Compound and thermosetting resin composition

Abstract

To provide a compound which enables production of a thermosetting resin composition that has low dielectric characteristics (low dielectric constant and low dielectric loss tangent), and high dimensional stability, and a thermosetting resin composition containing the compound.SOLUTION: A compound is represented by the following general formula (1). In the general formula (1), A is a substituent represented by the following general formula (2), and x is 0 to 2. In the general formula (2), L21 is a bonding group, CL21 is a crosslinking group, y is 1 to 6, and z is 0 to 4. Three or more CL21 exists in the compound represented by the general formula (1).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention provides a dielectric material having a low dielectric tangent, a high glass transition temperature, and high dimensional stability even in the high frequency range. The present invention relates to a compound capable of providing a thermosetting resin composition exhibiting qualitative properties, and a thermosetting resin composition containing the compound. [Background technology]

[0002] In recent years, with the dramatic increase in the volume of information and communication, there has been a demand for faster communication speeds than conventional levels, which has led to an unavoidable shift to fifth-generation communication (5G) using frequencies above 3 GHz, or to communication in the ultra-high frequency bands from the quasi-millimeter wave band (20 GHz to 30 GHz) to the millimeter wave band (30 GHz or higher), where it is easier to secure wider frequency bandwidths.

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

[0004] For example, Patent Document 1 discloses a thermosetting resin characterized by comprising an unsaturated group-containing polyphenylene ether resin and a benzocyclobutene group-containing compound as components, as a thermosetting resin that is excellent in low moisture absorption, heat resistance, mechanical properties, electrical properties, etc. and is suitable for sealing and fixing processes for electric and electronic components. Divinylsiloxane bisbenzocyclobutene (CYCLOTENE® 3022, manufactured by The Dow Chemical Company) is disclosed as the benzocyclobutene group-containing compound. However, the resin composition obtained by the technology described in Patent Document 1 does not have a sufficient dielectric loss tangent in the high frequency range, and further reduction in the dielectric loss tangent is desired.

[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 crosslinked resin that has a small dielectric loss tangent in the high frequency range and excellent properties such as adhesion and mechanical strength, making it suitable for electric circuit boards, etc. However, the resin composition obtained by the technique described in Patent Document 2 has two benzocyclobutene crosslinking groups, making it difficult to form a network structure during crosslinking, and therefore does not sufficiently improve heat resistance. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 9-194549 [Patent Document 2] Japanese Patent Application Laid-Open No. 2013-129718 Summary of the Invention [Problem to be solved by the invention]

[0007] In view of the above background art, an object of the present invention is to provide a compound capable of providing a thermosetting resin composition having low dielectric properties (low dielectric constant, low dielectric dissipation factor) and high dimensional stability, and a thermosetting resin composition containing this compound that can be suitably 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 intensive research to solve the above problems, the present inventors have found that by using (A) a benzocyclobutene compound having a specific structure, a thermosetting resin composition having low dielectric properties and excellent dimensional stability can be obtained, 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):

[0010] [ka]

[0011] (In formula (1), C represents a carbon atom, H represents a hydrogen atom, each A independently represents a substituent represented by the following general formula (2), and the subscript x represents an integer of 0 to 2.)

[0012] [ka]

[0013] (In formula (2), L 21 each independently represents a bonding group which may have a substituent, CL 21 are each independently a bridging group represented by the following general formula (3), the symbol * represents a bond to a carbon atom in formula (1), the subscript y is an integer of 1 to 6, the subscript z is an integer of 0 to 4, provided that when z is 0, the bonding group L 21 CL 21 In place of , a hydrogen atom is bonded. In addition, in the compound represented by general formula (1), 21 There are three or more.)

[0014] [ka]

[0015] In formula (3), Arom represents an aromatic ring having 3 to 30 carbon atoms which may have a substituent, and R 31 , R 32 each independently represents a hydrogen atom or an alkyl group, and the symbol * represents L in formula (2). 21 represents a bond with, and the bond with formula (2) bonds to Arom.)

[0016] [2] Bonding group L 21 is an oxygen atom, a sulfur atom, an alkylene group, or an aromatic group.

[0017] [3] The compound according to [1] or [2], wherein the subscript z is 0 to 2.

[0018] [4] A composition containing a resin and a compound according to any one of [1] to [3], wherein the thermosetting resin composition contains 1 part by mass or more of the compound according to any one of [1] to [3] per 100 parts by mass of the resin.

[0019] [5] The thermosetting resin composition according to [4], wherein the resin is a block copolymer having a polymer segment with a glass transition temperature of 20°C or less.

[0020] [6] The thermosetting resin composition according to [4] or [5], which is substantially free of a polymerization initiator or contains a polymerization initiator in an amount of 5 parts by mass or less per 100 parts by mass of the resin. [Effects of the Invention]

[0021] The compound of the present invention can provide a thermosetting resin composition having excellent low dielectric properties and high dimensional stability. The thermosetting resin composition of the present invention containing the compound of the present invention can provide a laminate and a cured product suitable for electronic components of high-speed communication technologies such as 5G communication due to its excellent low dielectric properties and high dimensional stability. DETAILED DESCRIPTION OF THE INVENTION

[0022] The present invention will be described in detail below. However, the following description is an example of an embodiment of the present invention, and the present invention is not limited to the following description as long as it does not deviate from the gist of the present invention. In the following, when the expression "~" is used, it is used to include the numerical values ​​or physical property values ​​before and after it.

