Compounds, thermosetting resin compositions, films, and laminates

Abstract

The present invention provides a compound that undergoes thermal curing at temperatures below 200°C, possesses excellent low dielectric properties, and exhibits high dimensional stability. Ultimately, it provides a resin composition, film, and laminate suitable for electronic components in high-speed communication technologies such as 5G communication. [Solution] A compound represented by the following general formula (1). TIFF2026100207000033.tif9170 (In formula (1), G is an aromatic hydrocarbon of C6-60, an aromatic heterocycle of C3-60, an alkyl group of C1-20, or a carbon atom; A is represented by the general formula (2) below, where the subscript x is an integer from 1 to 10, and when x is 2 or greater, multiple A's may be the same or different from one another.) TIFF2026100207000034.tif10170 (In formula (2), L 21 Each of these is independently a directly bonded or possibly substituted bonding group; CL 21 Each is independently a crosslinking group; the symbol * represents the bond with G in formula (1); the subscript y is an integer from 0 to 6, and the subscript z is an integer from 1 to 4, provided that the compound represented by formula (1) contains CL 21 There are at least two of them.

Description

[Technical Field]

[0001] The present invention relates to compounds that exhibit low dielectric loss tangent, high glass transition temperature, and high dimensional stability even in the high-frequency range, as well as thermosetting resin compositions, films, and laminates containing these compounds. More specifically, the present invention relates to compounds, thermosetting resin compositions, films, and laminates suitable for modules for high-speed communication. [Background technology]

[0002] In recent years, with the remarkable increase in the volume of information and communication traffic, it has become necessary to achieve communication speeds beyond conventional levels. This has necessitated a shift to fifth-generation communication (5G) using frequencies of 3GHz or higher, or to ultra-high frequency bands such as the quasi-millimeter wave band (20GHz~30GHz) to the millimeter wave band (30GHz or higher), where it is easier to secure wider frequency bandwidths.

[0003] Generally, transmission loss increases as the frequency of an electrical signal increases. To reduce transmission loss in the high-frequency band, it is necessary to reduce dielectric loss, and low-dielectric materials (low dielectric loss tangent, low dielectric constant) are required. In addition to the electrical properties of low-dielectric materials themselves, low water absorption for long-term stability of transmission characteristics, or high heat resistance for solder reflow resistance during mounting of electrical components are also required, and various curable resins have been proposed to meet these requirements.

[0004] For example, Patent Document 1 discloses a thermosetting resin that is suitable for sealing and fixing electrical and electronic components due to its excellent low moisture absorption, heat resistance, mechanical properties, and electrical properties, and is characterized by comprising an unsaturated group-containing polyphenylene ether resin and a benzocyclobutene group-containing compound. Divinylsiloxane bisbenzocyclobutene (CYCLOTENE® 3022, manufactured by Dow Chemical) is disclosed as the benzocyclobutene group-containing compound. However, the resin composition obtained by the technology described in Patent Document 1 requires further reduction of the dielectric loss tangent in the high-frequency range.

[0005] Patent Document 2 discloses a polymerizable composition comprising a cycloolefin monomer, a metathesis polymerization catalyst, and 1,3-bis(4-benzocyclobutenyl)-propane as a crosslinking resin suitable for electrical circuit boards and the like, exhibiting low dielectric loss tangent in the high-frequency range and excellent properties such as adhesion and mechanical strength. However, the resin composition obtained by the technology described in Patent Document 2 has two benzocyclobutene crosslinking groups, making it difficult to form a network structure during crosslinking, and thus not sufficient for improving heat resistance. Furthermore, the benzocyclobutene crosslinking group described in Patent Document 2 has the problem of requiring a temperature of 230°C or higher for thermosetting. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 9-194549 [Patent Document 2] Japanese Patent Publication No. 2013-129718 [Overview of the project] [Problems that the invention aims to solve]

[0007] In view of the aforementioned background technology, the present invention aims to provide a compound that undergoes thermosetting at a temperature of 200°C or lower, has low dielectric properties (low dielectric constant, low dielectric loss tangent), and has high dimensional stability, as well as a thermosetting resin composition, film, and laminate that can be used as a dielectric material, insulating material, or heat-resistant material in the field of the electrical and electronics industry. [Means for solving the problem]

[0008] As a result of diligent research to solve the aforementioned problems, the present inventors have discovered that a benzocyclobutene compound having a specific structure, or a thermosetting resin composition, film, and laminate containing the same, undergoes thermosetting at temperatures of 200°C or lower, exhibits excellent low dielectric properties and dimensional stability, and have completed the present invention. That is, the present invention is as follows.

[0009] [1] A compound represented by the following general formula (1).

Chem.

Chem.

Chem.

[10] A laminate comprising the film according to [9]. [Advantages of the Invention]

[0010] According to the present invention, it is possible to provide a compound having excellent low dielectric properties and high dimensional stability, and thus a thermosetting resin composition, a film, and a laminate suitable for electronic components of high-speed communication technologies such as 5G communication can be provided. [Embodiments for Carrying Out the Invention]

[0011] <Definition> In describing the compounds according to one embodiment of the present invention in detail below, unless otherwise specified, the common substructures are assumed to be the following structures.

[0012] [Aromatic group] Aromatic groups include aromatic hydrocarbon groups, aromatic heterocyclic groups, or structures in which multiple rings selected from these are linked together. When multiple aromatic hydrocarbon groups and / or aromatic heterocyclic groups are linked together, structures with 2 to 10 linked groups are common, but structures with 2 to 5 linked groups are particularly preferred. When multiple aromatic hydrocarbon groups and / or aromatic heterocyclic groups are linked together, the same structure may be linked, or different structures may be linked.

