Compound, curable resin composition and cured product thereof

Abstract

The present invention provides a compound having excellent low dielectric properties, a curable resin composition, and a cured product thereof. A compound obtained by reacting an acid-modified hydrogenated thermoplastic styrenic elastomer (AH-AB), which is an acid-modified product of a hydrogenated block copolymer (H-AB) consisting of block units (A) of a polymer made of a styrene monomer and block units (B) of a polymer made of a conjugated diene compound, with allylamine or allylamine hydrochloride.

Description

[Technical field]

[0001] The present invention relates to a compound having a specific structure, a curable resin composition and a cured product thereof, which are suitable for use in electrical and electronic components such as semiconductor encapsulants, printed wiring boards and build-up laminates, lightweight and high-strength materials such as carbon fiber reinforced plastics and glass fiber reinforced plastics, and 3D printing applications. [Background technology]

[0002] In recent years, the required characteristics of laminates on which electric and electronic components are mounted have become more extensive and sophisticated due to the expansion of the fields in which they are used. Conventional semiconductor chips were mainly mounted on metal lead frames, but semiconductor chips with high processing power, such as central processing units (hereinafter referred to as CPUs), are increasingly being mounted on laminates made of polymer materials.

[0003] The fifth generation communication system "5G", whose development is currently accelerating, is expected to further increase capacity and speed of communication. 5G will use higher and higher frequencies, but reducing transmission loss is important to achieve high-speed communication using high frequencies, and there will be a demand for even lower dielectric properties (low dielectric constant and low dielectric tangent) in circuit board materials. Transmission loss that occurs on printed circuit boards is due to conductor loss and dielectric loss. As described in Non-Patent Document 1, dielectric loss α D is the relative dielectric constant of the dielectric, ε γ Since the dielectric constant is proportional to the square root of the dielectric constant and the dielectric tangent tanδ, it can be said that reducing the dielectric tangent, which has a greater contribution than the relative dielectric constant, is effective in reducing dielectric loss. Thermoplastic materials such as PTFE (polytetrafluoroethylene) and LCP (liquid crystal polymer) are examples of low-dielectric materials, but they are less moldable than thermosetting resins. In light of this, there is a demand for the development of thermosetting resins with excellent low-dielectric properties.

[0004] In light of this background, thermosetting resins with excellent low dielectric properties have been studied. For example, Patent Document 1 proposes a thermosetting resin composition containing an imide compound having a maleimide group and a phenol aralkyl resin having an aliphatic unsaturated bond. However, on the other hand, since phenolic hydroxyl groups that do not participate in the reaction remain during the curing reaction, the electrical properties are not sufficient. Patent Document 2 also discloses an allyl ether-modified biphenyl aralkyl novolac resin in which an allyl group is added to a phenolic hydroxyl group. However, it has been shown that the Claisen rearrangement occurs in the allyl ether-modified biphenyl novolac resin at 190°C, and at 200°C, which is the molding temperature of a general substrate, phenolic hydroxyl groups that do not contribute to the curing reaction are generated, so the electrical properties are not satisfactory. [Prior art documents] [Non-patent literature]

[0005] [Non-Patent Document 1] "Factors of Signal Loss in High-Speed ​​Signal Transmission on Printed Circuit Boards", 29th Spring Conference of the Japan Institute of Electronics Packaging, Session ID: 16P1-17, 2015 [Patent documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 04-359911 [Patent Document 2] International Publication No. 2016 / 002704 Summary of the Invention [Problem to be solved by the invention]

[0007] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a compound having excellent low dielectric properties, a curable resin composition, and a cured product thereof. [Means for solving the problem]

[0008] That is, the present invention relates to the following [1] to

[11] . Note that in this application, "(Numerical value 1) to (Numerical value 2)" indicates that the upper and lower limits are included.

[0009] [1] A compound obtained by reacting an acid-modified hydrogenated thermoplastic styrenic elastomer (AH-AB), which is an acid-modified product of a hydrogenated block copolymer (H-AB) consisting of block units (A) of a polymer made of a styrene monomer and block units (B) of a polymer made of a conjugated diene compound, with allylamine or allylamine hydrochloride. [2] The compound according to item [1] above, wherein the block unit (A) of the polymer made of the styrene-based monomer has a structure represented by the following formula (a): [ka] In formula (1), R1 and R2 each represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, p represents an average value of the number of repetitions and represents a real number of 1 to 10,000. [3] The compound according to the above item [1], wherein the block unit (B) of the polymer made of the conjugated diene compound is obtained by polymerizing at least one diene compound selected from 1,3-butadiene, isoprene, farnesene, 2,3-dimethyl-1,3-butadiene, and 1,3-pentadiene. [4] The compound according to the above item [1], wherein the hydrogenated product of the block copolymer (H-AB) is a compound represented by the following formula (1):

[0010] [ka]

[0011] In formula (1), R1 and R2 are each a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, p is 1 to 5, and j, k, l, m, and n are the average number of repeats and represent real numbers of 1 to 10000. The order of each repeat unit bracketed by k and l, or j, m, and n, is not limited, and the bonding mode may be any of alternating, block, and random.

[0012] [5] The compound according to the above item [1], wherein the acid-modified hydrogenated thermoplastic styrene-based elastomer (AH-AB) is a compound represented by the following formula (2): [ka] In formula (2), R1 and R2 are each a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, p is 1 to 5, and j, k, l, m, and n are the average number of repeats and represent real numbers of 1 to 10000. The order of each repeat unit bracketed by k and l, or j, m, and n, is not limited, and the bonding mode may be any of alternating, block, and random.

[0013] [6] A compound represented by the following formula (3):

[0014] [ka]

[0015] (In formula (3), j, k, l, m, and n are average values ​​of the number of repetitions and represent real numbers from 1 to 10,000. The order of the repetition units grouped by k and l, or j, m, and n, is not limited, and the bonding pattern may be any of alternating, block, and random.)

[0016] [7] A curable resin composition comprising the compound according to any one of items [1] to [6] above. [8] The curable resin composition according to item [7] above, further comprising a polymerization initiator. [9] The curable resin composition according to item [7] or [8] above, further comprising at least one selected from the group consisting of a maleimide compound, a polyphenylene ether compound, a compound having an ethylenically unsaturated bond, a cyanate ester resin, polybutadiene and modified products thereof, polystyrene and modified products thereof, and polyethylene and modified products thereof.

[10] A cured product of the compound according to any one of the preceding items [1] to [6].

[11] A cured product of the curable resin composition according to any one of items [7] to [9] above. Effect of the Invention

[0017] According to the present invention, it is possible to provide a compound having excellent low dielectric properties, a curable resin composition, and a cured product thereof. [Brief description of the drawings]

[0018] [Figure 1] 1 shows a GPC chart of Synthesis Example 1. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0019] The compound of the present invention can be obtained by reacting an acid-modified hydrogenated thermoplastic styrenic elastomer (AH-AB), which is an acid-modified product of a hydrogenated block copolymer (H-AB) consisting of block units (A) of a polymer consisting of a styrene monomer and block units (B) of a polymer consisting of a conjugated diene compound, with allylamine or allylamine hydrochloride.

[0020] The block unit (A) of the polymer made of a styrene-based monomer preferably has a structure represented by the following formula (a).

[0021] [ka]

[0022] Each of R1 and R2 is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, particularly preferably a hydrogen atom or a methyl group, and most preferably a hydrogen atom. If the number of carbon atoms is more than 5, the dielectric tangent may deteriorate due to molecular vibration, and heat resistance may decrease. p is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1. q is the average number of repetitions and represents a real number of 1 to 10,000, and q is preferably 1 to 7,500, more preferably 1 to 5,000, and even more preferably 1 to 3,000.

[0023] The block unit (B) of the polymer made of a conjugated diene compound is obtained by polymerizing at least one diene compound selected from linear conjugated dienes such as 1,3-butadiene, isoprene, farnesene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, etc. From the viewpoint of availability of raw materials, among the linear conjugated dienes, 1,3-butadiene, isoprene, and farnesene are preferred, 1,3-butadiene and isoprene are more preferred, and 1,3-butadiene is most preferred.

[0024] Any known material may be used as the hydrogenated block copolymer (H-AB), but a compound represented by the following formula (1) is preferred.

[0025] [ka]

[0026] In formula (1), the values ​​and preferred ranges of R1, R2, and p are the same as those in formula (a). j, k, l, m, and n are the average number of repeats and represent real numbers of 1 to 10,000, preferably 1 to 9,000, and more preferably 1 to 8,000. The order of each repeat unit bounded by k and l, or j, m, and n, is not limited, and the bonding style may be any of alternating, block, and random. In particular, a compound represented by the following formula (1-1) is preferred. [ka]

[0027] In formula (1-1), the values ​​and preferred ranges of j, k, l, m, and n are the same as those in formula (1). The order of the repeating units bounded by k and l, or j, m, and n, is not limited, and the bonding pattern may be any of alternating, block, and random.

[0028] The most preferred embodiment of the hydrogenated block copolymer (H-AB) is a hydrogenated styrene-butadiene-styrene block copolymer (SEBS).

[0029] The compound represented by the formula (1) does not have a polar group or an unsaturated bond derived from an aliphatic hydrocarbon, so it is not easily oxidized even when exposed to temperatures of 125°C or higher, which is the temperature at which semiconductors are guaranteed to operate, for a long period of time, and the oxygen contained in the polar group is not easily incorporated into the skeleton. Therefore, deterioration of the dielectric properties after high-temperature storage tests can be reduced, and the compound also has excellent low water absorption properties.