[0023] [Compound] The compound of the present invention is a compound represented by the following general formula (1) (hereinafter, sometimes referred to as "compound (1)").

[0024] [ka]

[0025] (In formula (1), C represents a carbon atom, H represents a hydrogen atom, each A independently represents a substituent represented by the following general formula (2) (hereinafter, sometimes referred to as "substituent (2)"), and the subscript x represents an integer of 0 to 2.)

[0026] [ka]

[0027] (In formula (2), L 21 each independently represents a bonding group which may have a substituent, CL 21 are each independently a bridging group represented by the following general formula (3) (hereinafter, sometimes referred to as "bridging group (3)" or "benzocyclobutene bridging group"); the symbol * represents a bond to a carbon atom in formula (1); the subscript y is an integer of 1 to 6; the subscript z is an integer of 0 to 4; provided that when z is 0, the bonding group L 21 CL 21 In place of , a hydrogen atom is bonded. In addition, in the compound represented by general formula (1), 21 There are three or more.)

[0028] [ka]

[0029] In formula (3), Arom represents an aromatic ring having 3 to 30 carbon atoms which may have a substituent, and R 31 , R 32 each independently represents a hydrogen atom or an alkyl group, and the symbol * represents L in formula (2). 21 represents a bond with, and the bond with formula (2) bonds to Arom.)

[0030] In addition, x in the general formula (1) is 2, and two L 21 , C.L. 21 , y and z exist, two L 21 , C.L. 21 , y and z may be the same or different numbers.

[0031] <Definition> In the detailed description of the compound (1) of the present invention below, the common partial structure is assumed to be the following structure unless otherwise specified.

[0032] (aromatic group) The aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group, or a structure in which multiple rings selected from these are linked together. When multiple aromatic hydrocarbon groups or aromatic heterocyclic groups are linked together, typically, a structure in which 2 to 10 groups are linked together is mentioned, and a structure in which 2 to 5 groups are linked together is preferred. When multiple aromatic hydrocarbon groups and aromatic heterocyclic groups are linked together, the linked groups may be the same structure or different structures. The structure in which a plurality of aromatic hydrocarbon groups and aromatic heterocyclic groups are linked together is preferably a group derived from a phenylpyridine ring, a group derived from a diphenylpyridine ring, a group derived from a phenylcarbazole ring, or a group derived from a diphenylcarbazole ring.

[0033] (aromatic hydrocarbon group) The aromatic hydrocarbon group refers to a monovalent, divalent, or trivalent or higher aromatic hydrocarbon ring structure depending on the bonding state within the structure of compound (1). In the aromatic hydrocarbon ring structure, the number of carbon atoms is not usually limited, but is preferably 6 to 60, with the upper limit of the carbon number being more preferably 48 or less, and even more preferably 30 or less. Specific examples include 6-membered monocyclic or 2- to 5-condensed ring groups such as benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, and fluorene ring, or structures in which multiple groups selected from these are linked together. When multiple aromatic hydrocarbon rings are linked together, typically, structures in which 2 to 10 rings are linked together are exemplified, with structures in which 2 to 5 rings are linked together being preferred. When multiple aromatic hydrocarbon rings are linked together, the linked rings may be the same or different structures. Preferred aromatic hydrocarbon ring structures are a benzene ring, a biphenyl ring, i.e., a structure in which two benzene rings are linked together, a terphenyl ring, i.e., a structure in which three benzene rings are linked together, a quaterphenylene ring, i.e., a structure in which four benzene rings are linked together, a naphthalene ring, and a fluorene ring.

[0034] (aromatic heterocyclic group) The aromatic heterocyclic group refers to a monovalent, divalent, or trivalent or higher aromatic heterocyclic structure depending on the bonding state in the structure of compound (1). In the aromatic heterocyclic structure, the number of carbon atoms is usually not limited, but is preferably 3 to 60, and the upper limit of the number of carbon atoms is more preferably 48 or less, and even more preferably 30 or less. Specific examples thereof include divalent groups of a 5- or 6-membered monocyclic or 2- to 4-fused ring such as a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furopyrrole ring, a furofuran ring, a thienofuran ring, a benzisoxazole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a benzimidazole ring, a perimidine ring, a quinazoline ring, a quinazolinone ring, or an azulene ring, or groups in which a plurality of these are linked together. When a plurality of aromatic heterocycles are linked, they may have the same structure or different structures. When a plurality of aromatic heterocycles are linked, typically, a structure in which 2 to 10 rings are linked is mentioned, and a structure in which 2 to 5 rings are linked is preferred. The aromatic heterocyclic structure is preferably a thiophene ring, a benzothiophene ring, a pyrimidine ring, a triazine ring, a carbazole ring, a dibenzofuran ring, or a dibenzothiophene ring.

