Resin composition, resin sheet, laminate, cured sheet, and circuit board material

Abstract

To provide a sheet cured product and a circuit board material which have low dielectric characteristics and heat resistance, and a resin composition, a resin sheet and a laminate which enable manufacture of them.SOLUTION: A resin composition contains at least one kind of a thermoplastic resin (A), and a compound (B) represented by the following formula (1). In the general formula (1), A is a group containing a crosslinking group represented by the following general formula (3), and x is 0 to 2. In the general formula (3), Arom is an aromatic ring having 3 to 30 carbon atoms, and R31 and R32 are H or an alkyl group.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resin composition, a resin sheet, a laminate, a cured sheet, and a circuit board material. [Background technology]

[0002] In recent years, as electrical and electronic devices have become more powerful and functional, communication frequencies have become higher in order to improve communication speed and the amount of information transmitted. When a digital signal is transmitted through a circuit board, a portion of the transmitted digital signal is converted into heat within the circuit board, resulting in transmission loss. The amount of transmission loss is expressed as the product of the dielectric constant and the dielectric loss tangent, so achieving low-loss communication requires materials with low dielectric constants and dielectric loss tangents, i.e., components with low dielectric properties. Since transmission signals in the high-frequency range are particularly prone to being converted into heat, materials with even lower dielectric properties are in demand. On the other hand, as the circuits in electrical and electronic equipment become more highly integrated, the amount of heat generated inside the equipment also increases. As a result, circuit board materials are also required to be heat resistant.

[0003] 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. The benzocyclobutene group-containing compound disclosed is divinylsiloxane bisbenzocyclobutene (CYCLOTENE (registered trademark) 3022, manufactured by The Dow Chemical Company). Patent Document 2 discloses a polymer composition comprising a monomer mixture of copolymerized one or more addition-polymerizable arylcyclobutene-containing monomers A having one or more groups selected from alkyl, heteroatom-containing alkyl, aryl, heteroatom-containing aryl, or heteroatom-containing aryloxy as cyclobutene ring substituents, one or more second aromatic addition-polymerizable monomers, and one or more other addition-polymerizable monomers selected from a third addition-polymerizable nitrogen-heterocycle-containing monomer, a fourth addition-polymerizable monomer, or both the one or more third monomers and the one or more fourth monomers. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 9-194549 [Patent Document 2] Japanese Patent Application Publication No. 2019-085562 Summary of the Invention [Problem to be solved by the invention]

[0005] However, the thermosetting resin described in Patent Document 1 does not have a sufficient dielectric loss tangent in the high frequency range (on the order of GHz), and further improvement is required. Furthermore, the polymer composition described in Patent Document 2 has a low crosslink density in the cured product, making it difficult to form a network structure during crosslinking, and may not be sufficient to improve heat resistance.

[0006] Therefore, an object of the present invention is to provide a sheet cured product and a circuit board material having low dielectric properties and heat resistance, as well as a resin composition, a resin sheet, and a laminate from which the sheet cured product and the circuit board material having low dielectric properties and heat resistance can be produced. [Means for solving the problem]

[0007] As a result of extensive research into solving the above problems, the present inventors have found that the above problems can be solved by adding a specific crosslinking agent to a thermoplastic resin.

[0008] The gist of the present invention is as follows.

[0009] [1] A resin composition comprising at least one thermoplastic resin (A) selected from the group consisting of a styrene-based thermoplastic elastomer, an olefin-based thermoplastic elastomer, and an ethylene-based polymer, and a compound (B) 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 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 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] The resin composition according to [1], wherein the thermoplastic resin (A) contains a styrene-based thermoplastic elastomer.

[0017] [3] The resin composition according to [2], wherein the styrene content of the styrene-based thermoplastic elastomer is 10% by mass or more and 70% by mass or less.

[0018] [4] The bonding group L of the compound (B) 21 The resin composition according to any one of [1] to [3], wherein is an oxygen atom, a sulfur atom, an alkylene group, or an aromatic group.

[0019] [5] The resin composition according to any one of [1] to [4], wherein the subscript z of the compound (B) is 0 to 2.

[0020] [6] The resin composition according to any one of [1] to [5], which is substantially free of a polymerization initiator.

[0021] [7] A resin sheet made of the resin composition according to any one of [1] to [6].

[0022] [8] A laminate comprising a release film on one or both sides of the resin sheet described in claim 7.