[0030] Although any known material may be used as the acid-modified hydrogenated thermoplastic styrene-based elastomer (AH-AB), a compound represented by the following formula (2) is preferable.

[0031] [ka]

[0032] The values ​​and preferred ranges of R1, R2, p, j, k, l, m, and n in formula (2) are the same as those in formula (1). The order of the repeating units bounded by k and l, or j, m, and n, is not limited, and the bonding pattern may be any of alternating, block, and random.

[0033] In particular, a compound represented by the following formula (2-1) is preferred. [ka]

[0034] The values ​​and preferred ranges of j, k, l, m, and n in formula (2-1) are the same as those in formula (1). The order of the repeating units bounded by k and l, or j, m, and n, is not limited, and the bonding pattern may be any of alternating, block, and random.

[0035] The most preferred embodiment of the acid-modified hydrogenated thermoplastic styrene-based elastomer (AH-AB) is an acid-modified hydrogenated styrene-butadiene-styrene block copolymer (SEBS).

[0036] The compound represented by the formula (2) can be obtained by reacting the compound represented by the formula (1) with maleic anhydride in the presence of a radical polymerization initiator, or by reacting the compound represented by the formula (1) with maleic acid in the presence of a radical polymerization initiator, followed by dehydration. The compound represented by the formula (2-1) can be obtained by reacting the compound represented by the formula (1-1) with maleic anhydride in the presence of a radical polymerization initiator, or by reacting the compound represented by the formula (1-1) with maleic acid in the presence of a radical polymerization initiator, followed by dehydration.

[0037] The content of styrene-derived structural units in the acid-modified hydrogenated thermoplastic styrene-based elastomer (AH-AB) (hereinafter sometimes abbreviated as styrene content) may be 5 to 80 mass%, 5 to 70 mass%, 10 to 70 mass%, or 10 to 50 mass% from the viewpoints of high-frequency characteristics (low dielectric constant, low dielectric tangent), adhesion to a conductor, heat resistance, glass transition temperature, and thermal expansion coefficient. The melt flow rate (MFR) of the acid-modified hydrogenated thermoplastic styrene-based elastomer (AH-AB) is not particularly limited, but may be 0.1 to 20 g / 10 min or 0.5 to 15 g / 10 min under the measurement conditions of 230° C. and a load of 2.16 kgf (21.2 N).

[0038] Commercially available acid-modified hydrogenated thermoplastic styrene-based elastomers (AH-AB) include, for example, the Tuftec (registered trademark) M series manufactured by Asahi Kasei Corporation.

[0039] A preferred structure of the compound of the present invention obtained by reacting the acid-modified hydrogenated thermoplastic styrene-based elastomer (AH-AB) with allylamine or allylamine hydrochloride is represented by the following formula (3).

[0040] [ka]

[0041] The values ​​and preferred ranges of R1, R2, p, j, k, l, m, and n in formula (3) are the same as those in formula (1). The order of the repeating units bounded by k and l, or j, m, and n, is not limited, and the bonding pattern may be any of alternating, block, and random.

[0042] In particular, a compound represented by the following formula (3-1) is preferred. [ka] The values ​​and preferred ranges of j, k, l, m, and n in formula (3-1) are the same as those in formula (1). The order of the repeating units bounded by k and l, or j, m, and n, is not limited, and the bonding pattern may be any of alternating, block, and random.

[0043] The most preferred embodiment of the compound of the present invention is a compound having a structure derived from an acid-modified hydrogenated styrene-butadiene-styrene block copolymer (SEBS).

[0044] The reaction of the acid-modified hydrogenated thermoplastic styrene elastomer (AH-AB) with allylamine or allylamine hydrochloride may be carried out by any known imidization reaction method, for example, by reacting the acid-modified hydrogenated thermoplastic styrene elastomer (AH-AB) with allylamine or allylamine hydrochloride in a non-water-soluble aromatic hydrocarbon solvent such as toluene, xylene, mesitylene, etc., while removing the generated water from the system by azeotropy. As the imidization catalyst, a base catalyst such as triethylamine, or an acid catalyst such as activated clay, paratoluenesulfonic acid, methanesulfonic acid, hydrochloric acid, etc. may be used. In order to dissolve the amic acid and promote the imidization process, an aprotic polar solvent such as N-methyl-2-pyrrolidone or N,N-dimethylformamide may be used in combination. Allylamine or allylamine hydrochloride is preferably used in an amount of 0.5 to 1.5 mol per mol of the acid anhydride structure, more preferably 0.8 to 1.2 mol, and most preferably 0.9 to 1.1 mol. Outside the above range, the dielectric properties may be deteriorated due to the polar groups of the remaining raw materials. The reaction is carried out at 80 to 200°C, preferably 100 to 180°C, for 0.5 to 20 hours.

[0045] The number average molecular weight of the compound of the present invention, as determined by gel permeation chromatography (GPC), is preferably 10,000 or more and less than 1,000,000, more preferably 20,000 or more and less than 500,000, and even more preferably 30,000 or more and less than 250,000. If it is less than 10,000, the heat resistance in the solder reflow process may be impaired. If it is 1,000,000 or more, the solvent solubility may be impaired or the compound may not be sufficiently compatible with other thermosetting resin components.

[0046] The curable resin composition of the present invention can be used by mixing with the compound of the present invention as well as various materials shown below.

[0047] [Polymerization initiator] The curable resin composition of the present invention can also improve the curability by adding a polymerization initiator. The polymerization initiator is a compound capable of polymerizing an olefin functional group such as an ethylenically unsaturated bond, and examples of the polymerization initiator include an olefin metathesis polymerization initiator, an anionic polymerization initiator, a cationic polymerization initiator, and a radical polymerization initiator. Among these, it is preferable to use a radical polymerization initiator having curability and moderate stability. The radical polymerization initiator is a compound that generates radicals by irradiation with ultraviolet light or visible light or by heating, and initiates a chain polymerization reaction. Examples of radical polymerization initiators that can be used include organic peroxides, azo compounds, and benzopinacoles, and it is preferable to use an organic peroxide because it has little effect on curing temperature control, outgassing suppression, and electrical properties of decomposition products.

[0048] Examples of the organic peroxides include ketone peroxides such as methyl ethyl ketone peroxide and acetylacetone peroxide, diacyl peroxides such as benzoyl peroxide, dialkyl peroxides such as dicumyl peroxide and 1,3-bis-(t-butylperoxyisopropyl)-benzene, peroxyketals such as t-butyl peroxybenzoate and 1,1-di-t-butylperoxycyclohexane, α-cumyl peroxyneodecanoate, t-butyl peroxyneodecanoate, t-butyl peroxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-amyl peroxy-2-ethylhex ...amyl peroxy-2-ethylhexanoate, t-butyl peroxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-amyl peroxy-2-ethylhexanoate, t-butyl peroxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-amyl peroxy-2-ethylhexanoate, t-butyl peroxypivalate, 1,1, Examples of the peroxycarbonates include, but are not limited to, alkyl peresters such as t-amyl peroxy-2-ethylhexanoate, t-amyl peroxy-3,5,5-trimethylhexanoate, t-butyl peroxy-3,5,5-trimethylhexanoate, and t-amyl peroxybenzoate, peroxycarbonates such as di-2-ethylhexyl peroxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, t-butyl peroxyisopropyl carbonate, and 1,6-bis(t-butylperoxycarbonyloxy)hexane, t-butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxyoctoate, and lauroyl peroxide. These may be used alone or in combination. Among the above organic peroxides, ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, alkyl peresters, percarbonates, etc. are preferred, and dialkyl peroxides are more preferred.

[0049] Examples of the azo-based compound include, but are not limited to, azobisisobutyronitrile, 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2,4-dimethylvaleronitrile), etc. These may be used alone or in combination.

[0050] The amount of the polymerization initiator added is preferably 0.01 to 5 parts by mass, particularly preferably 0.01 to 3 parts by mass, in 100 parts by mass of the curable resin composition. If the amount of the polymerization initiator used is less than 0.01 part by mass, the molecular weight may not be sufficiently extended during the polymerization reaction, and if it is more than 5 parts by mass, the dielectric properties such as the dielectric constant and the dielectric loss tangent may be impaired.

[0051] [Cure accelerator] The curable resin composition of the present invention can also have improved curability by adding a curing accelerator. As the curing accelerator, an anionic curing accelerator that accelerates the curing reaction by generating anions upon irradiation with ultraviolet light or visible light or heating, or a cationic curing accelerator that accelerates the curing reaction by generating cations upon irradiation with ultraviolet light or visible light or heating, is preferred.

[0052] Examples of anionic curing accelerators include imidazoles such as 2-methylimidazole, 2-ethylimidazole, and 2-ethyl-4-methylimidazole, trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6,-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo(5,4,0)-undecene, with 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)-undecene being preferred. Other examples include phosphines such as triphenylphosphine, quaternary ammonium salts such as tetrabutylammonium salts, triisopropylmethylammonium salts, trimethyldecanylammonium salts, cetyltrimethylammonium salts, and hexadecyltrimethylammonium hydroxide, but are not limited thereto. These may be used alone or in combination.

[0053] Examples of cationic curing accelerators include quaternary phosphonium salts such as triphenylbenzylphosphonium salt, triphenylethylphosphonium salt, and tetrabutylphosphonium salt (counter ions of quaternary salts are halogen, organic acid ions, hydroxide ions, etc., and are not particularly specified, but organic acid ions and hydroxide ions are particularly preferred), transition metal compounds (transition metal salts) such as tin octylate, zinc carboxylate (zinc 2-ethylhexanoate, zinc stearate, zinc behenate, zinc myristate), and zinc phosphate (zinc octyl phosphate, zinc stearyl phosphate), but are not limited thereto. These may be used alone or in combination.