[0035] (substituent) In the following description of the structure of compound (1), unless otherwise specified, the substituent is any group, but is preferably a group selected from the following substituent group Z. Furthermore, in the description of the structure of compound (1) of the present invention, when it is stated that the substituent that may be possessed is selected from the substituent group Z, or that the substituent that may be possessed is preferably selected from the substituent group Z, the preferred substituents are also as described in the following substituent group Z.

[0036] (Substituent group Z) The substituent group Z is a group consisting 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 have any of a linear, branched, and cyclic structure.

[0037] More specifically, the substituent group Z includes the following structures. The alkyl group is linear, branched, or cyclic and has 1 or more, preferably 4 or more, and 24 or less, preferably 12 or less, further preferably 8 or less, and even more preferably 6 or less carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, a tert-butyl group, an n-hexyl group, a cyclohexyl group, and a dodecyl group.

[0038] The alkenyl group is linear, branched, or cyclic, and has 2 or more carbon atoms, and usually 24 or less, and preferably 12 or less. Specific examples include a vinyl group.

[0039] The alkynyl group is linear or branched and has 2 or more carbon atoms and 24 or less, preferably 12 or less carbon atoms. Specific examples include an ethynyl group.

[0040] The alkoxy group has 1 to 24 carbon atoms, preferably 12 or less. Specific examples include a methoxy group and an ethoxy group.

[0041] The aryloxy group and heteroaryloxy group have 4 or more, preferably 5 or more, carbon atoms and 36 or less, preferably 24 or less. Specific examples include a phenoxy group, a naphthoxy group, and a pyridyloxy group.

[0042] The halogen atom includes a fluorine atom, a chlorine atom, etc. A fluorine atom is preferred.

[0043] The haloalkyl group has 1 to 12 carbon atoms, preferably 6 or less. Specific examples include a trichloromethyl group, a trifluoromethyl group, a pentafluoroethyl group, and a nonafluorobutyl group. Particularly preferred are alkyl groups substituted with fluorine atoms, and most preferred is a trifluoromethyl group.

[0044] The aromatic hydrocarbon group has a carbon number of 6 or more and 36 or less, preferably 24 or less. Specific examples include a phenyl group, a naphthyl group, and a group in which multiple phenyl groups are linked together.

[0045] The aromatic heterocyclic group has 3 or more, preferably 4 or more, carbon atoms and 36 or less, preferably 24 or less. Specific examples include a thienyl group and a pyridyl group.

[0046] The above substituents may have any of a straight-chain, branched, or cyclic structure. When the above-mentioned substituents are adjacent to each other, the adjacent substituents may be bonded to each other to form a ring. The ring size is preferably a 4-membered ring, a 5-membered ring, or a 6-membered ring, and specific examples thereof include a cyclobutane ring, a cyclopentane ring, and a cyclohexane ring.

[0047] Among the above-mentioned substituent group Z, alkyl groups, alkoxy groups, haloalkyl groups, aromatic hydrocarbon groups, and aromatic heterocyclic groups are preferred, and from the viewpoint of improving dielectric properties, alkyl groups and aromatic hydrocarbon groups are particularly preferred.

[0048] Each of the substituents in the above-mentioned substituent group Z may further have a substituent. Examples of such a substituent include the same as those in the above-mentioned substituent group Z. Preferably, the further substituent is not present, or is an alkyl group having 8 or less carbon atoms, an alkoxy group having 8 or less carbon atoms, or a phenyl group, more preferably an alkyl group having 6 or less carbon atoms, or a phenyl group. From the viewpoint of charge transportability, it is more preferable that the further substituent is not present.

[0049] <L 21 > Bonding group L in substituent (2) 21 is preferably a chalcogen atom, an alkylene group or a divalent aromatic group. in particular, Examples of chalcogen atoms include oxygen atoms and sulfur atoms, with oxygen atoms being preferred. The alkylene group is linear, branched, or cyclic and has 1 or more, preferably 4 or more, and 24 or less, preferably 12 or less, further preferably 8 or less, and even more preferably 6 or less carbon atoms. Specific examples include divalent groups derived from methane, ethane, propane, butane, isobutane, hexane, cyclohexane, and dodecane. The aromatic group includes an aromatic hydrocarbon group and an aromatic heterocyclic group, and is preferably an aromatic hydrocarbon group. Specific examples include divalent groups derived from benzene, biphenyl, terphenyl, and fluorene. However, the aromatic group has 1 to 4 CL groups on the terminal aromatic ring. 21 , preferably 1 to 2 CL 21 In this case, it can be said to be a divalent or trivalent group.

[0050] <CL 21 > CL in substituent (2) 21 is a bridging group (3) represented by general formula (3).