[0013] Preferably, the structure consists of multiple aromatic hydrocarbon groups and aromatic heterocyclic groups linked together, and these groups are derived from a phenylpyridine ring, a 2,4,6-triphenyltriazine ring, or a phenylcarbazole ring.

[0014] (Aromatic hydrocarbon group) An aromatic hydrocarbon group refers to a monovalent, divalent, or trivalent or more aromatic hydrocarbon ring structure, depending on the bonding state within the structure of the compound described below. In the structure of an aromatic hydrocarbon ring, the number of carbon atoms is not usually limited, but preferably it is 6 or more and 60 or less, and more preferably 48 or less as the upper limit of the number of carbon atoms, and more preferably 30 or less. Specifically, examples include monocyclic or 2- to 5-fused rings of 6-membered rings such as benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, perylene rings, tetracene rings, pyrene rings, benzpyrene rings, chrysene rings, triphenylene rings, acenaphthene rings, fluorantene rings, and fluorene rings, or structures in which multiple groups selected from these are linked together. When multiple aromatic hydrocarbon rings are linked together, usually a structure with 2 to 10 linked rings is given, and among these, a structure with 2 to 5 linked rings is preferred. When multiple aromatic hydrocarbon rings are linked together, the same structure may be linked, or different structures may be linked. Preferred aromatic hydrocarbon ring structures include benzene rings, biphenyl rings (i.e., a structure in which two benzene rings are linked), terphenyl rings (i.e., a structure in which three benzene rings are linked), quarterphenylene rings (i.e., a structure in which four benzene rings are linked), naphthalene rings, and fluorene rings.

[0015] (Aromatic heterocyclic group) An aromatic heterocyclic group refers to an aromatic heterocyclic structure that is monovalent, divalent, or trivalent or more, depending on the bonding state within the structure of the compound described below. In the structure of an aromatic heterocycle, the number of carbon atoms is not usually limited, but preferably it is 3 to 60 carbon atoms, and more preferably 48 carbon atoms or less, and more preferably 30 carbon atoms or less. Specifically, examples include 5-6 membered monocyclic rings such as furan rings, benzofuran rings, thiophene rings, benzothiophene rings, pyrrole rings, pyrazole rings, imidazole rings, oxadiazole rings, indole rings, carbazole rings, pyrroloimidazole rings, pyrrolopyrrole rings, thienopyrrole rings, thienopyrrole rings, phlopyrrole rings, phlofuran rings, thienofuran rings, benzoisoxazole rings, benzoisothiazole rings, benzimidazole rings, pyridine rings, pyrazine rings, pyridazine rings, pyrimidine rings, triazine rings, quinoline rings, isoquinoline rings, sinnoline rings, quinoxaline rings, phenanthidine rings, benzimidazole rings, perimidine rings, quinazoline rings, quinazolinone rings, azulene rings, etc., or divalent groups of 2-4 fused rings, or groups formed by linking multiple such rings. When multiple aromatic heterocycles are linked together, the same structure may be linked, or different structures may be linked. When multiple aromatic heterocycles are linked together, a structure with 2 to 10 linked rings is typical, and a structure with 2 to 5 linked rings is preferred. Preferred aromatic heterocyclic structures include thiophene rings, benzothiophene rings, pyrimidine rings, triazine rings, carbazole rings, dibenzofuran rings, and dibenzothiophene rings.

[0016] [Substituent] In the following description of the compound structure in this embodiment, unless otherwise specified, a substituent is any group, but preferably a group selected from the substituent group Z below. Furthermore, in the description of the compound structure in this embodiment, if it is stated that the substituents that may be present are selected from substituent group Z, or that it is preferable that the substituents that may be present are selected from substituent group Z, the preferred substituents are also as listed in substituent group Z below.

[0017] (substituent group Z) The substituent group Z consists of alkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, aryloxy groups, heteroaryloxy groups, halogen atoms, haloalkyl groups, aromatic hydrocarbon groups, and aromatic heterocyclic groups. These substituents may include linear, branched, or cyclic structures.

[0018] More specifically, the substituent group Z includes the following structures. The alkyl group can be linear, branched, or cyclic, and usually has 1 or more carbon atoms, preferably 4 or more, with an upper limit of 24 or less, more preferably 12 or less, even more preferably 8 or less, and particularly preferably 6 or less. Specific examples include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-hexyl group, cyclohexyl group, dodecyl group, and the like.

[0019] The alkenyl group can be linear, branched, or cyclic, and typically has two or more carbon atoms, with an upper limit of 24 or less, preferably 12 or less. Specific examples include vinyl groups.

[0020] The alkynyl group is either linear or branched, usually has two or more carbon atoms, and is typically 24 or less, preferably 12 or less. Specific examples include the ethynyl group.

[0021] The alkoxy group typically has 1 to 24 carbon atoms, with a preferably upper limit of 12. Specific examples include methoxy groups and ethoxy groups.

[0022] The aryloxy group and heteroaryloxy group typically have 4 or more carbon atoms, preferably 5 or more, with an upper limit of 36 or fewer carbon atoms, preferably 24 or fewer. Specific examples include phenoxy group, naphthoxy group, and pyridyloxy group.

[0023] Examples of halogen atoms include fluorine atoms and chlorine atoms. Fluorine atoms are preferred.

[0024] The haloalkyl group has 1 to 12 carbon atoms, preferably with an upper limit of 6 carbon atoms. Specific examples include trichloromethyl, trifluoromethyl, pentafluoroethyl, and nonafluorobutyl groups, with fluorine-substituted alkyl groups being particularly preferred, and trifluoromethyl being the most preferred.

[0025] Aromatic hydrocarbon groups typically have 6 to 36 carbon atoms, with a preferred upper limit of 24. Specific examples include phenyl groups, naphthyl groups, and groups formed by linking multiple phenyl groups.