[0054] The curing accelerator is used in an amount of 0.01 to 5.0 parts by mass based on 100 parts by mass of the curable resin composition, as required.

[0055] [Inorganic filler] The curable resin composition of the present invention may contain an inorganic filler. Examples of inorganic fillers include powders such as fused silica, crystalline silica, porous silica, alumina, zircon, calcium silicate, calcium carbonate, quartz powder, silicon carbide, silicon nitride, boron nitride, zirconia, aluminum nitride, graphite, forsterite, steatite, spinel, mullite, titania, talc, clay, iron oxide asbestos, and glass powder, and inorganic fillers obtained by making these into a spherical or crushed shape, but are not limited thereto. In addition, these may be used alone or in combination.

[0056] When the inorganic filler is used to obtain a curable resin composition for semiconductor encapsulation, the amount of the inorganic filler used is preferably 80 to 92 parts by mass, more preferably 83 to 90 parts by mass, based on 100 parts by mass of the curable resin composition. When the curable resin composition is used to obtain a curable resin composition for an interlayer insulating layer forming material, a copper-clad laminate, a prepreg, an RCC, or other substrate material, the amount of the inorganic filler used is preferably 5 to 80 parts by mass, more preferably 10 to 60 parts by mass, based on 100 parts by mass of the curable resin composition.

[0057] [Polymerization inhibitor] The curable resin composition of the present invention may contain a polymerization inhibitor. By containing a polymerization inhibitor, storage stability is improved and the reaction initiation temperature can be controlled. By controlling the reaction initiation temperature, it becomes easy to ensure fluidity, impregnation into glass cloth and the like is not impaired, and B-stage such as prepreg formation is facilitated. If the polymerization reaction proceeds too much during prepreg formation, problems such as difficulty in lamination during the lamination process are likely to occur.

[0058] The polymerization inhibitor may be added when the compound of the present invention is synthesized or after the synthesis. The amount of the polymerization inhibitor used is 0.008 to 1 part by weight, preferably 0.01 to 0.5 part by weight, based on 100 parts by mass of the compound of the present invention.

[0059] Examples of the polymerization inhibitor include phenol-based, sulfur-based, phosphorus-based, hindered amine-based, nitroso-based, and nitroxyl radical-based. The polymerization inhibitor may be used alone or in combination. Among these, the phenol-based, hindered amine-based, nitroso-based, and nitroxyl radical-based are preferred in the present invention.

[0060] Examples of the phenol-based polymerization inhibitor include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, stearyl-β-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, 2,4-bis[(octylthio)methyl]-o ... Monophenols such as resol, 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol), 4,4'-thiobis(3-methyl-6-t-butylphenol), 4,4'-butylidenebis(3-methyl-6-t-butylphenol), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] , N,N'-Hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, 3,9-bis[1,1-dimethyl-2-{β-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}ethyl]2,4,8,10-tetraoxaspiro[5,5]undecane, bis(3,5-di-t-butyl Bisphenols such as calcium ethyl-4-hydroxybenzylsulfonate, 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, tetrakis-[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methane, bis[3,3'-bis-(4'-hydroxy-3'-t-butylphenyl)butyric acid]glycol ester, tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-tris(3',5'-di-t-butyl-4'-hydroxybenzyl)-S-triazine-2,4,6-(1H,3H,5H)trione, tocopherol and other polymeric phenols are included, but are not limited to these.

[0061] Examples of the sulfur-based polymerization inhibitor include, but are not limited to, dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, and distearyl-3,3'-thiodipropionate.

[0062] Examples of the phosphorus-based polymerization inhibitor include triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, tris(nonylphenyl) phosphite, diisodecyl pentaerythritol phosphite, tris(2,4-di-t-butylphenyl) phosphite, cyclic neopentane tetrayl bis(octadecyl) phosphite, cyclic neopentane tetrayl bis(2,4-di-t-butylphenyl) phosphite, cyclic neopentane tetrayl bis(2,4-di-t-butyl-4-methylphenyl) phosphite, bis[2- Examples of the phosphites include t-butyl-6-methyl-4-{2-(octadecyloxycarbonyl)ethyl}phenyl]hydrogen phosphite, and the like; and oxaphosphaphenanthrene oxides such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(3,5-di-t-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, but are not limited to these.

[0063] Examples of the hindered amine polymerization inhibitor include, but are not limited to, Adeka STAB LA-40MP, Adeka STAB LA-40Si, Adeka STAB LA-402AF, Adeka STAB LA-87, Adeka STAB LA-82, Adeka STAB LA-81, Adeka STAB LA-77Y, Adeka STAB LA-77G, Adeka STAB LA-72, Adeka STAB LA-68, Adeka STAB LA-63P, Adeka STAB LA-57, Adeka STAB LA-52, Chimassorb 2020FDL, Chimassorb 944FDL, Chimassorb 944LD, Tinuvin 622SF, Tinuvin PA144, Tinuvin 765, Tinuvin 770DF, Tinuvin XT55FB, Tinuvin 111FDL, Tinuvin 783FDL, Tinuvin 791FB, and the like.

[0064] Examples of the nitroso-based polymerization inhibitor include, but are not limited to, p-nitrosophenol, N-nitrosodiphenylamine, and ammonium salt of N-nitrosophenylhydroxyamine (cupferron), etc. Among these, the ammonium salt of N-nitrosophenylhydroxyamine (cupferron) is preferred.

[0065] Examples of the nitroxyl radical polymerization inhibitor include di-tert-butyl nitroxide, 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-amino-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-acetoxy-2,2,6,6-tetramethylpiperidine-1-oxyl, and 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl, but are not limited thereto.

[0066] [Flame retardant] The curable resin composition of the present invention may contain a flame retardant. Examples of the flame retardant include halogen-based flame retardants, inorganic flame retardants (antimony compounds, metal hydroxides, nitrogen compounds, boron compounds, etc.), and phosphorus-based flame retardants. From the viewpoint of achieving halogen-free flame retardancy, phosphorus-based flame retardants are preferred. The phosphorus-based flame retardant may be of reactive type or additive type. Specific examples include phosphoric acid esters such as trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylyleneyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylyleneyl phosphate, 1,3-phenylene bis(dixylyleneyl phosphate), 1,4-phenylene bis(dixylyleneyl phosphate), and 4,4'-biphenyl(dixylyleneyl phosphate), phosphanes such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 10(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, phosphorus-containing epoxy compounds obtained by reacting epoxy resins with active hydrogen of the phosphanes, red phosphorus, etc., but are not limited thereto. Also, these may be used alone or in combination. Of the above-listed substances, phosphates, phosphanes, or phosphorus-containing epoxy compounds are preferred, with 1,3-phenylenebis(dixylilenyl phosphate), 1,4-phenylenebis(dixylilenyl phosphate), 4,4'-biphenyl(dixylilenyl phosphate) or phosphorus-containing epoxy compounds being particularly preferred.

[0067] The content of the flame retardant is preferably in the range of 0.1 to 0.6 parts by mass in 100 parts by mass of the curable resin composition. If the content is less than 0.1 part by mass, the flame retardancy may be insufficient, and if the content is more than 0.6 part by mass, the moisture absorption and dielectric properties of the cured product may be adversely affected.

[0068] [Light stabilizer] The curable resin composition of the present invention may contain a light stabilizer. As the light stabilizer, a hindered amine light stabilizer, particularly HALS, etc., is preferable. Examples of HALS include the reaction product of dibutylamine·1,3,5-triazine·N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine and N-(2,2,6,6-tetramethyl-4-piperidyl)butylamine, the reaction product of dimethyl succinate-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, poly[{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidyl)imino}hexamethylene{(2,2,6,6-tetramethyl-4-piperidyl)imino}], bis(1,2 ,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl] butyl malonate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, 2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-n-butyl malonate bis(1,2,2,6,6-pentamethyl-4-piperidyl) and the like, but are not limited thereto. These may be used alone or in combination.

[0069] The content of the light stabilizer is preferably in the range of 0.001 to 0.1 parts by mass in 100 parts by mass of the curable resin composition. If the content is less than 0.001 parts by mass, the light stabilizing effect may be insufficient, and if the content is more than 0.1 parts by mass, the moisture absorption and dielectric properties of the cured product may be adversely affected.

[0070] [Binder resin] The curable resin composition of the present invention may use a binder resin. Examples of binder resins include, but are not limited to, butyral resins, acetal resins, acrylic resins, epoxy-nylon resins, NBR-phenol resins, epoxy-NBR resins, and silicone resins. These may be used alone or in combination.

[0071] The amount of the binder resin is preferably within a range that does not impair the flame retardancy and heat resistance of the cured product, and is preferably 0.05 to 50 parts by mass, and more preferably 0.05 to 20 parts by mass, per 100 parts by mass of the curable resin composition, as needed.

[0072] [Additives] The curable resin composition of the present invention may contain additives, such as modified acrylonitrile copolymers, polyethylene, fluororesins, silicone gels, silicone oils, surface treatment agents for fillers such as silane coupling agents, release agents, and colorants such as carbon black, phthalocyanine blue, and phthalocyanine green.

[0073] The amount of the additive is preferably 1 part by mass or less, and more preferably 0.7 parts by mass or less, based on 100 parts by mass of the curable resin composition.

