting of (meth)acryloyl, maleimide and vinylbenzyl as carbon-carbon unsaturated double bonds. By using the polyphenylene ether compound comprising these groups, there is a tendency to more effectively improve the dielectric properties and low water absorption of printed circuit boards, etc.

[0150] The following describes these details.

[0151] Examples of the polyphenylene ether compound (P) having a carbon-carbon unsaturated double bond at a terminal include compounds having a phenylene ether skeleton represented by the following formula (X1).

[0152]

[0153] (In formula (X1), R 24 , R 25 , R 26 and R 27 may be the same or different and represent an alkyl group, an aryl group, a halogen atom or a hydrogen atom having 6 or less carbon atoms.

[0154] The polyphenylene ether compound (P) having a carbon-carbon unsaturated double bond at a terminal may further contain a repeating unit represented by the formula (X2) and / or a repeating unit represented by the formula (X3).

[0155]

[0156] (In formula (X2), R 28 , R 29 , R 30 , R 34 , and R 35 R may be the same or different and represent an alkyl group having 6 or less carbon atoms or a phenyl group. 31 , R 32 , and, R 33 They may be the same or different and are a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.)

[0157]

[0158] (In formula (X3), R 36 , R 37 , R 38 , R 39 , R 40 , R 41 , R42 , and R 43 They may be the same or different and are a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. -A- is a linear, branched, or cyclic divalent hydrocarbon group having 20 or less carbon atoms.

[0159] The polyphenylene ether compound (P) having a carbon-carbon unsaturated double bond at the end is preferably a modified polyphenylene ether compound (hereinafter sometimes referred to as "modified polyphenylene ether compound (g)") in which a part or all of the terminal is functionalized with an ethylenically unsaturated group, and more preferably a modified polyphenylene ether compound having two or more groups selected from the group consisting of (meth) acryloyl, maleimide and vinyl benzyl at the end. By adopting such a modified polyphenylene ether compound (g), the dielectric loss tangent (Df) of the cured product of the resin composition can be further reduced, and low water absorption and metal foil peeling strength can be improved. These modified polyphenylene ether compounds (g) can be used alone or in combination of two or more.

[0160] Examples of the modified polyphenylene ether compound (g) include polyphenylene ether compounds represented by formula (OP).

[0161]

[0162] (In formula (OP), X represents an aromatic group, -(YO) n1 - represents a polyphenylene ether structure, n1 represents an integer of 1 to 100, and n2 represents an integer of 1 to 4. Rx is a group represented by formula (Rx-1) or formula (Rx-2).

[0163]

[0164] (In formula (Rx-1) and formula (Rx-2), R 1 , R 2 and R 3 Each independently represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group. * represents a bonding site with an oxygen atom. Mc each independently represents a hydrocarbon group having 1 to 12 carbon atoms. z represents an integer of 0 to 4. r represents an integer of 1 to 6.

[0165] The aromatic group represented by X may or may not have a substituent on the benzene ring, but preferably has a substituent. When having a substituent, the above-mentioned substituents can be listed, preferably at least one selected from the group consisting of an alkyl group having a carbon number of 6 or less, an aryl group, and a halogen atom, more preferably an alkyl group having a carbon number of 3 or less, and further preferably a methyl group.

[0166] In addition, the polyphenylene ether structure represented by -(YO)n1- may or may not have a substituent on the benzene ring, but preferably has a substituent. When having a substituent, for example, the above-mentioned substituents can be cited, preferably an alkyl group with a carbon number of 6 or less or a phenyl group, more preferably an alkyl group with a carbon number of 3 or less, and further preferably a methyl group.

[0167] When n1 and / or n2 are integers greater than 2, n1 structural units (YO) and / or n2 structural units may be the same or different. n2 is preferably 2 or greater, and more preferably 2.

[0168] In formula (Rx-1) and formula (Rx-2), R 1 , R 2 and R 3 Each independently represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group.

[0169] R 1 It is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group, and still more preferably a hydrogen atom.

[0170] R 2 and R 3 Each independently is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group, and further preferably a hydrogen atom.

[0171] As R 1 , R 2 and R 3 The carbon number of the alkyl, alkenyl or alkynyl group is preferably 5 or less, more preferably 3 or less.

[0172] In the formula (Rx-1), r represents an integer of 1 to 6, preferably an integer of 1 to 5, more preferably an integer of 1 to 4, further preferably an integer of 1 to 3, further preferably 1 or 2, and even more preferably 1.

[0173] In formula (Rx-1), Mc each independently represents a hydrocarbon group having 1 to 12 carbon atoms, preferably a hydrocarbon group having 1 to 10 carbon atoms, more preferably a straight-chain or branched alkyl group having 1 to 10 carbon atoms, further preferably a methyl group, ethyl group, isopropyl group, isobutyl group, tert-butyl group, pentyl group, octyl group or nonyl group, and even more preferably a methyl group, ethyl group, isopropyl group, isobutyl group or tert-butyl group.

[0174] In the formula (Rx-1), z represents an integer of 0 to 4, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, further preferably 0 or 1, and even more preferably 0.

[0175] A specific example of the group represented by the formula (Rx-1) is a vinylbenzyl group, and a specific example of the group represented by the formula (Rx-2) is a (meth)acryloyl group.

[0176] Examples of the modified polyphenylene ether compound (g) include compounds represented by formula (OP-1).

[0177]

[0178] (In formula (OP-1), X represents an aromatic group, -(YO)n2- represents a polyphenylene ether structure, and R 1 , R 2 and R 3 Each independently represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group, n1 represents an integer of 1 to 6, n2 represents an integer of 1 to 100, and n3 represents an integer of 1 to 4.)

[0179] The aromatic group represented by X may or may not have a substituent on the benzene ring, but preferably has a substituent. When having a substituent, the above-mentioned substituents can be cited, but preferably at least one selected from the group consisting of an alkyl group having a carbon number of 6 or less, an aryl group, and a halogen atom, more preferably an alkyl group having a carbon number of 3 or less, and further preferably a methyl group.

[0180] In addition, the polyphenylene ether structure represented by -(YO)n2- may or may not have a substituent on the benzene ring, but preferably has a substituent. When having a substituent, the above-mentioned substituents can be cited, but preferably an alkyl group with a carbon number of 6 or less or a phenyl group, more preferably an alkyl group with a carbon number of 3 or less, and further preferably a methyl group.

[0181] When n2 and / or n3 are integers greater than 2, n2 structural units (YO) and / or n3 structural units may be the same or different. n3 is preferably 2 or greater, more preferably 2.

[0182] The modified polyphenylene ether compound (g) in the present embodiment is preferably a compound represented by formula (OP-2).

[0183]

[0184] Here, -(OXO)- is preferably represented by Formula (OP-3) and / or Formula (OP-4).

[0185]

[0186] (In formula (OP-3), R 4 , R 5 , R 6 , R 10 and R 11 may be the same or different and are an alkyl group having 6 or less carbon atoms or a phenyl group. 7 , R 8 and R 9 They may be the same or different and are a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.)

[0187]

[0188] (In formula (OP-4), R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 and R 19 They may be the same or different and are a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. -A- is a linear, branched, or cyclic divalent hydrocarbon group having 20 or less carbon atoms.

[0189] In addition, -(YO)- is preferably represented by the formula (OP-5).

[0190]

[0191] (In formula (OP-5), R 20 , R 21 may be the same or different and are an alkyl group having 6 or less carbon atoms or a phenyl group. 22 , R 23 They may be the same or different and are a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.)

[0192] In particular, by making R 20 and R 21 Each independently being a group having one or more methyl and / or cyclohexyl groups, the rigidity of the obtained resin molecule is improved, and molecules with high rigidity have lower mobility than molecules with low rigidity, so the relaxation time during dielectric relaxation is increased, and low dielectric properties (Dk and / or Df) are excellent, which is preferred.

[0193] An example of the formula (OP-5) is the following structure.

[0194]

[0195] Regarding the polyphenylene ether compound having the above structure, reference can be made to the description of Japanese Patent Application Laid-Open No. 2019-194312, the contents of which are incorporated into this specification.

[0196] 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 each independently represent 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 are integers of 2 or more, two or more -(YO)- groups each independently may be arranged in one structure, or may be arranged in blocks or randomly in two or more structures.

[0197] When a plurality of compounds represented by the formula (OP-2) are included, the average value of a is preferably 1<a<10, and the average value of b is preferably 1<b<10.

[0198] Examples of -A- in formula (OP-4) include, but are not limited to, divalent organic groups such as methylene, ethylidine, 1-methylethylidene, 1,1-propylidene, 1,4-phenylenebis(1-methylethylidene), 1,3-phenylenebis(1-methylethylidene), cyclohexylidene, phenylmethylene, naphthylmethylene, and 1-phenylethylidene.

[0199] Among the compounds represented by the above formula (OP-2), preferably, R 4 , R 5 , R 6 , R 10 , R 11 , R 20 and R 21 is an alkyl group with a carbon number of 3 or less, and R 7 , R 8 , R 9 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 22 and R 23 The polyphenylene ether compound is a hydrogen atom or an alkyl group with a carbon number of 3 or less, and it is particularly preferred that -(OXO)- represented by formula (OP-3) or formula (OP-4) is formula (OP-9), formula (OP-10) and / or formula (OP-11), and -(YO)- represented by formula (OP-5) is formula (OP-12) or formula (OP-13). When a and / or b is an integer greater than 2, two or more -(YO)- can each independently be a structure in which two or more formulas (OP-12) and / or formula (OP-13) are arranged, or a structure in which formulas (OP-12) and (OP-13) are arranged in blocks or randomly.

[0200]

[0201] (In formula (OP-10), R 44 , R 45 , R 46 and R 47 They may be the same or different and are hydrogen atoms or methyl groups. -B- is a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms.

[0202] As specific examples of -B-, the same ones as the specific examples of -A- in formula (OP-4) can be given.

[0203]

[0204] (In formula (OP-11), -B- is a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms.)

[0205] As specific examples of -B-, the same ones as the specific examples of -A- in formula (OP-4) can be given.

[0206]

[0207] The modified polyphenylene ether compound (g) is more preferably a compound represented by formula (OP-14) and / or a compound represented by formula (OP-15), and is even more preferably a compound represented by formula (OP-15).

[0208]

[0209] (In formula (OP-14), a and b each independently represent an integer of 0 to 100, and at least one of a and b is an integer of 1 to 100.)

[0210] a and b in formula (OP-14) have the same meanings as a and b in formula (OP-2) independently, and the preferred ranges are also the same.

[0211]

[0212] (In formula (OP-15), a and b each independently represent an integer of 0 to 100, and at least one of a and b is an integer of 1 to 100.)

[0213] a and b in formula (OP-15) have the same meanings as a and b in formula (OP-2) independently, and the preferred ranges are also the same.

[0214] The polyphenylene ether compound (P) having a carbon-carbon unsaturated double bond at the end can be manufactured by a known method, or a commercially available product can be used. As a commercially available product, for example, as a modified polyphenylene ether compound having a methacryloyl group at the end, "SA9000" manufactured by SABIC Innovative Plastics can be cited. In addition, as a modified polyphenylene ether compound having a vinyl benzyl group at the end, "OPE-2St1200" and "OPE-2st2200" manufactured by Mitsubishi Gas Chemical Co., Ltd. can be cited. In addition, as a modified polyphenylene ether compound having a vinyl benzyl group at the end, a polyphenylene ether compound having a hydroxyl group at the end, such as "SA90" manufactured by SABIC Innovative Plastics, can also be used, which is modified to a vinyl benzyl group using vinyl benzyl chloride or the like.

[0215] In addition, for details of the polyphenylene ether compound (P) having a carbon-carbon unsaturated double bond at the terminal, reference can be made to Japanese Patent Application Publication Nos. 2006-028111, 2018-131519, WO2019-138992, and WO2022-054303, and these contents are incorporated into this specification.

[0216] The polyphenylene ether compound (P) (preferably a modified polyphenylene ether compound (g)) having a carbon-carbon unsaturated double bond at the terminal has a polystyrene-converted number average molecular weight (details are based on the method described in the examples described later) of 500 or more and 3,000 or less based on the GPC (gel permeation chromatography) method. By setting the number average molecular weight to 500 or more, there is a tendency to further suppress stickiness when the resin composition of the present embodiment is made into a coating film. By setting the number average molecular weight to 3,000 or less, there is a tendency to further improve solubility in a solvent.

[0217] In addition, the polyphenylene ether compound (P) (preferably a modified polyphenylene ether compound (g)) having a carbon-carbon unsaturated double bond at the terminal has a polystyrene-equivalent weight average molecular weight measured by GPC (details are based on the method described in the examples described later) of preferably 800 or more and 10,000 or less, and more preferably 800 or more and 5,000 or less. By making the weight average molecular weight above the lower limit, there is a tendency that the relative dielectric constant (Dk) and dielectric loss tangent (Df) of the cured product of the resin composition become lower, and by making it below the upper limit, the solubility, low viscosity and moldability of the resin composition in a solvent when preparing a varnish described later tend to be further improved.

[0218] Furthermore, in the case of the modified polyphenylene ether compound (g), the terminal carbon-carbon unsaturated double bond equivalent is preferably 400 to 5000 g per carbon-carbon unsaturated double bond, and more preferably 400 to 2500 g. By making the terminal carbon-carbon unsaturated double bond equivalent above the above lower limit, the relative dielectric constant (Dk) and dielectric loss tangent (Df) of the cured product of the resin composition tend to be lower, and by making it below the above upper limit, the solubility, low viscosity and moldability of the resin composition in a solvent tend to be further improved.

[0219] <<Polymer (V) having a structural unit represented by formula (V)>>

[0220] The resin composition of this embodiment may include a polymer (V) having a structural unit represented by formula (V). By including a polymer (V) having a structural unit represented by formula (V), a resin composition having excellent low dielectric properties (low dielectric constant, low dielectric loss tangent) can be obtained.

[0221]

[0222] (In formula (V), Ar represents an aromatic hydrocarbon linking group. * represents a bonding position.)

[0223] The aromatic hydrocarbon linking group may be a group consisting only of an aromatic hydrocarbon optionally having a substituent, or may be a group consisting of a combination of an aromatic hydrocarbon optionally having a substituent and other linking groups. The aromatic hydrocarbon linking group is preferably a group consisting only of an aromatic hydrocarbon optionally having a substituent. It should be noted that the substituent optionally possessed by the aromatic hydrocarbon may include a substituent Z (e.g., an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxyl group, an amino group, a carboxyl group, a halogen atom, etc.). In addition, the above-mentioned aromatic hydrocarbon preferably has no substituent.

[0224] The aromatic hydrocarbon linking group is usually a divalent linking group.

[0225] Specific examples of the aromatic hydrocarbon linking group include phenylene, naphthalene diyl, anthracene diyl, phenanthrene diyl, biphenyl diyl, and fluorene diyl, which may have a substituent, and among them, phenylene which may have a substituent is preferred. The substituent may be exemplified by the above-mentioned substituent Z, but the above-mentioned phenylene group preferably has no substituent.

[0226] The structural unit represented by formula (V) more preferably includes at least one of the structural unit represented by the following formula (V1), the structural unit represented by the following formula (V2), and the structural unit represented by the following formula (V3). It should be noted that the * in the following formula represents a bonding position. In addition, the structural units represented by formulas (V1) to (V3) are sometimes collectively referred to as "structural units (a)".

[0227]

[0228] In formulas (V1) to (V3), L 1 It is an aromatic hydrocarbon linking group (the carbon number is preferably 6 to 22, more preferably 6 to 18, and further preferably 6 to 10). Specifically, phenylene, naphthalene diyl, anthracene diyl, phenanthrene diyl, biphenyl diyl, and fluorene diyl, which may have a substituent, are listed, among which phenylene which may have a substituent is preferred. The substituent may be exemplified by the above-mentioned substituent Z, but the above-mentioned phenylene group and the like preferably have no substituent.

