Compound, curable resin composition, and hardened product thereof

Abstract

Provided are a compound having excellent heat resistance and low dielectric properties, a curable resin composition, and a cured product thereof. A compound is obtained by reacting a compound represented by the following formula (a) with a compound having two or more amino groups in the molecule. (In the formula (a), Y represents a hydrocarbon group having 1 to 20 carbon atoms.)

Description

Technical Field

[0001] The present invention relates to a compound having a specific structure, a curable resin composition, and a cured product of the curable resin composition, which can be preferably used in semiconductor sealing materials, printed wiring boards, electrical and electronic parts such as build-up laminates, lightweight and high-strength materials such as carbon fiber reinforced plastics and glass fiber reinforced plastics, and three-dimensional (3D) printing applications. Background Art

[0002] In recent years, laminates carrying electrical and electronic components have been required to have a wide range of advanced features due to the expansion of their application areas. While conventional semiconductor chips are primarily mounted on metal lead frames, high-performance semiconductor chips such as central processing units (CPUs) are often mounted on laminates made of polymer materials.

[0003] In particular, semiconductor packages (hereinafter referred to as PKGs) used in smartphones and other devices require thinner PKG substrates to meet the demands for miniaturization, thinness, and high density. However, as the PKG substrate becomes thinner, its rigidity decreases, and this can lead to significant warping and other problems caused by the heat generated when the PKG is soldered and mounted on a motherboard (printed circuit board (PCB)). To mitigate these issues, PKG substrate materials with a high Tg (Tg) above the soldering mounting temperature are required.

[0004] In addition, in the fifth-generation communication system "5G" currently being developed at an accelerated pace, it is expected that large capacity and high-speed communication will be further promoted. The high frequency used in 5G will be promoted, but in order to achieve high-speed communication using high frequencies, it is important to reduce transmission losses, and lower dielectric properties of the substrate material are required. The transmission loss occurring on the printed circuit board comes from conductor loss and dielectric loss. As described in non-patent document 1, since conductor loss is proportional to the square root of the relative dielectric constant and the dielectric loss tangent of the dielectric, it can be said that improving the dielectric loss tangent, which is more helpful in reducing transmission loss than the relative dielectric constant, is effective. As low dielectric materials, thermoplastic materials represented by polytetrafluoroethylene (PTFE) or liquid crystal polymer (LCP) can be listed, but they lack formability compared to thermosetting resins. Based on this situation, it is expected to develop thermosetting resins with excellent low dielectric properties.

[0005] Furthermore, the increasing use of electronics in the automotive industry, with the installation of precision electronic devices near engine drive units, demands higher levels of heat and humidity resistance. The increasing use of SiC semiconductors in electric vehicles and air conditioners requires extremely high heat resistance from encapsulants used in semiconductor elements, making existing epoxy resin encapsulants inadequate.

[0006] Against this backdrop, bismaleimide compounds have recently been studied to achieve both heat resistance and electrical properties superior to those of epoxy resins. However, common bismaleimide compounds suffer from a lack of solvent solubility, dissolving only in high-boiling-point aprotic polar solvents. While solvent solubility can be achieved by introducing a unique molecular structure, as described in Patent Document 1, the types of amine compounds used as raw materials are limited. Therefore, a more convenient method for imparting solvent solubility is desired.

[0007] In addition, Patent Documents 2 and 3 are studying polymer materials that can have both heat resistance and low dielectric loss tangent properties. For example, Patent Document 2 proposes a composition comprising a maleimide compound and a phenolic resin containing an acrylic group. However, on the other hand, since the phenolic hydroxyl groups that do not participate in the reaction remain during the curing reaction, it cannot be said that the electrical properties are sufficient. In addition, Patent Document 3 discloses an allyl ether resin that utilizes allyl groups to replace hydroxyl groups. However, it is shown that Claisen rearrangement occurs at 190°C, and at the molding temperature of a general substrate, i.e., 200°C, phenolic hydroxyl groups that do not contribute to the curing reaction are generated, and therefore the electrical properties cannot be satisfied.

[0008] Prior art literature

[0009] Non-patent literature

[0010] Non-Patent Document 1: "Causes of Signal Loss in High-Speed ​​Signal Transmission on Printed Circuit Boards (Mitsui Mining and Smelting Co., Ltd.) 29th Electronics Packaging Society Spring Conference 16, p. 1-17"

[0011] Patent Literature

[0012] Patent Document 1: Japanese Patent Application Publication No. 2018-012671

[0013] Patent Document 2: Japanese Patent Application Laid-Open No. 04-359911

[0014] Patent Document 3: International Publication No. 2016 / 002704 Summary of the Invention

[0015] Problems to be solved by the invention

[0016] 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 heat resistance and low dielectric properties, a curable resin composition, and a cured product of the curable resin composition.

[0017] Technical means to solve the problem

[0018] That is, the present invention relates to the following [1] to [7]. In addition, in this application, "(numerical value 1) to (numerical value 2)" means that the upper and lower limits are included. [1]

[0020] A compound obtained by reacting a compound represented by the following formula (a) with a compound having two or more amino groups in its molecule.

[0021]

[0022] (In the above formula (a), Y represents a hydrocarbon group having 1 to 20 carbon atoms) [2]

[0024] The compound according to the above item [1], wherein the compound having two or more amino groups in the molecule has an alicyclic ring or an aromatic ring. [3]

[0026] The compound according to the above item [1] or [2] is represented by the following formula (b).

[0027]

[0028] (In the above formula (b), a plurality of Ys each independently represent a hydrocarbon group having 1 to 20 carbon atoms, and X represents one or more of the following formulas (A) to (T))

[0029]

[0030] (In the above formulas (A) to (T), R represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, a represents an integer of 1 to 4, p and n represent repeating numbers, which are 1 to 20, and * represents the bonding position to the nitrogen atom in formula (2)) [4]

[0032] A curable resin composition comprising the compound according to any one of the above items [1] to [3]. [5]

[0034] The curable resin composition according to the aforementioned item [4] further contains a radical polymerization initiator. [6]

[0036] The curable resin composition according to the above item [4] or [5], further comprising a maleimide compound. [7]

[0038] A cured product obtained by curing the curable resin composition according to any one of the above items [4] to [6].

[0039] Effects of the Invention

[0040] The compound and curable resin composition of the present invention have high heat resistance and excellent low dielectric properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] Figure 1 The GPC chart of Example 1 is shown.

[0042] Figure 2 The GPC chart of Example 2 is shown. DETAILED DESCRIPTION

[0043] The compound of the present invention is obtained by reacting a compound represented by the following formula (a) with a compound having two or more amino groups in its molecule.

[0044]

[0045] In the formula (a), Y represents a hydrocarbon group having 1 to 20 carbon atoms, more preferably 2 to 20 carbon atoms, and even more preferably 4 to 20 carbon atoms. If the carbon number is 1 or more, the solvent solubility becomes good and the water absorption rate also decreases. In addition, if it is 20 or less, the heat resistance and solvent solubility also become good, and it can be purified by washing with water. Specific examples of the compound represented by the formula (a) include: tetrapropenyl succinic anhydride (commonly known as TPSA, where Y in the formula (a) is C9H 19 Compounds; may also contain isomer mixtures), dodecenyl succinic anhydride (Dodecenyl succinic anhydride) (commonly known as n-DDSA, Y in formula (a) is C9H 19 Compounds), octenyl succinic anhydride (Y in formula (a) is C5H 11 Compounds), nonyl succinic anhydride (Nonenyl succinic anhydride) (commonly known as NSA, Y in formula (a) is C6H 13 Compound), octadecenyl succinic anhydride (Y in formula (a) is C 15 H 31 ; may also contain isomeric compounds), tetradecenyl succinic anhydride (Y in formula (a) is C 11 H 23 The compound represented by the above formula (a) may be used alone or in combination with compounds having different Ys.