[0051] [ka]

[0052] In formula (3), Arom represents an aromatic ring having 3 to 30 carbon atoms which may have a substituent, and R 31 , R 32 each independently represents a hydrogen atom or an alkyl group, and the symbol * represents L in formula (2). 21 represents a bond with, and the bond with formula (2) bonds to Arom.)

[0053] <arom> Arom represents an aromatic ring having 3 to 30 carbon atoms which may have a substituent. The aromatic ring having 3 to 30 carbon atoms is preferably a monocyclic or fused ring of the above-mentioned aromatic hydrocarbon ring, or a monocyclic or fused ring of the above-mentioned aromatic heterocycle, preferably an aromatic hydrocarbon ring, more preferably a benzene ring or a naphthalene ring.

[0054] <x、z> In the general formula (1), x is an integer of 0 to 2, and in the general formula (2), z is an integer of 0 to 4. However, when CL is present in the compound (1), 21 There are three or more CL 21 However, when three or more of these groups are present in the compound, a network structure is formed during the crosslinking reaction, resulting in a thermosetting resin composition, laminate, and cured film with excellent thermal stability. When x is 0 or 1, the following cases are particularly preferred. That is, when x is 0, it is preferable that one of the four z's is 0 and three are 1, or that all are 1; when x is 1, it is preferable that all three z's are 1. When x is 2, it is preferred that one of the two z's is 2 and the other is 1, or that all are 2. In the general formula (2), when z is 0, L 21 CL 21 Instead, a hydrogen atom is bonded.

[0055] <y> In the general formula (2), y is an integer of 1 to 6. From the viewpoint of improving thermal properties, y is preferably an integer of 1 to 3.

[0056] <R 31 , R 32 > R in general formula (3) 31 , R 32 are each independently a hydrogen atom or an alkyl group. Examples of the alkyl group include the alkyl groups exemplified above as the substituent group Z, and the preferred examples are also the same. R 31 , R 32 is preferably a hydrogen atom from the viewpoint of reactivity since steric hindrance is reduced, and is preferably an alkyl group having 1 to 10 carbon atoms from the viewpoint of improving solubility and obtaining a uniform composition.

[0057] <Specific examples of compound (1)> Specific examples of compound (1) are shown below, but compound (1) of the present invention is not limited to the following examples.

[0058] [ka]

[0059] [ka]

[0060] [ka]

[0061] [ka]

[0062] [ka]

[0063] [ka]

[0064] <Method for producing compound (1)> Compound (1) can be obtained by a general synthesis method such as the reaction of an organic halogen compound with an alcohol derivative in the presence of a base / catalyst as described in the following documents 1 and 2, the cross-coupling reaction of an organic halogen compound with a Grignard reagent using a nickel phosphine complex catalyst as described in the following document 3, or the reaction of an aromatic halide with an organometallic compound such as a boron compound using a palladium catalyst as described in the following document 4. Reference 1: Macromolecules, 2021, 54(13), 6161-6170 Literature 2: Polymer Chemistry, 2017, 8(30), 4327-4331 Document 3: J. Am. Chem. Soc., 1972, 4374 Reference 4: Journal of Chemical Research, 2005, (3), 184-186 Examples of the organic halogen compound include alkyl halides such as 1,2,3-tribromopropane, pentaerythrityl tetrabromide, and 1,2,5,6-tetrabromohexane; cycloalkyl halides such as 1,3,5-tribromoadamantane; and aromatic halides such as tribromobenzene and tetrabromobiphenyl. Examples of alcohol derivatives include 4-hydroxybenzocyclobutene, 4-(2-hydroxyethoxy)benzo[b]cyclobutene, and the like. Examples of the base or catalyst include alkali metal hydrides such as sodium hydride, alkali metal carbonates such as potassium carbonate, palladium catalysts such as tetrakis(triphenylphosphine)palladium, palladium acetate, and palladium chloride, and copper catalysts such as copper iodide, copper chloride, and copper acetate. The Grignard reagent can be prepared, for example, by mixing metallic magnesium with an organic halide compound in a solvent. As organometallic compounds, R 1 -MgX, R 1 -B(OH)2, R 1 -SnR 2 3. R 1 -ZnX, etc., where R 1 represents an alkyl group or an aromatic group, and R 2 represents an alkyl group, and X represents a chlorine atom, a bromine atom, or an iodine atom. Asymmetric compounds can be obtained by carrying out the above reactions stepwise.

[0065] <Uses of compound (1)> As described below, compound (1) can be used as a crosslinking agent for a thermosetting resin composition. When compound (1) has three or more crosslinking groups (3), the linear thermal expansion coefficient of the resulting cured product is reduced, thereby improving dimensional stability and contributing to low dielectric properties and improved heat resistance.

[0066] [Thermosetting resin composition] The thermosetting resin composition contains the compound (1) of the present invention as a crosslinking agent, and further contains a resin as a base resin. The base agent can be an appropriate material depending on the intended use of the thermosetting resin composition. The thermosetting resin composition of the present invention, which contains compound (1) as a crosslinking agent, has low dielectric properties, a high glass transition temperature, and high dimensional stability. As a result, a film prepared using the thermosetting resin composition of the present invention is particularly suitable as an insulating film for a module for high-speed communication.