[0023] [9] A sheet cured product obtained by curing the resin sheet described in claim 7.

[0024]

[10] A circuit board material obtained by laminating an insulating layer made of the resin sheet according to claim 7 and a conductor.

[0025]

[11] A method for producing a resin sheet, comprising: a coating liquid preparation step of preparing a coating liquid comprising a resin composition containing at least one thermoplastic resin (A) selected from the group consisting of a styrene-based thermoplastic elastomer, an olefin-based thermoplastic elastomer, and an ethylene-based polymer, and a compound (B) represented by the following general formula (1); and a molding step of molding the coating liquid into a sheet.

[0026] [ka]

[0027] (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.)

[0028] [ka]

[0029] (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 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 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.)

[0030] [ka]

[0031] 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). 21represents a bond with, and the bond with formula (2) bonds to Arom.)

[0032]

[12] A method for producing a resin sheet, comprising a film-forming step of melt-kneading a resin composition containing at least one thermoplastic resin (A) selected from the group consisting of a styrene-based thermoplastic elastomer, an olefin-based thermoplastic elastomer, and an ethylene-based polymer, and a compound (B) represented by the following general formula (1), and forming the resulting composition into a sheet.

[0033] [ka]

[0034] (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.)

[0035] [ka]

[0036] (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 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 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.)

[0037] [ka]

[0038] In formula (3), Arom represents an aromatic ring having 3 to 30 carbon atoms which may have a substituent, and R 31 , R 32each 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.) [Effects of the Invention]

[0039] According to the present invention, it is possible to obtain a sheet cured product and a circuit board material having low dielectric properties and heat resistance, as well as a resin composition, a resin sheet, and a laminate from which the sheet cured product and the circuit board material having low dielectric properties and heat resistance can be produced. DETAILED DESCRIPTION OF THE INVENTION

[0040] 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.

[0041] [Resin composition] The resin composition of the present invention (hereinafter also referred to as "the composition") contains at least one thermoplastic resin (A) selected from the group consisting of a styrene-based thermoplastic elastomer, an olefin-based thermoplastic elastomer, and an ethylene-based polymer, and a compound (B) having a specific structure. Although the reason for the improved heat resistance of the cured sheet and circuit board material made from this composition is unclear, it is believed that this is because, upon curing, the thermoplastic resin (A) and compound (B) form a dense interpenetrating polymer network structure (hereinafter also referred to as a "semi-IPN structure"). A semi-IPN structure is a structure in which the molecular chains of the crosslinked product of the thermoplastic resin (A) and compound (B) are partially and physically entangled with each other, rather than the thermoplastic resin (A) and compound (B) forming chemical bonds. The formation of this semi-IPN structure results in a pseudo-higher crosslink density than that of the thermoplastic resin (A) alone. Furthermore, compound (B) has more crosslinking points than the benzocyclobutene compound described in Patent Document 2, which is thought to result in a higher crosslink density, an improved elastic modulus at high temperatures, and improved heat resistance. Each component of the composition will now be described.

[0042] 1. Thermoplastic resin (A) The thermoplastic resin (A) of the present composition is at least one selected from the group consisting of styrene-based thermoplastic elastomers, olefin-based thermoplastic elastomers, and ethylene-based polymers.

[0043] Examples of the styrene-based thermoplastic elastomer include styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), and hydrogenated versions of these, such as styrene-ethylene-butadiene-styrene block copolymer (SEBS) and styrene-ethylene-propylene-styrene block copolymer (SEPS).

[0044] The olefin-based thermoplastic elastomer contains a polyolefin as a hard segment and a rubber component as a soft segment. The olefin-based thermoplastic elastomer may be a mixture (polymer blend) of a polyolefin and a rubber component, a cross-linked product obtained by cross-linking a polyolefin and a rubber component, or a polymer obtained by polymerizing a polyolefin and a rubber component. Examples of the polyolefin include polypropylene and polyethylene. Examples of the rubber component include diene rubbers such as isoprene rubber, butadiene rubber, butyl rubber, propylene-butadiene rubber, acrylonitrile-butadiene rubber, and acrylonitrile-isoprene rubber; ethylene-propylene non-conjugated diene rubber; and ethylene-butadiene copolymer rubber.