[0046] As a compound having two or more amino groups in the molecule, any known amine compound can be used. For example, amine compounds represented by the following formula (A') to formula (T'), methylenediamine, ethylenediamine, propylenediamine, butylenediamine, pentamethylenediamine, hexamethylenediamine, trimethylhexamethylenediamine, dimer diamine, 1,3-bisaminomethylcyclohexane, isophoronediamine, bisaminomethyltricyclodecane, etc. are listed, preferably any one or more of the following formula (A') to formula (T'), and more preferably any one or more of the following formula (A') to formula (G') and formula (R') to formula (T'). In addition, by using an aromatic amine compound or an alicyclic amine compound having a molecular weight distribution, heat resistance or solvent solubility can be improved. These can be used alone or in combination. In addition, the so-called dimer diamine refers to a diamine in which the two terminal carboxylic acid groups (-COOH) of the dimer acid are substituted with a primary aminomethyl group (-CH2-NH2) or an amino group (-NH2). As the dimer diamine, a known commercially available product can be used.

[0047] Examples of commercially available products include Priamine (registered trademark) manufactured by Croda Japan Co., Ltd.

[0048]

[0049] In the formulae (A') to (T'), R represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and a represents an integer of 1 to 4. p and n represent the number of repetitions and represent an integer of 1 to 20.

[0050] In addition, the average value p of the number of repetitions of formula (E') and the average value n of the number of repetitions of formulae (A') to (D') and (F') can be calculated based on the number average molecular weight (Mn) value determined by gel permeation chromatography (hereinafter also referred to as GPC) of the compounds of formulae (A') to (E') or the area % of slice data of each peak (detector: differential refractive index detector), etc.

[0051] In Formulas (A') to (T'), R is typically a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, and more preferably 1 to 3 carbon atoms. Hydrocarbons having 10 or fewer carbon atoms are less likely to vibrate molecularly when exposed to high frequencies, resulting in excellent electrical properties. Furthermore, n is preferably 1<n<5.

[0052] The above formula (B') is particularly preferably when a is 0, that is, when it is the following formula (1).

[0053]

[0054] In formula (1), n ​​is the average value of the number of repetitions, and 1 ≤ n < 5. The average value of the number of repetitions n in formula (1) can be calculated from the value of the number average molecular weight (Mn) determined by gel permeation chromatography (hereinafter also referred to as GPC) of the compound of formula (1) or the area % of the slice data of each peak (detector: differential refractive index detector), etc.

[0055] The formula (E') is particularly preferably the following formula (2).

[0056]

[0057] In formula (2), R each independently represents a hydrocarbon group having 1 to 3 carbon atoms, and p represents the average value of the number of repetitions, and 0≦p≦20. The average value of the number of repetitions p in formula (2) can be calculated based on the value of the number average molecular weight (Mn) determined by gel permeation chromatography (hereinafter also referred to as GPC) of the compound of formula (2) or the area % of the slice data of each peak (detector: differential refractive index detector), etc.

[0058] The above formula (F') is particularly preferably when a is 2 and n is 0, that is, the following formula (3), or when a is 0, that is, the following formula (4).

[0059]

[0060] In formula (3), R each exists independently and represents a hydrocarbon group having 1 to 3 carbon atoms.

[0061]

[0062] In formula (4), n is the average value of the number of repetitions, and 1 ≤ n < 5. The average value of the number of repetitions n in formula (4) can be calculated based on the number average molecular weight (Mn) value determined by gel permeation chromatography (hereinafter also referred to as GPC) of the compound of formula (4) or the area % of slice data of each peak (detector: differential refractive index detector), etc.

[0063] The above formula (C') is particularly preferably when a is 0, that is, when it is the following formula (5).

[0064]

[0065] In formula (5), n is the average value of the number of repetitions, and 1 ≤ n < 5. The average value of the number of repetitions n in formula (5) can be calculated based on the value of the number average molecular weight (Mn) determined by gel permeation chromatography (hereinafter also referred to as GPC) of the compound of formula (5) or the area % of the slice data of each peak (detector: differential refractive index detector), etc.

[0066] The compound of the present invention is obtained by reacting the compound represented by the above formula (a) with a compound having two or more amino groups in the molecule, and can be represented by the following formula (b).

[0067]

[0068] In the formula (b), the presence of a plurality of Ys each independently represents a hydrocarbon group having 1 to 20 carbon atoms, more preferably 2 to 20 carbon atoms, and more preferably 4 to 20 carbon atoms. If the carbon number is 1 or more, the solvent solubility becomes good and the water absorption rate also decreases. In addition, if it is 20 or less, the heat resistance and solvent solubility also become good, and it can be purified by washing with water. Since Y is derived from the formula (a), as a specific example, C9H 19 、C5H 11 、C6H 13 、C 15 H 31 、C 11 H 23 The compound represented by the above formula (a) may be used alone or in combination with compounds having different Ys.

[0069] In the formula (b), since X is derived from a compound having two or more amino groups in the molecule, a structure derived from a compound having two or more amino groups in the molecule can be obtained. However, it is preferably any one or more of the following formulas (A) to (T), and is even more preferably any one or more of the following formulas (A) to (G) and (R) to (T).

[0070]

[0071] In the above formulae (A) to (T), R represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and a represents an integer of 1 to 4. p and n represent the number of repetitions, which are 1 to 20. * represents the bonding position to the nitrogen atom in formula (2).

[0072] In formulas (A) to (T), R is generally a hydrocarbon group having 1 to 10 carbon atoms, preferably a hydrocarbon group having 1 to 5 carbon atoms, and more preferably a hydrocarbon group having 1 to 3 carbon atoms. Hydrocarbons having 10 or fewer carbon atoms are less likely to vibrate molecularly when exposed to high frequencies, and thus exhibit excellent electrical properties.

[0073] The method for producing the compound of the present invention is not particularly limited, and the compound can be derived from the compound represented by the above formula (a) and a compound having two or more amino groups in the molecule.

[0074] Specifically, it can be obtained by the following method, that is, reacting the compound represented by the above formula (a) with a compound having two or more amino groups in the molecule in the presence of a catalyst in a solvent at a temperature range of 0°C to 200°C, preferably 0°C to 150°C, to close the ring and imidize the reaction. Examples of the solvent used include: aromatic solvents such as toluene and xylene; aliphatic solvents such as cyclohexane and n-hexane; ethers such as diethyl ether and diisopropyl ether; ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as methyl isobutyl ketone and cyclopentanone; and other non-water-soluble solvents, but are not limited to these, and two or more solvents may be used in combination. In addition to the above-mentioned non-water-soluble solvents, aprotic polar solvents may also be used in combination. Examples include: dimethyl sulfone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, N-methylpyrrolidone, etc., and two or more solvents may be used in combination. When using an aprotic polar solvent, it is preferred to use a solvent with a higher boiling point than the non-water-soluble solvent used in combination. During the reaction, in addition to using hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, p-toluenesulfonic acid, and methanesulfonic acid as catalysts, Lewis acids such as aluminum chloride and zinc chloride, activated clay, acid clay, white carbon, zeolite, solid acids such as silica alumina, and acidic ion exchange resins can also be used. These can be used alone or in combination of two or more. The amount of catalyst used is generally 0.1 to 0.8 moles, preferably 0.2 to 0.7 moles, relative to 1 mole of amino groups in the amine compound used. If the amount of catalyst used is too much, the viscosity of the reaction solution will be too high, and there is a risk of stirring becoming difficult. If the amount of catalyst used is too little, there is a risk of slowing down the reaction. In addition, as a co-catalyst for imidization, a basic co-catalyst such as triethylamine can also be used alone or in combination. When a sulfonic acid or the like is used as a catalyst, it can also be neutralized with an alkali metal such as sodium hydroxide or potassium hydroxide before entering the extraction step. In the extraction step, an aromatic hydrocarbon solvent such as toluene or xylene may be used alone, or a non-aromatic hydrocarbon such as cyclohexane or toluene may be used in combination. After extraction, the organic layer is washed with water until the drainage becomes neutral, and the solvent is distilled off using an evaporator to obtain the target compound.