[0067] <Content of Compound (1)> The content of compound (1) contained in the thermosetting resin composition of the present invention is 1 part by mass or more per 100 parts by mass of the resin as the main component. By containing 1 part by mass or more of compound (1), it is expected that the thermosetting resin composition will cure sufficiently. On the other hand, the content of compound (1) is less than 500 parts by mass per 100 parts by mass of resin. It is believed that by containing compound (1) less than 500 parts by mass, it is possible to obtain a thermosetting resin composition that fully utilizes the properties of the main component. The content of compound (1) per 100 parts by mass of resin is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and is usually 450 parts by mass or less, preferably 400 parts by mass or less, and more preferably 350 parts by mass or less.

[0068] <Resin> Examples of resins include polyolefins such as polyethylene, polypropylene, polystyrene, and ethylene-propylene copolymers, and derivatives thereof; 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 and polybenzoxazole precursors. These may be used alone or in combination of two or more.

[0069] Among these resins, heavy resins with a glass transition temperature of 20°C or less are used in order to increase the toughness of the cured film. It is preferable to use a block copolymer having a combined segment or a glass transition metal. It is more preferable to use a block copolymer having a polymer segment with a transition temperature of 0°C or less. I wish. Block copolymers having polymer segments with glass transition temperatures of 20°C or less are Rubbers such as styrene-conjugated diene block copolymers or hydrogenated styrene-conjugated diene block copolymers It is preferable that the body and the like are made of rubber.

[0070] The number-average molecular weight Mn of the block copolymer described above is not particularly limited, but may be in the range of 5,000 to 1,000,000, preferably 10,000 to 500,000, and more preferably 30,000 to 300,000. Furthermore, the molecular structure of the hydrogenated block copolymer may be linear, branched, radial, or any combination thereof. Here, the number-average molecular weight Mn of the block copolymer is a value measured by gel permeation chromatography (GPC) (polystyrene equivalent) using tetrahydrofuran as an eluent.

[0071] The content of the resin in the thermosetting resin composition of the present invention is preferably 20 to 60 mass % based on 100 mass % of the total composition, more preferably 30 to 50 mass % from the viewpoint of dielectric properties, and even more preferably 35 to 45 mass % from the viewpoint of adhesion and mechanical properties.

[0072] <Polymerization initiator> The thermosetting resin composition using the compound (1) as a crosslinking agent may contain a polymerization initiator. Examples of the polymerization initiator include organic peroxides such as hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxy esters, and ketone peroxides. More specific examples include hydroperoxides such as cumene hydroperoxide and t-butyl hydroperoxide; dialkyl peroxides such as dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane and 2,5-bis(tert-butylperoxy)-2,5-dimethyl-3-hexyne; diacyl peroxides such as lauryl peroxide and benzoyl peroxide; peroxy esters such as t-butyl peroxyacetate, t-butyl peroxybenzoate and t-butylperoxyisopropyl carbonate; and ketone peroxides such as cyclohexanone peroxide.

[0073] When the thermosetting resin composition of the present invention contains a polymerization initiator, the amount is preferably 0.01 part by mass or more, more preferably 0.1 part by mass or more, and even more preferably 1 part by mass or more, per 100 parts by mass of the resin, in terms of accelerating the curing reaction. Since the polymerization initiator contains many heteroatoms in its structure, an increase in its content is thought to deteriorate the dielectric properties. Therefore, in order to maintain low dielectric properties, the content is preferably 5 parts by mass or less, more preferably 3% by mass or less, even more preferably 1 part by mass or less, particularly preferably 0.1 part by mass or less, and most preferably substantially none, relative to 100 parts by mass of the resin. The above phrase "substantially free" means that it is not intentionally contained, and specifically means that the content of the polymerization initiator is 0 parts by mass or more and 0.05 parts by mass or less, more preferably 0 parts by mass or more and 0.01 parts by mass or less, per 100 parts by mass of the resin.

[0074] <Solvent> The thermosetting resin composition of the present invention may contain a solvent. The solvent is not particularly limited as long as it can dissolve the resin and compound (1) uniformly, and examples thereof include toluene, cyclohexane, tetrahydrofuran, and xylene. The solvent preferably has a boiling point of 200° C. or less so that it volatilizes during production of a cured product. When the thermosetting resin composition of the present invention contains a solvent, the content of the solvent is preferably 100 parts by mass or more and 500 parts by mass or less, and more preferably 200 parts by mass or more and 400 parts by mass or less, per 100 parts by mass of the resin, from the viewpoint of film-forming properties.

[0075] <Other ingredients> In addition to the above components, the thermosetting resin composition of the present invention may optionally further contain adhesion promoters such as silane coupling agents, plasticizers, flame retardants, crosslinking agents other than compound (1), crosslinking catalysts, ultraviolet absorbers, antistatic agents, antioxidants, colorants, dispersants, emulsifiers, elasticity reducing agents, diluents, antifoaming agents, ion trapping agents, thickeners, leveling agents, inorganic particles, organic particles, etc. These may be used alone or in combination of two or more.