[0045] The ethylene polymers include homopolymers of ethylene and copolymers of ethylene with other monomers. The copolymer of ethylene and another monomer preferably contains ethylene as a main component, where "containing ethylene as a main component" means that the copolymer contains 50 mol % or more, preferably 60 mol % or more, of ethylene structural units. The other monomer to be copolymerized with ethylene is not particularly limited as long as it is a monomer copolymerizable with ethylene. Preferred examples of the ethylene polymer include low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), polyethylene obtained by polymerization using a metallocene catalyst, etc. Among these, it is particularly preferable to use linear low-density polyethylene (LLDPE) because of its high flexibility.

[0046] Among the above, from the viewpoint of low dielectric properties and ease of processing, styrene-based thermoplastic elastomers are preferred, and styrene-ethylene-butadiene-styrene block copolymers (SEBS) are more preferred.

[0047] When a styrene-based thermoplastic elastomer is used as the thermoplastic resin (A), the styrene content of the styrene-based thermoplastic elastomer is preferably 10% by mass or more, more preferably 15% by mass or more, and is preferably 70% by mass or less, more preferably 60% by mass or less, even more preferably 50% by mass or less, and even more preferably 40% by mass or less. When the styrene content is within the above range, the dielectric loss tangent is low and the elastic modulus is also at an appropriate value, so that low dielectric properties and heat resistance can be achieved at the same time, and handling properties are also good.

[0048] The thermoplastic resin (A) may be modified by a known method, for example, a reaction product of the thermoplastic resin (A) exemplified above with an unsaturated carboxylic acid and / or an anhydride thereof. By modifying the thermoplastic resin (A), the polarity of the polymer increases, which is expected to improve adhesion to metal layers such as copper foil.

[0049] Examples of the unsaturated carboxylic acid and / or anhydride thereof include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, α-ethylacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, and nadic acids, and their anhydrides. Specific examples of the acid anhydride include maleic anhydride, citraconic anhydride, and nadic anhydrides. Examples of nadic acids or anhydrides thereof include endo-cis-bicyclo[2.2.1]hept-2,3-dicarboxylic acid (nadic acid), methyl-endo-cis-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid (methylnadic acid), and the like, and anhydrides thereof.

[0050] Among these unsaturated carboxylic acids and / or anhydrides thereof, acrylic acid, maleic acid, nadic acid, maleic anhydride, and nadic anhydride are preferred. The unsaturated carboxylic acid and / or anhydride thereof may be used alone or in combination of two or more kinds.

[0051] The storage modulus of the thermoplastic resin (A) at 24°C is preferably 0.1 MPa or more, more preferably 1 MPa or more, and is preferably less than 2000 MPa, more preferably less than 1500 MPa, even more preferably less than 1000 MPa, even more preferably less than 500 MPa, particularly preferably less than 300 MPa, especially preferably less than 100 MPa, and most preferably less than 50 MPa. By setting the storage modulus below the upper limit, the flexibility of the resulting cured sheet is improved, whereas by setting the storage modulus to at least the lower limit, the heat resistance and handleability of the resulting cured sheet are improved. The storage modulus was determined by measuring the dynamic viscoelasticity of a test piece obtained by heat-pressing a 300 μm thick resin sheet made of thermoplastic resin (A) at 250°C and 0.2 MPa for 30 minutes to obtain a cured sheet.

[0052] The density of thermoplastic resin (A) measured by the water displacement method (ISO 1183) is 980 g / cm 3 Preferably less than 950 g / cm 3 Less than 910 g / cm is more preferable. 3 On the other hand, the lower limit is not particularly limited, but is preferably 800 g / cm 3 The above is preferable. When the density is equal to or less than the above value, the flexibility of the obtained cured sheet is good.

[0053] The dielectric loss tangent of the thermoplastic resin (A) at 10 GHz is preferably less than 0.003, more preferably less than 0.002, and even more preferably less than 0.0015. On the other hand, there is no particular lower limit, and it is sufficient if it is 0 or more. The smaller the dielectric loss tangent, the smaller the dielectric loss, and therefore when the composition is used as a circuit board material, the transmission efficiency and speed of electric signals can be increased. The dielectric loss tangent was determined by measuring the in-plane dielectric constant and dielectric loss tangent of the cured sheet in the TE mode using a cavity resonator (manufactured by AET) and a network analyzer MS46 122B (manufactured by Anritsu Corporation) in TE mode. The test piece was a cured sheet obtained by heat-pressing a 300 μm-thick resin sheet made of thermoplastic resin (A) at 250°C and 0.2 MPa for 30 minutes.