[0229] As the compound forming the structural unit (a), a divinyl aromatic compound is preferably used. That is, the polymer (V) having the structural unit shown in formula (V) preferably includes a structural unit (a) derived from a divinyl aromatic compound. As the divinyl aromatic compound, for example: divinylbenzene, bis (1-methylvinyl) benzene, divinylnaphthalene, divinylanthracene, divinylbiphenyl, divinylphenanthrene, etc. can be cited. Among them, divinylbenzene is particularly preferred. These divinyl aromatic compounds can use one, and two or more can be used as needed.

[0230] As described above, the polymer (V) having the structural unit represented by the formula (V) may be a homopolymer of the structural unit (a) or a copolymer with a structural unit derived from another monomer.

[0231] When the polymer (V) having the structural unit shown in formula (V) is a copolymer, for its copolymerization ratio, the structural unit (a) is preferably 3 mol% or more, more preferably 5 mol% or more, further preferably 10 mol% or more, and may be 15 mol% or more. The upper limit is preferably 90 mol% or less, more preferably 85 mol% or less, further preferably 80 mol% or less, more preferably 70 mol% or less, further preferably 60 mol% or less, further preferably 50 mol% or less, further more preferably 40 mol% or less, particularly preferably 30 mol% or less, and may also be 25 mol% or less, 20 mol% or less.

[0232] As the structural unit derived from other monomers, a structural unit (b) derived from an aromatic compound having one vinyl group (monovinyl aromatic compound) is exemplified.

[0233] As the structural unit (b) derived from a monovinyl aromatic compound, it is preferred that the structural unit be a structural unit represented by the following formula (V4).

[0234]

[0235] In formula (V4), L 2is an aromatic hydrocarbon linking group, and preferred specific examples thereof include the above-mentioned L 1 Example. * indicates bonding position.

[0236] R V1 R is a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms (preferably an alkyl group). V1 When it is a hydrocarbon group, the carbon number is preferably 1 to 6, more preferably 1 to 3. V1 and L 2 The above-mentioned substituent Z may be present.

[0237] When the polymer (V) having the structural unit shown in formula (V) is a copolymer containing the structural unit (b) derived from a monovinyl aromatic compound, examples of monovinyl aromatic compounds include: vinyl aromatic compounds such as styrene, vinyl naphthalene, and vinyl biphenyl; ortho-methylstyrene, meta-methylstyrene, para-methylstyrene, ortho-p-dimethylstyrene, ortho-ethylvinylbenzene, meta-ethylvinylbenzene, para-ethylvinylbenzene, methylvinylbiphenyl, ethylvinylbiphenyl, and other core alkyl-substituted vinyl aromatic compounds. The monovinyl aromatic compounds exemplified herein may also appropriately have the above-mentioned substituent Z. In addition, these monovinyl aromatic compounds may be used in one or more kinds. Among them, the structural unit (b) preferably includes a structural unit derived from at least one selected from the group consisting of ortho-ethylvinylbenzene, meta-ethylvinylbenzene, and para-ethylvinylbenzene, and more preferably, not only includes a structural unit derived from at least one selected from the group consisting of ortho-ethylvinylbenzene, meta-ethylvinylbenzene, and para-ethylvinylbenzene, but also includes a structural unit derived from styrene.

[0238] When the polymer (V) having the structural unit shown in formula (V) is a copolymer containing the structural unit (b), the copolymerization ratio of the structural unit (b) is preferably 10 mol% or more, more preferably 15 mol% or more, and may also be 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. The upper limit is preferably 98 mol% or less, more preferably 90 mol% or less, and more preferably 85 mol% or less.

[0239] The polymer (V) having the structural unit shown in formula (V) may also have other structural units other than structural units (a) and structural units (b). As other structural units, for example, structural units (c) derived from cycloolefin compounds may be cited. As cycloolefin compounds, hydrocarbons having double bonds in the ring structure may be cited. Specifically, monocyclic cyclic olefins such as cyclobutene, cyclopentene, cyclohexene, and cyclooctene may be cited. In addition, compounds having a norbornene ring structure such as norbornene and dicyclopentadiene may also be cited; cycloolefin compounds formed by aromatic ring condensation such as indene and acenaphthene. As examples of norbornene compounds, the norbornene compounds described in paragraphs 0037 to 0043 of Japanese Patent Publication No. 2018-039995 may be cited, and the contents are introduced into this specification. It should be noted that the cycloolefin compounds exemplified herein may further have the above-mentioned substituent Z.

[0240] When the polymer (V) having the structural unit shown in formula (V) is a copolymer containing the structural unit (c), the copolymerization ratio of the structural unit (c) is preferably 10 mol% or more, more preferably 20 mol% or more, and further preferably 30 mol% or more. The upper limit is preferably 90 mol% or less, more preferably 80 mol% or less, further preferably 70 mol% or less, and can be 50 mol% or less, or 30 mol% or less.

[0241] Structural units (d) derived from different polymerizable compounds (hereinafter also referred to as other polymerizable compounds) may also be further introduced into the polymer (V) having the structural unit represented by formula (V). As other polymerizable compounds (monomers), for example, compounds containing three vinyl groups may be cited. Specifically, 1,3,5-trivinylbenzene, 1,3,5-trivinylnaphthalene, 1,2,4-trivinylcyclohexane may be cited. Alternatively, ethylene glycol diacrylate, 1,3-butadiene, isoprene, etc. may be cited. The copolymerization ratio (d) of structural units (d) derived from other polymerizable compounds is preferably 30 mol% or less, more preferably 20 mol% or less, and further preferably 10 mol% or less.

[0242] As an embodiment of the polymer (V) having a structural unit represented by formula (V), there can be exemplified a polymer that necessarily has structural unit (a) and contains at least one of structural units (b) to (d). Further, there can be exemplified an embodiment in which the total of structural units (a) to (d) accounts for 95 mol% or more of all structural units, and further an embodiment in which the total of structural units (a) to (d) accounts for 98 mol% or more.

[0243] As another embodiment of the polymer (V) having a structural unit represented by formula (V), it is preferably a polymer that must have structural unit (a), and in which structural units containing aromatic rings in all structural units except the terminal are 90 mol% or more, more preferably 95 mol% or more, and may also be 100 mol%.

[0244] In calculating the mol % relative to all structural units, one structural unit means a structural unit derived from one molecule of a monomer (e.g., a divinyl aromatic compound, a monovinyl aromatic compound, etc.) used when producing the polymer (V) having the structural unit represented by formula (V).

[0245] The method for producing the polymer (V) having the structural unit represented by formula (V) is not particularly limited and can be prepared by a common method, for example, by polymerizing a raw material containing a divinyl aromatic compound (in which a monovinyl aromatic compound, a cycloolefin compound, etc. are coexisted as necessary) in the presence of a Lewis acid catalyst. The Lewis acid catalyst can be a metal fluoride such as boron trifluoride or a complex thereof.

[0246] The structure of the chain end of the polymer (V) having the structural unit represented by formula (V) is not particularly limited, but when explaining the group derived from the above-mentioned divinyl aromatic compound, the structure of the following formula (E1) can be cited. 1 The same as those defined in the above formula (V1). * indicates a bonding position.

[0247] *-CH=CH-L 1 -CH=CH2(E1)

[0248] When the group derived from the monovinyl aromatic compound is a chain end, the structure of the following formula (E2) can be used. 2 and R V1 They have the same meanings as those defined in the aforementioned formula (V4). * indicates a bonding position.

[0249] *-CH=CH-L 2 -R V1 (E2)

[0250] The molecular weight of the polymer (V) having the structural unit represented by the formula (V) is preferably 300 or more, more preferably 500 or more, further preferably 1,000 or more, and even more preferably 1,500 or more in terms of number average molecular weight Mn. The upper limit of the number average molecular weight Mn is preferably 130,000 or less, more preferably 120,000 or less, further preferably 110,000 or less, even more preferably 100,000 or less, and may also be 30,000 or less, 10,000 or less, or 5,000 or less.

[0251] The molecular weight of the polymer (V) with the structural unit shown in formula (V) is preferably more than 3,000 in terms of weight average molecular weight Mw, more preferably more than 5,000, and more preferably more than 10,000. By being set to more than the aforementioned lower limit, the excellent low dielectric properties, especially Df, dielectric properties after moisture absorption, of the polymer (V) with the structural unit shown in formula (V) can be effectively exerted in the cured product of the resin composition. The upper limit of the weight average molecular weight Mw is preferably less than 130,000, more preferably less than 100,000, more preferably less than 80,000, and more preferably less than 50,000. By being set to less than the aforementioned upper limit, there is a tendency that poor filling is not easy to occur when prepreg or resin sheet are laminated on circuit forming substrate.

[0252] The monodispersity (Mw / Mn) represented by the ratio of the weight average molecular weight Mw to the number average molecular weight Mn is preferably 100 or less, more preferably 50 or less, further preferably 20 or less, and may be 15 or less, or 12 or less. As the lower limit, it is more practical to be 1.1 or more, preferably 2.0 or more, more preferably 4 or more, further preferably 5 or more, further preferably 7 or more, and even more preferably 8 or more.

[0253] The above-mentioned Mw and Mn are measured according to the description in the Examples described later.

[0254] When the resin composition of the present embodiment contains two or more polymers (V) having a structural unit represented by formula (V), it is preferred that Mw, Mn, and Mw / Mn of the mixture fall within the above ranges.

[0255] The equivalent of the vinyl group of the polymer (V) having the structural unit shown in formula (V) is preferably 200 g / eq. or more, more preferably 230 g / eq. or more, further preferably 250 g / eq. or more, and may be 300 g / eq. or more, 350 g / eq. or more. In addition, the equivalent of the vinyl group is preferably 1200 g / eq. or less, more preferably 1000 g / eq. or less, and may be 800 g / eq. or less, 600 g / eq. or less, 500 g / eq. or less, 400 g / eq. or less, 350 g / eq. or less. By making the equivalent of the vinyl group more than the aforementioned lower limit, there is a tendency to improve the storage stability of the resin composition and to improve the fluidity of the resin composition. Therefore, there is a tendency to improve formability, and it is not easy to generate voids when forming prepregs, etc., and a printed circuit board with higher reliability can be obtained. On the other hand, by making the equivalent of the vinyl group less than the aforementioned upper limit, there is a tendency to improve the heat resistance of the obtained cured product.

[0256] The glass transition temperature of the polymer (V) having the structural unit represented by formula (V) is preferably 170°C or higher, more preferably 180°C or higher, further preferably 190°C or higher, and even more preferably 200°C or higher. The upper limit of the glass transition temperature is preferably 350°C or lower, and may be 300°C or lower. The glass transition temperature can be measured using a dynamic viscoelasticity measuring device in accordance with JIS-K7244-4:1999 (Plastics - Test methods for dynamic mechanical properties - Part 4: Non-resonance method) under the conditions of a starting temperature of 30°C, an end temperature of 400°C, a heating rate of 5°C / min, and a measurement frequency of 1 Hz. The maximum value of the loss tangent (tanσ) obtained at this time is determined as the glass transition temperature. The dynamic viscoelasticity measuring device can be EXSTAR6000DMS6100 manufactured by Seiko Instruments Inc.

[0257] For the polymer (V) with the structural unit shown in formula (V), it is preferred that the low dielectric properties of its cured product are excellent. For example, the relative dielectric constant (Dk) at 10GHz measured by the cavity resonance perturbation method of the cured product of the polymer with the structural unit shown in formula (V) used in the present embodiment is preferably less than 2.80, more preferably less than 2.60, further preferably less than 2.50, and more preferably less than 2.40. In addition, the lower limit of the aforementioned relative dielectric constant is, for example, more than 1.80 and more practical. In addition, the dielectric loss tangent (Df) at 10GHz measured by the cavity resonance perturbation method of the cured product of the polymer (V) with the structural unit shown in formula (V) is preferably less than 0.0030, more preferably less than 0.0020, and more preferably less than 0.0010. In addition, the lower limit of the aforementioned dielectric loss tangent is, for example, more than 0.0001 and more practical.

[0258] The relative dielectric constant (Dk) and the dielectric loss tangent (Df) were measured by the following method.

[0259] 4.5 g of resin powder was spread on a 100 mm × 30 mm × 1.0 mm high frame of a stainless steel mold, placed in a vacuum press (manufactured by Kitagawa Seiki Co., Ltd.), maintained at 200°C, 220°C and 240°C for 1.5 hours, and pressed at a surface pressure of 1.9 MPa to produce a cured plate.

[0260] The cured plate was miniaturized to 1.0 mm in width and dried at 120° C. for 60 minutes, and then the relative dielectric constant (Dk) and dielectric loss tangent (Df) after drying were measured at 10 GHz using a perturbation cavity resonator. The measurement temperature was 23° C.

[0261] Agilent 8722ES manufactured by Agilent Technologies was used as the perturbation method cavity resonator.

[0262] For the polymer (V) having a structural unit represented by formula (V) in this specification, reference may be made to the compounds and their synthesis reaction conditions described in paragraphs 0029 to 0058 of International Publication No. 2017 / 115813, the compounds and their synthesis reaction conditions described in paragraphs 0013 to 0058 of Japanese Patent Application Publication No. 2018-039995, and the compounds and their synthesis reaction conditions described in paragraphs 0008 to 0043 of Japanese Patent Application Publication No. 2018-168347. The compounds and their synthesis reaction conditions, etc., the compounds and their synthesis reaction conditions, etc. described in paragraphs 0014 to 0042 of Japanese Patent Application Laid-Open No. 2006-070136, the compounds and their synthesis reaction conditions, etc. described in paragraphs 0014 to 0061 of Japanese Patent Application Laid-Open No. 2006-089683, and the compounds and their synthesis reaction conditions, etc., described in paragraphs 0008 to 0036 of Japanese Patent Application Laid-Open No. 2008-248001, and are incorporated into the present specification.

[0263] In the resin composition of the present embodiment, the content of the thermosetting compound (C) is preferably 1 mass part or more relative to 100 mass parts of resin solids, more preferably 5 mass parts or more, further preferably 10 mass parts or more, further preferably 20 mass parts or more, more preferably 25 mass parts or more.By being set to above the lower limit, there is a tendency that hygroscopic heat resistance is further improved.In addition, the upper limit of the content of the thermosetting compound (C) is preferably 90 mass parts or less relative to 100 mass parts of resin solids, more preferably 75 mass parts or less, further preferably 60 mass parts or less, further preferably 50 mass parts or less, more preferably 40 mass parts or less.By being set to below the upper limit, there is a tendency that low dielectric properties are further improved.

[0264] The resin composition of the present embodiment may contain only one thermosetting compound (C) or two or more thermosetting compounds (C). When the resin composition of the present embodiment contains two or more thermosetting compounds (C), the total amount is preferably within the above range.

[0265] <Other thermosetting compounds (D)>

[0266] The resin composition of the present embodiment may further contain one or more other thermosetting compounds (D) (sometimes referred to simply as “other thermosetting compounds (D)” in this specification) selected from the group consisting of maleimide compounds, epoxy compounds, phenol compounds, oxetane resins, benzoxazine compounds, and cyanate compounds.

[0267] In the present embodiment, it is more preferred that the other thermosetting compound (D) contains at least one of a maleimide compound and a cyanate compound.

[0268] <<Maleimide Compounds>>

[0269] The resin composition of the present embodiment may include a maleimide compound. Maleimide compounds can be widely used as compounds commonly used in the field of printed circuit boards. The resin composition of the present embodiment is preferably a compound having one or more (preferably two or more, more preferably 2 to 12, further preferably 2 to 6, further preferably 2 to 4, more preferably 2 or 3, further preferably 2) maleimide groups in one molecule.

[0270] In this embodiment, the maleimide compound preferably includes one or more selected from the group consisting of compounds represented by formula (M0) to formula (M5), more preferably includes one or more selected from the group consisting of compounds represented by formula (M0), compounds represented by formula (M1), compounds represented by formula (M3) and compounds represented by formula (M5), and further preferably includes the compound represented by formula (M3).