[0075] [Hardening accelerator]

[0076] The curing properties of the curable resin composition of the present invention can also be enhanced by adding a curing accelerator. The curing accelerator is preferably an anionic curing accelerator that generates anions upon irradiation with ultraviolet light or visible light or heating, thereby accelerating the curing reaction, or a cationic curing accelerator that generates cations upon irradiation with ultraviolet light or visible light or heating, thereby accelerating the curing reaction.

[0077] Examples of anionic hardening 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, trimethyldecylammonium salts, cetyltrimethylammonium salts, and hexadecyltrimethylammonium hydroxide, but are not limited to these. These may be used alone or in combination.

[0078] Examples of cationic hardening accelerators include, but are not limited to, quaternary phosphonium salts such as triphenylbenzylphosphonium salts, triphenylethylphosphonium salts, and tetrabutylphosphonium salts (the counter ions of the quaternary salts are halogens, organic acid ions, hydroxide ions, etc., although not particularly limited thereto, with organic acid ions and hydroxide ions being particularly preferred), transition metal compounds (transition metal salts) such as tin octylate, zinc carboxylates (zinc 2-ethylhexanoate, zinc stearate, zinc behenate, zinc myristate), and zinc phosphates (zinc octylphosphate, zinc stearylphosphate). These may be used alone or in combination.

[0079] The curing accelerator is added in an amount of 0.01 to 5.0 parts by mass based on 100 parts by mass of the curable resin composition, as needed.

[0080] [Inorganic fillers]

[0081] The curable resin composition of the present invention may contain an inorganic filler. Examples of inorganic fillers include, but are not limited to, fused silica, crystalline silica, porous silica, alumina, zircon, calcium silicate, calcium carbonate, quartz powder, silicon carbide, silicon nitride, boron nitride, zirconium oxide, aluminum nitride, graphite, forsterite, steatite, spinel, mullite, titanium dioxide, talc, clay, iron oxide, asbestos, and powdered glass, as well as spherical or crushed versions of these. These fillers may be used alone or in combination.

[0082] The amount of inorganic filler used in obtaining a curable resin composition for semiconductor sealing 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. Furthermore, when obtaining a curable resin composition for use as an interlayer insulating layer forming material, a copper sheet laminate or prepreg, or a substrate material such as RCC, 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.

[0083] [Polymerization initiator]

[0084] The curable resin composition of the present invention can also be enhanced in its curability by adding a polymerization initiator. A polymerization initiator is a compound capable of polymerizing olefin functional groups such as ethylenically unsaturated bonds. Examples include olefin metathesis polymerization initiators, anionic polymerization initiators, cationic polymerization initiators, and free radical polymerization initiators. Among these, free radical polymerization initiators that exhibit both curability and moderate stability are preferred. Free radical polymerization initiators are compounds that generate free radicals upon exposure to ultraviolet or visible light or heating, initiating chain polymerization reactions. Examples of usable free radical polymerization initiators include organic peroxides, azo compounds, and benzopinacols. Organic peroxides are preferred because they minimize the effects of curing temperature control, exhaust gas suppression, and the effects of decomposition products on electrical properties.

[0085] Examples of the organic peroxide 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(tert-butylperoxyisopropyl)benzene; peroxyketals such as tert-butyl peroxybenzoate and 1,1-di-tert-butylperoxycyclohexane; α-cumyl peroxyneodecanoate, tert-butyl peroxyneodecanoate, tert-butyl peroxytrimethylacetate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, tert-amylperoxy-2-ethylhexanoate, Examples of the organic peroxides include, but are not limited to, alkyl peroxyesters such as tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-butyl peroxy-3,5,5-trimethylhexanoate, and tert-amyl peroxybenzoate; peroxycarbonates such as di-2-ethylhexyl peroxydicarbonate, bis(4-tert-butylcyclohexyl)peroxydicarbonate, tert-butyl peroxyisopropyl carbonate, and 1,6-bis(tert-butylperoxycarbonyloxy)hexane; and tert-butyl hydroperoxide, cumene hydroperoxide, tert-butyl peroxyoctanoate, and lauroyl peroxide. These organic peroxides may be used alone or in combination. Among the organic peroxides, ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, alkyl peroxyesters, and peroxycarbonates are preferred, with dialkyl peroxides being more preferred.

[0086] Examples of the azo compounds include, but are not limited to, azobisisobutyronitrile, 4,4'-azobis(4-cyanovaleric acid), and 2,2'-azobis(2,4-dimethylvaleronitrile).

[0087] The amount of polymerization initiator added is preferably 0.01 to 5 parts by mass, particularly preferably 0.01 to 3 parts by mass, per 100 parts by mass of the curable resin composition. If the amount of polymerization initiator used is less than 0.01 parts by mass, the molecular weight may not be sufficiently increased during the polymerization reaction. If the amount is more than 5 parts by mass, dielectric properties such as the dielectric constant and dielectric loss tangent may be impaired.

[0088] [Polymerization inhibitor]

[0089] The curable resin composition of the present invention may also contain a polymerization inhibitor. The inclusion of a polymerization inhibitor improves storage stability and controls the reaction initiation temperature. Controlling the reaction initiation temperature facilitates flowability and facilitates B-stage formation, such as prepreg formation, without compromising impregnation into glass fiber cloth, etc. However, excessive polymerization during prepreg formation can easily lead to problems such as difficulty in lamination.

[0090] The polymerization inhibitor may be added during or after the synthesis of the compound of the present invention. The amount of the polymerization inhibitor used is 0.008 to 1 part by mass, preferably 0.01 to 0.5 parts by mass, relative to 100 parts by mass of the compound of the present invention.

[0091] Examples of polymerization inhibitors include phenolic, sulfuric, phosphorus-based, hindered amine-based, nitroso-based, and nitroxyl free radical-based inhibitors. A single polymerization inhibitor may be used, or a combination of multiple polymerization inhibitors may be used. Among these, phenolic, hindered amine-based, nitroso-based, and nitroxyl free radical-based inhibitors are preferred in the present invention.

[0092] Examples of the phenolic polymerization inhibitor include monophenols such as 2,6-di-tert-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-tert-butyl-p-ethylphenol, stearyl-β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, isooctyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylaniline)-1,3,5-triazine, and 2,4-bis[(octylthio)methyl]-o-cresol, and 2,2'-methylenebis(4-methyl -6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 4,4'-butylenebis(3-methyl-6-tert-butylphenol), triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamic acid), 2,2'-thiodiethylene Bisphenols such as bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 3,5-di-tert-butyl-4-hydroxybenzyl phosphate-diethyl ester, 3,9-bis[1,1-dimethyl-2-{β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}ethyl]2,4,8,10-tetraoxaspiro[5,5]undecane, bis(3,5-di-tert-butyl-4-hydroxybenzylsulfonic acid ethyl ester) calcium; 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4, Examples of the present invention include, but are not limited to, high-molecular-weight phenols such as 6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tetrakis-[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane, bis[3,3'-bis-(4'-hydroxy-3'-tert-butylphenyl)butyrate]ethylene glycol, tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(3',5'-di-tert-butyl-4'-hydroxybenzyl)-s-triazine-2,4,6-(1H,3H,5H)trione, and tocopherol.