[0054] 2. Compound (B) The compound (B) of the present composition is represented by the following general formula (1).

[0055] [ka]

[0056] (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.)

[0057] [ka]

[0058] (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.)

[0059] [ka]

[0060] 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.)

[0061] 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.

[0062] <Definition> In the following detailed description of the compound (B) according to the present invention, the common partial structure is assumed to be the following structure unless otherwise specified.

[0063] (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.

[0064] (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 (B). 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 benzene rings, biphenyl rings, i.e., structures in which two benzene rings are linked together, terphenyl rings, i.e., structures in which three benzene rings are linked together, quaterphenylene rings, i.e., structures in which four benzene rings are linked together, naphthalene rings, and fluorene rings.

[0065] (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 (B). In the aromatic heterocyclic structure, the number of carbon atoms is usually not limited, but is preferably 3 to 60 carbon atoms, 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, usually, 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.

[0066] (substituent) In the following description of the structure of compound (B), 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 (B) of the present invention, when it is stated that the substituent that may be possessed is selected from substituent group Z, or that the substituent that may be possessed is preferably selected from substituent group Z, the preferred substituents are also as described in the following substituent group Z.

[0067] (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.

[0068] 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.

[0069] 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.

[0070] 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.

[0071] The alkoxy group has 1 to 24 carbon atoms, preferably 12 or less. Specific examples include a methoxy group and an ethoxy group.

[0072] 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.

[0073] The halogen atom includes a fluorine atom, a chlorine atom, etc. A fluorine atom is preferred.

[0074] 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.

[0075] 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.

[0076] 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.

[0077] 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.

[0078] 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.

[0079] 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.

[0080] <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.

[0081] <CL 21 > CL in substituent (2) 21 is a bridging group (3) represented by general formula (3).

[0082] [ka]

[0083] 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.)

[0084] <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.

[0085] <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 contained in the compound (B), 21 There are three or more CL 21 When three or more of these groups are present in the compound, a network structure is formed during the crosslinking reaction, resulting in the composition, as well as the resin sheet, laminate, cured sheet, and circuit board material, having 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.

[0086] <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.

[0087] <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.

[0088] <Specific examples of compound (B)> Specific examples of the compound (B) are shown below, but the compound (B) used in the present invention is not limited to the following examples.

[0089] [ka]

[0090] [ka]

[0091] [ka]

[0092] [ka]

[0093] [ka]

[0094] [ka]

[0095] <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.

[0096] <Content of Compound (B)> The content of compound (B) in the present composition is preferably 1 part by mass or more and less than 500 parts by mass, more preferably 3 parts by mass or more and 450 parts by mass or less, more preferably 5 parts by mass or more and 400 parts by mass or less, and even more preferably 10 parts by mass or more and 350 parts by mass or less, per 100 parts by mass of thermoplastic resin (A). When the content of compound (B) is within the above range, a semi-IPN structure with high crosslink density is easily formed while maintaining low dielectric properties, and the heat resistance of the resulting cured sheet is therefore good.

[0097] 3. Solvent (C) When a resin sheet is produced from the present composition through a coating step, the composition may contain a solvent (C). The solvent (C) is not particularly limited as long as it can uniformly dissolve the thermoplastic resin (A) and the compound (B), and examples thereof include toluene, cyclohexane, tetrahydrofuran, and xylene.

[0098] The solvent (C) preferably has a boiling point of 200° C. or less so that it volatilizes when the resin sheet is dried.

[0099] From the viewpoint of film-forming properties, the content of the solvent (C) in the present composition is preferably 100 to 500 parts by mass, more preferably 200 to 400 parts by mass, per 100 parts by mass of the thermoplastic resin (A).

[0100] 4. Other ingredients The present composition may contain, as components other than those described above, a thermoplastic elastomer other than the thermoplastic resin (A), a crosslinking agent other than the compound (B), a polymerization initiator, a crosslinking catalyst, an ultraviolet absorber, an antistatic agent, an antioxidant, a coupling agent, a plasticizer, a flame retardant, a colorant, a dispersant, an emulsifier, an elasticity reducing agent, a diluent, an antifoaming agent, an ion trapping agent, a thickener, a leveling agent, inorganic particles, organic particles, etc.