[0074] The curable resin composition of the present invention may further include epoxy resins, active ester compounds, phenolic resins, polyphenylene ether compounds, amine resins, compounds having ethylenically unsaturated bonds, isocyanate resins, polyamide resins, maleimide compounds, cyanate ester resins, polyimide resins, polybutadiene and modified products thereof, polystyrene and modified products thereof, polyethylene and modified products thereof, etc., which may be used alone or in combination. Among these compounds, it is preferable to contain maleimide compounds, polyphenylene ether compounds, compounds having ethylenically unsaturated bonds, cyanate ester resins, polybutadiene and modified products thereof, polystyrene and modified products thereof, and polyethylene and modified products thereof, from the perspective of the balance of heat resistance, adhesion, and dielectric properties. By containing these compounds, the brittleness of the cured product and adhesion to metals can be improved, and cracks in the package during solder reflow and during reliability tests such as thermal cycles can be suppressed. The total amount of the above compounds used is preferably 10 times by mass or less, more preferably 5 times by mass or less, and particularly preferably 3 times by mass or less, relative to the compound of the present invention, unless otherwise specified. The lower limit is preferably 0.1 times by mass or more, more preferably 0.25 times by mass or more, and even more preferably 0.5 times by mass or more. By being within the above range, the effect of the low dielectric property of the compound of the present invention can be utilized while the effect of each compound added can be added. As these components, the following examples can be used.

[0075] [Epoxy resin] Preferred examples of the epoxy resin are shown below, but the epoxy resin is not limited thereto. The epoxy resin may be liquid or solid, and may be used alone or in combination.

[0076] Examples of liquid epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, phenol novolac type epoxy resins, alicyclic epoxy resins having an ester skeleton, cyclohexane type epoxy resins, cyclohexane dimethanol type epoxy resins, glycidyl amine type epoxy resins, and epoxy resins having a butadiene structure. Specific examples include "RE310S", "RE410S" (all manufactured by Nippon Kayaku Co., Ltd., bisphenol A type epoxy resin), "RE303S", "RE304S", "RE403S", "RE404S" (all manufactured by Nippon Kayaku Co., Ltd., bisphenol F type epoxy resin), "HP4032", "HP4032D", "HP4032SS" (all manufactured by DIC Corporation, naphthalene type epoxy resin), "828US", "jER828EL", "825", "828EL" (all manufactured by Mitsubishi Chemical Corporation, bisphenol A type epoxy resin), "jE807", "1750" (all manufactured by Mitsubishi Chemical Corporation, bisphenol F type epoxy resin), "jER152" (manufactured by Mitsubishi Chemical Corporation, phenol Novolac type epoxy resin), "630", "630LSD" (all manufactured by Mitsubishi Chemical Corporation, glycidylamine type epoxy resin), "ZX1059" (manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin), "EX-721" (manufactured by Nagase ChemteX Corporation, glycidyl ester type epoxy resin), "Celloxide 2021P" (manufactured by Daicel Corporation, alicyclic epoxy resin having an ester skeleton), "PB-3600" (manufactured by Daicel Corporation, epoxy resin having a butadiene structure), "ZX1658", "ZX1658GS" (all manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., liquid 1,4-glycidylcyclohexane type epoxy resin), etc. may be mentioned. These may be used alone or in combination of two or more.

[0077] Preferred examples of solid epoxy resins include bixylenol type epoxy resins, naphthalene type epoxy resins, naphthalene type tetrafunctional epoxy resins, cresol novolac type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol type epoxy resins, naphthol type epoxy resins, biphenyl type epoxy resins, naphthylene ether type epoxy resins, anthracene type epoxy resins, bisphenol A type epoxy resins, bisphenol AF type epoxy resins, and tetraphenylethane type epoxy resins, and examples of such solid epoxy resins include naphthol type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, and biphenyl type epoxy resins.Specific examples include "HP4032H" (manufactured by DIC Corporation, naphthalene type epoxy resin), "HP-4700", and "HP-4710" (all manufactured by DIC Corporation, naphthalene type tetrafunctional epoxy resin), "N-690" (manufactured by DIC Corporation, cresol novolac type epoxy resin), "N-695" (manufactured by DIC Corporation, cresol novolac type epoxy resin), "HP-7200" (manufactured by DIC Corporation, dicyclopentadiene type epoxy resin), "HP-7200", "HP-7200HH", and "HP-7200H" (all manufactured by DIC Corporation, dicyclopentadiene type epoxy resin). epoxy resin), "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP-6000" (all manufactured by DIC, naphthylene ether type epoxy resin), "EPPN-502H" (manufactured by Nippon Kayaku Co., Ltd., trisphenol type epoxy resin), "NC-7000L", "NC-7300" (all manufactured by Nippon Kayaku Co., Ltd., naphthol-cresol novolac type epoxy resin), "NC-3000H", "NC-3000", "NC-3000L", "NC-3100" (all manufactured by Nippon Kayaku Co., Ltd., biphenyl ether type epoxy resin). arylalkyl type epoxy resin), "XD-1000-2L", "XD-1000-L", "XD-1000-H", "XD-1000-H" (all manufactured by Nippon Kayaku Co., Ltd., dicyclopentadiene type epoxy resin), "ESN475V" (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., naphthol type epoxy resin), "ESN485" (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., naphthol novolac type epoxy resin), "YX-4000H", "YX-4000", "YL6121" (all manufactured by Mitsubishi Chemical Corporation, biphenyl type epoxy resin), "YX-4000HK" (manufactured by Mitsubishi Chemical Corporation, bixyl Examples of epoxy resins that can be used include "YX-8800" (manufactured by Mitsubishi Chemical Corporation, anthracene type epoxy resin), "PG-100", "CG-500" (manufactured by Osaka Gas Chemical Co., Ltd., fluorene type epoxy resin), "YL-7760" (manufactured by Mitsubishi Chemical Corporation, bisphenol AF type epoxy resin), "YL-7800" (manufactured by Mitsubishi Chemical Corporation, fluorene type epoxy resin), "jER1010" (manufactured by Mitsubishi Chemical Corporation, solid bisphenol A type epoxy resin), and "jER1031S" (manufactured by Mitsubishi Chemical Corporation, tetraphenylethane type epoxy resin).These may be used alone or in combination of two or more.

[0078] [Active ester compounds] The active ester compound refers to a compound that contains at least one ester bond in the structure and has an aliphatic chain, an aliphatic ring, or an aromatic ring bonded to both sides of the ester bond. Examples of the active ester compound include compounds having two or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, and are obtained by a condensation reaction between at least one compound of a carboxylic acid compound, an acid chloride, or a thiocarboxylic acid compound and at least one compound of a hydroxy compound or a thiol compound. In particular, from the viewpoint of improving heat resistance, it is preferable to obtain it from a carboxylic acid compound or an acid chloride and a hydroxy compound, and the hydroxy compound is preferably a phenol compound or a naphthol compound. The active ester compound may be used alone or in combination of two or more types.

[0079] Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.

[0080] Examples of the acid chloride include acetyl chloride, acrylic acid chloride, methacrylic acid chloride, malonyl chloride, succinic acid dichloride, diglycolyl chloride, glutaric acid dichloride, suberic acid dichloride, sebacic acid dichloride, adipic acid dichloride, dodecandioyl dichloride, azelaic acid chloride, 2,5-furandicarbonyl dichloride, phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, trimesic acid chloride, bis(4-chlorocarbonylphenyl) ether, 4,4'-diphenyldicarbonyl chloride, and 4,4'-azodibenzoyl dichloride.

[0081] Examples of the phenol compounds and naphthol compounds include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene-type diphenol compounds, phenol novolac, and phenol resins described below. Here, the term "dicyclopentadiene-type diphenol compounds" refers to diphenol compounds obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.

[0082] Preferred specific examples of the active ester compound include an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, an active ester compound containing a benzoylated product of phenol novolac, a compound described in Example 2 of International Publication No. 2020 / 095829, and a compound disclosed in International Publication No. 2020 / 059625. Among them, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene-type diphenol structure are more preferred. The dicyclopentadiene-type diphenol structure refers to a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

[0083] Commercially available active ester compounds include, for example, "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "HPC-8000H-65TM", "EXB-8000L-65TM", and "EXB-8150-65T" (manufactured by DIC Corporation) as active ester compounds containing a dicyclopentadiene-type diphenol structure, "EXB9416-70BK" (manufactured by DIC Corporation) as an active ester compound containing a naphthalene structure, and "phenolnoxamine" (manufactured by DIC Corporation). Examples of active ester compounds containing acetylated phenol novolac include "DC808" (manufactured by Mitsubishi Chemical Corporation); active ester compounds containing benzoylated phenol novolac include "YLH1026," "YLH1030," and "YLH1048" (manufactured by Mitsubishi Chemical Corporation); "DC808" (manufactured by Mitsubishi Chemical Corporation) is an active ester curing agent which is an acetylated phenol novolac; and "EXB-9050L-62M" (manufactured by DIC Corporation) is an active ester curing agent containing a phosphorus atom.

[0084] Regarding the compounding ratio of the active ester compound and the epoxy resin, the ratio (α / β) of the active ester equivalent (α) to the epoxy equivalent (β) is preferably 0.5 to 1.5, more preferably 0.8 to 1.2, and even more preferably 0.90 to 1.10. If it is out of the above range, there is a risk that excess epoxy groups or active ester groups will remain in the system, and the characteristics may deteriorate in a high-temperature storage test (e.g., 150°C, 1000 hours) or a long-term reliability test under high-temperature and high-humidity conditions (e.g., temperature: 85°C, humidity: 85%).