[0026] Aromatic heterocyclic groups typically have 3 or more carbon atoms, preferably 4 or more, with an upper limit of 36 or fewer carbon atoms, preferably 24 or fewer. Specific examples include thienyl groups and pyridyl groups.

[0027] The substituents may include linear, branched, or cyclic structures. If the substituents are adjacent, they may bond to each other to form a ring. Preferred ring sizes are 4-membered, 5-membered, and 6-membered rings, with specific examples being cyclobutane rings, cyclopentane rings, and cyclohexane rings.

[0028] Among the substituent group Z mentioned above, alkyl groups, alkoxy groups, haloalkyl groups, aromatic hydrocarbon groups, and aromatic heterocyclic groups are preferred, and alkyl groups and aromatic hydrocarbon groups are particularly preferred from the viewpoint of improving dielectric properties.

[0029] Furthermore, each substituent of substituent group Z may have further substituents. Examples of these substituents are the same as those of substituent group Z. From the viewpoint of charge transport, it is preferable not to have further substituents, but if further substituents are present, they are preferably alkyl groups having 8 or fewer carbon atoms, alkoxy groups having 8 or fewer carbon atoms, or phenyl groups, more preferably alkyl groups having 6 or fewer carbon atoms, or phenyl groups.

[0030] The present invention will be described below based on examples of embodiments for carrying out the present invention. However, the present invention is not limited to the embodiments described below.

[0031] In this specification, "x and / or y (where x, y are any combination)" means at least one of x and y, and can mean x only, y only, or x and y. In this specification, when "X~Y" (where X and Y are any numbers) is used, unless otherwise specified, it means "X or greater and Y or less," and also includes the meanings of "preferably greater than X" or "preferably less than Y." In this specification, when we use the terms "X or more" (where X is any number) or "Y or less" (where Y is any number), we also mean "preferably greater than X" or "preferably less than Y." In this specification, the numerical ranges described in stages may be arbitrarily combined with the upper or lower limits of the numerical ranges in any stage. Furthermore, in the numerical ranges described herein, the upper or lower limits may be replaced with the values ​​shown in the examples. In this specification, the total solids content of a composition refers to all components other than the solvent contained in the composition, and components other than the solvent are included in the solids content even if they are liquid at room temperature (23°C).

[0032] The compound according to one embodiment of the present invention (hereinafter sometimes referred to as "the compound") is the following compound.

[0033] <Compounds represented by general formula (1)> [ka] (In formula (1), G represents an optionally substituted aromatic hydrocarbon group having 6 to 60 carbon atoms, an optionally substituted aromatic heterocyclic group having 3 to 60 carbon atoms, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted carbon atom.) A is expressed by the following general formula (2): The subscript x represents an integer between 1 and 10. When x is 2 or greater, multiple A's may be the same or different from one another. [ka] (In formula (2), L 21 Each of these independently represents a bonded group that is directly bonded or may have a substituent. CL 21 Each of these independently represents a bridging group represented by the following general formula (3): The symbol * represents the bond with G in equation (1), The subscript y represents an integer from 0 to 6. The subscript z represents an integer from 1 to 4. However, if the compound represented by general formula (1) contains CL 21 There are at least two of them.

[0034] (L 21 ) Bonding group L 21 This is a chalcogen atom, an alkyl group, or an aromatic group. Specifically, examples of chalcogen atoms include oxygen atoms and sulfur atoms, with oxygen atoms being preferred. The alkyl group can be linear, branched, or cyclic, with one or more carbon atoms, preferably four or more, and an upper limit of 24 or less, preferably 12 or less, more preferably 8 or less, and even more preferably 6 or less. Specific examples include divalent groups derived from methane, ethane, propane, butane, isobutane, hexane, cyclohexane, and dodecane. Aromatic groups include aromatic hydrocarbon groups and aromatic heterocyclic groups, with aromatic hydrocarbon groups being preferred. Specific examples include divalent groups derived from benzene rings, biphenyl rings, terphenyl rings, and fluorene rings.

[0035] (CL 21 ) CL 21 This is a structure represented by general formula (3). [ka] (In formula (3), Ar 1 This represents an aromatic ring having 3 to 30 carbon atoms, which may have substituents. Ar 2 This represents an aromatic ring group having 6 to 60 carbon atoms, which may have substituents, or an aromatic heterocyclic group having 3 to 60 carbon atoms, which may have substituents. X represents an oxygen atom or a sulfur atom. R 31 This represents a hydrogen atom or an alkyl group. The subscript α represents an integer from 1 to 4. The symbol * represents L in equation (2). 21 This represents the bond with L in equation (2). 21 The coupling with is Ar 1 Or Ar 2 (To be joined.)

[0036] (Ar 1 ) Ar 1 represents an aromatic ring having 3 to 30 carbon atoms, which may have substituents. The aromatic ring having 3 to 30 carbon atoms is preferably a monocyclic or fused ring of the aromatic hydrocarbon ring, or a monocyclic or fused ring of the aromatic heterocyclic ring. More preferably an aromatic hydrocarbon ring, even more preferably a benzene ring or a naphthalene ring, and most preferably a benzene ring.

[0037] Regarding (X) X represents an oxygen atom or a sulfur atom. X is preferably an oxygen atom.

[0038] (Regarding subscript x) In general formula (1), the subscript x is an integer between 1 and 10. However, if the compound contains CL 21 There are at least two of them. CL 21 However, the presence of two or more elements in the compound forms a network structure during the crosslinking reaction, resulting in a composition, laminate, or cured film with excellent thermal stability. From the viewpoint of thermal stability, the subscript x is preferably 2 or more, and more preferably 3 or more. On the other hand, from the viewpoint of compound stability, the subscript x is preferably 7 or less, more preferably 6 or less, even more preferably 5 or less, and most preferably 4 or less.