[0101] Examples of crosslinking agents other than the compound (B) include bismaleimide compounds and epoxy compounds.

[0102] 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.

[0103] The content of the polymerization initiator 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, relative to 100 parts by mass of the thermoplastic resin (A) in terms of promoting the curing reaction, while it is preferably 5 parts by mass or less, more preferably 1 part by mass or less, even more preferably 0.1 part by mass or less, and most preferably substantially none, in terms of maintaining low dielectric properties. The above-mentioned "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, relative to 100 parts by mass of the thermoplastic resin (A).

[0104] Examples of inorganic particles include calcium carbonate, magnesium carbonate, barium carbonate, magnesium sulfate, barium sulfate, calcium sulfate, zinc oxide, magnesium oxide, calcium oxide, titanium oxide, aluminum oxide, zinc oxide, alumina, aluminum hydroxide, hydroxyapatite, silica, magnesium silicate, mica, talc, kaolin, clay, glass powder, asbestos powder, zeolite, and clay silicate. Examples of organic particles include (meth)acrylate resin particles, styrene resin particles, silicone resin particles, nylon resin particles, polyethylene resin particles, benzoguanamine resin particles, and urethane resin particles.

[0105] <Resin sheet> The resin sheet of the present invention (hereinafter also referred to as "the present resin sheet") is obtained by molding the present composition in an uncured state into a sheet.

[0106] The thickness of the present resin sheet after curing is preferably from 1 to 300 μm, more preferably from 2 to 250 μm, and even more preferably from 5 to 200 μm. When the thickness of the resin sheet after curing is equal to or greater than the lower limit, the resin sheet has good handleability. When the thickness is equal to or less than the upper limit, the resin sheet can conform well to uneven surfaces of the circuit board when used as a circuit board material. The thickness is measured with a micrometer on a cured sheet obtained by heat pressing the resin sheet at 250° C. and 0.2 MPa for 30 minutes.

[0107] The relative dielectric constant of the resin sheet after curing is preferably 4 or less, more preferably 3 or less, and even more preferably 2.5 or less. On the other hand, there is no particular lower limit, and it is sufficient if it is 1 or more. The dielectric loss tangent of the resin sheet after curing is preferably 0.003 or less, more preferably 0.002 or less, and even more preferably 0.0015 or less. On the other hand, there is no particular lower limit, and it is sufficient if it is 0 or more. The above-mentioned relative permittivity and dielectric loss tangent were determined by measuring the in-plane relative permittivity and dielectric loss tangent of the cured sheet in TE mode using a cavity resonator (manufactured by AET) and a network analyzer MS46 122B (manufactured by Anritsu Corporation) on a test piece obtained by heat pressing the resin sheet at 250°C and 0.2 MPa for 30 minutes.

[0108] The storage modulus (130°C) of the resin sheet after curing is preferably 0.01 MPa or more, more preferably 0.05 MPa or more, and even more preferably 0.1 MPa or more, from the viewpoint of heat resistance. The upper limit is preferably 10,000 MPa or less, more preferably 1,000 MPa or less, from the viewpoint of flexibility. The storage modulus was determined by measuring the dynamic viscoelasticity of a test piece obtained by heat pressing the resin sheet at 250° C. and 0.2 MPa for 30 minutes to obtain a cured sheet.

[0109] The linear thermal expansion coefficient of the resin sheet after curing is preferably 1000 ppm / K or less, more preferably 750 ppm / K or less, even more preferably 500 ppm / K or less, and even more preferably 400 ppm / K or less. On the other hand, the lower limit of the linear thermal expansion coefficient is not particularly limited, but is preferably 0 ppm / K or more. When the linear thermal expansion coefficient is equal to or less than the upper limit, when the resin sheet is used as a circuit board material, warping when it is bonded to a conductor can be suppressed, and high reliability can be obtained. The above linear thermal expansion coefficient was determined as an average value from 0 to 120°C using a test piece obtained by heat-pressing the resin sheet at 250°C and 0.2 MPa for 30 minutes and using the cured sheet as a test piece according to the method described in the examples.