[0076] <Crosslinking temperature / curing time> In the thermosetting resin composition of the present invention, the curing temperature of the solid content obtained by distilling off the solvent may be any temperature at which the resin does not flow and at which the crosslinking reaction of compound (1) proceeds. Specifically, the crosslinking rate is generally accelerated at 80°C or higher, and therefore the temperature is preferably 120°C or higher, more preferably 150°C or higher, and even more preferably 180°C or higher. In addition, 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, in order to prevent decomposition of the resin. The curing time is not particularly limited, but is usually 5 minutes or more, and in order to further increase the hardness, it is preferably 10 minutes or more, more preferably 20 minutes or more, and even more preferably 30 minutes or more. In order to suppress decomposition of the resin, the time is usually 3 hours or less, preferably 2 hours or less, and more preferably 1 hour or less.

[0077] <Dielectric loss tangent> The thermosetting resin composition of the present invention has a dielectric loss tangent of 2.5×10 -3 It is preferable that the dielectric loss tangent is 2.5×10 or less. -3 If the dielectric loss tangent exceeds this value, the communication speed may be slowed in the high frequency band of 28 GHz or higher. There is no particular limit to the lower limit of the dielectric loss tangent, but the lower the dielectric loss tangent, the better. The dielectric loss tangent of the thermosetting resin composition is measured by the method described in the Examples section below.

[0078] [High-speed communication module] The thermosetting resin composition of the present invention has low dielectric properties and can achieve a high glass transition temperature and high dimensional stability, and therefore a film produced using the thermosetting resin composition of the present invention is particularly suitable as an insulating film for a module for high-speed communication. In this specification, a high-speed communication module refers to a circuit board for transmitting transmission signals with a frequency of 1 GHz or higher. Examples of high-speed communication modules include a high-frequency circuit board or a semiconductor package in which an antenna and an IC chip are integrated. Furthermore, the frequency of the transmission signal is preferably 3 GHz or higher, more preferably 5 GHz or higher, even more preferably 8 GHz or higher, and particularly preferably 10 GHz or higher. The frequency of the transmission signal is not particularly limited, but is 400 GHz or less, preferably 300 GHz or less. In the present invention, the upper and lower limit values ​​of the frequency can be combined arbitrarily. [Example]

[0079] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples in any way.

[0080] [Synthesis of Compound A] [ka]

[0081] A solution of 4-hydroxybenzocyclobutane (141.8 g) in ethanol (100 mL) was added to a solution of potassium hydroxide (106.9 g) in ethanol (700 mL). After stirring at room temperature for 20 minutes, the solvent was evaporated under reduced pressure. The residue was diluted with DMF (1100 mL), and 1,3-dibromo-2,2-bis(bromomethyl)propane (64.1 g) was added in three portions at room temperature with stirring, followed by a reaction at 135°C for 4.5 hours. After cooling to room temperature, 1.1 L of purified water was added, and the mixture was extracted with ethyl acetate / hexane. The organic layer was washed with aqueous sodium chloride. The mixture was dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain Compound A (83.6 g). 1 H-NMR: 3.06-3.09(m, 16H), 4.27(s, 8H), 6.67(s, 4H), 6.74(d, J=8Hz, 4H), 6.90(d, J=8Hz, 4H)

[0082] [Synthesis of Compound B] <Synthesis of Intermediate B-1> [ka]

[0083] A solution of 1,1,1-tris(4-hydroxyphenyl)ethane (93.1 g) and triethylamine (161.4 g) in methylene chloride (1400 mL) was cooled to -40°C, and a solution of trifluoromethanesulfonic anhydride (308.7 g) in methylene chloride (300 mL) was added dropwise. After the addition was complete, the temperature was raised to room temperature and the mixture was stirred for 12 hours. Under ice cooling, 2N hydrochloric acid (1000 mL) was added dropwise, the oil layer was separated, and the aqueous layer was extracted with methylene chloride. The organic layers were combined, washed with purified water, saturated aqueous sodium bicarbonate, and saturated aqueous sodium chloride, then dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was suspended and washed in methanol, and Intermediate B-1 (190.7 g) was collected by filtration.

[0084] <Synthesis of Compound B> [ka]

[0085] Under an argon stream, 2M aqueous potassium carbonate solution (1010 mL) was added to a solution of intermediate B-1 (188.4 g) and benzocyclobuten-4-ylboronic acid (166.7 g) in dimethoxyethane (3770 mL). The mixture was degassed by argon bubbling, and tetrakistriphenylphosphine palladium (27.9 g) was added. The mixture was stirred under reflux for 8 hours and 30 minutes and allowed to cool to room temperature. Extraction was performed with toluene, and the organic layer was washed with purified water, dried over anhydrous sodium sulfate, and then filtered. The filtrate was concentrated under reduced pressure, and the residue was subjected to silica gel column chromatography to obtain compound B (116.5 g). 1 H-NMR: 2.27(s, 1H), 3.19-3.24(m, 1H), 7.10(d, J=7.6Hz,3H), 7.21-7.24(m, 6H), 7.29(s, 3H), 7.43(d, J=8Hz, 3H), 7.46-7.49(m, 6H)