[0271]

[0272] (In formula (M0), R 51 Each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a phenyl group, and R 52 Each independently represents a hydrogen atom or a methyl group, and n1 represents an integer greater than 1.)

[0273] R 51 Each independently preferably is a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, or a phenyl group, more preferably is a hydrogen atom and a methyl group, and further preferably is a hydrogen atom.

[0274] R 52 Preferred is methyl.

[0275] n1 is preferably an integer of 1 to 10, more preferably an integer of 1 to 5, further preferably an integer of 1 to 3, further preferably 1 or 2, and even more preferably 1.

[0276] The compound represented by formula (M0) may be a single compound or a mixture of two or more compounds. Examples of the mixture include a mixture of compounds having different n1, a mixture of compounds having different n1, and a mixture of compounds having different n1. 51 and / or R 52 A mixture of compounds having different types of substituents, a mixture of compounds having different bonding positions (meta, para, or ortho) of the maleimide group and the oxygen atom relative to the benzene ring, and a mixture of compounds having two or more different positions. The same also applies to the compounds represented by formulas (M1) to (M5).

[0277]

[0278] (In formula (M1), R M1 , R M2 , R M3 , and R M4 Each independently represents a hydrogen atom or an organic group. M5 and R M6 Each independently represents a hydrogen atom or an alkyl group. M represents a divalent aromatic group. A is a 4- to 6-membered alicyclic group. M7 and R M8 Each is independently an alkyl group. mx is 1 or 2, and lx is 0 or 1. M9 and R M10 Each independently represents a hydrogen atom or an alkyl group. M11 , R M12 , R M13 , and R M14 Each independently represents a hydrogen atom or an organic group. M15 Each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a halogen atom, a hydroxyl group or a mercapto group. px represents an integer of 0 to 3. nx represents an integer of 1 to 20.)

[0279] R in the formula M1 , R M2 , R M3 and R M4 Each independently represents a hydrogen atom or an organic group. The organic group here is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, further preferably an alkyl group having 1 to 6 carbon atoms, still more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and particularly preferably a methyl group. M1 and R M3 Each is independently preferably an alkyl group, R M2 and R M4 Preferred is a hydrogen atom.

[0280] R M5 and R M6 Each independently represents a hydrogen atom or an alkyl group, preferably an alkyl group. Here, the alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, further preferably a methyl group, an ethyl group, a propyl group, and a butyl group, and particularly preferably a methyl group.

[0281] Ar M Ar represents a divalent aromatic group, preferably phenylene, naphthalene diyl, phenanthrene diyl, anthracene diyl, more preferably phenylene, and further preferably m-phenylene. MIt may have a substituent, and the substituent is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, further preferably an alkyl group having 1 to 6 carbon atoms, still more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and particularly preferably a methyl group. M No substitution is preferred.

[0282] A is a 4- to 6-membered alicyclic group, more preferably a 5-membered alicyclic group (preferably a group condensed with a benzene ring to form an indane ring). M7 and R M8 Each independently represents 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.

[0283] mx is 1 or 2, preferably 2.

[0284] lx is 0 or 1, preferably 1.

[0285] R M9 and R M10 Each independently represents a hydrogen atom or an alkyl group, and an alkyl group is more preferred. Here, the alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, further preferably a methyl group, an ethyl group, a propyl group, and a butyl group, and among these, a methyl group is particularly preferred.

[0286] R M11 , R M12 , R M13 and R M14 Each independently represents a hydrogen atom or an organic group. The organic group here is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, further preferably an alkyl group having 1 to 6 carbon atoms, still more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and particularly preferably a methyl group. M12 and R M13 Each independently preferably an alkyl group, R M11 and R M14 A hydrogen atom is preferred.

[0287] R M15 Each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a halogen atom, a hydroxyl group or a mercapto group, and is preferably an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms.

[0288] px represents an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, and further preferably 0.

[0289] nx represents an integer of 1 to 20. nx may be an integer of 10 or less.

[0290] It should be noted that the resin composition of the present embodiment may include only one compound belonging to the compound shown in the formula (M1) and at least a compound having different values ​​of nx, or may include more than two kinds. When including more than two kinds, in order to make a low melting point (low softening point) and a person having low melt viscosity and excellent operability, the average value (average number of repeating units) n of nx in the compound shown in the formula (M1) in the resin composition is preferably more than 0.92, more preferably more than 0.95, further preferably more than 1.0, and more preferably more than 1.1. In addition, n is preferably less than 10.0, more preferably less than 8.0, further preferably less than 7.0, more preferably less than 6.0, and may also be less than 5.0. The same is true for formula (M1-1) etc. described later.

[0291] The compound represented by the formula (M1) is preferably a compound represented by the following formula (M1-1).

[0292]

[0293] (In formula (M1-1), R M21 , R M22 , R M23 , and R M24 Each independently represents a hydrogen atom or an organic group. M25 and R M26 Each independently represents a hydrogen atom or an alkyl group. M27 , R M28 , R M29 , and R M30 Each independently represents a hydrogen atom or an organic group. M31 and R M32 Each independently represents a hydrogen atom or an alkyl group. M33 , R M34 , R M35 , and R M36 Each independently represents a hydrogen atom or an organic group. M37 , R M38 , and R M39 Each independently represents a hydrogen atom or an alkyl group. nx represents an integer of 1 to 20.

[0294] R in the formula M21 , R M22 , R M23 and R M24 Each independently represents a hydrogen atom or an organic group. The organic group here is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, further preferably an alkyl group having 1 to 6 carbon atoms, still more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and particularly preferably a methyl group. M21 and R M23 Preferably, alkyl, R M22 and R M24A hydrogen atom is preferred.

[0295] R M25 and R M26 Each independently represents a hydrogen atom or an alkyl group, preferably an alkyl group. The alkyl group herein is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, further preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and particularly preferably a methyl group.

[0296] R M27 , R M28 , R M29 and R M30 Each independently represents a hydrogen atom or an organic group, preferably a hydrogen atom. The organic group here is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, further preferably an alkyl group having 1 to 6 carbon atoms, further preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and particularly preferably a methyl group.

[0297] R M31 and R M32 Each independently represents a hydrogen atom or an alkyl group, preferably an alkyl group. The alkyl group herein is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, further preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and particularly preferably a methyl group.

[0298] R M33 , R M34 , R M35 and R M36 Each independently represents a hydrogen atom or an organic group. The organic group here is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, further preferably an alkyl group having 1 to 6 carbon atoms, further preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and particularly preferably a methyl group.

[0299] R M33 and R M36 Preferably a hydrogen atom, R M34 and R M35 An alkyl group is preferred.

[0300] R M37 , R M38 and R M39 Each independently represents a hydrogen atom or an alkyl group, preferably an alkyl group. The alkyl group herein is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, further preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and particularly preferably a methyl group.

[0301] nx represents an integer of 1 to 20. nx may be an integer of 10 or less.

[0302] The compound represented by formula (M1-1) is preferably a compound represented by the following formula (M1-2).

[0303]

[0304] (In formula (M1-2), R M21 , R M22 , R M23 , and R M24 Each independently represents a hydrogen atom or an organic group. M25 and R M26 Each independently represents a hydrogen atom or an alkyl group. M27 , R M28 , R M29 , and R M30 Each independently represents a hydrogen atom or an organic group. M31 and R M32 Each independently represents a hydrogen atom or an alkyl group. M33 , R M34 , R M35 , and R M36 Each independently represents a hydrogen atom or an organic group. M37 , R M38 , and R M39 Each independently represents a hydrogen atom or an alkyl group. nx represents an integer of 1 to 20.

[0305] 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 , R M34 , R M35 , R M36 , R M37 , R M38 , R M39 and nx are respectively the same as R in formula (M1-1) M21 , R M22 , R M23 , R M24 , R M25 , R M26 , R M27 , R M28 , R M29 , R M30 , R M31 , R M32 , R M33 , R M34 , R M35 , R M36 , RM37 , R M38 , R M39 It has the same meaning as nx and has the same preferred range.

[0306] The compound represented by the formula (M1-1) is more preferably a compound represented by the following formula (M1-3), and even more preferably a compound represented by the following formula (M1-4).

[0307]

[0308] (In formula (M1-3), nx represents an integer of 1 to 20.)

[0309] nx may be an integer less than 10.

[0310]

[0311] (In formula (M1-4), nx represents an integer of 1 to 20.)

[0312] The molecular weight of the compound shown in formula (M1) is preferably 500 or more, more preferably 600 or more, and further preferably 700 or more. By setting it to above the aforementioned lower limit, there is a tendency that the low dielectric properties and low water absorption of the obtained solidified material are further improved. In addition, the molecular weight of the compound shown in formula (M1) is preferably 10000 or less, more preferably 9000 or less, further preferably 7000 or less, more preferably 5000 or less, and further preferably 4000 or less. By setting it to below the aforementioned upper limit, there is a tendency that the heat resistance and operability of the obtained solidified material are further improved.

[0313]

[0314] (In formula (M2), R 54 Each independently represents a hydrogen atom or a methyl group, and n4 represents an integer greater than 1.)

[0315] n4 is preferably an integer of 1 to 10, more preferably an integer of 1 to 5, further preferably an integer of 1 to 3, further preferably 1 or 2, and may be 1.

[0316] The compound represented by formula (M2) may be a mixture of compounds having different n4, preferably a mixture. In addition, as described in the compound represented by formula (M0), it may be a mixture of compounds having different other parts.

[0317]

[0318] (In formula (M3), R 55Each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group, and n5 represents an integer of 1 to 10.

[0319] R 55 Each independently preferably is a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, or a phenyl group, more preferably is a hydrogen atom and a methyl group, and further preferably is a hydrogen atom.

[0320] n5 is preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and even more preferably 1 or 2.

[0321] The compound represented by formula (M3) may be a mixture of compounds having different n5, preferably a mixture. In addition, as described in the compound represented by formula (M0), it may be a mixture of compounds having different other parts.

[0322]

[0323] (In formula (M4), R 56 Each independently represents a hydrogen atom, a methyl group or an ethyl group, and R 57 Each independently represents a hydrogen atom or a methyl group. )

[0324]

[0325] (In formula (M5), R 58 Each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a phenyl group, and R 59 Each independently represents a hydrogen atom or a methyl group, and n6 represents an integer greater than 1.)

[0326] R 58 Each independently preferably is a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, or a phenyl group, more preferably is a hydrogen atom and a methyl group, and further preferably is a hydrogen atom.

[0327] R 59 Preferred is methyl.

[0328] n6 is preferably an integer of 1 to 10, more preferably an integer of 1 to 5, further preferably an integer of 1 to 3, further preferably 1 or 2, and may be 1.

[0329] The compound represented by formula (M5) may be a mixture of compounds having different n6, preferably a mixture. In addition, as described in the compound represented by formula (M0), it may be a mixture of compounds having different other parts.

[0330] In addition to the above, as maleimide compounds, reference may be made to the compounds described in paragraphs 0061 to 0066 of International Publication No. 2020 / 262577 and Japanese Patent No. 7160151, and the contents thereof are incorporated herein.

[0331] Maleimide compounds can be manufactured by known methods, or commercial products can be used. As commercial products, for example, as a compound represented by formula (M0), KI Chemical Industry Co., Ltd. "BMI-80" can be listed, as a compound represented by formula (M1), DIC Corporation "NE-X-9470S" can be listed, as a compound represented by formula (M2), DAIWA KASEI KOGYO, CO., LTD "BMI-2300" can be listed, as a compound represented by formula (M3), Nippon Kayaku Co., Ltd. "MIR-3000" can be listed, as a compound represented by formula (M4), KI Chemical Industry Co., Ltd. "BMI-70" can be listed, as a compound represented by formula (M5), Nippon Kayaku Co., Ltd. "MIR-5000" can be listed, and in addition, Nippon Kayaku Co., Ltd. "MIZ-001" and "NE-X-9500" can be listed.

[0332] In addition, as maleimide compounds other than the above, compounds having two or more maleimide groups can be exemplified, specifically, m-phenylene bismaleimide, 2,2-bis(4-(4-maleimidophenoxy)-phenyl)propane, 4-methyl-1,3-phenylene bismaleimide, 1,6-bismaleimido-(2,2,4-trimethyl)hexane, 4,4'-diphenyl ether bismaleimide, 4,4'-diphenyl sulfone bismaleimide, 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene, and prepolymers thereof, prepolymers of these maleimides and amines, etc.

[0333] When the resin composition of the present embodiment includes a maleimide compound, the lower limit of its content is preferably more than 1 mass part relative to 100 mass parts of resin solids in the resin composition, more preferably more than 5 mass parts, more preferably more than 10 mass parts, more preferably more than 15 mass parts, more preferably more than 20 mass parts. By making the content of the maleimide compound more than 1 mass part, there is a tendency for the flame retardancy of the obtained cured product to improve. In addition, the upper limit of the content of the maleimide compound is preferably less than 90 mass parts relative to 100 mass parts of resin solids in the resin composition, more preferably less than 70 mass parts, more preferably less than 60 mass parts, more preferably less than 50 mass parts, more preferably less than 40 mass parts, and can also be less than 30 mass parts. By making the content of the maleimide compound less than 90 mass parts, there is a tendency for metal foil peeling strength and low water absorption to improve.

[0334] The resin composition in the present embodiment may contain only one maleimide compound or may contain two or more thereof. When containing two or more thereof, the total amount is preferably within the above range.

[0335] <<Epoxides>>

[0336] The resin composition of the present embodiment may contain an epoxy compound.

[0337] The epoxy compound is not particularly limited as long as it is a compound or resin having one or more (preferably 2 to 12, more preferably 2 to 6, further preferably 2 to 4, further preferably 2 or 3, further preferably 2) epoxy groups in one molecule, and a wide range of compounds commonly used in the field of printed wiring boards can be used.

[0338] Examples of the epoxy compound include bisphenol A epoxy resin, bisphenol E epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, bisphenol A novolac epoxy resin, glycidyl ester epoxy resin, aralkyl novolac epoxy resin, biphenyl aralkyl epoxy resin, naphthyl ether epoxy resin, cresol novolac epoxy resin, polyfunctional phenol epoxy resin, naphthalene epoxy resin, anthracene epoxy resin, naphthalene skeleton modified novolac epoxy resin, phenol aralkyl epoxy resin, naphthol aralkyl epoxy resin, dicyclopentadiene epoxy resin, biphenyl epoxy resin, alicyclic epoxy resin, polyol epoxy resin, phosphorus-containing epoxy resin, glycidylamine, glycidyl ester, compounds obtained by epoxidizing double bonds of butadiene or the like, compounds obtained by reacting hydroxyl-containing silicone resins with epichlorohydrin, and the like. By using them, the moldability and adhesion of the resin composition are improved. Among them, biphenyl aralkyl type epoxy resins, naphthyl ether type epoxy resins, polyfunctional phenol type epoxy resins, and naphthalene type epoxy resins are preferred from the viewpoint of further improving flame retardancy and heat resistance, and biphenyl aralkyl type epoxy resins are more preferred.

[0339] The resin composition of the present embodiment preferably includes epoxy compounds within the scope of not damaging the effect of the present invention. When the resin composition of the present embodiment includes epoxy compounds, its content is preferably 0.1 mass parts or more relative to 100 mass parts of resin solid components in the resin composition, more preferably 1 mass parts or more, and further preferably 2 mass parts or more. By making the content of epoxy compounds more than 0.1 mass parts, there is a tendency to improve metal foil peel strength and toughness. When the resin composition of the present embodiment includes epoxy compounds, the upper limit of the content of epoxy compounds is preferably less than 50 mass parts relative to 100 mass parts of resin solid components in the resin composition, more preferably less than 30 mass parts, further preferably less than 20 mass parts, more preferably less than 10 mass parts, and can also be less than 8 mass parts, less than 5 mass parts. By making the content of epoxy compounds less than 50 mass parts, there is a tendency to improve the electrical properties of the cured product obtained.