[0110] <Laminate> In order to improve the handling properties of the resin sheet, it is preferable to provide a release film on one or both surfaces of the resin sheet to form a laminate. As the release film, for example, a resin film whose main component is polyolefin such as polyethylene or polypropylene; polyester such as polyethylene terephthalate or polyethylene naphthalate; polyimide; polycarbonate, etc. can be used. The peel strength may be adjusted by applying a silicone resin release agent or the like. The thickness of the release film is preferably from 1 μm to 300 μm, more preferably from 5 μm to 200 μm, even more preferably from 10 μm to 150 μm, and even more preferably from 20 μm to 120 μm. The surface of the release film that comes into contact with the resin sheet may be subjected to a matte treatment, a corona treatment, or an antistatic treatment.

[0111] The laminate may be wound around a core to form a wound body. In this wound body, the length of the laminate is preferably 10 m or more, more preferably 20 m or more. When the resin sheet is used as a flexible laminate or a stretchable laminate, for example, the length of the laminate is 10 m or more, which allows for continuous production of electronic components and provides excellent continuous film production properties. The upper limit of the length is not particularly limited, but is preferably 1000 m or less. The material of the core is not particularly limited, but examples thereof include paper, resin-impregnated paper, acrylonitrile / butadiene / styrene copolymer (ABS resin), fiber-reinforced plastic (FRP), phenolic resin, inorganic resin, etc. An adhesive may be used for the core.

[0112] <Method of manufacturing resin sheet> Hereinafter, a method for producing the resin sheet will be described, but the method for producing the resin sheet is not limited to the following method.

[0113] [First manufacturing method] The first method for producing the present resin sheet includes a coating liquid preparation step of preparing a coating liquid comprising the present composition, and a molding step of molding the coating liquid into a sheet. The first production method is preferable in that the thermoplastic resin (A) and the compound (B) are suitably compatible with each other, and an optimum semi-IPN structure can be constructed after curing, resulting in good low dielectric properties.

[0114] (1) Coating liquid preparation process In the coating liquid preparation step, the thermoplastic resin (A), the compound (B), and the solvent (C) and other components added as needed are stirred and mixed uniformly to obtain the coating liquid. For mixing, a general mixing / stirring device such as a mixer, blender, three-roll kneader, ball mill, kneader, single-screw or twin-screw kneader can be used, and heating may be performed during mixing, if necessary.

[0115] (2) Molding process In the molding step, the coating liquid is molded into a sheet to obtain a resin sheet. The coating solution can be formed into a sheet by any known method, such as a doctor blade method, a solvent casting method, or an extrusion film formation method. A preferred forming method includes the following steps (2-1) coating and (2-2) drying.

[0116] (2-1) Coating process In the coating step, a coating liquid is applied to the surface of a release film to form a coating film. The coating method may be a common method such as a dipping method, a spin coating method, a spray coating method, a blade method, etc. Coating devices such as a spin coater, a slit coater, a die coater, and a blade coater can be used for coating, and this makes it possible to form a coating film of a predetermined thickness uniformly on the release film.

[0117] (2-2) Drying process In the drying step, 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. When the drying temperature is equal to or lower than the upper limit, the crosslinking reaction of the compound (B) in the coating film is suppressed. When the drying temperature is equal to or higher than the lower limit, foaming of the resin sheet is suppressed, the solvent can be effectively removed, and productivity is improved. The drying time can be adjusted appropriately depending on the state of the coating film, the drying environment, etc. It is preferably 1 minute or more, more preferably 2 minutes or more, even more preferably 5 minutes or more, still more preferably 10 minutes or more, particularly preferably 20 minutes or more, and most preferably 30 minutes or more. On the other hand, it is preferably 4 hours or less, more preferably 3 hours or less, and even more preferably 2 hours or less. When the drying time is equal to or longer than the lower limit, the solvent can be sufficiently removed. When the drying time is equal to or shorter than the upper limit, the productivity can be improved and the production cost can be reduced. The solvent in the resin composition can be easily removed by using a hot plate, a hot air oven, an IR heating oven, a vacuum dryer, or a high-frequency oven. It can be removed by a known heating method such as a heating machine.

[0118] From the viewpoint of preventing contamination of the surface of the resin sheet and improving handling properties, a release film may be laminated on the resin sheet after the drying step.

[0119] [Second manufacturing method] The second method for producing the present resin sheet includes a film-forming step of melt-kneading the present composition and forming it into a sheet-like film. The second production method does not require the use of a solvent and is therefore preferable in terms of cost, ease of multi-layering, and less susceptibility to problems caused by residual solvent.