[0039] (Regarding the subscript y) In general formula (2), the subscript y is an independent integer between 0 and 6. From the viewpoint of improving thermal properties, it is preferable that the subscript y is an integer between 0 and 3.

[0040] (Regarding the subscript z) In general formula (2), the subscript z is an integer between 1 and 4. From the viewpoint of thermal stability, it is preferable that the subscript z is an integer between 1 and 2.

[0041] (Subscript α) In general formula (3), the subscript α is an integer between 1 and 4. From the viewpoint of thermal stability, it is preferable that the subscript α is an integer between 1 and 2.

[0042] The specific structure of this compound is not particularly limited, but examples include the following compounds.

[0043] [ka] TIFF2026100207000008.tif56170 TIFF2026100207000009.tif38170 TIFF2026100207000010.tif33170 TIFF2026100207000011.tif48170 [ka] TIFF2026100207000013.tif41170 TIFF2026100207000014.tif41170 TIFF2026100207000015.tif56170 TIFF2026100207000016.tif56170

[0044] <Thermosetting resin composition> Next, a thermosetting resin composition according to a second embodiment of the present invention (hereinafter sometimes referred to as "the resin composition") will be described. This resin composition refers to a resin composition containing a resin and this compound, and this compound can be used as a crosslinking agent for thermosetting resin compositions. The resin can be an appropriate material depending on the application of this resin composition.

[0045] [Content of this compound] The amount of the compound represented by formula (1) contained in this resin composition is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more, relative to the total solid content of the resin composition. The upper limit is usually 90% by mass or less, preferably 80% by mass or less, and more preferably 75% by mass or less, and the upper and lower limits are, for example, 1 to 90% by mass, 5 to 80% by mass, 10 to 75% by mass, etc. By including an amount above the lower limit, it is expected that the thermosetting resin composition will cure sufficiently. It is believed that by setting the amount within this range, a resin composition that fully utilizes the properties of the resin can be obtained.

[0046] From the viewpoint of achieving both dielectric properties and dimensional stability of the cured film of this resin composition, the content of the compound represented by formula (1) is preferably 5 to 40% by mass, more preferably 10 to 30% by mass, and even more preferably 10 to 25% by mass.

[0047] [resin] Examples of resins include polyolefins and their derivatives such as polyethylene, polypropylene, polystyrene, and ethylene-propylene copolymers; rubbers such as styrene-conjugated diene block copolymers; rubbers such as hydrogenated styrene-conjugated diene block copolymers; rubbers such as polybutadiene and polyisoprene; and heat-resistant resins such as polyimide precursors or polybenxazole precursors. These resins can be used individually or in combination of two or more. Among these resins, it is preferable to use or combine block copolymers having polymer segments with a glass transition temperature of 20°C or lower in order to increase the toughness of the cured film, and it is more preferable to use block copolymers having polymer segments with a glass transition temperature of 0°C or lower. Preferred examples of block copolymers having polymer segments with a glass transition temperature of 20°C or lower include rubbers such as styrene-conjugated diene block copolymers, or rubbers such as hydrogenated styrene-conjugated diene block copolymers. Among these, styrene-ethylene-butarene-styrene block copolymers are more preferred. Furthermore, the molecular structure of the block copolymer may be linear, branched, radial, or any combination thereof.

[0048] ~Number average molecular weight of resins~ The number-average molecular weight Mn of the block copolymer described above is not particularly limited, but is often in the range of 5,000 to 1,000,000, preferably 10,000 to 500,000, and more preferably 30,000 to 300,000.

[0049] ~Resin content~ The resin content is preferably 20% by mass or more, preferably 95% by mass or less, and more preferably 90% by mass or less, relative to the total solid content of the resin composition. For example, it is preferably 20 to 95% by mass, and more preferably 20 to 90% by mass, relative to the total solid content of the resin composition. Furthermore, from the viewpoint of dielectric properties, it is preferably 60 to 90% by mass, more preferably 70 to 90% by mass, relative to the total solid content of the resin composition, and even more preferably 75 to 90% by mass, from the viewpoint of adhesion and mechanical properties.

[0050] [Polymerization initiator] A thermosetting resin composition using this compound as a crosslinking agent may also contain a polymerization initiator. Examples of polymerization initiators include organic peroxides such as hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyesters, and ketone peroxides. More specifically, examples include hydroperoxides such as cumene hydroperoxide and t-butyl hydroperoxide; dialkylperoxides such as dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, and 2,5-bis(t-butylperoxy)-2,5-dimethyl-3-hexine; diacylperoxides such as lauryl peroxide and benzoyl peroxide; peroxyesters such as t-butyl peroxyacetate, t-butyl peroxybenzoate, and t-butyl peroxyisopropyl carbonate; and ketone peroxides such as cyclohexanone peroxide. These can be used individually or in combination of two or more types.

[0051] ~Polymerization initiator content~ If the resin composition contains a polymerization initiator, the content of the polymerization initiator is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and even more preferably 1% by mass or more, relative to the total solid content of the resin composition, in terms of promoting the curing reaction. Polymerization initiators contain many heteroatoms in their structure, and it is believed that an increase in their content will worsen the dielectric properties. Therefore, the content of polymerization initiators is preferably 5% by mass or less, more preferably 3% by mass or less, even more preferably 1% by mass or less, and most preferably 0.1% by mass or less, relative to the total solid content of the resin composition, in order to maintain low dielectric properties. It is most preferable that they are substantially absent. Furthermore, the phrase "substantially does not contain" means that it is not intentionally contained, and specifically, it means that the polymerization initiator content is 0% by mass or more and 0.05% by mass or less, more preferably 0% by mass or more and 0.01% by mass or less.