[0340] The resin composition in the present embodiment may contain only one epoxy compound or two or more epoxy compounds. When two or more epoxy compounds are contained, the total amount is preferably within the above range.

[0341] In addition, the resin composition in the present embodiment may be configured to be substantially free of epoxy compounds. Substantially free means that the content of epoxy compounds is less than 0.1 parts by mass, preferably less than 0.01 parts by mass, and may also be less than 0.001 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition.

[0342] <<Phenol compounds>>

[0343] The resin composition of the present embodiment may contain a phenol compound.

[0344] The phenol compound is not particularly limited as long as it has one or more (preferably 2 to 12, more preferably 2 to 6, further preferably 2 to 4, further preferably 2 or 3, further preferably 2) phenolic hydroxyl groups in one molecule, and a wide range of compounds commonly used in the field of printed wiring boards can be used.

[0345] Examples of the phenolic compound include bisphenol A type phenolic resin, bisphenol E type phenolic resin, bisphenol F type phenolic resin, bisphenol S type phenolic resin, phenol novolac resin, bisphenol A novolac type phenolic resin, glycidyl ester type phenolic resin, aralkyl novolac phenolic resin, biphenyl aralkyl type phenolic resin, cresol novolac type phenolic resin, multifunctional phenolic resin, naphthol resin, naphthol novolac resin, multifunctional naphthol resin, anthracene type phenolic resin, naphthalene skeleton modified novolac type phenolic resin, phenol aralkyl type phenolic resin, naphthol aralkyl type phenolic resin, dicyclopentadiene type phenolic resin, biphenyl type phenolic resin, alicyclic phenolic resin, polyol type phenolic resin, phosphorus-containing phenolic resin, hydroxyl-containing silicone resins, and the like. Among them, at least one selected from the group consisting of biphenyl aralkyl phenol resins, naphthol aralkyl phenol resins, phosphorus-containing phenol resins and hydroxyl-containing silicone resins is preferred from the viewpoint of further improving the flame retardancy of the obtained cured product.

[0346] The resin composition of the present embodiment preferably includes a phenolic compound within the range of not damaging the effect of the present invention. When the resin composition of the present embodiment includes a phenolic compound, its content is preferably 0.1 mass parts or more relative to 100 mass parts of the resin solids in the resin composition, more preferably 1 mass part or more, and further preferably 2 mass parts or more. In addition, preferably 50 mass parts or less, more preferably 30 mass parts or less, further preferably 20 mass parts or less, more preferably 10 mass parts or less, and can also be 5 mass parts or less.

[0347] The resin composition in the present embodiment may contain only one phenol compound or two or more phenol compounds. When two or more phenol compounds are contained, the total amount is preferably within the above range.

[0348] The resin composition in the present embodiment may be configured to contain substantially no phenol compound. Substantially containing no phenol compound means that the content of the phenol compound is less than 0.1 parts by mass based on 100 parts by mass of the resin solid content in the resin composition.

[0349] <<Oxetane Resin>>

[0350] The resin composition of the present embodiment may contain an oxetane resin.

[0351] The oxetane resin is not particularly limited as long as it is a compound having one or more (preferably 2 to 12, more preferably 2 to 6, further preferably 2 to 4, further preferably 2 or 3, further preferably 2) oxetane groups, and a wide variety of compounds commonly used in the field of printed wiring boards can be used.

[0352] Examples of the oxetane resin include oxetane, alkyloxetane (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.), and OXT-121 (manufactured by TOAGOSEI CO., LTD.).

[0353] The resin composition of the present embodiment preferably includes oxetane resin within the scope of not damaging the effect of the present invention. When the resin composition of the present embodiment includes oxetane resin, its content is preferably more than 0.1 mass parts relative to 100 mass parts of resin solids in the resin composition, more preferably more than 1 mass part, and more preferably more than 2 mass parts. By making the content of oxetane resin more than 0.1 mass parts, there is a tendency to improve metal foil peel strength and toughness. When the resin composition of the present embodiment includes oxetane resin, the upper limit of the content of oxetane resin is preferably less than 50 mass parts relative to 100 mass parts of resin solids in the resin composition, more preferably less than 30 mass parts, more preferably less than 20 mass parts, more preferably less than 10 mass parts, and can also be less than 5 mass parts. By making the content of oxetane resin less than 50 mass parts, there is a tendency to improve the electrical properties of the cured product obtained.

[0354] The resin composition in the present embodiment may contain only one oxetane resin or two or more oxetane resins. When two or more oxetane resins are contained, the total amount is preferably within the above range.

[0355] The resin composition in the present embodiment may be configured to contain substantially no oxetane resin. Substantially containing no oxetane resin means that the content of the oxetane resin is less than 0.1 parts by mass based on 100 parts by mass of the resin solid content in the resin composition.

[0356] <<Benzoxazine compounds>>

[0357] The resin composition of the present embodiment may contain a benzoxazine compound.

[0358] The benzoxazine compound is not particularly limited 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, further preferably 2 or 3, further preferably 2) dihydrobenzoxazine rings in one molecule, and a wide range of compounds commonly used in the field of printed wiring boards can be used.

[0359] Examples of the benzoxazine compound include bisphenol A type benzoxazine BA-BXZ (manufactured by KONISHI CHEMICAL IND CO., LTD.), bisphenol F type benzoxazine BF-BXZ (manufactured by KONISHI CHEMICAL IND CO., LTD.), and bisphenol S type benzoxazine BS-BXZ (manufactured by KONISHI CHEMICAL IND CO., LTD.).

[0360] The resin composition of the present embodiment preferably contains a benzoxazine compound within a range that does not impair the effects of the present invention. When the resin composition of the present embodiment contains a benzoxazine compound, the content thereof is preferably 0.1 parts by mass or more, and more preferably 50 parts by mass or less, relative to 100 parts by mass of the resin solid content in the resin composition.

[0361] The resin composition in the present embodiment may contain only one benzoxazine compound or may contain two or more benzoxazine compounds. When containing two or more benzoxazine compounds, the total amount is preferably within the above range.

[0362] The resin composition in the present embodiment may be configured to contain substantially no benzoxazine compound. Substantially containing no benzoxazine compound means that the content of the benzoxazine compound is less than 0.1 parts by mass based on 100 parts by mass of the resin solid content in the resin composition.

[0363] <<Compounds containing a (meth)allyl group>>

[0364] The resin composition of the present embodiment preferably contains a compound containing a (meth)allyl group, and more preferably contains a compound containing an allyl group.

[0365] The compound containing a (meth)allyl group is preferably a compound containing two or more (meth)allyl groups, and more preferably a compound containing two or more allyl groups.

[0366] The compound containing a (meth)allyl group preferably contains at least one selected from the group consisting of an allyl isocyanurate compound, an allyl-substituted nadic imide compound, an allyl compound having a glycoluril structure, and diallyl phthalate, more preferably contains at least one selected from the group consisting of an allyl isocyanurate compound, an allyl-substituted nadic imide compound, and an allyl compound having a glycoluril structure, further preferably contains an allyl-substituted nadic imide compound, and even more preferably contains an alkenyl-substituted nadic imide compound.

[0367] The alkenyl-substituted nadic acid imide compound is not particularly limited as long as it is a compound having one or more alkenyl-substituted nadic acid imide groups in the molecule. Among them, the compound represented by formula (AN-1) is preferred. By using such an alkenyl-substituted nadic acid imide compound, there is a tendency that the thermal expansion coefficient of the obtained cured product is lower and the heat resistance is further improved.

[0368]

[0369] (In formula (AN-1), R1 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R2 represents an alkylene group having 1 to 6 carbon atoms, a phenylene group, a biphenylene group, a naphthylene group, a group represented by formula (AN-2), or a group represented by formula (AN-3).)

[0370]

[0371] (In formula (AN-2), R3 represents methylene, isopropylidene, -C(=O)-, -O-, -S- or -S(=O)2-.)

[0372]

[0373] (In formula (AN-3), R4 each independently represents an alkylene group having 1 to 4 carbon atoms or a cycloalkylene group having 5 to 8 carbon atoms.)

[0374] Among the compounds represented by formula (AN-1), the compounds represented by formula (AN-4) and (AN-5) are preferred. By using such alkenyl-substituted nadic imide compounds, the thermal expansion coefficient of the obtained cured product tends to be lower and the heat resistance is further improved.

[0375]

[0376]

[0377] In addition, commercially available alkenyl-substituted nadic acid imide compounds may be used. The commercially available alkenyl-substituted nadic acid imide compounds are not particularly limited, and examples thereof include BANI-M (manufactured by Maruzen Petrochemical Co., Ltd., a compound represented by formula (AN-4)), BANI-X (manufactured by Maruzen Petrochemical Co., Ltd., a compound represented by formula (AN-5)), and the like.

[0378] The resin composition of the present embodiment preferably contains a compound containing a (meth)allyl group (preferably an alkenyl-substituted nadic imide compound) within a range that does not impair the effects of the present invention. When the resin composition of the present embodiment contains a compound containing a (meth)allyl group (preferably an alkenyl-substituted nadic imide compound), its content is preferably 0.1 parts by mass or more relative to 100 parts by mass of the resin solid content in the resin composition, and is preferably 50 parts by mass or less.

[0379] The resin composition in the present embodiment may contain only one (meth)allyl group-containing compound (preferably an alkenyl-substituted nadic imide compound), or may contain two or more thereof. When containing two or more thereof, the total amount is preferably within the above range.

[0380] In addition, the resin composition in the present embodiment may be configured to be substantially free of alkenyl-substituted nadic imide compounds (and compounds containing (meth)allyl groups). Substantially free means that the content of the alkenyl-substituted nadic imide compounds (and compounds containing (meth)allyl groups) is less than 0.1 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition.

[0381] <<Cyanate Ester Compounds>>

[0382] The resin composition of the present embodiment preferably contains a cyanate compound.

[0383] The cyanate compound is not particularly limited as long as it contains one or more (preferably two or more, more preferably 2 to 12, further preferably 2 to 6, further preferably 2 to 4, further preferably 2 or 3, further preferably 2) cyanate groups (cyano groups) in one molecule, and a wide range of compounds commonly used in the field of printed circuit boards can be used. In addition, the cyanate compound is preferably a compound in which the cyanate group is directly bonded to an aromatic skeleton (aromatic ring).

[0384] As the cyanate compound, for example, at least one selected from the group consisting of phenol novolac type cyanate compounds, naphthol aralkyl type cyanate compounds (naphthol aralkyl type cyanate), naphthol ether type cyanate compounds, biphenyl aralkyl type cyanate compounds, xylene resin type cyanate compounds, trisphenol 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 can be cited. Among them, from the viewpoint of further improving the low water absorption of the obtained cured product, at least one selected from the group consisting of phenol novolac type cyanate compounds, naphthol aralkyl type cyanate compounds, naphthol 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 preferred, at least one selected from the group consisting of phenol novolac type cyanate compounds and naphthol aralkyl type cyanate compounds is more preferred, and naphthol aralkyl type cyanate compounds are further preferred. These cyanate compounds can be prepared by known methods, and commercial products can also be used. It should be noted that the functional group equivalent number of the cyanate compounds with a naphthol aralkyl skeleton, a naphthyl ether skeleton, a xylene skeleton, a triphenol methane skeleton or an adamantane skeleton is relatively large, and there are few unreacted cyanate groups, so the cured product of the resin composition using them has a tendency to be more excellent in low water absorption. In addition, mainly because of having an aromatic skeleton or an adamantane skeleton, there is a tendency to improve the plating adhesion.

[0385] The naphthol aralkyl type cyanate ester compound is more preferably a compound represented by the following formula (1).

[0386]

[0387] (In formula (1), R 3 Each independently represents a hydrogen atom or a methyl group, and n3 represents an integer greater than 1.)

[0388] In formula (1), R 3 Each independently represents a hydrogen atom or a methyl group, and among them, a hydrogen atom is preferred.

[0389] In formula (1), n3 is an integer of 1 or more, preferably an integer of 1-20, more preferably an integer of 1-10, and further preferably an integer of 1-6.

[0390] The novolac-type cyanate compound is not particularly limited, but is preferably a compound represented by the following formula (VII), for example.

[0391]

[0392] (In formula (VII), R 6Each independently represents a hydrogen atom or a methyl group, and n7 represents an integer greater than 1.)

[0393] In formula (VII), R 6 Each independently represents a hydrogen atom or a methyl group, and among them, a hydrogen atom is preferred.

[0394] In formula (VII), n7 is an integer of 1 or more, preferably an integer of 1-20, more preferably an integer of 1-10, and further preferably an integer of 1-6.

[0395] As the bisphenol A type cyanate ester compound, one or more selected from the group consisting of 2,2-bis(4-cyanophenyl)propane and a prepolymer of 2,2-bis(4-cyanophenyl)propane can be used.

[0396] The resin composition of the present embodiment preferably includes cyanate compounds within the scope of not damaging the effect of the present invention.When the resin composition of the present embodiment includes cyanate compounds, the lower limit of its content is preferably more than 0.1 mass parts relative to 100 mass parts of resin solids in the resin composition, more preferably more than 2 mass parts, more preferably more than 5 mass parts, more preferably more than 8 mass parts.By making the content of cyanate compounds more than 0.1 mass parts, there is the tendency of heat resistance, combustion resistance, chemical resistance, low dielectric properties (low relative dielectric constant, low dielectric loss tangent) and insulation improvement of the cured product obtained.When the resin composition of the present embodiment includes cyanate compounds, the upper limit of the content of cyanate compounds is preferably less than 70 mass parts relative to 100 mass parts of resin solids in the resin composition, more preferably less than 50 mass parts, more preferably less than 40 mass parts, more preferably less than 30 mass parts, more preferably less than 20 mass parts.

[0397] The resin composition in the present embodiment may contain only one cyanate compound or two or more cyanate compounds. When two or more cyanate compounds are contained, the total amount is preferably within the above range.

[0398] In the resin composition of the present embodiment, the content (total amount) of other thermosetting compounds (D) is preferably more than 1 mass part relative to 100 mass parts of resin solids, more preferably more than 5 mass parts, further preferably more than 10 mass parts, more preferably more than 20 mass parts, more preferably more than 25 mass parts, and can also be more than 30 mass parts. By being set to more than the aforementioned lower limit, there is a tendency to improve heat resistance, plating adhesion, low thermal expansion, etc. more. In addition, the upper limit of the content of other thermosetting compounds (D) is preferably less than 100 mass parts relative to 100 mass parts of resin solids, more preferably less than 90 mass parts, more preferably less than 80 mass parts, more preferably less than 70 mass parts, more preferably less than 60 mass parts, more preferably less than 50 mass parts, and can also be less than 40 mass parts.

[0399] The resin composition of the present embodiment may contain only one other thermosetting compound (D), or may contain two or more thereof. When containing two or more thereof, the total amount is preferably within the above range.

[0400] <Flame retardant (F)>

[0401] The resin composition of the present embodiment may contain a flame retardant (F). Examples of the flame retardant (F) include phosphorus-based flame retardants, halogen-based flame retardants, inorganic-based flame retardants, and silicone-based flame retardants, and phosphorus-based flame retardants are preferred.

[0402] As the flame retardant (F), known products can be used, for example, red phosphorus, tricresyl phosphate, triphenyl phosphate, cresyl diphenyl phosphate, tricresyl phosphate, trialkyl phosphate, dialkyl phosphate, tris(chloroethyl) phosphate, phosphazene, 1,3-phenylenebis(2,6-di(xylyl)phosphate), 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide and other phosphorus-based flame retardants, brominated epoxy resins, Halogen flame retardants such as esters, brominated polycarbonate, brominated polystyrene, brominated styrene, brominated phthalimide, tetrabromobisphenol A, pentabromobenzyl (meth) acrylate, pentabromotoluene, tribromophenol, hexabromobenzene, decabromodiphenyl ether, bis-1,2-pentabromophenylethane, chlorinated polystyrene, chlorinated paraffin, etc., inorganic flame retardants such as aluminum hydroxide, magnesium hydroxide, some boehmite, boehmite, zinc borate, antimony trioxide, etc., and silicone flame retardants such as silicone rubber and silicone resin.