[0120] In the film-forming process, the thermoplastic resin (A), the compound (B), and other components added as necessary are kneaded in a single-screw or twin-screw extruder, and then extruded onto a release film using an extruder or the like under temperature conditions that are equal to or higher than the melting point of the thermoplastic resin (A) and lower than the crosslinking temperature of the compound (B) to form a film. The method for extruding the resin composition is not particularly limited, but a more specific example is T-die molding.

[0121] <Cured sheet> The sheet cured product of the present invention (hereinafter also referred to as "main cured product") is obtained by curing the above-mentioned resin sheet.

[0122] The curing temperature may be any temperature at which the thermoplastic resin (A) does not flow and the crosslinking reaction of the compound (B) proceeds. Specifically, the curing temperature is usually 80°C or higher, and to further accelerate the crosslinking rate, the temperature is preferably 120°C or higher, more preferably 150°C or higher, and even more preferably 180°C or higher. Moreover, from the viewpoint of suppressing decomposition of the resin, 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 further increasing the hardness, it is 10 minutes or more, preferably 20 minutes or more, and 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.

[0123] <Applications of the resin composition, resin sheet, and cured sheet> Examples of applications of the resin composition, resin sheet, and cured sheet of the present invention include, but are not limited to, copper foil laminates, stretchable substrates, flexible printed circuit boards, multilayer printed wiring boards, circuit board materials for electric and electronic devices such as capacitors, underfill materials, interchip fills for 3D-LSI, insulating sheets, vibration damping materials, adhesives, solder resists, semiconductor encapsulants, hole filling resins, and component embedding resins.

[0124] <Circuit board materials> The resin sheet of the present invention can be used as a circuit board material by laminating it with a conductor.

[0125] The conductor may be a metal foil made of a conductive metal such as copper or aluminum, or an alloy containing such a metal, or a metal layer formed by plating or sputtering.

[0126] When used as a circuit board material for electric and electronic devices, the thickness of the resin sheet is preferably 10 μm or more and 500 μm or less, and the thickness of the conductor is preferably 0.2 μm or more and 70 μm or less.

[0127] <Method of manufacturing circuit board materials> The circuit board material of the present invention can be produced, for example, by the following method. After laminating the resin sheet of the present invention on a conductor, the resin sheet is heat-cured to form an insulating layer, on which a conductor is further laminated, and such layers are stacked as many times as necessary.

[0128] The curing temperature of the resin sheet may be any temperature at which the thermoplastic resin (A) does not flow and the crosslinking reaction of the compound (B) proceeds. Specifically, the curing temperature is usually 80°C or higher, and to further accelerate the crosslinking rate, the curing temperature is preferably 120°C or higher, more preferably 150°C or higher, and even more preferably 180°C or higher. Moreover, from the viewpoint of suppressing decomposition of the resin, 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 further increasing the hardness, it is 10 minutes or more, preferably 20 minutes or more, and 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.

[0129] The lamination of the resin sheet and the conductor may be performed by directly laminating a conductive metal foil on the resin sheet, by bonding the resin sheet and the conductive metal foil with an adhesive, by forming a conductive metal layer by plating or sputtering, or by combining these methods. The method may also include a step of drilling holes in the insulating layer to form via holes, and a step of roughening the surface of the insulating layer. [Example]

[0130] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples in any way.

[0131] <Raw materials> [Thermoplastic resin (A)] a-1: Styrene-ethylene-butadiene-styrene block copolymer (SEBS: Asahi Kasei Corporation's "Tuftec H1052", styrene content = 20% by mass, storage modulus (24°C) = 6.2 MPa, density = 890 g / cm 3 , dielectric tangent (10GH2) = 0.0004)

[0132] [Compound (B)] b-1: Compound A prepared by the following method was used as compound b-1. [Synthesis of Compound A] [ka]

[0133] 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)

[0134] b-2: Compound B prepared by the following method was used as compound b-2. [Synthesis of Compound B] <Synthesis of Intermediate B-1> [ka]

[0135] 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.

[0136] <Synthesis of Compound B> [ka]

[0137] 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)

[0138] b-3: Compound C prepared by the following method was used as compound b-3. [Synthesis of Compound C] <Synthesis of Intermediate C-1> [ka]

[0139] 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).

[0140] <Synthesis of Intermediate C-2> [ka]

[0141] 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).

[0142] <Synthesis of intermediate C-3> [ka]

[0143] 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).