[0086] [Synthesis of Compound C] <Synthesis of Intermediate C-1> [ka]

[0087] A flask was charged with 4'-bromoacetophenone (13.2 g, 66.41 mmol), phenol (75.0 g, 796.94 mmol), and 85 mL of acetic acid under a nitrogen stream and stirred at room temperature. To this was added 240 mL of hydrochloric acid (12 M), and the mixture was heated to reflux at 90 °C for 24 hours. After the reaction, the reaction solution was poured into hot water, and the insoluble matter was collected and dissolved in ethyl acetate. The mixture was further extracted with ethyl acetate, separated, dried over magnesium sulfate, and concentrated. The mixture was further purified by silica gel column chromatography (hexane:ethyl acetate = 4:1) to obtain intermediate C-1 (11.73 g).

[0088] <Synthesis of Intermediate C-2> [ka]

[0089] 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 in a flask under a nitrogen stream and stirred at room temperature. 75 mL of 2 M aqueous potassium carbonate solution was added, and nitrogen was bubbled through at room temperature for 30 minutes. Tetrakis(triphenylphosphine)palladium (0.75 g, 0.65 mmol) was then added, and the mixture was heated to reflux under nitrogen for 5 hours. After cooling, the mixture 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).

[0090] <Synthesis of intermediate C-3> [ka]

[0091] 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 at -5°C, and 31.9 g (113.13 mmol) of trifluoromethanesulfonic anhydride dissolved in 70 mL of methylene chloride was slowly added dropwise. The reaction was completed after 4 hours, and the reaction solution was poured into ice water, extracted with methylene chloride, and separated. The extract was 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).

[0092] <Synthesis of intermediate C-4> [ka]

[0093] Under a nitrogen atmosphere, 200 mL of dimethyl sulfoxide, intermediate C-3 (19.5 g, 29.70 mmol), bis(pinacolato)diboron (18.1 g, 71.28 mmol), and potassium acetate (17.5 g, 178.2 mmol) were placed in a 500 mL flask and stirred at 60 °C for 30 minutes. Then, 1,1'-bis(diphenylphosphino)ferrocene-palladium(II) dichloride-dichloromethane [PdCl2(dppf)CHCl2] (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, and the filtrate was extracted with toluene, dried over anhydrous magnesium sulfate, and then filtered. The resulting solution was concentrated and added to methanol to give intermediate C-4 as a colorless solid (15.0 g, 82.5%).

[0094] <Synthesis of Intermediate C-5> [ka]

[0095] 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 placed in a 1000 mL flask and heated with stirring for 30 minutes. Tetrakis(triphenylphosphine)palladium [Pd(PPh3)4] (0.57 g, 0.49 mmol) was then added and refluxed for 5 hours. The reaction mixture was then poured into water, extracted with toluene, and treated with anhydrous magnesium sulfate and activated clay. Purification was performed by adsorption silica gel column chromatography (developing solvent: n-hexane:methylene chloride = 4:1) to obtain Intermediate C-5 as a colorless solid (yield: 4.8 g, 29.2%).

[0096] <Synthesis of Compound C> [ka]

[0097] 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 aqueous potassium phosphate solution (2 M, i.e., 2 mol / L concentration) were placed in a 500 mL flask and heated with stirring for 30 minutes. Tetrakis(triphenylphosphine)palladium [Pd(PPh3)4] (0.87 g, 0.76 mmol) was then 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 filtered product was dissolved in methylene chloride and treated with activated clay. The mixture was further filtered under reduced pressure, the filtrate concentrated, and the filtered product was washed with 100 mL of methanol and 100 mL of ethanol, followed by vacuum filtration. The filtered product was dried to obtain compound C as a colorless solid (yield: 8.9 g, 88.4%).

[0098] In the following examples and comparative examples, the following resins were used. a-1: Styrene-ethylene-butadiene-styrene block copolymer (SEBS: Asahi Kasei Corporation, "Tuftec H1052", glass transition temperature of polymer segment = -45°C, number average molecular weight (Mn) = 66,000)

[0099] [Example 1] The raw materials were blended in the proportions shown in Table 1 and heated to approximately 80°C to completely dissolve the raw materials, thereby preparing a resin composition. The prepared resin composition was spread in the form of a sheet on the release-treated surface of a 50 μm-thick release film (PET film manufactured by Mitsubishi Chemical Corporation) that had been treated with silicone release agent, 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. The resin sheet spread on the release film was dried in an oven at 100°C for 1 hour, after which a 75 μm-thick release film (Chukoh Flow G-type processed product, manufactured by Chukoh Chemical Industries, Ltd.) was laminated on top of the resin sheet. The PET film was removed, and the same release film was laminated on this side to form a double-sided laminate. This laminate was then held in a heat press at 250°C for 30 minutes under a pressure of approximately 0.2 MPa to completely cure the resin sheet, after which the release films on both sides were peeled off to obtain a cured sheet. The dielectric properties, storage modulus, and linear thermal expansion coefficient of the resulting cured sheet were measured using the following measurement methods. The results are shown in Table 1.