[0403] In the present embodiment, among these, 1,3-phenylenebis(2,6-di(xylyl)phosphate) is preferred because it does not impair the low dielectric properties.

[0404] When the resin composition of the present embodiment includes a flame retardant (F), its content is preferably 1 mass part or more relative to 100 mass parts of the resin solid content in the resin composition, more preferably 5 mass parts or more, further preferably 10 mass parts or more, and may be 13 mass parts or more. In addition, the lower limit of the content of the flame retardant (F) is preferably 30 mass parts or less, more preferably 25 mass parts or less, and may be 20 mass parts or less.

[0405] The flame retardant (F) may be used alone or in combination of two or more. When two or more are used, the total amount is within the above range.

[0406] <Other filling materials (G)>

[0407] The resin composition of the present embodiment may further contain other fillers (G) other than the fluororesin filler (A) (hereinafter referred to simply as “other fillers (G)”).

[0408] The other fillers (G) used in the present embodiment are more preferably excellent in low dielectric properties. For example, the relative dielectric constant (Dk) of the other fillers (G) used in the present embodiment at a frequency of 10 GHz measured by the resonant cavity perturbation method is preferably 8.0 or less, more preferably 6.0 or less, and further preferably 4.0 or less. In addition, the lower limit of the relative dielectric constant is, for example, more than 2.0 and more practical. In addition, the dielectric loss tangent (Df) of the other fillers (G) used in the present embodiment at a frequency of 10 GHz measured by the resonant cavity perturbation method is preferably less than 0.05, more preferably less than 0.01. In addition, the lower limit of the dielectric loss tangent is, for example, more than 0.0001 and more practical. The relative dielectric constant (Dk) and the dielectric loss tangent (Df) are measured by the method described in the embodiments described later.

[0409] As other fillers (G) used in this embodiment, there is no particular limitation on their types, and those commonly used in this technical field can be appropriately used. Specifically, they include: natural silica, fused silica, synthetic silica, amorphous silica, fumed silica (AEROSIL), hollow silica and other silicas; metal oxides such as aluminum oxide, white carbon, titanium dioxide, titanium oxide, zinc oxide, magnesium oxide, and zirconium oxide; composite oxides such as zinc borate, zinc stannate, forsterite, barium titanate, strontium titanate, and calcium titanate; nitrides such as boron nitride, condensed boron nitride, silicon nitride, and aluminum nitride; metal hydroxides (including hydrates) such as aluminum hydroxide, aluminum hydroxide heat-treated products (substances obtained by heating aluminum hydroxide and removing part of the crystal water), boehmite, and magnesium hydroxide; molybdenum oxide, molybdenum Molybdenum compounds such as zinc sulfate; barium sulfate, clay, kaolin, talc, calcined clay, calcined kaolin, calcined talc, mica, E-glass, A-glass, NE-glass, C-glass, L-glass, D-glass, S-glass, M-glass G20, glass staple fibers (including glass micropowders such as E glass, T glass, D glass, S glass, Q glass, etc.), hollow glass, spherical glass, etc. Inorganic fillers (inorganic fillers) can also be listed; in addition, styrene-type, butadiene-type, acrylic-type rubber powders, core-shell-type rubber powders, silicone resin powders, silicone rubber powders, silicone composite powders, etc. can also be listed. Organic fillers (organic fillers)

[0410] In the present embodiment, other fillers (G) preferably include one or more selected from the group consisting of silica, aluminum hydroxide, aluminum nitride, boron nitride, forsterite, titanium oxide, barium titanate, strontium titanate, calcium titanate and aluminum titanate, and more preferably include one or more selected from the group consisting of silica, aluminum hydroxide, aluminum nitride, boron nitride and forsterite. From the viewpoint of low dielectric properties, other fillers (G) more preferably include one or more selected from the group consisting of silica and aluminum hydroxide, and further preferably include silica. From the viewpoint of high thermal conductivity, other fillers (G) more preferably include boron nitride. In particular, in the resin composition of the present embodiment, by using these inorganic fillers (preferably silica) and fluororesin filler (A), the peel strength can be further improved.

[0411] The average particle size (D50) of other fillers (G) is not particularly limited, but is preferably 0.1 μm or more, more preferably 0.5 μm or more. In addition, from the viewpoint of dispersibility, the average particle size (D50) of other fillers (G) is preferably 3 μm or less, more preferably 1 μm or less.

[0412] It should be noted that the average particle size (D50) refers to the value when the volume accumulation from the smallest particles reaches 50% of the total volume, measured by a particle size distribution measuring device such as a laser diffraction / scattering method, in which a predetermined amount of powder is added to a dispersion medium. When the dispersion medium herein includes a solvent, it refers to the solvent.

[0413] In the resin combination of the present embodiment, the content of other filling materials (G) can be appropriately set according to desired characteristics, is not particularly limited, and is preferably more than 10 mass parts relative to 100 mass parts of the resin solids in the resin combination, more preferably more than 20 mass parts, more preferably more than 40 mass parts, more preferably more than 60 mass parts.By being set to more than the aforementioned lower limit, there is a tendency that low thermal expansion, low dielectric loss tangent are more improved.In addition, the upper limit of the content of other filling materials (G) is preferably less than 1000 mass parts relative to 100 mass parts of resin solids, more preferably less than 800 mass parts, more preferably less than 500 mass parts, more preferably less than 300 mass parts, more preferably less than 200 mass parts, can also be less than 100 mass parts, less than 80 mass parts, less than 70 mass parts.By being set to less than the aforementioned upper limit, there is a tendency that formability is more improved.

[0414] In the resin combination of the present embodiment, the content of other filling materials (G) can also be 0 mass parts relative to 100 mass parts of fluororesin filler (A), but preferably more than 50 mass parts, more preferably more than 70 mass parts, and more preferably more than 90 mass parts.By being set to more than the aforementioned lower limit, there is a tendency that peel strength is more improved.In addition, the upper limit of the content of the aforementioned other filling materials (G) is preferably less than 500 mass parts relative to 100 mass parts of fluororesin filler (A), more preferably less than 400 mass parts, more preferably less than 300 mass parts, more preferably less than 250 mass parts, more preferably less than 200 mass parts, more preferably less than 150 mass parts.By being set to less than the aforementioned upper limit, there is a tendency that hygroscopic heat resistance, low dielectric properties are more improved.

[0415] The resin composition of the present embodiment may contain only one type of other filler (G), or may contain two or more types. When containing two or more types, the total amount is preferably within the above range.

[0416] In the resin composition of the present embodiment, as one example of a preferred embodiment, the content of the fluororesin filler (A) and the other filler (G) is 30% by mass to 80% by mass of the components excluding the solvent.

[0417] In the resin composition of the present embodiment, when other fillers (G) are used, especially when inorganic fillers are used, a silane coupling agent may be further included. By including a silane coupling agent, there is a tendency to further improve the dispersibility of other fillers (G), the bonding strength between the resin component and other fillers (G) and the substrate described later.

[0418] There is no particular limitation on the silane coupling agent, and examples thereof include silane coupling agents commonly used for surface treatment of inorganic substances, such as aminosilane compounds (e.g., γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, etc.), epoxysilane compounds (e.g., γ-glycidoxypropyltrimethoxysilane, etc.), vinylsilane compounds (e.g., vinyltrimethoxysilane, etc.), styrylsilane compounds (e.g., p-styryltrimethoxysilane, etc.), acrylic silane compounds (e.g., γ-acryloxypropyltrimethoxysilane, etc.), cationic silane compounds (e.g., N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride, etc.), phenylsilane compounds, etc. The silane coupling agent can be used alone or in combination of two or more. Among these, the silane coupling agent is preferably an epoxysilane compound. Examples of the epoxysilane-based compound include "KBM-403", "KBM-303", "KBM-402", and "KBE-403" manufactured by Shin-Etsu Chemical Co., Ltd.

[0419] The content of the silane coupling agent is not particularly limited, and may be 0.1 to 5.0 parts by mass based on 100 parts by mass of the resin solid content.

[0420] In addition, in the present embodiment, other fillers (G), particularly inorganic fillers, may be those that have been surface-treated in advance with the above-mentioned silane coupling agent.

[0421] <Active ester compound>

[0422] The resin composition of the present embodiment may also contain an active ester compound within a range that does not impair the effects of the present invention. The active ester compound is not particularly limited, and for example, reference may be made to paragraphs 0064 to 0066 of International Publication No. 2021 / 172317, and the contents thereof are incorporated herein.

[0423] When the resin composition of the present embodiment contains an active ester compound, the amount thereof is preferably 1 part by mass or more and preferably 50 parts by mass or less relative to 100 parts by mass of the resin solid content in the resin composition.

[0424] The resin composition in the present embodiment may contain only one active ester compound or two or more thereof. When containing two or more thereof, the total amount is preferably within the above range.

[0425] In addition, the resin composition in the present embodiment may be configured to be substantially free of active ester compounds. Substantially free means that the content of active ester compounds is less than 1 part by mass, preferably less than 0.1 part by mass, and more preferably less than 0.01 part by mass, relative to 100 parts by mass of the resin solid content in the resin composition.

[0426] <Other elastomers>

[0427] The resin composition of this embodiment may also contain an elastomer (other elastomer) other than the thermoplastic elastomer (B) having a basic group and / or an acidic group. The elastomer other than the thermoplastic elastomer (B) having a basic group and / or an acidic group is an elastomer that does not contain a basic group and an acidic group.

[0428] In the present embodiment, there is no particular limitation on other elastomers, and examples thereof include 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 butylene styrene, styrene propylene styrene, styrene ethylene propylene styrene, fluororubber, silicone rubber, their hydrides, their alkyl compounds and their copolymers.

[0429] In addition, the other elastomer may be a thermoplastic elastomer or a thermosetting elastomer, but is preferably a thermoplastic elastomer.

[0430] The number average molecular weight of the other elastomer used in this embodiment is preferably 50,000 or more. By making the number average molecular weight 50,000 or more, there is a tendency that the low dielectric properties of the obtained cured product are more excellent. The aforementioned number average molecular weight is preferably 60,000 or more, more preferably 70,000 or more, and further preferably 80,000 or more. The upper limit of the number average molecular weight of the other elastomer is preferably 400,000 or less, more preferably 350,000 or less, and further preferably 300,000 or less. By setting it below the aforementioned upper limit, the solubility of the other elastomer components in the resin composition tends to be improved.

[0431] When the resin composition of the present embodiment contains two or more other elastomers, it is preferred that the number average molecular weight of the mixture thereof satisfy the above range.

[0432] In the present embodiment, the other elastomer is preferably a thermoplastic elastomer containing a styrene monomer unit and a conjugated diene monomer unit (hereinafter referred to as "thermoplastic elastomer (E)"). By using such a thermoplastic elastomer (E), the obtained cured product has more excellent low dielectric properties.

[0433] The thermoplastic elastomer (E) contains styrene monomer units. By containing styrene monomer units, the solubility of the thermoplastic elastomer (E) in the resin composition is improved. As styrene monomers, styrene, α-methylstyrene, p-methylstyrene, divinylbenzene (vinyl styrene) and the like are exemplified, among which, from the viewpoint of availability and productivity, one or more selected from the group consisting of styrene, α-methylstyrene and p-methylstyrene are preferred. Among them, styrene is particularly preferred.

[0434] The content of the styrene monomer unit in the thermoplastic elastomer (E) is preferably in the range of 10 to 50% by mass of all monomer units, more preferably in the range of 13 to 45% by mass, and further preferably in the range of 15 to 40% by mass. If the content of the styrene monomer unit is 50% by mass or less, the adhesion and adhesiveness to the substrate etc. are better. In addition, if it is 10% by mass or more, excessive adhesion can be suppressed, and residual glue and stop marks are not easy to occur, and the easy peelability of the bonding surfaces each other tends to become good, so it is preferred.

[0435] The thermoplastic elastomer (E) may contain only one type of styrene monomer unit or two or more types thereof. When two or more types are contained, the total amount is preferably within the above range.

[0436] In addition, the method for measuring the content of the styrene monomer unit in the thermoplastic elastomer (E) can refer to the description of International Publication No. 2017 / 126469, the content of which is incorporated into the present specification. The same applies to the conjugated diene monomer unit described later.

[0437] The thermoplastic elastomer (E) contains conjugated diene monomer units. By containing conjugated diene monomer units, the solubility of the thermoplastic elastomer (E) in the resin composition is improved. As a conjugated diene monomer, there is no particular limitation as long as it is a diene with one pair of conjugated double bonds. Conjugated diene monomers include, for example, 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, and farnesene, preferably 1,3-butadiene and / or isoprene, more preferably 1,3-butadiene.

[0438] The thermoplastic elastomer (E) may contain only one type of the conjugated diene monomer unit, or may contain two or more types.

[0439] In the thermoplastic elastomer (E), the mass ratio of the styrene monomer unit to the conjugated diene monomer unit is preferably in the range of styrene monomer unit / conjugated diene monomer unit=5 / 95 to 80 / 20, more preferably in the range of 7 / 93 to 77 / 23, and further preferably in the range of 10 / 90 to 70 / 30. If the mass ratio of the styrene monomer unit to the conjugated diene monomer unit is in the range of 5 / 95 to 80 / 20, excessive adhesion can be suppressed, and the adhesive force can be maintained at a high level, and the easy peelability of the adhesive surfaces becomes good.

[0440] In the thermoplastic elastomer (E), the conjugated diene bonds of the thermoplastic elastomer may be all hydrogenated, partially hydrogenated, or unhydrogenated.

[0441] The thermoplastic elastomer (E) may or may not contain other monomer units in addition to the styrene monomer units and the conjugated diene monomer units. Examples of other monomer units include aromatic vinyl compound units other than the styrene monomer units.

[0442] In the thermoplastic elastomer (E), the total content of the styrene monomer units and the conjugated diene monomer units is preferably 90% by mass or more, more preferably 95% by mass or more, further preferably 97% by mass or more, and even more preferably 99% by mass or more of all monomer units.

[0443] In the thermoplastic elastomer (E), the styrene monomer unit and the conjugated diene monomer unit may each contain only one kind or two or more kinds. When two or more kinds are contained, it is preferred that the total amount is within the above range.

[0444] The thermoplastic elastomer (E) may be a block polymer or a random polymer. In addition, the conjugated diene monomer unit may be a hydrogenated elastomer that has been hydrogenated, an unhydrogenated elastomer that has not been hydrogenated, or a partially hydrogenated partially hydrogenated elastomer.

[0445] In one embodiment of the present embodiment, the thermoplastic elastomer (E) is a hydrogenated elastomer. Here, the hydrogenated elastomer refers to, for example, an elastomer in which the double bonds based on the conjugated diene monomer units are hydrogenated, and includes not only those with a hydrogenation rate (hydrogenation rate) of 100%, but also those with a hydrogenation rate of 80% or more. The hydrogenation rate of the hydrogenated elastomer is preferably 85% or more, more preferably 90% or more, and further preferably 95% or more. In this embodiment, the hydrogenation rate is 1 The measurement results of H-NMR spectrum measurement were calculated.

[0446] In one embodiment of the present embodiment, the thermoplastic elastomer (E) is an unhydrogenated elastomer. Here, the unhydrogenated elastomer means an elastomer having a ratio of hydrogenated double bonds based on conjugated diene monomer units in the elastomer, that is, a hydrogenation rate (hydrogenation rate) of 20% or less. The hydrogenation rate in the unhydrogenated elastomer is preferably 15% or less, more preferably 10% or less, and further preferably 5% or less.

[0447] On the other hand, the partially hydrogenated elastomer refers to an elastomer in which a part of the double bonds based on the conjugated diene monomer units in the elastomer are hydrogenated, and generally refers to an elastomer with a hydrogenation rate (hydrogenation rate) of less than 80% and more than 20%.