[0052] [Other ingredients] In addition to this compound and the resin, the resin composition may optionally contain adhesion-enhancing agents such as silane coupling agents, plasticizers, flame retardants, solvents, etc., which can be used individually or in combination of two or more.

[0053] <Membrane> Next, a film according to the third embodiment of the present invention (hereinafter sometimes referred to as "the cured film") will be described. The cured film refers to a film formed by curing the thermosetting resin composition, and is not particularly limited as long as it is formed by curing the thermosetting resin composition, but the following methods are examples of how it can be produced.

[0054] <Method for fabricating the membrane> The method for producing the cured film includes a coating liquid preparation step of preparing a coating liquid consisting of the thermosetting resin composition described above, and a molding step of forming the coating liquid into a film.

[0055] (1) Coating solution preparation process In the coating solution preparation process, the resin, the compound, and any additional solvents, as needed, are stirred and uniformly mixed to obtain the coating solution. For mixing, general mixing and stirring equipment such as mixers, blenders, three-roll kneaders, ball mills, kneaders, and single-screw or twin-screw kneaders can be used, and heating may be applied during mixing as needed.

[0056] (2) Molding process In the molding process, the above coating liquid is formed into a film to obtain a film. A known method can be used to form the above coating liquid into a film. For example, methods such as the doctor blade method, solvent casting method, or extrusion film formation method may be used. A preferred forming method is one that includes the following steps: (2-1) coating step, (2-2) drying step, and (2-3) curing step.

[0057] (2-1) Coating process In the coating process, a coating solution is applied to the surface of the release film to form a coating film. The coating method may be a general method such as the dip method, spin coating method, spray coating method, or blade method. For coating, coating equipment such as a spin coater, slit coater, die coater, or blade coater can be used, which makes it possible to uniformly form a coating film of a predetermined thickness on the release film.

[0058] (2-2) Drying process In the drying process, the solvent is removed from the coating film formed above. The drying temperature is not particularly limited, but is usually 10°C to 150°C, preferably 25°C to 120°C, and more preferably 30°C to 110°C. A drying temperature below the upper limit suppresses the crosslinking reaction of the compound in the coating film. Furthermore, a drying temperature above the lower limit suppresses foaming of the resin film, effectively removing the solvent and improving productivity. The drying time can be adjusted as appropriate depending on the condition of the coating film, the drying environment, etc. Preferably, it is 1 minute or more, more preferably 2 minutes or more, even more preferably 5 minutes or more, even more preferably 10 minutes or more, particularly preferably 20 minutes or more, and most preferably 30 minutes or more. On the other hand, preferably it is 4 hours or less, more preferably 3 hours or less, and even more preferably 2 hours or less. If the drying time is above the lower limit, the solvent can be sufficiently removed. If the drying time is below the upper limit, productivity can be improved and manufacturing costs can be suppressed. Solvents in the resin composition can be removed by known heating methods such as hot plates, hot air furnaces, IR heating furnaces, vacuum dryers, and high-frequency heaters.

[0059] Furthermore, from the viewpoint of preventing contamination of the film surface and improving handling, a release film may be laminated on top of the film after the drying process described above.

[0060] (2-3) Curing process In the curing process, the film formed above is heated and cured. The curing temperature should be such that the resin does not flow and the crosslinking reaction of the compound proceeds. Specifically, it is usually 80°C or higher, preferably 120°C or higher, more preferably 150°C or higher, and even more preferably 180°C or higher, as this accelerates the crosslinking rate. Furthermore, from the viewpoint of suppressing resin decomposition, the temperature is usually 350°C or lower, preferably 310°C or lower, more preferably 300°C or lower, and even more preferably 270°C or lower. The curing time is not particularly limited, but is usually 5 minutes or more, and from the viewpoint of increasing hardness, it is 10 minutes or more, preferably 20 minutes or more, and more preferably 30 minutes or more. Also, in order to suppress the decomposition of the resin, it is usually 3 hours or less, preferably 2 hours or less, and more preferably 1 hour or less.

[0061] <Dielectric loss tangent> This cured film has a dielectric loss tangent of 1 × 10⁻¹⁰ at 10 GHz. -3 Preferably less than 0.9 × 10 -3 More preferably, 0.7 × 10 -3 The following is true: The dielectric loss tangent is 1 × 10⁻⁶. -3 If it is less than 28 GHz, the delay in communication speed in the high frequency band above 28 GHz tends to be suppressed. There is no particular limit to the lower limit of the dielectric loss tangent, but a lower dielectric loss tangent is preferable, usually 1 × 10⁻⁶. -4 That is all. The upper and lower limits are 1 × 10 -4 The above 1 x 10 -3 It is less than.

[0062] <Relative permittivity> The cured film preferably has a relative permittivity of 3.5 or less at 10 GHz, more preferably 3.0 or less, and even more preferably 2.5 or less. A relative permittivity within this range tends to exhibit superior transmission loss. While there are no particular restrictions on the lower limit of the relative permittivity, a lower value is preferable, typically 1.6 or higher, with an upper and lower limit range of 1.6 to 3.5.

[0063] <Coefficient of linear expansion> The cured film preferably has a coefficient of thermal expansion of 350 ppm / K or less, more preferably 300 ppm / K or less, even more preferably 280 ppm / K or less, particularly preferably 250 ppm / K or less, and especially preferably 200 ppm / K or less. There is no particular limit to the lower limit of the coefficient of thermal expansion, but a lower coefficient of thermal expansion is preferable, usually 0 ppm / K, and the upper and lower limits are in the range of 0 to 350 ppm / K.