[0093] 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.

[0094] Examples of the phosphorus-based polymerization inhibitor include triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, tris(nonylphenyl) phosphite, pentaerythritol diisodecyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite, cyclic neopentanetetraylbis(octadecyl)phosphite, cyclic neopentanetetraylbis(2,4-di-tert-butylphenyl)phosphite, cyclic neopentanetetraylbis(2,4-di-tert-butyl-4-methylphenyl)phosphite, and bis[2- Phosphites such as tert-butyl-6-methyl-4-{2-(octadecyloxycarbonyl)ethyl}phenyl]hydrogen phosphite, oxaphosphaphenanthrene oxides such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(3,5-di-tert-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, are not limited thereto.

[0095] Examples of the hindered amine polymerization inhibitor include Adekastab LA-40MP, Adekastab LA-40Si, Adekastab LA-402AF, Adekastab LA-87, Adekastab LA-82, Adekastab LA-81, Adekastab LA-77Y, Adekastab LA-77G, Adekastab LA-72, Adekastab LA-68, and Adekastab. LA-63P, Adekastab LA-57, Adekastab LA-52, Chimassorb 2020FDL, Chimassorb 944FDL, Chimassorb 944LD, Tinuvin 622SF, Tinuvin PA144, Tinuvin 765, Tinuvin 770DF, Tinuvin XT55FB, Tinuvin 111FDL, Tinuvin 783FDL, Tinuvin 791FB, etc., but not limited to these.

[0096] Examples of the nitroso polymerization inhibitor include, but are not limited to, p-nitrosophenol, N-nitrosodiphenylamine, and ammonium salts of N-nitrosophenylhydroxylamine (cupferron). Among these, ammonium salts of N-nitrosophenylhydroxylamine (cupferron) are preferred.

[0097] Examples of the nitroxyl radical polymerization inhibitor include, but are not limited to, di-tert-butyl nitroxide, 2,2,6,6-tetramethylpiperidin-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidin-1-oxyl, 4-amino-2,2,6,6-tetramethylpiperidin-1-oxyl, 4-methoxy-2,2,6,6-tetramethylpiperidin-1-oxyl, 4-acetoxy-2,2,6,6-tetramethylpiperidin-1-oxyl, and 4-benzoyloxy-2,2,6,6-tetramethylpiperidin-1-oxyl.

[0098] [Flame retardant]

[0099] 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 (such as antimony compounds, metal hydroxides, nitrogen compounds, and boron compounds), and phosphorus-based flame retardants. From the perspective of achieving halogen-free flame retardancy, phosphorus-based flame retardants are preferred.

[0100] The phosphorus-based flame retardant may be a reactive or additive type. Specific examples include: phosphates such as trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixyl phosphate, tolyl diphenyl phosphate, tolyl-2,6-dixyl phosphate, 1,3-phenylene bis(dixyl phosphate), 1,4-phenylene bis(dixyl phosphate), and 4,4'-biphenyl(dixyl phosphate); and phosphanes such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide. Examples include phosphorus-containing epoxy compounds obtained by reacting epoxy resins with the active hydrogen of the phosphanes, and red phosphorus, but are not limited to these. These may be used alone or in combination. Among the above-mentioned exemplified substances, phosphates, phosphanes or phosphorus-containing epoxy compounds are preferred, and 1,3-phenylenebis(di(xylyl)phosphate), 1,4-phenylenebis(di(xylyl)phosphate), 4,4′-biphenyl(di(xylyl)phosphate) or phosphorus-containing epoxy compounds are particularly preferred.

[0101] The content of the flame retardant is preferably in the range of 0.1 to 10 parts by mass per 100 parts by mass of the curable resin composition. If it is less than 0.1 parts by mass, the flame retardancy may be insufficient, while if it is more than 10 parts by mass, the hygroscopicity and dielectric properties of the cured product may be adversely affected.

[0102] [Light stabilizer]

[0103] The curable resin composition of the present invention can use a light stabilizer. As the light stabilizer, a hindered amine light stabilizer is preferred, and a hindered amine light stabilizer (HALS) is particularly preferred. Examples of HALS include a reaction product of dibutylamine-1,3,5-triazine-N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexamethylenediamine and N-(2,2,6,6-tetramethyl-4-piperidinyl)butylamine, a reaction product of dimethyl succinate-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidinyl, and poly{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidinyl)imino}hexamethylene{(2,2,6,6-tetramethyl-4

[0014] Examples of the present invention include, but are not limited to, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)imino}], bis(1,2,2,6,6-pentamethyl-4-piperidinyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate, bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl)sebacate, and bis(1,2,2,6,6-pentamethyl-4-piperidinyl)2-(3,5-di-tert-butyl-4-hydroxybenzyl)-2-n-butylmalonate. These may be used alone or in combination.

[0104] The content of the light stabilizer is preferably in the range of 0.001 to 0.1 parts by mass per 100 parts by mass of the curable resin composition. If it is less than 0.001 parts by mass, the light stabilization effect may be insufficient, while if it is more than 0.1 parts by mass, the hygroscopicity and dielectric properties of the cured product may be adversely affected.

[0105] [Binder resin]

[0106] The curable resin composition of the present invention may be used as a binder resin. Examples of the binder resin include, but are not limited to, butyral resins, acetal resins, acrylic resins, epoxy-nylon resins, nitrile butadiene rubber (NBR)-phenol resins, epoxy-NBR resins, and silicone resins. These resins may be used alone or in combination.

[0107] The amount of the binder resin added 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, more preferably 0.05 to 20 parts by mass, based on 100 parts by mass of the curable resin composition.

[0108] [additive]

[0109] The curable resin composition of the present invention may contain additives. Examples of such additives include modified acrylonitrile copolymers, polyethylene, fluororesins, silicone gels, silicone oils, surface treatment agents for fillers such as silane coupling agents, mold release agents, and colorants such as carbon black, phthalocyanine blue, and phthalocyanine green.

[0110] The amount of the additives added is preferably 1 part by mass or less, more preferably 0.7 part by mass or less, per 100 parts by mass of the curable resin composition.

[0111] The curable resin composition of the present invention can further use epoxy resins, active ester compounds, phenol resins, polyphenylene oxide compounds, amine resins, compounds with ethylenically unsaturated bonds, isocyanate resins, polyamide resins, cyanate resins, polyimide resins, polybutadiene and its modified products, polystyrene and its modified products, polyethylene and its modified products, etc. These can be used in one or more combinations. Among these compounds, in terms of heat resistance, adhesion, and the balance of dielectric properties, it is preferred to contain polyphenylene oxide compounds, compounds with ethylenically unsaturated bonds, maleimide compounds, cyanate resins, polybutadiene and its modified products, polystyrene and its modified products. By containing these compounds, the brittleness of the cured product and the adhesion to metal can be improved, and the cracks of the package in the reliability test such as reflow soldering or hot and cold cycles can be suppressed. With regard to the total usage amount of these compounds, unless otherwise specified, relative to the compound of the present invention, it is preferably 10 parts by mass or less, and further preferably 5 parts by mass or less, and particularly preferably 3 parts by mass or less. In addition, the preferred lower limit is more than 0.1 mass parts, more preferably more than 0.25 mass parts, and then preferably more than 0.5 mass parts. By being set within the scope, it is possible to effectively utilize the heat resistance of the compound of the present invention or the effect of dielectric properties while adding the effect of each compound added. About these components, the following exemplification can be used.