[0085] [Phenol resin] A phenolic resin is a compound having two or more phenolic hydroxyl groups in a molecule. Examples of phenolic resins include, but are not limited to, reaction products of phenols and aldehydes, reaction products of phenols and diene compounds, reaction products of phenols and ketones, reaction products of phenols and substituted biphenyls, reaction products of phenols and substituted phenyls, and reaction products of bisphenols and aldehydes. These may be used alone or in combination. Specific examples of the above-mentioned raw materials are given below, but the raw materials are not limited thereto. <Phenols> Phenol, alkyl-substituted phenol, aromatic-substituted phenol, hydroquinone, resorcin, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc. <Aldehydes> Formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, furfural, and the like. <Diene compounds> Dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, and the like. <Ketones> Acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, fluorenone, etc. <Substituted biphenyls> 4,4'-bis(chloromethyl)-1,1'-biphenyl, 4,4'-bis(methoxymethyl)-1,1'-biphenyl, 4,4'-bis(hydroxymethyl)-1,1'-biphenyl and the like. <Substituted phenyls> 1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene, 1,4-bis(hydroxymethyl)benzene and the like.

[0086] [Polyphenylene ether compounds] From the viewpoint of heat resistance and electrical properties, the polyphenylene ether compound is preferably a polyphenylene ether compound having an ethylenically unsaturated bond, and more preferably a polyphenylene ether compound having an acrylic group, a methacrylic group, or a styrene structure. Commercially available products include SA-9000 (manufactured by SABIC, a polyphenylene ether compound having a methacrylic group) and OPE-2St 1200 (manufactured by Mitsubishi Gas Chemical, a polyphenylene ether compound having a styrene structure). The number average molecular weight (Mn) of the polyphenylene ether compound is preferably 500 to 5000, more preferably 2000 to 5000, and more preferably 2000 to 4000. If the molecular weight is less than 500, the heat resistance of the cured product tends to be insufficient. If the molecular weight is more than 5000, the melt viscosity increases and sufficient fluidity cannot be obtained, which tends to lead to molding defects. In addition, the reactivity decreases, the curing reaction takes a long time, and the amount of unreacted material that is not incorporated into the curing system increases, which decreases the glass transition temperature of the cured product and tends to decrease the heat resistance of the cured product. If the number average molecular weight of the polyphenylene ether compound is 500 to 5000, it is possible to exhibit excellent heat resistance, moldability, etc. while maintaining excellent dielectric properties. The number average molecular weight here can be specifically measured using gel permeation chromatography, etc.

[0087] The polyphenylene ether compound may be one obtained by a polymerization reaction, or one obtained by a redistribution reaction of a high molecular weight polyphenylene ether compound having a number average molecular weight of about 10,000 to 30,000. In addition, these may be used as raw materials and reacted with a compound having an ethylenically unsaturated bond, such as methacryl chloride, acrylic chloride, or chloromethylstyrene, to impart radical polymerizability. The polyphenylene ether compound obtained by the redistribution reaction is obtained, for example, by heating a high molecular weight polyphenylene ether compound in a solvent such as toluene in the presence of a phenolic compound and a radical initiator to cause a redistribution reaction. The polyphenylene ether compound obtained by the redistribution reaction in this way has hydroxyl groups derived from a phenolic compound that contributes to curing at both ends of the molecular chain, and is therefore preferable in that it can maintain even higher heat resistance, and that functional groups can be introduced at both ends of the molecular chain even after modification with a compound having an ethylenically unsaturated bond. In addition, the polyphenylene ether compound obtained by the polymerization reaction is preferable in that it exhibits excellent fluidity.

[0088] The molecular weight of the polyphenylene ether compound can be adjusted by adjusting the polymerization conditions, etc., in the case of a polyphenylene ether compound obtained by a polymerization reaction. In addition, in the case of a polyphenylene ether compound obtained by a redistribution reaction, the molecular weight of the obtained polyphenylene ether compound can be adjusted by adjusting the conditions of the redistribution reaction, etc. More specifically, it is possible to adjust the amount of the phenolic compound used in the redistribution reaction. That is, the greater the amount of the phenolic compound, the lower the molecular weight of the obtained polyphenylene ether compound. In this case, poly(2,6-dimethyl-1,4-phenylene ether) and the like can be used as the high molecular weight polyphenylene ether compound that undergoes the redistribution reaction. In addition, the phenolic compound used in the redistribution reaction is not particularly limited, but for example, a multifunctional phenolic compound having two or more phenolic hydroxyl groups in the molecule, such as bisphenol A, phenol novolac, cresol novolac, etc., is preferably used. These may be used alone or in combination of two or more.

[0089] [Amine resin] Amine resins are compounds having two or more amino groups in the molecule. Examples of amine resins include diaminodiphenylmethane, diaminodiphenylsulfone, isophoronediamine, naphthalenediamine, aniline novolac (a reaction product of aniline and formalin), N-methylaniline novolac (a reaction product of N-methylaniline and formalin), orthoethylaniline novolac (a reaction product of orthoethylaniline and formalin), a reaction product of 2-methylaniline and formalin, a reaction product of 2,6-diisopropylaniline and formalin, a reaction product of 2,6-diethylaniline and formalin, a reaction product of 2-ethyl-6-ethylaniline and formalin, a reaction product of 2,6-dimethylaniline and formalin, and a reaction product obtained by reacting aniline and xylylene chloride. Examples of the aniline resin include, but are not limited to, the aniline resin disclosed in Japanese Patent No. 6429862, a reaction product of aniline and a substituted biphenyl (4,4'-bis(chloromethyl)-1,1'-biphenyl, 4,4'-bis(methoxymethyl)-1,1'-biphenyl, etc.), a reaction product of aniline and a substituted phenyl (1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene, 1,4-bis(hydroxymethyl)benzene, etc.), 4,4'-(1,3-phenylenediisopropylidene)bisaniline, 4,4'-(1,4-phenylenediisopropylidene)bisaniline, a reaction product of aniline and diisopropenylbenzene, dimer diamine, etc. Furthermore, these may be used alone or in combination.

[0090] [Compounds containing ethylenically unsaturated bonds] A compound containing an ethylenically unsaturated bond is a compound that has one or more ethylenically unsaturated bonds in the molecule that can be polymerized by heat or light, regardless of whether a polymerization initiator is used or not. Examples of compounds containing ethylenically unsaturated bonds include, but are not limited to, reaction products of the above-mentioned phenol resins and halogen-based compounds containing ethylenically unsaturated bonds (chloromethylstyrene, allyl chloride, methallyl chloride, acrylic acid chloride, methacrylic acid chloride, etc.), reaction products of phenols containing ethylenically unsaturated bonds (2-allylphenol, 2-propenylphenol, 4-allylphenol, 4-propenylphenol, eugenol, isoeugenol, etc.) and halogen-based compounds (1,4-bis(chloromethyl)benzene, 4,4'-bis(chloromethyl)biphenyl, 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-dibromobenzophenone, cyanuric chloride, etc.), reaction products of epoxy resins or alcohols and (meth)acrylic acids (acrylic acid, methacrylic acid, etc.), and acid-modified products thereof. In addition, these may be used alone or in combination.

[0091] [Isocyanate resin] An isocyanate resin is a compound that has two or more isocyanate groups in its molecule. Examples of the isocyanate resin include aromatic diisocyanates such as p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and naphthalene diisocyanate; aliphatic or alicyclic diisocyanates such as isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, norbornene diisocyanate, and lysine diisocyanate; polyisocyanates such as one or more biuret forms of isocyanate monomers or isocyanate forms obtained by trimerizing the above diisocyanate compounds; and polyisocyanates obtained by a urethanization reaction between the above isocyanate compounds and polyol compounds, but are not limited thereto. These may be used alone or in combination.

[0092] [Polyamide resin] Examples of polyamide resins include reaction products of one or more of diamines, diisocyanates, and oxazolines with dicarboxylic acids, reaction products of diamines with acid chlorides, and ring-opening polymers of lactam compounds. These may be used alone or in combination. Specific examples of the above-mentioned raw materials are given below, but the raw materials are not limited thereto. <Diamine> Ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decanediamine, undecanediamine, dodecanediamine, tridecanediamine, tetradecanediamine, pentadecanediamine, hexadecanediamine, heptadecanediamine, octadecanediamine, nonadecanediamine, eicosanediamine, 2-methyl-1,5-diaminopentane, 2-methyl 1,8-diaminooctane, dimer diamine, cyclohexane diamine, bis-(4-aminocyclohexyl)methane, bis(3-methyl-4-aminocyclohexyl)methane, xylylene diamine, norbornane diamine, isophorone diamine, bisaminomethyltricyclodecane, phenylenediamine, diethyltoluenediamine, naphthalenediamine, diaminodiphenylmethane, bis(4-amino-3,5-dimethylphenyl)methane, bis(4-amino-3,5-diethylphenyl)methane , 4,4'-methylenebis-o-toluidine, 4,4'-methylenebis-o-ethylaniline, 4,4'-methylenebis-2-ethyl-6-methylaniline, 4,4'-methylenebis-2,6-diisopropylaniline, 4,4-ethylenedianiline, diaminodiphenyl sulfone, diaminodiphenyl ether, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 4,4-bis(4-aminophenoxy)biphenyl, 2,2-bis[4-(4-amino 4,4'-(1,3-phenylenediisopropylidene)bisaniline, 4,4'-(1,4-phenylenediisopropylidene)bisaniline, 9,9-bis(4-aminophenyl)fluorene, 2,7-diaminofluorene, aminobenzylamine, diaminobenzophenone, and the like. <Diisocyanate> Benzene diisocyanate, toluene diisocyanate, 1,3-bis(isocyanatomethyl)benzene, 1,3-bis(isocyanatomethyl)cyclohexane, bis(4-isocyanatophenyl)methane, isophorone diisocyanate, 1,3-bis(2-isocyanato-2-propyl)benzene, 2,2-bis(4-isocyanatophenyl)hexafluoropropane, dicyclohexylmethane-4,4'-diisocyanate, and the like. <Dicarboxylic acid> Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, 5-hydroxyisophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, cyclohexanedicarboxylic acid, biphenyldicarboxylic acid, naphthalenedicarboxylic acid, benzophenonedicarboxylic acid, furandicarboxylic acid, 4,4'-dicarboxydiphenyl ether, 4,4'-dicarboxydiphenyl sulfide, etc. <Acid chloride> Acetyl chloride, acrylic acid chloride, methacrylic acid chloride, malonyl chloride, succinic acid dichloride, diglycolyl chloride, glutaric acid dichloride, suberic acid dichloride, sebacic acid dichloride, adipic acid dichloride, dodecandioyl dichloride, azelaic acid chloride, 2,5-furandicarbonyl dichloride, phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, trimesic acid chloride, bis(4-chlorocarbonylphenyl) ether, 4,4'-diphenyldicarbonyl chloride, 4,4'-azodibenzoyl dichloride, and the like. <Lactam> ε-caprolactam, ω-undecanelactam, ω-laurolactam, and the like.