[0064] Because this cured film contains the compound in the resin composition before curing, it has low dielectric properties and can achieve high dimensional stability. Furthermore, even when using a block copolymer having polymer segments with a glass transition temperature of 20°C or less, a high glass transition temperature can be achieved by mixing and curing with this compound. As a result, films made using this resin composition are particularly suitable as insulating films for high-speed communication modules.

[0065] In this specification, a high-speed communication module refers to a circuit board for transmitting signals with a frequency of 1 GHz or higher. Examples of high-speed communication modules include high-frequency circuit boards or semiconductor packages that integrate an antenna and an IC chip. Furthermore, preferably the frequency of the transmission signal is 3 GHz or higher, more preferably 5 GHz or higher, even more preferably 8 GHz or higher, and particularly preferably 10 GHz or higher. There are no particular restrictions on the frequency of the transmission signal, but it is preferably 400 GHz or less, and more preferably 300 GHz or less. In this embodiment, the upper and lower limits of the frequency can be arbitrarily combined. [Examples]

[0066] The present invention will be described in detail below based on examples, but the present invention is not limited to these examples.

[0067] <Synthesis of Compound A> [ka]

[0068] Under a nitrogen atmosphere, 1,1,1-tris(4-hydroxyphenyl)ethane (11.8 g, 38.5 mmol) and potassium carbonate (79.8 g, 577.8 mmol) were mixed with N,N-dimethylformamide (150 mL). Then, 1-bromobenzocyclobutene (42.3 g, 231.0 mmol) dissolved in N,N-dimethylformamide (50 mL) was added, and the mixture was stirred at 70°C for 6 hours. Desalted water was added, and extraction was performed using ethyl acetate. The organic layer was washed with saturated sodium chloride aqueous solution, dried over magnesium sulfate, and the solvent was removed under reduced pressure. The residue was subjected to silica gel column chromatography to obtain compound A (yield 17.0 g, yield 72% by mass).

[0069] <Synthesis of Compound B> [Synthesis of Intermediate B-1] [ka]

[0070] A solution of 1,1,1-tris(4-hydroxyphenyl)ethane (93.1 g, 303.9 mmol) and triethylamine (161.4 g, 1.60 mol) in methylene chloride (1400 mL) was cooled to -40°C, and a solution of trifluoromethanesulfonic anhydride (308.7 g, 1.09 mol) in methylene chloride (300 mL) was added dropwise. After the addition was complete, the temperature was raised to room temperature (23°C) and the mixture was stirred for 12 hours. Under ice cooling, 2N hydrochloric acid (1000 mL) was added dropwise, and after separating the oil layer, the aqueous layer was extracted with methylene chloride. The organic and aqueous layers were combined, washed with purified water, saturated sodium bicarbonate solution, and saturated sodium chloride solution, dried over magnesium sulfate, and the solvent was removed under reduced pressure. The residue was suspended and washed with methanol, and intermediate B-1 (yield 190.7 g, yield 89%) was collected by filtration.

[0071] [Synthesis of Compound B] [ka]

[0072] Under an argon stream, intermediate B-1 (188.4 g, 268.2 mmol) and benzocyclobutene-4-ylboronic acid (166.7 g, 1.13 mol) were dissolved in dimethoxyethane (3770 mL) to which 1010 mL of 2 M potassium carbonate aqueous solution was added. The mixture was degassed by argon bubbling and tetrakis(triphenylphosphine)palladium [Pd(PPh3)4] (27.9 g, 24.1 mmol) was added. The mixture was stirred under reflux for 8 hours and 30 minutes. After cooling to room temperature, it was extracted with toluene, the organic layer was washed with purified water, dried over anhydrous sodium sulfate, and filtered. The filtrate was concentrated under reduced pressure, and the residue was subjected to silica gel column chromatography to obtain compound B (yield 116.5 g, yield 77%).

[0073] <Synthesis of Compound C> [Synthesis of intermediate C-1] [ka]

[0074] In a flask, 13.2 g (66.41 mmol) of 4-bromoacetophenone, 75.0 g (796.94 mmol) of phenol, and 85 mL of acetic acid were added under a nitrogen stream and stirred at room temperature. 240 mL of hydrochloric acid (12 M) was added, and the mixture was heated under reflux at 90°C for 24 hours. After the reaction, the reaction mixture was poured into hot water, the insoluble matter was collected and dissolved in ethyl acetate, then extracted with ethyl acetate and separated. After drying over magnesium sulfate, the mixture was concentrated. Further purification by silica gel column chromatography (hexane:ethyl acetate = 4:1) yielded intermediate C-1 (11.73 g).

[0075] [Synthesis of intermediate C-2] [ka]

[0076] In a flask, intermediate C-1 (11.73 g, 31.77 mmol), compound 1 (8.05 g, 34.94 mmol), and 200 mL of 1,2-dimethoxyethane were placed under a nitrogen stream and stirred at room temperature. 75 mL of 2 M potassium carbonate aqueous solution was added, and nitrogen bubbling was performed at room temperature for 30 minutes. Next, tetrakis(triphenylphosphine)palladium (0.75 g, 0.65 mmol) was added, and the mixture was heated under nitrogen and refluxed for 5 hours. After cooling, the solution was extracted with ethyl acetate, separated, dried over magnesium sulfate, and concentrated. Further purification by silica gel column chromatography (hexane:ethyl acetate = 3:1) yielded intermediate C-2 (10.8 g).

[0077] [Synthesis of intermediate C-3] [ka]

[0078] At -5°C, intermediate C-2 (14.8 g, 37.71 mmol) was dissolved in methylene chloride (250 mL) and 19.0 g (188.5 mmol) of triethylamine. 31.9 g (113.13 mmol) of trifluoromethanesulfonic anhydride was dissolved in 70 mL of methylene chloride and slowly added dropwise. The reaction was completed after 4 hours. The reaction mixture was poured into ice water, extracted with methylene chloride, separated, dried over magnesium sulfate, and concentrated. Further purification by silica gel column chromatography (hexane:methylene chloride = 3:1) yielded intermediate C-3 (19.5 g).