[0448] Examples of commercially available products of the thermoplastic elastomer (E) used in the present embodiment include SEPTON (registered trademark) 2104 manufactured by Kuraray Co., Ltd., SOE (registered trademark) S1606, S1613, S1609, and S1605 manufactured by Asahi Kasei Corporation, and DYNARON (registered trademark) 9901P and TR2250 manufactured by JSR Corporation.

[0449] When the resin composition of the present embodiment includes other elastomers (preferably thermoplastic elastomer (E)), its content is preferably more than 1 mass part relative to 100 mass parts of resin solids, more preferably more than 5 mass parts, further preferably more than 10 mass parts, and can also be more than 15 mass parts, more than 20 mass parts. By being set to more than the aforementioned lower limit, there is a tendency that low dielectric properties are further improved. In addition, the upper limit of the content of other elastomers is preferably less than 45 mass parts relative to 100 mass parts of resin solids, more preferably less than 40 mass parts, further preferably less than 35 mass parts, more preferably less than 30 mass parts, and can also be less than 25 mass parts. By being set to less than the aforementioned upper limit, there is a tendency that heat resistance is further improved.

[0450] The resin composition of the present embodiment may contain only one type of other elastomer or two or more types thereof. When two or more types thereof are contained, the total amount is preferably within the above range.

[0451] When the resin composition of the present embodiment contains other elastomers (preferably thermoplastic elastomer (E)), the mass ratio of thermoplastic elastomer (B) to other elastomers is preferably in the range of thermoplastic elastomer (B) / other elastomer = 5 / 95 to 95 / 5, more preferably in the range of 10 / 90 to 93 / 7, further preferably in the range of 30 / 70 to 90 / 10, and may also be in the range of 40 / 60 to 85 / 15.

[0452] <Aromatic oligomers>

[0453] The resin composition of the present embodiment may also include an aromatic oligomer. An aromatic oligomer is an oligomer having a structural unit derived from an aromatic vinyl compound, and generally refers to a compound having a weight average molecular weight of less than 3000. In addition, an aromatic oligomer is generally a thermoplastic oligomer. It should be noted that the aromatic oligomer in the present embodiment does not include a polymer (V) having a structural unit shown in formula (V) or a thermoplastic elastomer.

[0454] As the aforementioned aromatic vinyl compound, for example, 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 etc. can be mentioned. These aromatic vinyl compounds can be used alone or in combination of two or more. Among them, styrene, α-methylstyrene, 4-methylstyrene are preferred, and α-methylstyrene is more preferred.

[0455] The aromatic oligomer may also 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-vinyl indole, N-vinyl phthalimide, N-vinyl pyrrolidone, N-vinyl carbazole, and N-vinyl caprolactam.

[0456] The content of the structural unit derived from the aromatic vinyl compound in the aromatic oligomer is preferably 60 mass % or more, more preferably 70 mass % or more, further preferably 80 mass % or more, further preferably 90 mass % or more, and further preferably 95 mass % or more.

[0457] The weight average molecular weight (Mw) of the aromatic oligomer is preferably 300 or more, more preferably 500 or more, and further preferably 1,000 or more. It is usually less than 3,000, preferably 2,800 or less, more preferably 2,500 or less, and may 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 and converted to standard polystyrene.

[0458] Examples of the aromatic oligomer 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 the aromatic oligomer may be used alone or in combination of two or more.

[0459] As the aromatic oligomer, a commercially available product may be used. Examples of commercially available aromatic oligomers include aromatic polymers manufactured by Eastman Co., Ltd., such as Piccolastic A5 (polystyrene, softening point 5° C., Mw 350), Piccolastic A-75 (polystyrene, softening point 74° C., Mw 1300), Piccotex 75 (α-methylstyrene / 4-methylstyrene copolymer, softening point 75° C., Mw 1100), Piccotex LC (α-methylstyrene / 4-methylstyrene copolymer, softening point 91° C., Mw 1350), Kristalex 3070 (styrene / α-methylstyrene copolymer, softening point 70° C., Mw 950), Kristalex 3085 (styrene / α-methylstyrene copolymer, softening point 85° C., Mw 1150), and Kristalex 3100 (styrene / α-methylstyrene copolymer, softening point 100° C., Mw 1500), and YS resin SX-100 (polystyrene, softening point 100°C, Mw 2500; manufactured by Yasuhara Chemical Co., Ltd.), FMR-0150 (styrene / aromatic hydrocarbon copolymer, softening point 145°C, Mw 2040; manufactured by Mitsui Chemicals, Inc.), FTR-6100 (styrene / aliphatic hydrocarbon copolymer, softening point 95°C, Mw 1210; manufactured by Mitsui Chemicals, Inc.), FTR-6110 (styrene / aliphatic hydrocarbon copolymer, softening point 110°C, Mw 1570; manufactured by Mitsui Chemicals, Inc.), FTR-6125 (styrene / aliphatic hydrocarbon copolymer, softening point 145°C, Mw 2040; manufactured by Mitsui Chemicals, Inc.), Softening point 125°C, Mw 1950; manufactured by Mitsui Chemicals, Inc.), FTR-7100 (styrene / α-methylstyrene / aliphatic hydrocarbon copolymer, softening point 100°C, Mw 1440; manufactured by Mitsui Chemicals, Inc.), FTR-0100 (poly α-methylstyrene, softening point 100°C, Mw 1960; manufactured by Mitsui Chemicals, Inc.), FTR-2120 (styrene / α-methylstyrene copolymer, softening point 120°C, Mw 2630; manufactured by Mitsui Chemicals, Inc.), etc.

[0460] In addition to the above, details of the aromatic oligomer can be used in the description of paragraphs 0069 to 0087 of International Publication No. 2017 / 135168 that correspond to the aromatic oligomer, and the contents are incorporated into the present specification.

[0461] When the resin combination of the present embodiment includes aromatic oligomer, its content is preferably more than 1 mass part relative to 100 mass parts of resin solids, more preferably more than 2 mass parts, further preferably more than 3 mass parts, and can also be more than 4 mass parts.By being set to more than the aforementioned lower limit, there is the tendency that can further reduce relative dielectric constant and dielectric loss tangent.In addition, the upper limit value of the content of aromatic oligomer is preferably less than 45 mass parts relative to 100 mass parts of resin solids, more preferably less than 30 mass parts, further preferably less than 15 mass parts, more preferably less than 10 mass parts, and can also be less than 8 mass parts.By being set to less than the aforementioned upper limit, there is the tendency that chemical resistance improves more.

[0462] The resin composition of the present embodiment may contain only one aromatic oligomer or two or more aromatic oligomers. When two or more aromatic oligomers are contained, the total amount is preferably within the above range.

[0463] <Dispersant>

[0464] The resin composition of the present embodiment may also include a dispersant. The dispersant may be suitably a dispersant commonly used for coating applications, and its type is not particularly limited. The dispersant is preferably a copolymer-based wetting dispersant, and specific examples thereof include: DISPERBYK (registered trademark) -110, 111, 161, 180, 2009, 2152, 2155, BYK (registered trademark) -W996, W9010, W903, W940, etc. manufactured by BYK Japan KK.

[0465] When the resin composition of the present embodiment includes a dispersant, the lower limit of its content is preferably 0.01 mass parts or more relative to 100 mass parts of the resin solids in the resin composition, more preferably 0.1 mass parts or more, and can also be 0.3 mass parts or more. In addition, the upper limit of the content of the dispersant is preferably 10 mass parts or less relative to 100 mass parts of the resin solids in the resin composition, more preferably 5 mass parts or less, and can also be 3 mass parts or less.

[0466] The dispersants may be used alone or in combination of two or more. When two or more are used, the total amount is within the above range.

[0467] <Curing Accelerator>

[0468] The resin composition of the present embodiment may further include a curing accelerator. There is no particular limitation on the curing accelerator, and examples thereof include: imidazoles such as 2-ethyl-4-methylimidazole and triphenylimidazole; organic peroxides such as benzoyl peroxide, lauroyl peroxide, acetyl peroxide, p-chlorobenzoyl peroxide, di(tert-butyl)-di-perphthalate, α,α'-di(tert-butylperoxide)diisopropylbenzene, 2,5-dimethyl-2,5-di(tert-butylperoxide)hexane, 2,5-dimethyl-2,5-bis(tert-butylperoxide)hex-3-yne; azo compounds such as azobisnitrile; N,N-dimethylbenzylamine, N,N-dimethylaniline, N,N-dimethyltoluidine, 2-N-ethylanilinoethanol, tri-n-butylamine, pyridine, etc. Tertiary amines such as anthracene, quinoline, N-methylmorpholine, triethanolamine, triethylenediamine, tetramethylbutylenediamine, and N-methylpiperidine; phenols such as phenol, xylenol, cresol, resorcinol, and catechol; high-temperature decomposition type free radical generators such as 2,3-dimethyl-2,3-diphenylbutane; organic metal salts such as lead naphthenate, lead stearate, zinc naphthenate, zinc octoate, manganese octoate, tin oleate, dibutyltin maleate, manganese naphthenate, cobalt naphthenate, and ferric acetylacetonate; those obtained by dissolving these organic metal salts in hydroxyl-containing compounds such as phenol and bisphenol; inorganic metal salts such as tin chloride, zinc chloride, and aluminum chloride; organic tin compounds such as dioctyltin oxide, other alkyl tins, and alkyl tin oxides, etc.

[0469] In the present embodiment, preferred curing accelerators are imidazoles and organic metal salts, and it is more preferred to use both imidazoles and organic metal salts in combination.

[0470] In addition, in the present embodiment, the composition may be substantially free of polymerization initiators such as organic peroxides and azo compounds. Substantially free of polymerization initiators means that the content of the polymerization initiator is less than 0.1 parts by mass based on 100 parts by mass of the resin solid content in the resin composition.

[0471] When the resin combination of the present embodiment includes a curing accelerator, the lower limit of its content is preferably 0.005 mass parts or more relative to 100 mass parts of the resin solids in the resin combination, more preferably 0.01 mass parts or more, and further preferably 0.1 mass parts or more. In addition, the upper limit of the content of the curing accelerator is preferably 10 mass parts or less relative to 100 mass parts of the resin solids in the resin combination, more preferably 5 mass parts or less, and further preferably 2 mass parts or less.

[0472] The curing accelerator may be used alone or in combination of two or more. When two or more are used, the total amount is within the above range.

[0473] <Solvent>

[0474] The resin composition of the present embodiment may also include a solvent, preferably an organic solvent. When including a solvent, the resin composition of the present embodiment is preferably at least a portion of the above-mentioned various resin solid components, preferably all dissolved in a solvent or a form (solution or varnish) compatible with a solvent. As long as the solvent can be at least a portion of the above-mentioned various resin solid components, preferably all dissolved or compatible polar organic solvents or non-polar organic solvents, there is no particular restriction, as a polar organic solvent, for example: ketones (such as acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), cellosolves (such as propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc.), esters (such as ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl methoxypropionate, methyl hydroxyisobutyrate, etc.), amides (such as dimethoxyacetamide, dimethylformamide, etc.), as non-polar organic solvents, aromatic hydrocarbons (such as toluene, xylene, etc.) can be listed.

[0475] The solvent may be used alone or in combination of two or more. When two or more solvents are used, the total amount is within the above range.

[0476] <Other ingredients>

[0477] The resin composition of the present embodiment may further include various polymer compounds such as thermoplastic resins and oligomers thereof, and various additives in addition to the above-mentioned components. Examples of additives include low molecular weight compounds, ultraviolet light absorbers, antioxidants, photopolymerization initiators, fluorescent whitening agents, photosensitizers, dyes, pigments, thickeners, flow regulators, lubricants, defoamers, leveling agents, brighteners, polymerization inhibitors, etc. These additives may be used alone or in combination of two or more.

[0478] <Purpose>

[0479] The resin combination of the present embodiment can be made into a cured product and used. Specifically, the resin combination of the present embodiment can be suitably used as a low relative dielectric constant material and / or a low dielectric loss tangent material, as an insulating layer of a printed circuit board, a semiconductor packaging material and other electronic materials resin combination use. The resin combination of the present embodiment can be suitably used as a prepreg, a metal foil laminated plate using a prepreg, a resin composite sheet and a printed circuit board material.

[0480] The relative dielectric constant (Dk) when the resin composition of the present embodiment is preferably formed into a cured plate (laminated plate) with a thickness of 0.8mm is low. Specifically, the relative dielectric constant (Dk) at a frequency of 10GHz measured by a cavity resonance perturbation method is preferably less than 3.2, more preferably less than 3.2, further preferably less than 3.1, and more preferably less than 3.0. For the lower limit of the relative dielectric constant (Dk), there is no particular limitation, but for example, more than 0.01 is more practical.

[0481] Such low dielectric properties can be achieved by blending a fluororesin filler (A). In the present embodiment, since the fluororesin filler (A) is less likely to aggregate in the cured product, a larger amount of the fluororesin filler (A) can be blended.

[0482] The relative dielectric constant (Dk) of the cured plate is more specifically measured by the method described in Examples below.

[0483] The resin composition of the present embodiment is preferably used as a layered material (including the concepts of film, sheet, etc.) such as a prepreg, a resin composite sheet, etc., which becomes the insulating layer of a printed circuit board. When the layered material is made, its thickness is preferably 10 μm or more, and more preferably 30 μm or more. The upper limit of the thickness is preferably 200 μm or less, and more preferably 180 μm or less. It should be noted that for the thickness of the above-mentioned layered material, for example, when the resin composition of the present embodiment is impregnated with glass cloth, it refers to the thickness including the glass cloth.

[0484] <<Prepreg>>

[0485] The prepreg of the present embodiment is formed by a substrate (prepreg substrate) and a resin composition of the present embodiment. The prepreg of the present embodiment can be obtained, for example, by applying (e.g., impregnating and / or coating) the resin composition of the present embodiment to the substrate, and then semi-curing it by heating (e.g., drying it at 120 to 220°C for 2 to 15 minutes, etc.). At this time, the amount of the resin composition attached to the substrate, that is, the amount of the resin composition (including the fluororesin filler (A) and other filling materials (G)) is preferably in the range of 20 to 99% by mass relative to the total amount of the semi-cured prepreg, and more preferably in the range of 20 to 80% by mass.

[0486] As a substrate, there is no particular limitation as long as it is a substrate used for various printed circuit board materials. As the material of the substrate, for example, glass fiber (such as E-glass, D-glass, L-glass, S-glass, T-glass, Q-glass, UN-glass, NE-glass, spherical glass, etc.), inorganic fibers other than glass (such as quartz, etc.), organic fibers (such as polyimide, polyamide, polyester, liquid crystal polyester, polytetrafluoroethylene, etc.) are listed. There is no particular limitation on the form of the substrate, and woven fabrics, non-woven fabrics, coarse yarns, short glass fiber mats, surface-processed mats, etc. can be listed. These substrates can be used alone or in combination of two or more. Among these substrates, from the viewpoint of dimensional stability, woven fabrics that have been subjected to super fiber opening treatment and hole filling treatment are preferred. From the viewpoint of strength and low water absorption, the substrate preferably has a thickness of less than 200 μm and a mass of 250 g / m 2The following glass woven fabrics are preferably glass woven fabrics surface-treated with silane coupling agents such as epoxysilane and aminosilane from the viewpoint of moisture absorption and heat resistance. From the viewpoint of electrical properties, low dielectric glass cloths composed of glass fibers such as L-glass, NE-glass, and Q-glass that exhibit low relative dielectric constant and low dielectric loss tangent are more preferred.

[0487] As a substrate with low relative dielectric constant, for example, a substrate with a relative dielectric constant of 5.0 or less (preferably 3.0 to 4.9) is exemplified. As a substrate with low dielectric loss tangent, for example, a substrate with a dielectric loss tangent of 0.006 or less (preferably 0.001 to 0.005) is exemplified. The relative dielectric constant and dielectric loss tangent are set to the values ​​measured by the perturbation method cavity resonator at a frequency of 10 GHz.