[0112] [Epoxy resin]

[0113] Preferred epoxy resins are exemplified below, but are not limited thereto. Epoxy resins may be in liquid or solid form, and may be used alone or in combination of two or more.

[0114] Examples of the liquid epoxy resin include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol AF epoxy resin, naphthalene epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, phenol novolac epoxy resin, alicyclic epoxy resins having an ester skeleton, cyclohexane epoxy resin, cyclohexanedimethanol epoxy resin, and epoxy resins having a butadiene structure. Specific examples include: "RE310S", "RE410S" (all manufactured by Nippon Kayaku Co., Ltd., bisphenol A type epoxy resins), "RE303S", "RE304S", "RE403S", "RE404S" (all manufactured by Nippon Kayaku Co., Ltd., bisphenol F type epoxy resins), "HP4032", "HP4032D", "HP4032SS" (all manufactured by DIC Corporation, naphthalene type epoxy resins), "828US", "jER828EL", "825", "828EL" (All of the above are bisphenol A epoxy resins manufactured by Mitsubishi Chemical Corporation), "jE807", "1750" (All of the above are bisphenol F epoxy resins manufactured by Mitsubishi Chemical Corporation), "jER152" (All of the above are phenol novolac epoxy resins manufactured by Mitsubishi Chemical Corporation), "630", "630LSD" (All of the above are glycidylamine epoxy resins manufactured by Mitsubishi Chemical Corporation), "ZX1059" (Mixture of bisphenol A epoxy resin and bisphenol F epoxy resin manufactured by Nippon Steel & Sumikin Chemicals Co., Ltd.), "EX-721" (Nagase Chemicals Co., Ltd.) ChemteX, a glycidyl ester-type epoxy resin), "Celloxide 2021P" (a cycloaliphatic epoxy resin with an ester skeleton, manufactured by Daicel), "PB-3600" (an epoxy resin with a butadiene structure, manufactured by Daicel), "ZX1658" and "ZX1658GS" (both manufactured by Nippon Steel & Sumikin Chemicals, liquid 1,4-glycidylcyclohexane-type epoxy resins), etc. These may be used alone or in combination of two or more.

[0115] Preferred solid epoxy resins include, for example, bixylene-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. Examples thereof 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, a naphthalene-type epoxy resin), "HP-4700", "HP-4710" (the above are naphthalene-type tetrafunctional epoxy resins manufactured by DIC Corporation), "N-690" (manufactured by DIC Corporation, a cresol novolac-type epoxy resin), "N-695" (manufactured by DIC Corporation, a cresol novolac-type epoxy resin), "HP-7200", "HP-7200HH", "HP- 7200H" (all manufactured by DIC, dicyclopentadiene type 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" (manufactured by Nippon Kayaku Co., Ltd., "NC-3000H", "NC-3000", "NC-3000L", "NC-3100" (all manufactured by Nippon Kayaku Co., Ltd., biphenyl aralkyl type epoxy resins); "XD-1000-2L", "XD-1000-L", "XD-1000-H", "XD-1000-H" (all manufactured by Nippon Kayaku Co., Ltd., dicyclopentadiene type epoxy resins); "ESN475V" (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., Naphthol-type epoxy resin), "ESN485" (manufactured by Nippon Steel & Sumitomo Metal Chemicals, naphthol novolac-type epoxy resin), "YX-4000H", "YX-4000", "YL6121" (manufactured by Mitsubishi Chemical Corporation, biphenyl-type epoxy resin), "YX-4000HK" (manufactured by Mitsubishi Chemical Corporation, dimethylphenol-type epoxy resin), "YX-8800" (manufactured by Mitsubishi Chemical Corporation, anthracene-type epoxy resin), "PG-100", "CG-500" (manufactured by Osaka Gas Chemicals, Gas Chemicals, fluorene-based epoxy resin), "YL-7760" (bisphenol AF epoxy resin, manufactured by Mitsubishi Chemical Corporation), "YL-7800" (fluorene-based epoxy resin, manufactured by Mitsubishi Chemical Corporation), "jER1010" (solid bisphenol A epoxy resin, manufactured by Mitsubishi Chemical Corporation), "jER1031S" (tetraphenylethane-based epoxy resin, manufactured by Mitsubishi Chemical Corporation), etc. These may be used alone or in combination of two or more.

[0116] [Active ester compound]

[0117] So-called active ester compound refers to a compound comprising at least one ester bond in a structure and having an aliphatic chain, an aliphatic ring or an aromatic ring bonded to both sides of the ester bond. As active ester compound, for example, phenolic esters, thiophenolic esters, N-hydroxylamine esters, esters of heterocyclic hydroxy compounds, etc., having two or more ester groups with high reactive activity in one molecule, can be enumerated. It can be obtained by the condensation reaction of at least one compound of a carboxylic acid compound, an acyl chloride or a thiocarboxylic acid compound with at least one compound of a hydroxy compound or a thiol compound. In particular, from the viewpoint of improving heat resistance, it is preferably obtained from a carboxylic acid compound or an acyl chloride and a hydroxy compound, and as the hydroxy compound, it is preferably a phenolic compound or a naphthol compound. Active ester compound can be used alone or in combination of two or more.

[0118] 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.

[0119] Examples of the acid chloride include acetyl chloride, acryloyl chloride, methacryloyl chloride, malonyl chloride, succinyl dichloride, diglycolyl chloride, glutaryl dichloride, suberyl dichloride, sebacoyl dichloride, adipoyl dichloride, dodecanedioyl dichloride, azelaoyl chloride, 2,5-furandicarbonyl dichloride, phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, trimesoyl chloride, bis(4-chlorocarbonylphenyl) ether, 4,4'-diphenyldicarbonyl chloride, and 4,4'-azobisbenzoyl dichloride.

[0120] Examples of the phenolic compound and the naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, acid phenolphthalein, 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, pyrogallol, dicyclopentadiene-type diphenolic compounds, phenol novolacs, and the phenolic resins described below. Here, the term "dicyclopentadiene-type diphenolic compound" refers to a diphenolic compound obtained by condensing two molecules of phenol into one molecule of dicyclopentadiene.

[0121] As preferred specific examples of active ester compounds, active ester compounds comprising dicyclopentadiene-type diphenol structures, active ester compounds comprising naphthalene structures, active ester compounds comprising acetylated products of phenol novolacs, active ester compounds comprising benzoylated products of phenol novolacs, compounds described in Example 2 of International Publication No. 2020 / 095829, and compounds disclosed in International Publication No. 2020 / 059625, etc., can be cited. Among them, active ester compounds comprising naphthalene structures and active ester compounds comprising dicyclopentadiene-type diphenol structures are more preferred. The so-called dicyclopentadiene-type diphenol structure represents a divalent structural unit comprising phenylene-dicyclopentylene-phenylene.