[0093] [Polyimide resin] Examples of polyimide resins include, but are not limited to, reaction products of the diamines and the tetracarboxylic dianhydrides shown below. These may be used alone or in combination. <Tetracarboxylic acid dianhydride> 4,4'-(Hexafluoroisopropylidene)diphthalic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-cyclohexene-1,2 dicarboxylic anhydride, pyromellitic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 2,2',3, 3'-Biphenyltetracarboxylic dianhydride, methylene-4,4'-diphthalic dianhydride, 1,1-ethylidene-4,4'-diphthalic dianhydride, 2,2'-propylidene-4,4'-diphthalic dianhydride, 1,2-ethylene-4,4'-diphthalic dianhydride, 1,3-trimethylene-4,4'-diphthalic dianhydride, 1,4-tetramethylene-4,4'-diphthalic dianhydride, 1,5-pentamethylene-4,4'-diphthalic dianhydride, 4,4'-oxydiphthalic dianhydride, thio-4,4'-diphthalic dianhydride, sulfonyl-4,4'-diphthalic acid Dianhydride, 1,3-bis(3,4-dicarboxyphenyl)benzene dianhydride, 1,3-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 1,3-bis[2-(3,4-dicarboxyphenyl)-2-propyl]benzene dianhydride, 1,4-bis[2-(3,4-dicarboxyphenyl)-2-propyl]benzene dianhydride, bis[3-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride, bis[4-(3,4-dicarboxyphenoxy)phenyl]methane 2,2-bis[3-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, bis(3,4-dicarboxyphenoxy)dimethylsilane dianhydride, 1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldisiloxane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3,4,9,10-Perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, ethylenetetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride tetracarboxylic dianhydride, 3,3',4,4'-bicyclohexyltetracarboxylic dianhydride, carbonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, methylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,2-ethylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,1-ethylidene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 2,2-propylidene- 4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, oxy-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, thio-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, sulfonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, rel-[1S,5R,6R]-3-oxabicyclo[3,2 ,1]Octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, ethylene glycol-bis-(3,4-dicarboxylic anhydride phenyl) ether, 4,4'-biphenyl bis(trimellitic acid monoester acid anhydride), 9,9'-bis(3,4-dicarboxyphenyl)fluorene dianhydride, etc.,

[0094] [Maleimide compounds] The curable resin composition of the present invention may contain a maleimide compound. A maleimide compound is a compound having one or more maleimide groups in the molecule. Examples of the maleimide compound include 4,4'-diphenylmethane bismaleimide, polyphenylmethane maleimide, m-phenylene bismaleimide, 2,2'-bis[4-(4-maleimidophenoxy)phenyl]propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 4,4'-diphenylether bismaleimide, 4,4'-diphenylsulfone bismaleimide, 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene), Xylox type maleimide compound (anilix), Maleimide, manufactured by Mitsui Chemicals Fine Co., Ltd.), biphenylaralkyl-type maleimide compound (solidified by distilling off the solvent under reduced pressure from a resin solution containing the maleimide compound (M2) described in Example 4 of JP 2009-001783 A), bisaminocumylbenzene-type maleimide (maleimide compound described in WO 2020 / 054601 A), maleimide compounds having an indane structure described in Japanese Patent No. 6629692 or WO 2020 / 217679, MATERIAL STAGE Vol. 18, No. 12 2019 ``~Continued Epoxy Resin CAS Number Story~ Hardener CAS Number Memorandum No. 31 Bismaleimide (1)'' and MATERIAL STAGE Vol. 19, No. 2 2019 ``~Continued Epoxy Resin CAS Number Story~ Hardener CAS Number Memorandum No. 32 Bismaleimide (2) and the like can be used, but are not limited thereto. These can be used alone or in combination.

[0095] [Cyanate ester resin] Cyanate ester resins are cyanate ester compounds obtained by reacting phenolic resins with cyanogen halides, and specific examples include dicyanatobenzene, tricyanatobenzene, dicyanatonaphthalene, dicyanatobiphenyl, 2,2'-bis(4-cyanatophenyl)propane, bis(4-cyanatophenyl)methane, bis(3,5-dimethyl-4-cyanatophenyl)methane, 2,2'-bis(3,5-dimethyl-4-cyanatophenyl)propane, 2,2'-bis(4-cyanatophenyl)ethane, 2,2'-bis(4-cyanatophenyl)hexafluoropropane, bis(4-cyanatophenyl)sulfone, bis(4-cyanatophenyl)thioether, phenol novolac cyanate, and phenol-dicyclopentadiene co-condensates in which the hydroxyl groups have been converted to cyanate groups, but are not limited thereto. These may be used alone or in combination. Furthermore, the cyanate ester compound, the synthesis method of which is described in JP-A-2005-264154, is particularly preferred as the cyanate ester compound because it has low moisture absorption, excellent flame retardancy, and excellent dielectric properties. The cyanate ester resins can optionally contain a catalyst, such as zinc naphthenate, cobalt naphthenate, copper naphthenate, lead naphthenate, zinc octoate, tin octoate, lead acetylacetonate, or dibutyltin maleate, to trimerize the cyanate groups to form sym-triazine rings.

[0096] The catalyst is preferably used in an amount of 0.0001 to 0.10 parts by mass, and more preferably 0.00015 to 0.0015 parts by mass, based on 100 parts by mass of the cyanate ester resin and the curable resin composition.

[0097] [Polybutadiene and its modified products] The polybutadiene and its modified products are polybutadiene or compounds having a structure derived from polybutadiene in the molecule. The unsaturated bonds in the polybutadiene-derived structure may be partially or entirely converted to single bonds by hydrogenation. Examples of polybutadiene and modified products thereof include, but are not limited to, polybutadiene, hydroxyl-terminated polybutadiene, (meth)acrylate-terminated polybutadiene, carboxylic acid-terminated polybutadiene, amine-terminated polybutadiene, styrene-butadiene rubber, and the like. These may be used alone or in combination. Among these, polybutadiene or styrene-butadiene rubber is preferred from the viewpoint of dielectric properties. Examples of styrene-butadiene rubber (SBR) include RICON-100, RICON-181, RICON-184 (all manufactured by Cray Valley), 1,2-SBS (manufactured by Nippon Soda Co., Ltd.), and examples of polybutadiene include B-1000, B-2000, B-3000 (all manufactured by Nippon Soda Co., Ltd.). The molecular weight of polybutadiene and styrene-butadiene rubber is preferably a weight average molecular weight of 500 to 10,000, more preferably 750 to 7,500, and even more preferably 1,000 to 5,000. Below the lower limit of the above range, the amount of volatilization is large, making it difficult to adjust the solid content during prepreg preparation, and above the upper limit of the above range, the compatibility with other curable resins is deteriorated. In general, in the case of compounds containing heteroatoms such as oxygen and nitrogen, such as bismaleimide and polymaleimide, it is difficult to ensure compatibility with low-polarity compounds such as compounds mainly composed of hydrocarbons or compounds composed only of hydrocarbons due to their polarity. On the other hand, the compound of the present invention is excellent in compatibility with materials having low polarity and low dielectric properties and compounds composed only of hydrocarbons, due to the fact that the compound itself does not have a skeleton design in which heteroatoms such as oxygen and nitrogen are actively introduced.