[0079] [Synthesis of intermediate C-4] [ka]

[0080] Under a nitrogen atmosphere, 200 mL of dimethyl sulfoxide, intermediate C-3 (19.5 g, 29.70 mmol), bis(pinacolato)diborone (18.1 g, 71.28 mmol), and potassium acetate (17.5 g, 178.2 mmol) were added to a 500 mL flask and stirred at 60 °C for 30 minutes. Then, 1,1'-bis(diphenylphosphino)ferrocene-palladium(II) dichloride-dichloromethane [PdCl2(dppf)CH2Cl2] (1.2 g, 1.49 mmol) was added and the mixture was reacted at 85 °C for 4 hours. The reaction mixture was filtered under reduced pressure, the filtrate was extracted with toluene, dried over anhydrous magnesium sulfate, filtered, and the resulting solution was concentrated and beaten with methanol to obtain intermediate C-4 as a colorless solid (yield 15.0 g, yield 82.5%).

[0081] [Synthesis of intermediate C-5] [ka]

[0082] Under a nitrogen atmosphere, 300 mL of toluene, 100 mL of ethanol, intermediate C-4 (15.0 g, 24.49 mmol), 1-bromo-4-iodobenzene (14.5 g, 51.43 mmol), and 100 mL of aqueous potassium phosphate solution (2 M, i.e., 2 mol / L concentration) were added to a 1000 mL flask and heated, stirring for 30 minutes. Then, tetrakis(triphenylphosphine)palladium [Pd(PPh3)4] (0.57 g, 0.49 mmol) was added and refluxed for 5 hours. Water was added to the reaction mixture, extracted with toluene, and treated with anhydrous magnesium sulfate and activated clay. Purification by adsorption silica gel column chromatography (eluent: n-hexane:methylene chloride = 4:1) yielded a colorless solid intermediate C-5 (yield 4.8 g, yield 29.2%).

[0083] [Synthesis of compound C] [ka]

[0084] Under a nitrogen atmosphere, 100 mL of toluene, 50 mL of ethanol, intermediate C-5 (10.15 g, 15.14 mmol), phenylboronic acid (5.54 g, 45.41 mmol), and 46 mL of potassium phosphate aqueous solution (2 M, i.e., 2 mol / L concentration) were added to a 500 mL flask and heated, stirring for 30 minutes. Then, tetrakis(triphenylphosphine)palladium [Pd(PPh3)4] (0.87 g, 0.76 mmol) was added and the mixture was reacted at 90°C for 2 hours. 50 mL of water and 50 mL of ethanol were added to the reaction mixture, and the precipitate was filtered under reduced pressure. The filter material was dissolved in methylene chloride and treated with activated clay. Further filtering under reduced pressure was performed, the filtrate was concentrated, and the filter material was washed with 100 mL of methanol and 100 mL of ethanol, and filtered under reduced pressure. The filter material was dried to obtain compound C as a colorless solid (yield 8.9 g, yield 88.4%).

[0085] <Synthesis of Compound D> [ka]

[0086] Under a nitrogen atmosphere, 1,6-dibromohexane (464 mg, 1.90 mmol), 4-hydroxybenzocyclobutene (458 mg, 3.81 mmol), and 4.6 mL of N-methylpyrrolidone (NMP) were added to a 20 mL Schlenk tube and stirred. Then, anhydrous potassium carbonate (1.314 g, 9.50 mmol) was added and the mixture was stirred at 120 °C for 3 hours and 40 minutes. After cooling to room temperature, 4-hydroxybenzocyclobutene (114 mg, 0.951 mmol) was added and the mixture was stirred at 120 °C for 20 hours. After cooling the reaction mixture to room temperature, it was poured into 14 mL of water, and the precipitate was filtered under reduced pressure. 8 mL of dichloromethane was dissolved in the filter, and anhydrous Glauber's salt (approximately several hundred mg) was added. The mixture was filtered under reduced pressure and washed with 8 mL of dichloromethane. The resulting filtrate was slowly added dropwise to 64 mL of methanol, and the precipitate was filtered under reduced pressure. The filter extract was washed with 30 mL of methanol. The filter extract was dried to obtain compound D as a pale yellow solid (yield 476 mg, yield 78%).

[0087] <Crosslinking start temperature> Differential scanning calorimetry (DSC, under atmospheric conditions, heating rate 10°C / min) was performed on compound A of Example 1 using a Shimadzu DSC-50. Exothermic reaction associated with the crosslinking reaction was observed, and the peak rise temperature, which is the crosslinking initiation temperature, was 153°C. Similarly, differential scanning calorimetry was performed on compound B of the comparative example, and exothermic reaction associated with the crosslinking reaction was observed, with the peak rise temperature for compound B being 229°C. Compound A, which corresponds to this compound, shows a crosslinking initiation temperature of 200°C or lower, indicating that thermosetting proceeds at temperatures below 200°C.