[0122] Examples of commercially available active ester compounds include "EXB9451," "EXB9460," "EXB9460S," "HPC-8000-65T," "HPC-8000H-65TM," "EXB-8000L-65TM," and "EXB-8150-65T" (manufactured by DIC Corporation), which are active ester compounds containing a dicyclopentadiene-type diphenol structure; and "EXB9416-70BK" (manufactured by DIC Corporation), which is an active ester compound containing a naphthalene structure. ; "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing an acetylated product of phenol novolac; "YLH1026", "YLH1030", and "YLH1048" (manufactured by Mitsubishi Chemical Corporation) as active ester compounds containing a benzoylated product of phenol novolac; "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester hardener for an acetylated product of phenol novolac; "EXB-9050L-62M" manufactured by DIC Corporation as an active ester hardener containing a phosphorus atom, etc.

[0123] [Phenolic resin]

[0124] A phenol resin is a compound having two or more phenolic hydroxyl groups in its molecule. Examples of phenol 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.

[0125] Specific examples of the raw materials are shown below, but the raw materials are not limited to these.

[0126] <Phenols>

[0127] Phenol, alkyl-substituted phenol, aromatic-substituted phenol, hydroquinone, resorcinol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.

[0128] <Aldehydes>

[0129] Formaldehyde, acetaldehyde, alkyl aldehydes, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, o-phthalaldehyde, crotonaldehyde, cinnamaldehyde, furfural, etc.

[0130] <Diene compounds>

[0131] Dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.

[0132] Ketones

[0133] Acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, fluorenone, etc.

[0134] Substituted biphenyls

[0135] 4,4'-bis(chloromethyl)-1,1'-biphenyl, 4,4'-bis(methoxymethyl)-1,1'-biphenyl, 4,4'-bis(hydroxymethyl)-1,1'-biphenyl, etc.

[0136] <Substituted phenyl groups>

[0137] 1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene, 1,4-bis(hydroxymethyl)benzene, etc.

[0138] [Polyphenylene ether compound]

[0139] As the polyphenylene ether compound, from the viewpoint of heat resistance and electrical properties, a polyphenylene ether compound having an ethylenically unsaturated bond is preferred, and a polyphenylene ether compound having an acrylic group, a methacrylic group, or a styrene structure is more preferred. Commercially available products include SA-9000 (a polyphenylene ether compound having a methacrylic group, manufactured by Saudi Basic Industries (SABIC)) and OPE-2St 1200 (a polyphenylene ether compound having a styrene structure, manufactured by Mitsubishi Gas Chemical Co., Ltd.).

[0140] The number average molecular weight (Mn) of the polyphenylene ether compound is preferably 500 to 5000, more preferably 2000 to 5000, and even more preferably 2000 to 4000. If the molecular weight is less than 500, the heat resistance of the cured product tends to be insufficient. On the other hand, if the molecular weight is greater than 5000, the melt viscosity becomes high, insufficient fluidity is obtained, and the product tends to be poorly formed. In addition, the reactivity is reduced, the curing reaction takes a long time, the amount of unreacted substances that do not enter the curing system increases, the glass transition temperature of the cured product decreases, and the heat resistance of the cured product tends to decrease.

[0141] When the number average molecular weight of the polyphenylene ether compound is 500 to 5000, it can exhibit excellent heat resistance and moldability while maintaining excellent dielectric properties. Specifically, the number average molecular weight can be measured using gel permeation chromatography or the like.

[0142] The polyphenylene ether compound can be obtained by polymerization reaction or by 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, free radical polymerizability can be imparted by reacting these as raw materials with compounds having ethylenically unsaturated bonds such as methacryloyl chloride, acryloyl chloride, and chloromethylstyrene. The polyphenylene ether compound obtained by redistribution reaction can be obtained by, for example, heating a high molecular weight polyphenylene ether compound in a solvent such as toluene in the presence of a phenol compound and a free radical initiator and performing a redistribution reaction. The polyphenylene ether compound obtained by the redistribution reaction has hydroxyl groups at both ends of the molecular chain that are derived from phenolic compounds that contribute to hardening, so it is not only possible to maintain higher heat resistance, but also to introduce functional groups at both ends of the molecular chain after modification with a compound having ethylenically unsaturated bonds, which is preferred in terms of the above aspect. In addition, the polyphenylene ether compound obtained by polymerization reaction shows excellent fluidity, which is preferred in terms of the above aspect.

[0143] In the case of a polyphenylene ether compound obtained by a polymerization reaction, the molecular weight of the polyphenylene ether compound can be adjusted by adjusting the polymerization conditions, etc. 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 considered to adjust the amount of the phenolic compound used in the redistribution reaction. That is, the more the amount of the phenolic compound is, the lower the molecular weight of the obtained polyphenylene ether compound. At this time, as a high molecular weight polyphenylene ether compound subjected to the redistribution reaction, poly(2,6-dimethyl-1,4-phenylene ether) can be used. In addition, as the phenolic compound used in the redistribution reaction, there is no particular limitation, and preferably a multifunctional phenolic compound having two or more phenolic hydroxyl groups in the molecule, such as bisphenol A, phenol novolac, cresol novolac, etc. can be used. These can be used alone or in combination of two or more.

[0144] [Amine resin]

[0145] The so-called amine resin is a compound having two or more amino groups in the molecule. Examples of the amine resin include diaminodiphenylmethane, diaminodiphenylsulfone, isophoronediamine, naphthalene diamine, aniline novolac (a reaction product of aniline and formalin), N-methylaniline novolac (a reaction product of N-methylaniline and formalin), n-ethylaniline novolac (a reaction product of n-ethylaniline 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, a reaction product of aniline and dichloroxylene (xylylene) Examples of the present invention include, but are not limited to, aniline resins obtained by reacting aniline with diisopropylbenzene (such as 4,4'-bis(chloromethyl)-1,1'-biphenyl and 4,4'-bis(methoxymethyl)-1,1'-biphenyl) as described in Japanese Patent No. 6429862, reaction products of aniline with substituted biphenyls (such as 1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene and 1,4-bis(hydroxymethyl)benzene), 4,4'-(1,3-phenylenediisopropylidene)bisaniline, 4,4'-(1,4-phenylenediisopropylidene)bisaniline, reaction products of aniline with diisopropylbenzene, and dimer diamines. These may be used alone or in combination.

[0146] [Compounds containing ethylenically unsaturated bonds]

[0147] The ethylenically unsaturated bond-containing compound is a compound having one or more ethylenically unsaturated bonds in its molecule that can be polymerized by heat or light with or without the use of a polymerization initiator.

[0148] Examples of the compound containing an ethylenically unsaturated bond include reaction products of the phenol resin and a halogen compound containing an ethylenically unsaturated bond (such as chloromethylstyrene, allyl chloride, methylallyl chloride, acryloyl chloride, and methacryloyl chloride); reaction products of phenols containing an ethylenically unsaturated bond (such as 2-allylphenol, 2-propenylphenol, 4-allylphenol, 4-propenylphenol, eugenol, and isoeugenol) and a halogen compound (such as 1,4-bis(chloromethyl)benzene, 4,4'-bis(chloromethyl)biphenyl, 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-dibromobenzophenone, and cyanuric chloride); reaction products of epoxy resins or alcohols and (meth)acrylic acids (such as acrylic acid and methacrylic acid); and acid-modified products thereof, but are not limited thereto. These may be used alone or in combination of two or more.

[0149] [Isocyanate resin]

[0150] The so-called isocyanate resin is a compound having two or more isocyanate groups in the molecule. Examples of the isocyanate resin include aromatic diisocyanates such as p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene 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 biuret forms of one or more isocyanate monomers or isocyanate forms obtained by trimerization of the diisocyanate compounds; and polyisocyanates obtained by urethanization reaction of the isocyanate compounds with polyol compounds. These may be used alone or in combination of two or more.