[0100] [Examples 2 to 5, Comparative Examples 1 and 2] A cured sheet was produced in the same manner as in Example 1, except that the raw materials were blended according to the proportions shown in Table 1. The dielectric properties, storage modulus, and linear thermal expansion coefficient of the obtained cured sheet were measured using the methods described below. The results are shown in Table 1.

[0101] [Measurement method] (1) Dielectric properties The in-plane dielectric constant and dielectric loss tangent of the cured sheet were measured in TE mode using a cavity resonator (manufactured by AET) and a network analyzer MS46 122B (manufactured by Anritsu Corporation) at a measurement frequency of 10 GHz.

[0102] (2) Storage modulus The dynamic viscoelasticity of the cured sheets was measured under the following conditions using a viscoelasticity spectrometer DVA-200 (manufactured by IT Measurement Control Co., Ltd.) From the measurement results, the storage modulus at 130°C was taken as the storage modulus of each cured sheet. <Measurement conditions> Vibration frequency: 10Hz Distortion: 0.1% Heating rate: 3°C / min Measurement temperature: -100℃~300℃

[0103] (3) Linear thermal expansion coefficient The dimensional change of the cured sheets was measured under the following conditions using a thermomechanical analyzer TMA7100 (manufactured by Hitachi High-Tech Science Corp.) From the measurement results, the average value of the dimensional change rate in the third step from 0 to 120°C was taken as the linear thermal expansion coefficient of each cured sheet. <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℃

[0104] [Table 1]

[0105] Table 1 reveals the following: From the results of compound A in Example 1 (intramolecular crosslinking group (3): 4), compound B in Example 2 (intramolecular crosslinking group (3): 3), and compound C in Comparative Example 2 (intramolecular crosslinking group (3): 1), it can be seen that the linear thermal expansion coefficient decreases as the number of benzocyclobutene crosslinking groups contained in one molecule increases. Examples 1 to 5 and Comparative Example 1 show that by adding compound (1) having a specific structure to a resin, it is possible to suppress deformation (flow) of the resin composition even at a temperature (130°C) at which the resin alone (Comparative Example 1) would flow, while maintaining low dielectric properties, and also to suppress the linear expansion coefficient and improve heat resistance. In Comparative Example 2, since there was only one benzocyclobutene crosslinking group in the molecule of compound (C), it was difficult to increase the crosslinking density, and the storage modulus at 130°C was low, which is thought to be why heat resistance was not improved. Although a styrene-based elastomer is used as the resin in the above examples, the same effect can be expected even when a resin other than a styrene-based elastomer is used, based on the mechanism that heat resistance can be improved by entanglement of molecular chains of the crosslinked product of the resin and compound (1). From the above results, it can be seen that the structure of compound (1) of the present invention, which contains three or more benzocyclobutene crosslinking groups in the molecule that easily form a network structure, is suitable for resin compositions, laminates, and cured products used in electronic components for high-speed communication technology.< / y> < / arom>

Claims

1. A compound represented by the following general formula (1): 【Chemistry 1】 (In formula (1), C represents a carbon atom, H represents a hydrogen atom, each A independently represents a substituent represented by the following general formula (2), and the subscript x represents an integer of 0 to 2.) 【Chemistry 2】 (In formula (2), L ２１ each independently represents an oxygen atom, a sulfur atom, an alkylene group, a phenylene group, a biphenylene group, a terphenylene group, a quaternary phenylene group, a naphthalenediyl group, or a fluorenediyl group; CL ２１ are each independently a bridging group represented by the following general formula (3), the symbol * represents a bond to the carbon atom in formula (1), the subscript y is an integer of 1 to 6, the subscript z is an integer of 0 to 4, provided that when z is 0, the linking group L ２１ CL ２１ In addition, in the compound represented by general formula (1), a hydrogen atom is bonded instead of CL. ２１ There are three or more.) 【Transformation 3】 (In formula (3), Arom represents a benzene ring or a naphthalene ring which may have a substituent, and R ３１ , R ３２ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and the symbol * represents L in formula (2). ２１ represents a bond with, and the bond with formula (2) is bonded to Arom.

2. The compound according to claim 1, wherein the subscript z is 0 to 2.

3. A thermosetting resin composition comprising a resin and the compound according to claim 1 or 2, wherein the compound according to claim 1 or 2 is contained in an amount of 1 part by mass or more per 100 parts by mass of the resin.

4. 4. The thermosetting resin composition according to claim 3, wherein the resin is a block copolymer having a polymer segment having a glass transition temperature of 20° C. or less.

5. 5. The thermosetting resin composition according to claim 3, which is substantially free of a polymerization initiator, or the content of the polymerization initiator is 5 parts by mass or less per 100 parts by mass of the resin.

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