[0088] [Table 1]

[0089] In the following examples and comparative examples, the following resins were used. a-1: Styrene-ethylene-butane-styrene block copolymer (SEBS: manufactured by Asahi Kasei Corporation, "ToughTec H1052", glass transition temperature of polymer segment = -45°C, number average molecular weight (Mn) = 66,000)

[0090] [Example 1] The raw materials were mixed in the proportions shown in Table 2 and heated to approximately 80°C to completely dissolve the raw materials and prepare a resin composition. The prepared resin composition was spread in a sheet-like manner onto the release surface of a 50 μm thick release film A (PET film manufactured by Mitsubishi Chemical Corporation) that had been silicone-released, to obtain a resin sheet. The thickness of the resin sheet was adjusted so that the thickness of the sheet after curing would be approximately 300 μm. After drying a resin sheet spread on release film A in a 100°C oven for 1 hour, a 75 μm thick release film B (manufactured by Chukoh Chemical Industries, Ltd., processed Chukoh Flow G type) was laminated on top of the resin sheet. After removing release film A, release film B was laminated onto the resin sheet to form a laminate with release film B laminated on both sides. This laminate was held in a 250°C hot press at a pressure of approximately 0.2 MPa for 30 minutes to completely cure the resin sheet, and then the release films B on both sides were peeled off to obtain a cured sheet (cured film). The dielectric properties of the obtained cured sheet (cured film) were measured using the measurement method shown below. The results are shown in Table 2.

[0091] [Example 2, Comparative Examples 1-4] Sheet cured products (cured films) were prepared in the same manner as in Example 1, except that the raw materials were blended according to the proportions shown in Table 2. The dielectric properties of the obtained sheet cured products (cured films) were measured using the measurement method shown below. The results are shown in Table 2.

[0092] (1) Dielectric properties The relative permittivity and dielectric loss tangent in the in-plane direction of the sheet cured material (cured film) were measured in TE mode using a cavity resonator (AET) and a network analyzer MS46122B (Anritsu) at a measurement frequency of 10 GHz. Dielectric properties were evaluated according to the following criteria. A: Dielectric loss tangent is less than 0.001 B: Dielectric loss tangent is 0.001 or greater

[0093] [Table 2]

[0094] For Examples 1 and 2 and Comparative Examples 1 to 3, where the dielectric properties were "A", the coefficient of linear expansion was measured using the measurement method described below. The results are shown in Table 3.

[0095] (2) Coefficient of linear expansion The dimensional changes of the sheet cured material (cured film) were measured using a thermomechanical analyzer (Hitachi High-Tech Science Corporation, TMA7100) under the following conditions. From the measurement results, the average value of the dimensional change rate in the 3rd Step from 0 to 120°C was used as the linear expansion coefficient of each sheet cured material (cured film). Furthermore, the linear expansion coefficient was evaluated according to the following criteria. (Measurement conditions) Measurement mode: Tensile mode Atmosphere: 200 mL / min nitrogen flow Heating rate: 5°C / min Measurement temperature: 1st Step: 0~100℃ 2nd Step: 100~0℃ 3rd step: 0~120℃ (standard) A: Coefficient of linear expansion is 300 ppm / K or less B: Coefficient of linear expansion exceeds 300 ppm / K

[0096] [Table 3]

[0097] The results in Tables 2 and 3 show that the example product using this compound exhibited excellent low dielectric properties and high dimensional stability. In contrast, comparative examples similar to this compound but lacking a specific skeleton either had inferior dielectric properties or, even if they exhibited excellent dielectric properties, had a large coefficient of thermal expansion and poor dimensional stability. [Industrial applicability]

[0098] The compounds of the present invention undergo thermal curing at temperatures below 200°C, and the resin compositions, films, and laminates obtained using them exhibit excellent low dielectric properties and dimensional stability, making them suitable for use in electronic components for high-speed communication technologies such as 5G communication.

Claims

1. A compound represented by the following general formula (1). 【Chemistry 1】 (In formula (1), G represents an optionally substituted aromatic hydrocarbon group having 6 to 60 carbon atoms, an optionally substituted aromatic heterocyclic group having 3 to 60 carbon atoms, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted carbon atom.) A is expressed by the following general formula (2): The subscript x represents an integer between 1 and 10. When x is 2 or greater, multiple A's may be identical or distinct from one another. 【Chemistry 2】 (In formula (2), L ２１ Each of these independently represents a bonded group that is directly bonded or may have a substituent. CL ２１ Each of these independently represents a bridging group represented by the following general formula (3): The symbol * represents the bond with G in equation (1), The subscript y represents an integer from 0 to 6. The subscript z represents an integer from 1 to 4. However, if the compound represented by general formula (1) contains Cl ２１ There are at least two of them. 【Transformation 3】 (In formula (3), Ar １ This represents an aromatic ring having 3 to 30 carbon atoms, which may have substituents. Ar ２ This represents an aromatic ring group having 6 to 60 carbon atoms, which may have substituents, or an aromatic heterocyclic group having 3 to 60 carbon atoms, which may have substituents. X represents an oxygen atom or a sulfur atom, R ３１ This represents a hydrogen atom or an alkyl group. The subscript α represents an integer from 1 to 4. The symbol * represents the bond with L in formula (2), and the bond with L in formula (2) is bonded to Ar ２１ or Ar ２１ . １ or Ar ２ .)

2. In formula (2), L ２１ The compound according to claim 1, wherein the compound is a chalcogen atom, an alkyl group, or an aromatic group.

3. The compound according to claim 1, wherein X is an oxygen atom in formula (3).

4. In formula (3), Ar ２ The compound according to claim 1, wherein is a phenyl group.

5. The compound according to claim 1, wherein the subscript z in formula (2) is 1 to 2.

6. A thermosetting resin composition comprising a resin and a compound according to any one of claims 1 to 5, wherein the content of the compound is 1% by mass or more.

7. The thermosetting resin composition according to claim 6, wherein the resin is a block copolymer having polymer segments with a glass transition temperature of 20°C or lower.

8. A thermosetting resin composition according to claim 6, which is substantially free of polymerization initiators.

9. A film obtained by curing the thermosetting resin composition described in claim 6.

10. A laminate comprising the film described in claim 9.

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