[0098] [Polystyrene and its modified products] Polystyrene and modified products thereof are polystyrene or compounds having a structure derived from polystyrene in the molecule. Examples of polystyrene and modified products thereof include polystyrene, styrene-2-isopropenyl-2-oxazoline copolymers (Epocross RPS-1005, RP-61, both manufactured by Nippon Shokubai Co., Ltd.), SEP (styrene-ethylene-propylene copolymer: Septon 1020, manufactured by Kuraray Co., Ltd.), SEPS (styrene-ethylene-propylene-styrene copolymer: Septon 2002, Septon 2004F, Septon 2005, Septon 2006, Septon 2063, Septon 2104, all manufactured by Kuraray Co., Ltd.), SEEPS (styrene-ethylene / ethylene-propylene-styrene block copolymer: Septon 4003, Septon 4044, Septon 4055, Septon 4077, Septon 4099, all manufactured by Kuraray Co., Ltd.), SEBS (styrene-ethylene-butylene-styrene block copolymer: Septon 4003, Septon 4044, Septon 4055, Septon 4077, Septon 4099, all manufactured by Kuraray Co., Ltd.), Examples of the block copolymer include Septon 8004, Septon 8006, and Septon 8007L (all manufactured by Kuraray Co., Ltd.), SEEPS-OH (a compound having a hydroxyl group at the end of a styrene-ethylene / ethylene-propylene-styrene block copolymer: Septon HG252 manufactured by Kuraray Co., Ltd.), SIS (styrene-isoprene-styrene block copolymer: Septon 5125 and Septon 5127 manufactured by Kuraray Co., Ltd.), hydrogenated SIS (hydrogenated styrene-isoprene-styrene block copolymer: Hybler 7125F and Hybler 7311F manufactured by Kuraray Co., Ltd.), SIBS (styrene-isobutylene-styrene block copolymer: SIBSTAR073T, SIBSTAR102T, and SIBSTAR103T (all manufactured by Kaneka Co., Ltd.), and Septon V9827 (manufactured by Kuraray Co., Ltd.)), but are not limited thereto. These may be used alone or in combination. Polystyrene and its modified products are preferably those that do not have unsaturated bonds, since they have higher heat resistance and are less susceptible to oxidation deterioration. The weight-average molecular weight of polystyrene and its modified products is not particularly limited as long as it is 10,000 or more, but if it is too large, the compatibility with not only polyphenylene ether compounds, but also low molecular weight components with weight-average molecular weights of about 50 to 1,000 and oligomer components with weight-average molecular weights of about 1,000 to 5,000 deteriorates, making it difficult to ensure mixing and solvent stability, so it is preferably about 10,000 to 300,000.

[0099] [Polyethylene and its modified products] Polyethylene and its modified products are compounds having polyethylene or a structure derived from polyethylene in the molecule. Examples of polyethylene and its modified products include ethylene-propylene copolymers, ethylene-styrene copolymers, ethylene-propylene-ethylidenenorbornene copolymers (EBT: K-8370EM, K-9330M, etc., manufactured by Mitsui Chemicals), ethylene-propylene-vinylnorbornene copolymers (VNB-EPT: PX-006M, PX-008M, PX-009M, etc., manufactured by Mitsui Chemicals), ethylene-vinyl alcohol copolymers, ethylene-vinyl acetate copolymers, etc., but are not limited thereto. From the viewpoint of improving heat resistance, it is preferable to use ethylene-propylene-ethylidenenorbornene copolymers and ethylene-propylene-vinylnorbornene copolymers containing a crosslinkable structure. In addition, these may be used alone or in combination. There are no particular limitations on the weight-average molecular weight of polyethylene and modified products thereof as long as it is 10,000 or more. However, if it is too large, compatibility with not only polyphenylene ether compounds but also low molecular weight components having a weight-average molecular weight of about 50 to 1,000 and oligomer components having a weight-average molecular weight of about 1,000 to 5,000 deteriorates, making it difficult to ensure mixing and solvent stability. Therefore, it is preferably about 10,000 to 300,000.

[0100] The curable resin composition of the present invention can be obtained by preparing the above-mentioned components in a predetermined ratio, pre-curing at 130 to 180° C. for 30 to 500 seconds, and then post-curing at 150 to 200° C. for 2 to 15 hours, so that the curing reaction proceeds sufficiently to obtain the cured product of the present invention. Alternatively, the components of the curable resin composition can be uniformly dispersed or dissolved in a solvent or the like, and cured after removing the solvent.

[0101] The method for preparing the curable resin composition of the present invention is not particularly limited, but each component may be mixed uniformly or may be prepolymerized. For example, a mixture containing the compound of the present invention is heated in the presence or absence of a curing accelerator or a polymerization initiator, and in the presence or absence of a solvent to form a prepolymer. Similarly, an amine compound, a compound having an ethylenically unsaturated bond, a maleimide compound, a cyanate ester compound, polybutadiene and its modified products, polystyrene and its modified products, inorganic fillers, and other additives may be added to form a prepolymer. The mixing or prepolymerization of each component is carried out using, for example, an extruder, a kneader, a roll, etc. in the absence of a solvent, and a reaction kettle with a stirrer, etc. in the presence of a solvent.

[0102] As a method of uniformly mixing, the mixture is kneaded at a temperature in the range of 50 to 100°C using a device such as a kneader, roll, or planetary mixer to obtain a uniform resin composition. The obtained resin composition is crushed and then molded into a cylindrical tablet shape using a molding machine such as a tablet machine, or into a granular powder or powder molded body, or these compositions can be melted on a surface support and molded into a sheet with a thickness of 0.05 mm to 10 mm to obtain a molded curable resin composition. The obtained molded body is a non-sticky molded body at 0 to 20°C, and even if stored at -25 to 0°C for one week or more, the flowability and curability are hardly reduced. The obtained molded article can be molded into a cured product using a transfer molding machine or a compression molding machine.

[0103] The curable resin composition of the present invention can be made into a varnish-like composition (hereinafter, simply referred to as varnish) by adding an organic solvent. The curable resin composition of the present invention can be dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. as necessary to make a varnish, and impregnated into a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc., and dried by heating to obtain a prepreg, which can be hot-press molded to obtain a cured product of the curable resin composition of the present invention. The solvent used in this case is in an amount of 10 to 70% by weight, preferably 15 to 70% by weight, in the mixture of the curable resin composition of the present invention and the solvent. In addition, if the composition is in a liquid state, a cured product of the curable resin containing carbon fiber can be obtained as it is, for example, by the RTM method.

[0104] The curable resin composition of the present invention can also be used as a modifier for a film-type composition. Specifically, it can be used to improve flexibility in the B-stage. Such a film-type resin composition is obtained as a sheet-type adhesive by applying the curable resin composition of the present invention as a varnish onto a release film, removing the solvent under heating, and then performing B-stage formation. This sheet-type adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like.

[0105] The curable resin composition of the present invention can be heated and melted to reduce the viscosity, and impregnated into reinforcing fibers such as glass fibers, carbon fibers, polyester fibers, polyamide fibers, and alumina fibers to obtain a prepreg. Specific examples thereof include glass fibers such as E glass cloth, D glass cloth, S glass cloth, Q glass cloth, spherical glass cloth, NE glass cloth, and T glass cloth, inorganic fibers other than glass, and organic fibers such as polyparaphenylene terephthalamide (Kevlar (registered trademark), manufactured by DuPont), wholly aromatic polyamide, polyester, polyparaphenylene benzoxazole, polyimide, and carbon fibers, but are not particularly limited thereto. The shape of the substrate is not particularly limited, but examples thereof include woven fabric, nonwoven fabric, roving, chopped strand mat, and the like. In addition, as the weaving method of the woven fabric, plain weave, saddle weave, twill weave, and the like are known, and these known weaves can be appropriately selected and used depending on the intended use and performance. In addition, woven fabrics that have been subjected to fiber opening treatment and glass woven fabrics that have been surface-treated with a silane coupling agent or the like are preferably used. The thickness of the substrate is not particularly limited, but is preferably about 0.01 to 0.4 mm. A prepreg can also be obtained by impregnating reinforcing fibers with the varnish and drying the fibers by heating.

[0106] The prepreg can also be used to manufacture a laminate. The laminate is not particularly limited as long as it has one or more prepregs, and may have any other layers. The method for manufacturing the laminate can be appropriately applied by a generally known method, and is not particularly limited. For example, a multi-stage press machine, a multi-stage vacuum press machine, a continuous molding machine, an autoclave molding machine, etc. can be used when molding a metal foil-clad laminate, and the prepregs are laminated together and heated and pressurized to obtain a laminate. At this time, the heating temperature is not particularly limited, but is preferably 65 to 300 ° C, and more preferably 120 to 270 ° C. In addition, the pressure to be applied is not particularly limited, but if the pressure is too high, it is difficult to adjust the solid content of the resin in the laminate, and the quality is not stable, and if the pressure is too low, air bubbles and adhesion between the laminates are deteriorated, so that the pressure is preferably 2.0 to 5.0 MPa, and more preferably 2.5 to 4.0 MPa. The laminate of this embodiment can be suitably used as a metal foil-clad laminate described later by providing a layer made of metal foil. The prepreg is cut into a desired shape and laminated with copper foil or the like if necessary. The laminate is then heated and cured while applying pressure thereto by press molding, autoclave molding, sheet winding molding, or the like, to obtain an electrical and electronic laminate (printed wiring board) or a carbon fiber reinforced material.

[0107] The curable resin composition of the present invention can also be made into a resin sheet. As a method for obtaining a resin sheet from the curable resin composition of the present invention, for example, a method of applying the curable resin composition onto a support film (support), drying it, and forming a resin composition layer on the support film can be mentioned. When the curable resin composition of the present invention is used for a resin sheet, it is essential that the film softens under the temperature conditions (70°C to 140°C) for lamination in the vacuum lamination method, and exhibits a fluidity (resin flow) that allows resin filling into via holes or through holes present in the circuit board at the same time as laminating the circuit board, and it is preferable to mix each of the above components so as to express such characteristics. In addition, in the obtained resin sheet or circuit board (copper-clad laminate, etc.), a phenomenon that locally different characteristic values ​​are exhibited due to phase separation or the like does not occur, and a certain performance is expressed at any part, so that a uniform appearance is required.

[0108] Here, the through-holes in the circuit board have a diameter of 0.1 to 0.5 mm and a depth of 0.1 to 1.2 mm, and it is preferable that the resin be filled within this range. When laminating both sides of the circuit board, it is preferable that about half of the through-holes are filled.

[0109] A specific method for producing the resin sheet includes preparing a resin composition varnished by blending an organic solvent, applying the varnished resin composition to the surface of a support film (Y), and then drying the organic solvent by heating or blowing hot air or the like to form a resin composition layer (X).