[0151] [Polyamide resin]

[0152] Examples of the polyamide resin include reaction products of one or more of diamine, diisocyanate, and oxazoline with dicarboxylic acid, reaction products of diamine and acid chloride, and ring-opening polymers of lactam compounds.

[0153] Specific examples of the raw materials are shown below, but the raw materials are not limited to these.

[0154] <Diamine>

[0155] 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, cyclohexanediamine, bis-(4-aminocyclohexyl)methane, bis(3-methyl-4-aminocyclohexyl)methane, xylenediamine, norbornanediamine, isophoronediamine, 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-ethylenediphenylamine, 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-aminophenoxy)] [4-(4-aminophenoxy)phenyl]propane, bis[4-(4-aminophenoxy)phenyl]sulfone, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-(1,3-phenylenediisopropylidene)dianiline, 4,4'-(1,4-phenylenediisopropylidene)dianiline, 9,9-bis(4-aminophenyl)fluorene, 2,7-diaminofluorene, aminobenzylamine, diaminobenzophenone, etc.

[0156] <Diisocyanate>

[0157] Phenylene 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, etc.

[0158] <Dicarboxylic acid>

[0159] 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 sulfoisophthalate, hexahydroterephthalic acid, hexahydroisophthalic acid, cyclohexanedicarboxylic acid, biphenyldicarboxylic acid, naphthalene dicarboxylic acid, benzophenone dicarboxylic acid, furandicarboxylic acid, 4,4'-dicarboxydiphenyl ether, 4,4'-dicarboxydiphenyl sulfide, etc.

[0160] <Acid chloride>

[0161] Acetyl chloride, acryloyl chloride, methacryloyl chloride, malonyl chloride, succinyl chloride, diacetyl chloride oxide, glutaryl chloride, suberyl chloride, sebacoyl chloride, adipoyl chloride, dodecanedioyl chloride, azelayl chloride, 2,5-furandicarbonyl dichloride, phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, trimesoyl chloride, bis(4-chlorocarbonylphenyl) ether, 4,4'-diphenyldicarbonyl chloride, 4,4'-azodibenzoyl chloride, etc.

[0162] <Lactam>

[0163] ε-caprolactam, ω-undecanolactam, ω-laurolactam, etc.

[0164] [Polyimide resin]

[0165] Examples of the polyimide resin include reaction products of the above-mentioned diamine and the tetracarboxylic dianhydride exemplified below, but the present invention is not limited thereto.

[0166] <Tetracarboxylic dianhydride>

[0167] 4,4'-(Hexafluoroisopropylidene)diphthalic anhydride, 5-(2,5-dioxotetrahydro-3-furyl)-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-ethylene-4,4'-diphthalic dianhydride, 2,2'-propylene-4,4'-diphthalic dianhydride, 1,2- Ethyl-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 dianhydride, 1,3-bis(3,4-dicarboxyphenyl)phthalic dianhydride, 1,3-bis(3,4-dicarboxyphenoxy)phthalic dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)phthalic dianhydride, 1,3-bis[2-(3,4-dicarboxyphenyl)-2-propyl]phthalic dianhydride, 1,4-bis[2-(3,4-dicarboxyphenyl)-2 -propyl]phthalic dianhydride, bis[3-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride, bis[4-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride, 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, 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride, carbonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic) dianhydride, methylene-4,4'-bis(cyclohexane-1,2-dicarboxylic) dianhydride, 1,2-ethylene-4,4'-bis(cyclohexane-1,2-dicarboxylic) dianhydride, 1,1-ethylene-4,4'-bis(cyclohexane-1,2-dicarboxylic) dianhydride, 2,2-propylene-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 anhydride), 9,9'-bis(3,4-dicarboxyphenyl)fluorene dianhydride, etc.

[0168] [Maleimide compound]

[0169] The curable resin composition of the present invention may also contain a maleimide compound. The so-called maleimide compound refers to a compound having one or more maleimide groups in the molecule. Examples of maleimide compounds include 4,4'-diphenylmethane bismaleimide, polyphenylmethane maleimide, m-phenylene bismaleimide, 2,2'-bis[4-(4-maleimidephenoxy)phenyl]propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 4,4'-diphenyl ether bismaleimide, 4,4'-diphenyl sulfone bismaleimide, 1,3-bis(3-maleimidephenoxy)benzene, 1,3-bis(4-maleimidephenoxy)benzene, and Xyloc-type maleimide compounds. (Anilix maleimide, manufactured by Mitsui Chemicals Co., Ltd.), biphenyl aralkyl type maleimide compound (solidified by removing the solvent from the resin solution containing the maleimide compound (M2) described in Example 4 of Japanese Patent Laid-Open No. 2009-001783 under reduced pressure), bisaminocumylbenzene type maleimide (maleimide compound described in International Publication No. 2020 / 054601), maleimide compound having an indane structure described in Japanese Patent No. 6629692 or International Publication No. 2020 / 217679, "MATERIAL STAGE (MATERIAL STAGE) The maleimide compounds described in "MATERIAL STAGE)" Vol. 18, No. 12, 2019 "~Continued·Epoxy Resin CAS Number Phrases~Hardener CAS Number Memorandum No. 31 Bismaleimide (1)" or "MATERIAL STAGE)" Vol. 19, No. 2, 2019 "~Continued·Epoxy Resin CAS Number Phrases~Hardener CAS Number Memorandum No. 32 Bismaleimide (2)" are not limited thereto. In addition, these may be used alone or in combination of two or more.

[0170] [Cyanate ester resin]

[0171] Cyanate resins are cyanate compounds obtained by reacting a phenol resin with a cyanogen halide. Specific examples include dicyanatobenzene, tricyanatobenzene, dicyanonaphthalene, dicyanobiphenyl, 2,2'-bis(4-cyanophenyl)propane, bis(4-cyanophenyl)methane, bis(3,5-dimethyl-4-cyanophenyl)methane, 2,2'-bis(3,5-dimethyl-4-cyanophenyl)propane, 2,2'-bis(4-cyanophenyl)ethane, 2,2'-bis(4-cyanophenyl)hexafluoropropane, bis(4-cyanophenyl)sulfone, bis(4-cyanophenyl)sulfide, phenol novolac cyanate, and products obtained by converting the hydroxyl groups of a phenol-dicyclopentadiene co-condensate into cyanate groups. These resins may be used alone or in combination.

[0172] Furthermore, cyanate compounds whose synthesis method is described in Japanese Patent Application Laid-Open No. 2005-264154 are particularly preferred as cyanate compounds because they have low hygroscopicity, flame retardancy, and excellent dielectric properties.

[0173] The cyanate resin may contain a catalyst such as zinc naphthenate, cobalt naphthenate, copper naphthenate, lead naphthenate, zinc octylate, tin octylate, lead acetylacetonate, or dibutyltin maleate in order to trimerize the cyanate group to form a s-triazine ring as needed.

[0174] The catalyst is used in an amount of preferably 0.0001 to 0.10 parts by mass, more preferably 0.00015 to 0.0015 parts by mass, based on 100 parts by mass of the cyanate ester resin.

[0175] [Polybutadiene and its modified products]

[0176] Polybutadiene and its modified products are compounds having a structure derived from polybutadiene or polybutadiene in the molecule. The structure derived from polybutadiene can be hydrogenated to convert some or all of the unsaturated bonds into single bonds.