[0488] <<Metal foil clad laminate>>

[0489] The metal foil clad laminate of the present embodiment comprises at least one layer formed by the prepreg of the present embodiment and a metal foil disposed on one or both sides of the layer formed by the aforementioned prepreg. As a method for making the metal foil clad laminate of the present embodiment, for example, a method of configuring at least one prepreg of the present embodiment (preferably overlapping more than 2 sheets) and performing stacking molding after configuring metal foil on one or both sides thereof can be cited. In more detail, it can be made by configuring metal foils such as copper and aluminum on one or both sides of the prepreg and performing stacking molding. As the number of sheets of prepreg, preferably 1 to 10 sheets, more preferably 2 to 10 sheets, and further preferably 2 to 9 sheets. As a metal foil, as long as it is a metal foil used in a printed circuit board material, there is no particular restriction, and examples include copper foils such as rolled copper foil and electrolytic copper foil. The thickness of the metal foil (preferably copper foil) is not particularly limited, and can also be about 1.5 to 70 μm. In addition, when copper foil is used as the metal foil, as the copper foil, it is preferred to adjust the roughness Rz of the copper foil surface measured in accordance with JIS B0601: 2013 to 0.2 to 7.0 μm. By setting the roughness Rz of the copper foil surface to 0.2 μm or more, there is a tendency that the roughness of the copper foil surface becomes an appropriate size and the peel strength is further improved. On the other hand, by setting the roughness Rz of the copper foil surface to 7.0 μm or less, there is a tendency that the roughness of the copper foil surface becomes an appropriate size and the dielectric loss tangent characteristics of the obtained cured product are further improved. From the perspective of peel strength, the roughness Rz of the copper foil surface is more preferably 0.5 μm or more, further preferably 0.6 μm or more, and particularly preferably 0.7 μm or more. In addition, from the perspective of reducing the dielectric loss tangent, the roughness Rz of the copper foil surface is more preferably 4.0 μm or less, further preferably 3.5 μm or less, more preferably 3.0 μm or less, and particularly preferably 2.0 μm or less.

[0490] As the lamination forming method, as the forming method, there can be mentioned the method generally used when forming the laminated board and the multilayer board for printed wiring boards, and more specifically, there can be mentioned the method using a multistage press, a multistage vacuum press, a continuous forming machine, an autoclave forming machine, etc., at a temperature of about 180 to 350°C, a heating time of about 100 to 300 minutes, a surface pressure of 20 to 100 kg / cm 2 A method for laminating and forming about. In addition, a multilayer board can also be made by combining the prepreg of this embodiment and a wiring board for the inner layer prepared separately and laminating and forming. As a method for manufacturing a multilayer board, for example, a copper foil of about 35 μm can be arranged on both sides of one piece of prepreg of this embodiment, and an inner layer circuit is formed after laminating and forming by the above-mentioned forming method, and the circuit is subjected to blackening treatment to form an inner layer circuit board, and then, the inner layer circuit board and the prepreg of this embodiment are alternately arranged piece by piece, and then copper foil is arranged on the outermost layer, and laminating and forming is preferably performed under vacuum under the above-mentioned conditions, thereby making a multilayer board. The metal foil-clad laminated board of this embodiment can be suitably used as a printed circuit board.

[0491] The peel strength of the metal foil-clad laminate of the present embodiment measured according to the provisions of JIS C64815.7 "peel strength" is preferably 0.30 kN / m or more, more preferably 0.40 kN / m or more, and more preferably 0.50 kN / m or more. The upper limit of the peel strength is not particularly limited, for example, 2.00 kN / m or less. In the present embodiment, by combining an inorganic filler (preferably silica) in addition to the fluororesin filler (A), a particularly high peel strength can be achieved.

[0492] The peel strength was measured according to the description in the examples described later.

[0493] As described above, the resin composition for electronic materials obtained using the resin composition of the present embodiment (a resin composition composed of a combination of specific components) can be made into a cured product having low dielectric properties (low dielectric constant, low dielectric loss tangent), moisture absorption and heat resistance, peel strength (copper foil adhesion), crack resistance, cured product appearance, and excellent low thermal expansion properties.

[0494] <<Printed Circuit Board>>

[0495] The printed circuit board of the present embodiment comprises an insulating layer and a conductor layer disposed on the surface of the aforementioned insulating layer, and the aforementioned insulating layer comprises at least one of a layer formed by the resin composition of the present embodiment and a layer formed by the prepreg of the present embodiment. Such a printed circuit board can be manufactured by a common method, and its manufacturing method is not particularly limited. An example of a manufacturing method of a printed circuit board is illustrated below. First, a metal foil-clad laminate such as the above-mentioned copper-clad laminate is prepared. Then, an etching process is applied to the surface of the metal foil-clad laminate to form an inner layer circuit and make an inner layer substrate. The inner layer circuit surface of the inner layer substrate is subjected to a surface treatment for improving the bonding strength as required, and then the required number of prepregs are overlapped on its inner layer circuit surface, followed by stacking the metal foil for the outer layer circuit on its outside, and then heating and pressing to form an integral body. Thus, a multilayer laminate having an insulating layer formed by a cured product of a substrate and a resin composition is manufactured between the metal foil for the inner layer circuit and the outer layer circuit. Then, after the multi-layer laminate is subjected to hole drilling processing for through holes and guide holes, a plated metal film is formed on the wall of the hole to connect the metal foil used for the inner layer circuit and the outer layer circuit. The metal foil used for the outer layer circuit is then etched to form the outer layer circuit, thereby manufacturing a printed circuit board.

[0496] The printed circuit board obtained in the above manufacturing example has the following structure: an insulating layer and a conductor layer formed on the surface of the insulating layer, and the insulating layer contains the resin composition of the present embodiment and / or its cured product. That is, the prepreg of the present embodiment (for example, a prepreg formed of a substrate and the resin composition of the present embodiment impregnated or coated thereon) and the layer formed of the resin composition of the metal foil-clad laminate of the present embodiment become the insulating layer of the present embodiment.

[0497] In addition, this embodiment also relates to a semiconductor device including the printed circuit board. For details of the semiconductor device, reference can be made to paragraphs 0200 to 0202 of Japanese Patent Application Laid-Open No. 2021-021027, and these contents are incorporated into this specification.

[0498] In addition, for the insulating layer formed by the cured product of the resin composition of the present embodiment, it is preferred to reduce the surface roughness of the roughening treatment of the insulating layer. Specifically, the arithmetic mean roughness Ra of the surface of the insulating layer after the roughening treatment is preferably less than 200nm, more preferably less than 150nm, and particularly preferably less than 100nm. The lower limit of the arithmetic mean roughness Ra is not particularly limited, for example, it can be more than 10nm. The determination of the arithmetic mean roughness Ra of the surface of the insulating layer uses a non-contact surface roughness meter, and 50 times the lens is used to measure and obtain in VSI mode.

[0499] As a non-contact surface roughness meter, WYKONT3300 manufactured by Veeco Instruments Inc. was used.

[0500] <<Resin composite sheet>>

[0501] The resin composite sheet of the present embodiment includes a support, and a layer formed by the resin composition of the present embodiment disposed on the surface of the aforementioned support. The resin composite sheet can be used as a laminated film or a dry film solder resist. There is no particular limitation on the method for manufacturing the resin composite sheet, and examples thereof include a method for obtaining a resin composite sheet by applying (coating) a solution obtained by dissolving the resin composition of the present embodiment in a solvent to a support and drying it.

[0502] The support used here includes, for example, polyethylene film, polypropylene film, polycarbonate film, polyethylene terephthalate film, ethylene tetrafluoroethylene copolymer film, release film obtained by coating a release agent on the surface of these films, organic film substrates such as polyimide film, conductor foil such as copper foil and aluminum foil, glass plate, SUS (Steel Use Stainless) plate, FRP (Fiber-Reinforced Plastics) and the like, without particular limitation.

[0503] As a coating method (coating method), for example, a method of applying a solution obtained by dissolving the resin composition of the present embodiment in a solvent to a support by a rod coater, a die coater, a scraper, a Baker applicator, etc. In addition, a single-layer sheet can be prepared by peeling off or etching the support from a resin composite sheet formed by laminating the support and the resin composition after drying. It should be noted that a solution obtained by dissolving the resin composition of the present embodiment in a solvent can be supplied to a mold having a sheet-shaped die groove, and dried, etc. to form a sheet, thereby obtaining a single-layer sheet without using a support.

[0504] It should be noted that when the single-layer sheet or resin composite sheet of the present embodiment is produced, there is no particular restriction on the drying conditions when removing the solvent, but if it is a low temperature, the solvent is likely to remain in the resin composition, and if it is a high temperature, the resin composition will be cured, so it is preferably dried at a temperature of 20°C to 200°C for 1 to 90 minutes. In addition, the single-layer sheet or resin composite sheet can be used in an uncured state where only the solvent is dried, or it can be used in a semi-cured (B-stage) state as needed. In addition, the thickness of the resin layer in the single-layer sheet or resin composite sheet of the present embodiment can be adjusted by the concentration of the solution of the resin composition of the present embodiment used during coating (coating) and the coating thickness. There are no particular restrictions. Generally speaking, if the coating thickness becomes thicker, the solvent is likely to remain during drying, so it is preferably 0.1 to 500 μm.

[0505] Example

[0506] The present invention will be described in more detail below by giving examples. The materials, usage amounts, ratios, processing contents, processing steps, etc. shown in the following examples may be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

[0507] If the measuring equipment used in the examples is difficult to obtain due to discontinuation of production, other equipment with equivalent performance may be used for measurement.

[0508] <Determination of Weight Average Molecular Weight and Number Average Molecular Weight>

[0509] The weight average molecular weight (Mw) and number average molecular weight (Mn) of the following polymer (va) having a structural unit represented by formula (V) were measured by gel permeation chromatography (GPC). A liquid delivery pump (LC-20AD manufactured by Shimadzu Corporation), a differential refractive index detector (RID-10A manufactured by Shimadzu Corporation), and a GPC column (GPC KF-801, 802, 803, 804 manufactured by Showa Denko K.K.) were used, tetrahydrofuran was used as a solvent, the flow rate was 1.0 mL / min, the column temperature was 40°C, and a calibration curve based on monodisperse polystyrene was used.

[0510] <Synthesis Example 1 Synthesis of Modified Polyphenylene Ether Compound>

[0511] <<Synthesis of Bifunctional Phenylene Ether Oligomer>>

[0512] 9.36 g (42.1 mmol) of CuBr2, 1.81 g (10.5 mmol) of N,N'-di-tert-butylethylenediamine, 67.77 g (671.0 mmol) of n-butyldimethylamine, and 2,600 g of toluene were placed in a 12 L vertical reactor equipped with a stirring device, a thermometer, an air inlet pipe, and a baffle. The mixture was stirred at a reaction temperature of 40°C while nitrogen and air were mixed and adjusted to a mixed gas with an oxygen concentration of 8% by volume at a flow rate of 5.2 L / min. A mixed solution of 129.32 g (0.48 mol) of 2,2',3,3',5,5'-hexamethyl-(1,1'-biphenol)-4,4'-diol, 878.4 g (7.2 mol) of 2,6-dimethylphenol, 1.22 g (7.2 mmol) of N,N'-di-tert-butylethylenediamine, and 26.35 g (260.9 mmol) of n-butyldimethylamine, which was previously dissolved in 2,300 g of methanol, was added dropwise over 230 minutes while bubbling, and stirred. After the addition was completed, 1,500 g of water in which 48.06 g (126.4 mmol) of tetrasodium ethylenediaminetetraacetate was dissolved was added to stop the reaction. The aqueous layer and the organic layer were separated, and the organic layer was washed with a 1N hydrochloric acid aqueous solution and then washed with pure water. The obtained solution was concentrated to 50% by mass using an evaporator to obtain 1981 g of a toluene solution of a bifunctional phenylene ether oligomer (resin "A"). The polystyrene-equivalent number average molecular weight of resin "A" obtained by GPC method was 1,975, the polystyrene-equivalent weight average molecular weight obtained by GPC method was 3,514, and the hydroxyl equivalent was 990.

[0513] <<Synthesis of modified polyphenylene ether compounds>>

[0514] In a reactor equipped with a stirring device, a thermometer and a reflux tube, 833.4 g of a toluene solution of resin "A", 76.7 g of vinylbenzyl chloride (AGC Seimi Chemical Co., Ltd., "CMS-P"), 1,600 g of dichloromethane, 6.2 g of benzyldimethylamine, 199.5 g of pure water, and 83.6 g of a 30.5% by mass NaOH aqueous solution were added and stirred at a reaction temperature of 40°C. After stirring for 24 hours, the organic layer was washed with a 1N hydrochloric acid aqueous solution and then with pure water. The obtained solution was concentrated with an evaporator, added dropwise to methanol for solidification, and the solid was recovered by filtration and vacuum dried to obtain 450.1 g of a modified polyphenylene ether compound. The number average molecular weight of the modified polyphenylene ether compound based on the polystyrene conversion of the GPC method is 2,250, the weight average molecular weight based on the polystyrene conversion of the GPC method is 3,920, and the vinyl equivalent is 1189 g / vinyl.

[0515] <Synthesis Example 2 Synthesis of Naphthol Arylalkyl Cyanate Compound (SNCN)>

[0516] Solution 1 was prepared by dissolving 300 g (1.28 mol in terms of OH group) of 1-naphthol aralkyl resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) and 194.6 g (1.92 mol) of triethylamine (1.5 mol per 1 mol of hydroxyl group) in 1800 g of dichloromethane.

[0517] 125.9 g (2.05 mol) of cyanogen chloride (1.6 mol per 1 mol of hydroxyl groups), 293.8 g of dichloromethane, 194.5 g (1.92 mol) of 36% hydrochloric acid (1.5 mol per 1 mol of hydroxyl groups), and 1205.9 g of water were added to solution 1 over 30 minutes while stirring, keeping the liquid temperature between -2°C and -0.5°C. After the addition of solution 1, stirring was performed at the same temperature for 30 minutes, and then a solution (solution 2) in which 65 g (0.64 mol) of triethylamine (0.5 mol per 1 mol of hydroxyl groups) was dissolved in 65 g of dichloromethane was added over 10 minutes. After the addition of solution 2, stirring was performed at the same temperature for 30 minutes to terminate the reaction.

[0518] After that, the reaction solution was allowed to stand to separate the organic phase and the aqueous phase. The obtained organic phase was washed five times with 1300 g of water. The conductivity of the waste water after the fifth water washing was 5 μS / cm, confirming that the removable ionic compounds were sufficiently removed by water washing.

[0519] The organic phase after washing was concentrated under reduced pressure and finally concentrated to dryness at 90°C for 1 hour to obtain 331 g of the target naphthol aralkyl cyanate compound (SNCN) (orange viscous substance). The weight average molecular weight of the obtained SNCN was 600. In addition, the IR spectrum of SNCN showed 2250 cm -1 The absorption of the cyanate group was not shown.

[0520] <Synthesis Example 3 Synthesis of a polymer (va) having a structural unit represented by formula (V)>

[0521] 2.25 mol (292.9 g) of divinylbenzene, 1.32 mol (172.0 g) of ethylvinylbenzene, 11.43 mol (1190.3 g) of styrene, and 15.0 mol (1532.0 g) of n-propyl acetate were placed in a reactor, and 600 mmol of a diethyl ether complex of boron trifluoride was added at 70° C. to react for 4 hours. After the polymerization reaction was stopped by an aqueous sodium bicarbonate solution, the oil layer was washed three times with pure water, and decompression and devolatilization were performed at 60° C. to recover a polymer (va) having a structural unit represented by formula (V). The obtained polymer (va) having a structural unit represented by formula (V) was weighed, and 860.8 g of a polymer (va) having a structural unit represented by formula (V) was confirmed.