[0110] The organic solvent used here is preferably, for example, ketones such as acetone, methyl ethyl ketone, cyclohexanone, etc., acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, etc., carbitols such as cellosolve, butyl carbitol, etc., aromatic hydrocarbons such as toluene, xylene, etc., dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. It is also preferable to use the organic solvent in such a ratio that the nonvolatile content is 30 to 60 mass% of the total.

[0111] The thickness of the resin composition layer (X) to be formed must be equal to or greater than the thickness of the conductor layer of the circuit board to which the resin composition layer (X) is laminated. Since the thickness of the conductor layer of the circuit board is in the range of 5 to 70 μm, the thickness of the resin composition layer (X) is preferably 10 to 100 μm. The resin composition layer (X) in the present invention may be protected with a protective film described below. By protecting the resin composition layer (X) with a protective film, it is possible to prevent the adhesion of dirt and the like to the surface of the resin composition layer (X) and to prevent scratches.

[0112] The support film and the protective film may be made of polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate, polycarbonate, polyimide, and even release paper and metal foils such as copper foil and aluminum foil. The support film and the protective film may be subjected to a release treatment in addition to a mud treatment and a corona treatment. The thickness of the support film is not particularly limited, but is in the range of 10 to 150 μm, and preferably 25 to 50 μm. The thickness of the protective film is preferably 1 to 40 μm.

[0113] The support film (Y) is peeled off after laminating the resin composition layer (X) onto a circuit board, or after forming an insulating layer by heat-curing the resin composition layer (X). If the support film (Y) is peeled off after the resin composition layer (X) constituting the resin sheet is heat-cured, adhesion of dust and the like during the curing process can be prevented. When the support film (Y) is peeled off after the resin composition layer (X) is heat-cured, the support film (Y) is previously subjected to a release treatment.

[0114] A multilayer printed circuit board can be manufactured from the resin sheet obtained as described above. For example, when the resin composition layer (X) is protected with a protective film, the protective film is peeled off from the resin composition layer (X), and then the resin composition layer (X) is laminated on one or both sides of the circuit board so as to be in direct contact with the circuit board, for example, by a vacuum lamination method. The lamination method may be a batch method or a continuous method using a roll. If necessary, the resin sheet and the circuit board may be heated (preheated) before lamination. The lamination conditions are preferably a pressure bonding temperature (lamination temperature) of 70 to 140°C and a pressure bonding pressure of 1 to 11 kgf / cm. 2 (9.8×10 4 ~107.9×10 4 N / m 2 ), and lamination is preferably performed under reduced air pressure of 20 mmHg (26.7 hPa) or less.

[0115] Furthermore, the curable resin composition of the present invention can be used to manufacture a semiconductor device, such as a DIP (dual in-line package), a QFP (quad flat package), a BGA (ball grid array), a CSP (chip size package), a SOP (small outline package), a TSOP (thin small outline package), or a TQFP (thin quad flat package).

[0116] The curable resin composition of the present invention and its cured product can be used in a wide range of fields. Specifically, it can be used in various applications such as molding materials, adhesives, composite materials, and paints. The cured product of the curable resin composition of the present invention exhibits excellent heat resistance and dielectric properties, and is therefore suitable for use in electrical and electronic components such as encapsulants for semiconductor elements, encapsulants for liquid crystal display elements, encapsulants for organic EL elements, laminates (printed wiring boards, BGA substrates, build-up substrates, etc.), composite materials for lightweight and high-strength structural materials such as carbon fiber reinforced plastics and glass fiber reinforced plastics, 3D printing, etc. EXAMPLES

[0117] The present invention will now be described in more detail with reference to examples. Unless otherwise specified, all parts are by weight. However, the present invention is not limited to these examples.

[0118] Various analytical methods used in the examples are described below. ·GPC (gel permeation chromatography) analysis Equipment: Online degassing unit (DGU-20A), liquid delivery unit (LC-20AD), autosampler (SIL-20A), photodiode array detector (SPD-M40), column oven (CT-20A), system controller (CBM-20A), all manufactured by Shimadzu Corporation Columns: SHODEX GPC KF-601 (2 columns), KF-602, KF-602.5, KF-603 Flow rate: 1.5ml / min. Column temperature: 40℃ Solvent used: THF (tetrahydrofuran) Detector: Differential refractometer (RID-20A), manufactured by Shimadzu Corporation

[0119] [Example 1] An aspirator and a base trap were installed in a flask equipped with a thermometer, a cooling tube, and a stirrer. 20 parts of Tuftec M1913 (manufactured by Asahi Kasei Corporation) as an acid-modified hydrogenated thermoplastic styrene-based elastomer (AH-AB), 180 parts of toluene, and 0.34 parts of allylamine hydrochloride (manufactured by Tokyo Kasei Co., Ltd.) were added to the flask, and the mixture was reacted at 110°C for 12 hours while collecting the generated hydrogen chloride with a base trap. After cooling, the reaction solution was dropped into 1 L of acetone to cause reprecipitation. The mixture was dried at room temperature for 12 hours, and the target compound (AA) was obtained as 18.2 g (light yellow solid). (Mn: 69462, Mw: 95623). The GPC chart of the obtained compound is shown in Figure 1.

[0120] [Examples 2 and 3, Comparative Examples 1 and 2] Using the compound (AA) obtained in Example 1, polyphenylene ether compound: SA-9000 (manufactured by SABIC), styrene butadiene rubber: Ricon-100 (manufactured by Cray Valley), and polymerization initiator: dicumyl peroxide (DCP) in the amounts shown in Table 1, a toluene solution with a solid content of 30% by weight was prepared in Examples 2 and 3, and a toluene solution with a solid content of 70% by weight was prepared in Comparative Examples 1 and 2. The toluene solution was applied to a mirror-finished copper foil (T4X: manufactured by Fukuda Metal Copper Foil Co., Ltd.) using an applicator with a coating thickness of 200 μm, and then cured in an inert oven at 220 ° C. for 2 hours to obtain a cured product. For evaluation, a test piece of the desired size was cut out using a laser cutter as necessary.

[0121] <Dielectric tangent test> The test was performed at 25°C using a 10GHz cavity resonator manufactured by AET Co., Ltd., using a cavity resonator perturbation method. The sample size was 1.7mm wide x 100mm long, and the thickness was 0.3mm. The evaluation results are shown in Table 1.

[0122] [Table 1] SA-9000: Methacrylate-terminated polyphenylene ether (SABIC) Ricon-100: Styrene butadiene rubber (Cray Valley) DCP: Dicumyl peroxide

[0123] From the results in Table 1, it was confirmed that the compound (AA) obtained in Example 1 had a smaller dielectric tangent than those of Comparative Examples 1 and 2, and was excellent in low dielectric properties. This application claims priority to Japanese Patent Application No. 2023-15088, filed February 3, 2023. [Industrial Applicability]

[0124] The compound of the present invention is suitably used for electric and electronic parts such as semiconductor encapsulation materials, printed wiring boards, and build-up laminates.

Claims

1. A compound obtained by reacting an acid-modified hydrogenated thermoplastic styrenic elastomer (AH-AB), which is an acid-modified product of a hydrogenated block copolymer (H-AB) composed of block units (A) of a polymer composed of a styrene monomer and block units (B) of a polymer composed of a conjugated diene compound, with allylamine or allylamine hydrochloride.

2. The compound according to claim 1 , wherein the block unit (A) of the polymer made of the styrene-based monomer has a structure represented by the following formula (a): 【Chemistry 1】 (In formula (1), R １ and R ２ are each a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, p is 1 to 5, and q is the average number of repetitions and represents a real number from 1 to 10,000.

3. The compound according to claim 1, wherein the block unit (B) of the polymer made of the conjugated diene compound is obtained by polymerizing at least one diene compound selected from 1,3-butadiene, isoprene, farnesene, 2,3-dimethyl-1,3-butadiene, and 1,3-pentadiene.

4. The compound according to claim 1, wherein the hydrogenated product of the block copolymer (H-AB) is a compound represented by the following formula (1): 【Chemistry 2】 (In formula (1), R １ and R ２ are each a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, p is 1 to 5, and j, k, l, m, and n are the average number of repetitions and represent real numbers from 1 to 10,000. The order of the repeating units bounded by k and l, or j, m, and n, is not limited, and the bonding style may be any of alternating, block, and random.

5. The compound according to claim 1, wherein the acid-modified hydrogenated thermoplastic styrene-based elastomer (AH-AB) is a compound represented by the following formula (2): 【Chemistry 3】 (In formula (2), R １ and R ２ are each a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, p is 1 to 5, and j, k, l, m, and n are the average number of repetitions and represent real numbers from 1 to 10,000. The order of the repeating units bounded by k and l, or j, m, and n, is not limited, and the bonding style may be any of alternating, block, and random.

6. A compound represented by the following formula (3): 【Chemistry 4】 (In formula (3), R １ and R ２ are each a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, p is 1 to 5, and j, k, l, m, and n are the average number of repetitions and represent real numbers from 1 to 10,000. The order of the repeating units bounded by k and l, or j, m, and n, is not limited, and the bonding style may be any of alternating, block, and random.

7. A curable resin composition comprising the compound according to claim 1 .

8. The curable resin composition according to claim 7 , further comprising a polymerization initiator.

9. The curable resin composition according to claim 7, further comprising at least one selected from the group consisting of a maleimide compound, a polyphenylene ether compound, a compound having an ethylenically unsaturated bond, a cyanate ester resin, polybutadiene and modified products thereof, polystyrene and modified products thereof, and polyethylene and modified products thereof.

10. A cured product of the compound according to any one of claims 1 to 6.

11. A cured product of the curable resin composition according to claim 7.

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