[0144] <Synthesis of intermediate C-4> [ka]

[0145] 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%).

[0146] <Synthesis of Intermediate C-5> [ka]

[0147] 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%).

[0148] <Synthesis of Compound C> [ka]

[0149] 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%).

[0150] [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.

[0151] [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.

[0152] [Example 6] The raw materials were fed to a Plastograph (manufactured by Toyo Seiki Co., Ltd.) in the proportions shown in Table 1 and melt-kneaded at a temperature of 150°C, a rotation speed of 60 rpm, and a kneading time of 10 minutes. A 75 μm-thick release film (Chukoh Flow G-type processed product, manufactured by Chukoh Chemical Industries, Ltd.) was laminated on both sides of the resulting resin composition to form a laminate. This laminate was 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 thickness of the resin sheet was adjusted so that the thickness of the cured sheet was approximately 300 μm. The dielectric properties, storage modulus, and linear thermal expansion coefficient of the obtained cured sheet were measured by the following methods. The results are shown in Table 1.

[0153] [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.

[0154] (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℃

[0155] (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℃

[0156] [Table 1]

[0157] Examples 1 to 6 and Comparative Example 1 demonstrate that by adding a compound (B) having a specific structure to a thermoplastic resin (A), it is possible to suppress deformation (flow) of the resin composition even at a temperature (130°C) at which the thermoplastic resin (A) alone would flow, while maintaining low dielectric properties, and also to suppress the coefficient of linear thermal expansion and improve heat resistance. In Comparative Example 2, since there was only one benzocyclobutene crosslinking group in the molecule of compound (B), it was difficult to increase the crosslinking density, the storage modulus at 130°C was low, and heat resistance was not improved.

[0158] In the above examples, no olefin-based thermoplastic elastomer or ethylene-based polymer was used as the thermoplastic resin (A). However, based on the mechanism that the heat resistance can be improved by entanglement of the molecular chains of the crosslinked product of the thermoplastic resin (A) and the compound (B), the same effects as those of the styrene-based thermoplastic elastomer can be expected.< / y> < / arom>

Claims

1. A resin composition comprising at least one thermoplastic resin (A) selected from the group consisting of a styrene-based thermoplastic elastomer, an olefin-based thermoplastic elastomer, and an ethylene-based polymer, and a compound (B) 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 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 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 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) is bonded to Arom.

2. The resin composition according to claim 1 , wherein the thermoplastic resin (A) comprises a styrene-based thermoplastic elastomer.

3. The resin composition according to claim 2 , wherein the styrene content of the styrene-based thermoplastic elastomer is 10% by mass or more and 70% by mass or less.

4. The bonding group L of the compound (B) ２１ The resin composition according to any one of claims 1 to 3, wherein is an oxygen atom, a sulfur atom, an alkylene group, or an aromatic group.

5. The resin composition according to any one of claims 1 to 4, wherein the subscript z of the compound (B) is 0 to 2.

6. The resin composition according to any one of claims 1 to 5, which is substantially free of a polymerization initiator.

7. A resin sheet comprising the resin composition according to any one of claims 1 to 6.

8. A laminate comprising the resin sheet according to claim 7 and a release film on one or both surfaces thereof.

9. A cured sheet obtained by curing the resin sheet according to claim 7.

10. A circuit board material obtained by laminating an insulating layer made of the resin sheet according to claim 7 and a conductor.

11. a coating liquid preparation step of preparing a coating liquid comprising a resin composition containing at least one thermoplastic resin (A) selected from the group consisting of a styrene-based thermoplastic elastomer, an olefin-based thermoplastic elastomer, and an ethylene-based polymer, and a compound (B) represented by the following general formula (1); and a molding step of molding the coating liquid into a sheet. 【Chemistry 4】 (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.) 【Transformation 5】 (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 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 6】 (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) is bonded to Arom.

12. A method for producing a resin sheet, comprising a film-forming step of melt-kneading a resin composition containing at least one thermoplastic resin (A) selected from the group consisting of a styrene-based thermoplastic elastomer, an olefin-based thermoplastic elastomer, and an ethylene-based polymer, and a compound (B) represented by the following general formula (1), and forming the resulting mixture into a sheet. 【Transformation 7】 (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.) 【Transformation 8】 (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 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.) 【Chemistry 9】 (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) is bonded to Arom.

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