[0522] The obtained polymer (va) having a structural unit represented by formula (V) had a number average molecular weight Mn of 2,060, a weight average molecular weight Mw of 30,700, and a monodispersity Mw / Mn of 14.9. 13 C-NMR and 1 In the H-NMR analysis, for the polymer (va) having the structural unit represented by formula (V), resonance lines derived from each monomer unit used as a raw material were observed. Based on the NMR measurement results and GC analysis results, the ratio of each monomer unit (structural unit derived from each raw material) in the polymer (va) having the structural unit represented by formula (V) was calculated as follows.

[0523] Structural units derived from divinylbenzene: 20.9 mol% (24.3 mass%)

[0524] Structural units derived from ethylvinylbenzene: 9.1 mol% (10.7 mass%)

[0525] Structural unit derived from styrene: 70.0 mol% (65.0 mass%)

[0526] The content of structural units having residual vinyl groups derived from divinylbenzene was 16.7 mol% (18.5 mass%).

[0527] Example 1

[0528] 30 parts by mass of the modified polyphenylene ether compound synthesized in Synthesis Example 1, 25 parts by mass of a maleimide compound (MIR-3000-70MT, manufactured by Nippon Kayaku Co., Ltd.) with the following structure, 10 parts by mass of the naphthol aralkyl type cyanate compound (SNCN) obtained in Synthesis Example 2, 15 parts by mass of a phosphorus flame retardant (PX-200, manufactured by DAIHACHI CHEMICAL INDUSTRY CO., LTD., 1,3-phenylenebis(2,6-di(xylyl)phosphate)), and silica (SC2050-MNU, average particle size 0.5 μm, manufactured by ADMATECHS COMPANY LIMITED), 70 parts by mass of a fluororesin filler having an acidic group (EA-2000, melting point 300°C, average particle size 2 μm, AGC Corporation), 30 parts by mass of an amine-modified elastomer (SEBS, TUFTEC-MP-10, styrene monomer unit content 30% by mass, Asahi Kasei Corporation), and 5 parts by mass of a styrene oligomer (KA-3085 (trade name), Eastman Chemical Co., Ltd.) were dissolved and mixed in methyl ethyl ketone to obtain a varnish. It should be noted that the above-mentioned amounts of addition represent the solid content.

[0529] MIR-3000

[0530]

[0531] <Manufacturing of 0.8 mm Thick Copper-Clad Laminated Board>

[0532] The obtained varnish was impregnated and coated on NE glass fabric (Nitto Boseki Co., Ltd., 2013S101S) with a thickness of 0.070 mm, and dried by heating at 165° C. for 5 minutes to obtain a prepreg (thickness 0.1 mm) containing 60% by mass of the resin composition. The properties of the NE glass fabric used are shown below.

[0533] IPC corresponding varieties: 2013

[0534] Density (root / 25mm) vertical: 46

[0535] Density (root / 25mm) horizontal: 44

[0536] Thickness(mm): 0.070

[0537] Mass (g / m 2 ):80.7

[0538] Eight sheets of the obtained prepreg were stacked, and copper foil (3EC-M3-VLP, manufactured by Mitsui Mining & Smelting Co., Ltd.) with a thickness of 12 μm was placed on both sides. 2 The film was vacuum pressed at 220° C. for 120 minutes to obtain a copper-clad laminate with an insulating layer thickness of 0.8 mm.

[0539] The copper-clad laminate obtained was used to evaluate relative dielectric constant (Dk), moisture absorption heat resistance, and peel strength. The evaluation results are shown in Table 1.

[0540] <Measurement Method and Evaluation Method>

[0541] (1) Relative dielectric constant (Dk)

[0542] The copper foil of the copper-clad laminate with a thickness of 0.8 mm obtained above was removed by etching, and the obtained test piece was processed into 1.0 mm×100 mm, dried at 120° C. for 60 minutes, and then the relative dielectric constant (Dk) after drying was measured at 10 GHz using a perturbation cavity resonator. The measurement temperature was set to 23° C.

[0543] As the perturbation method cavity resonator, Agilent 8722ES manufactured by Agilent Technologies was used.

[0544] The relative dielectric constant (Dk) was evaluated as follows.

[0545] S: 3.0 or less

[0546] A: greater than 3.0 and less than 3.1

[0547] B: greater than 3.1 and less than 3.2

[0548] C: greater than 3.2

[0549] (2) Moisture absorption and heat resistance

[0550] For the copper-clad laminate with a thickness of 0.8 mm obtained above, the copper foil on one side is completely removed by etching, and on the other side, half of the copper foil on the side is removed by etching, and the obtained test piece is cut (miniaturized) into 50 mm × 50 mm to obtain a sample for measuring hygroscopic heat resistance. The obtained sample is placed in a pressure cooker tester at 121°C and 2 atmospheres of saturated water vapor for 5 hours, and then dipped in a solder tank at 260°C for 30 seconds, and the appearance change is observed visually to see if there is any abnormality. The pressure cooker tester is made by HIRAYAMA Manufacturing Corporation, PC-3 type.

[0551] Evaluation was performed as follows.

[0552] A: No stratification confirmed

[0553] C: Confirmed to layer

[0554] (3) Peel strength

[0555] Using the copper-clad laminate (10 mm×100 mm×0.8 mm) having a thickness of 0.8 mm obtained above, the copper foil peel strength (adhesive strength) was measured twice in accordance with 5.7 “Peel Strength” of JIS C6481, and the average value was calculated. The measurement temperature was set at 23°C.

[0556] Evaluation was performed as follows.

[0557] A: 0.40kN / m or more

[0558] B: 0.30 kN / m or more and less than 0.40 kN / m

[0559] C: less than 0.30kN / m

[0560] Example 2

[0561] The same procedures were followed as in Example 1 except that the content of silica (SC2050-MNU, manufactured by ADMATECHS COMPANY LIMITED) was changed to 50 parts by mass and the content of the fluororesin filler having an acidic group (EA-2000, manufactured by AGC Corporation) was changed to 50 parts by mass.

[0562] Example 3

[0563] In Example 1, the same procedures were carried out except that silica (SC2050-MNU, manufactured by ADMATECHS COMPANY LIMITED) was not blended and the content of the fluororesin filler having an acidic group (EA-2000, manufactured by AGC Corporation) was changed to 100 parts by mass.

[0564] Example 4

[0565] In Example 1, the same procedure was followed except that the modified polyphenylene ether compound synthesized in Synthesis Example 1 was changed to an equal amount of the polymer (va) having a structural unit represented by the formula (V) synthesized in Synthesis Example 3.

[0566] Comparative Example 1

[0567] The same procedures were followed as in Example 1 except that the amine-modified elastomer (TUFTEC-MP-10, manufactured by Asahi Kasei Corporation) was replaced with an equal amount of a hydrogenated elastomer having no acidic group and no basic group (SEPTON 2104, manufactured by Kuraray Co., Ltd.).

[0568] Comparative Example 2

[0569] In Example 1, the modified polyphenylene ether compound synthesized in Example 1 was not mixed, the content of the maleimide compound (MIR-3000-70MT, manufactured by Nippon Kayaku Co., Ltd.) was set to 50 parts by mass, and the content of the naphthol aralkyl cyanate compound (SNCN) was set to 15 parts by mass, and the same procedures were followed.

[0570] Comparative Example 3

[0571] In Example 1, the same procedures were followed except that the content of silica (SC2050-MNU, manufactured by ADMATECHS COMPANY LIMITED) was 100 parts by mass and the fluororesin filler having an acidic group (EA-2000, manufactured by AGC Corporation) was not blended.

[0572] [Table 1]

[0573] Evaluation Project Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Relative dielectric constant A A S A A B C Moisture absorption and heat resistance A A A A C C A Peel strength A A B A A A A

Claims

1. A resin composition comprising: A fluororesin filler A having an acidic group and / or a basic group; a thermoplastic elastomer B having a basic group and / or an acidic group having opposite characteristics to the acidic group and / or basic group of the fluororesin filler A; and A thermosetting compound C that is compatible with the thermoplastic elastomer B.

2. The resin composition according to claim 1, wherein The fluororesin filler A comprises a fluororesin filler A having an acidic group, The thermoplastic elastomer B includes a thermoplastic elastomer B having a basic group.

3. The resin composition according to claim 1, wherein The fluororesin filler A comprises a fluororesin filler having a carboxyl group, The thermoplastic elastomer B includes a thermoplastic elastomer having an amino group.

4. The resin composition according to claim 1, wherein The fluororesin filler A comprises one or more selected from the group consisting of perfluoroalkoxy polyolefins having carboxyl groups and / or acid anhydride groups and (ethylene / tetrafluoroethylene) copolymer polyolefins having carboxyl groups and / or acid anhydride groups.

5. The resin composition according to any one of claims 1 to 4, wherein The thermoplastic elastomer B includes a styrene monomer unit and has a number average molecular weight of 50,000 or more and 800,000 or less.

6. The resin composition according to claim 5, wherein The thermoplastic elastomer B further comprises a conjugated diene monomer unit.

7. The resin composition according to any one of claims 1 to 4, wherein The thermosetting compound C includes a thermosetting compound having an aromatic ring and a carbon-carbon unsaturated bond other than an aromatic ring.

8. The resin composition according to any one of claims 1 to 4, wherein The thermosetting compound C comprises one or more selected from the group consisting of a polymer V having a structural unit represented by formula (V) and a polyphenylene ether compound P having a carbon-carbon unsaturated double bond at a terminal; In formula (V), Ar represents an aromatic hydrocarbon linking group; * represents a bonding position.

9. The resin composition according to any one of claims 1 to 4, wherein The thermoplastic elastomer B is contained in an amount of 1 to 70 parts by mass based on 100 parts by mass of the fluororesin filler A.

10. The resin composition according to any one of claims 1 to 4, wherein The content of the fluororesin filler A is 10 to 300 parts by mass based on 100 parts by mass of the resin solid content.

11. The resin composition according to any one of claims 1 to 4, wherein The content of the thermoplastic elastomer B is 1 to 90 parts by mass based on 100 parts by mass of the resin solid content.

12. The resin composition according to any one of claims 1 to 4, wherein The content of the thermosetting compound C is 1 to 90 parts by mass based on 100 parts by mass of the resin solid content.

13. The resin composition according to any one of claims 1 to 4, further comprising one or more other thermosetting compounds D selected from the group consisting of maleimide compounds, epoxy compounds, phenol compounds, oxetane resins, benzoxazine compounds and cyanate compounds.

14. The resin composition according to claim 13, wherein The maleimide compound comprises one or more selected from the group consisting of a compound represented by formula (M0), a compound represented by formula (M1), a compound represented by formula (M3) and a compound represented by formula (M5); In formula (M0), R 51 Each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a phenyl group, and R 52 Each independently represents a hydrogen atom or a methyl group, and n1 represents an integer greater than 1; In formula (M1), R M1 , R M2 , R M3 and R M4 Each independently represents a hydrogen atom or an organic group; R M5 and R M6 Each independently represents a hydrogen atom or an alkyl group; Ar M represents a divalent aromatic group; A is a 4- to 6-membered alicyclic group; 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 independently represents a hydrogen atom or an alkyl group; R M11 , R M12 , R M13 and R M14 Each independently represents a hydrogen atom or an organic group; R M15 Each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a halogen atom, a hydroxyl group or a mercapto group; px represents an integer of 0 to 3; and nx represents an integer of 1 to 20; In formula (M3), R 55 Each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group, and n5 represents an integer of 1 to 10; In formula (M5), R 58 Each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a phenyl group, and R 59 Each independently represents a hydrogen atom or a methyl group, and n6 represents an integer greater than 1. 15 . The resin composition according to claim 1 , further comprising a flame retardant F.

16. The resin composition according to claim 15, wherein The flame retardant F includes a phosphorus-based flame retardant. 17 . The resin composition according to claim 1 , further comprising a filler G other than the fluororesin filler A.

18. The resin composition according to claim 17, wherein The filler G includes one or more selected from the group consisting of silicon dioxide, aluminum hydroxide, aluminum nitride, boron nitride, and forsterite.

19. The resin composition according to claim 17, wherein The content of the filler G is 10 to 1000 parts by mass based on 100 parts by mass of the resin solid content.

20. The resin composition according to claim 17, wherein The content of the filler G is 50 to 500 parts by mass based on 100 parts by mass of the fluororesin filler A.

21. The resin composition according to claim 1, wherein The fluororesin filler A comprises one or more selected from the group consisting of perfluoroalkoxy polyolefin having a carboxyl group and / or an acid anhydride group and (ethylene / tetrafluoroethylene) copolymer polyolefin having a carboxyl group and / or an acid anhydride group, The thermoplastic elastomer B contains styrene monomer units and has a number average molecular weight of 50,000 or more and 800,000 or less, The thermoplastic elastomer B further comprises a conjugated diene monomer unit, The thermosetting compound C comprises one or more selected from the group consisting of a polymer V having a structural unit represented by formula (V) and a polyphenylene ether compound P having a carbon-carbon unsaturated double bond at a terminal. The resin composition contains 1 to 70 parts by mass of the thermoplastic elastomer B based on 100 parts by mass of the fluororesin filler A. The content of the fluororesin filler A is 10 to 300 parts by mass based on 100 parts by mass of the resin solid content. The content of the thermoplastic elastomer B is 1 to 90 parts by mass based on 100 parts by mass of the resin solid content. The content of the thermosetting compound C is 1 to 90 parts by mass relative to 100 parts by mass of the resin solid content. The resin composition further comprises one or more other thermosetting compounds D, wherein the other thermosetting compounds D are selected from the group consisting of maleimide compounds, epoxy compounds, phenol compounds, oxetane resins, benzoxazine compounds and cyanate compounds, The maleimide compound comprises one or more selected from the group consisting of a compound represented by formula (M0), a compound represented by formula (M1), a compound represented by formula (M3) and a compound represented by formula (M5), The resin composition further comprises a flame retardant F, The flame retardant F comprises a phosphorus-based flame retardant, The resin composition further comprises other filler materials G in addition to the fluororesin filler A, The filler G includes one or more selected from the group consisting of silicon dioxide, aluminum hydroxide, aluminum nitride, boron nitride and forsterite, The content of the filler G is 10 to 1000 parts by mass relative to 100 parts by mass of the resin solid content. The content of the filler G is 50 to 500 parts by mass relative to 100 parts by mass of the fluororesin filler A; In formula (V), Ar represents an aromatic hydrocarbon linking group; * represents a bonding position; In formula (M0), R 51 Each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a phenyl group, and R 52 Each independently represents a hydrogen atom or a methyl group, and n1 represents an integer greater than 1; In formula (M1), R M1 , R M2 , R M3 and R M4 Each independently represents a hydrogen atom or an organic group; R M5 and R M6 Each independently represents a hydrogen atom or an alkyl group; Ar M represents a divalent aromatic group; A is a 4- to 6-membered alicyclic group; 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 independently represents a hydrogen atom or an alkyl group; R M11 , R M12 , R M13 and R M14 Each independently represents a hydrogen atom or an organic group; R M15 Each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a halogen atom, a hydroxyl group or a mercapto group; px represents an integer of 0 to 3; and nx represents an integer of 1 to 20; In formula (M3), R 55 Each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group, and n5 represents an integer of 1 to 10; In formula (M5), R 58 Each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a phenyl group, and R 59 Each independently represents a hydrogen atom or a methyl group, and n6 represents an integer greater than 1. 22 . A cured product, which is a cured product of the resin composition according to claim 1 .

23. A prepreg comprising a base material and the resin composition according to any one of claims 1 to 4 and 21. 24 . A metal foil-clad laminate comprising at least one layer formed of the prepreg according to claim 23 and a metal foil disposed on one or both surfaces of the layer formed of the prepreg. 25 . A resin composite sheet comprising a support and a layer formed from the resin composition according to claim 1 and disposed on a surface of the support. 26 . A printed wiring board comprising an insulating layer and a conductor layer disposed on a surface of the insulating layer, wherein the insulating layer comprises a layer formed from the resin composition according to claim 1 .

27. A semiconductor device comprising the printed circuit board according to claim 26.

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