[0177] As polybutadiene and its modified product, for example, polybutadiene, hydroxyl-terminated polybutadiene, terminal (meth) acrylated polybutadiene, carboxylic acid-terminated polybutadiene, amine-terminated polybutadiene, styrene-butadiene rubber etc. can be enumerated, but it is not limited to these. In addition, these can use one kind, also can use multiple kinds. Among these, with respect to the viewpoint of dielectric properties, preferably polybutadiene or styrene-butadiene rubber. As styrene-butadiene rubber (Styrene Butadiene Rubber, SBR), for example, can be enumerated: Liken (RICON) -100, Liken (RICON) -181, Liken (RICON) -184 (all are manufactured by Cray Valley (Cray Valley) company), 1,2-SBS (manufactured by Japan Soda Co., Ltd.), etc., as polybutadiene, B-1000, B-2000, B-3000 (all are manufactured by Japan Soda Co., Ltd.) etc. can be enumerated. As the molecular weight of polybutadiene and styrene butadiene rubber, it is preferred that the weight average molecular weight is 500 to 10,000, more preferably 750 to 7,500, and further preferably 1,000 to 5,000. Below the lower limit of the range, the amount of volatility is large, making it difficult to adjust the solid content when the prepreg is made, and above the upper limit of the range, the compatibility with other curable resins deteriorates. Generally speaking, in the case of compounds containing heteroatoms such as oxygen or nitrogen, such as bismaleimide or polymaleimide, it is difficult to ensure compatibility with low-polarity compounds such as compounds mainly containing hydrocarbons or compounds containing only hydrocarbons due to their polarity. On the other hand, the compound of the present invention, by introducing an alkenyl group, has a decreased polarity compared to maleimide compounds, and in addition to having excellent dielectric properties or low water absorption properties, it also has excellent compatibility with materials having low polarity and low dielectric properties, or compounds containing only hydrocarbons.

[0178] [Polystyrene and its modified products]

[0179] Polystyrene and its modified products are compounds having a structure of polystyrene or a structure derived from polystyrene in the molecule.

[0180] Examples of polystyrene and modified products thereof include polystyrene, styrene-2-isopropenyl-2-oxazoline copolymers (Epocros RPS-1005 and RP-61, both manufactured by Nippon Catalyst Co., Ltd.), SEP (styrene-ethylene-propylene copolymer: Septon 1020 manufactured by Kuraray), SEPS (styrene-ethylene-propylene-styrene copolymers: Septon 2002, Septon 2004F, Septon 2005, Septon 2006, Septon 2007, Septon 2008, Septon 2009, Septon 2010, Septon 2011, Septon 2013, Septon 2014, Septon 2015, Septon 2016, Septon 2017, Septon 2018, Septon 2019, Septon 2020, Septon 2021, Septon 2022, Septon 2023, Septon 2024, Septon 2025, Septon 2026, Septon 2027, Septon 2028, Septon 2029, Septon 2029, Septon Septon 2006, Septon 2063, Septon 2104 are all manufactured by Kuraray), SEEPS (styrene-ethylene / ethylene-propylene-styrene block copolymer: Septon 4003, Septon 4044, Septon 4055, Septon 4077, Septon 4099 are all manufactured by Kuraray), SEBS (styrene-ethylene-butylene-styrene block copolymer Septon 8004, Septon 8006, Septon 8007L are all manufactured by Kuraray), SEEPS-OH (a compound having a hydroxyl group at the end of a styrene-ethylene / ethylene-propylene-styrene block copolymer: Septon HG252 is manufactured by Kuraray), SIS (styrene-isoprene-styrene block copolymer: Septon 5125 and Septon 5127 are all manufactured by Kuraray), ay), hydrogenated SIS (hydrogenated styrene-isoprene styrene block copolymer: Hybrar 7125F and Hybrar 7311F are both manufactured by Kuraray), SIBS (styrene-isobutylene-styrene block copolymer: SIBSTAR073T, SIBSTAR102T, SIBSTAR103T (all manufactured by Kaneka Chemical), Septon V9827 (manufactured by Kuraray)), etc., but are not limited to these. In addition, these can be used alone or in combination. Polystyrene and its modified products have higher heat resistance and are not easily degraded by oxidation, so they preferably do not have unsaturated bonds.The weight average molecular weight of polystyrene and its modified products is not particularly limited as long as it is 10,000 or more. However, if it is too large, the compatibility with 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, in addition to the polyphenylene ether compound, deteriorates, making mixing and ensuring solvent stability difficult. Therefore, it is preferably about 10,000 to 300,000.

[0181] [Polyethylene and its modified products]

[0182] So-called polyethylene and its modified substance refer to polyethylene or a compound having a structure derived from polyethylene in the molecule. As polyethylene and its modified substance, for example, ethylene-propylene copolymer, ethylene-styrene copolymer, ethylene-propylene-ethylidene norbornene copolymer (EBT manufactured by Mitsui Chemicals: K-8370EM, K-9330M, etc.), ethylene-propylene-vinyl norbornene copolymer (VNB-EPT manufactured by Mitsui Chemicals: PX-006M, PX-008M, PX-009M, etc.), ethylene-vinyl alcohol copolymer, ethylene-vinyl acetate copolymer, etc., but are not limited to these. With regard to the viewpoint of improving heat resistance, it is preferred to use ethylene-propylene-ethylidene norbornene copolymer and ethylene-propylene-vinyl norbornene copolymer containing a structure capable of crosslinking. In addition, these can use one or more. There are no particular restrictions on the weight average molecular weight of polyethylene and its modified products as long as it is 10,000 or more. However, if the weight average molecular weight of polyethylene and its modified products is too large, not only will the compatibility with the polyphenylene ether compound deteriorate, but the compatibility with low molecular weight components with a weight average molecular weight of about 50 to 1,000 and oligomer components with a weight average molecular weight of about 1,000 to 5,000 will also deteriorate, making mixing difficult and ensuring solvent stability. Therefore, it is preferably about 10,000 to 300,000.

[0183] The curable resin composition of the present invention can be obtained by preparing the aforementioned components in a predetermined ratio, pre-curing at 130°C to 180°C for 30 to 500 seconds, and then post-curing at 150°C to 200°C for 2 to 15 hours to allow sufficient curing reaction to proceed, thereby obtaining a cured product of the present invention. Alternatively, the components of the curable resin composition may be uniformly dispersed or dissolved in a solvent, etc., and then cured after removing the solvent.

[0184] The method for preparing the curable resin composition of the present invention is not particularly limited. The components may be simply mixed uniformly, or prepolymerized. For example, prepolymerization can be achieved by heating a mixture containing the compound of the present invention in the presence or absence of a curing accelerator or polymerization initiator, and in the presence or absence of a solvent. Similarly, prepolymerization can be achieved by adding compounds such as amine compounds, compounds having ethylenically unsaturated bonds, maleimide compounds, cyanate compounds, polybutadiene and its modified products, polystyrene and its modified products, inorganic fillers, and other additives. The mixing or prepolymerization of the components can be performed using, for example, an extruder, kneader, or rollers in the absence of a solvent, or a reactor equipped with a stirrer in the presence of a solvent.

[0185] As a method for uniform mixing, mixing is performed by fusion at a temperature within the range of 50°C to 100°C using a kneader, roller, planetary mixer, or other device to produce a uniform resin composition. The resulting resin composition can also be pulverized and then formed into a cylindrical ingot using a tablet press or other molding machine, or into a granular powder or powdered molded article. Alternatively, the composition can be melted onto a surface support and molded into a sheet with a thickness of 0.05 mm to 10 mm to produce a curable resin composition molded article. The resulting molded article is non-tacky at temperatures between 0°C and 20°C, and exhibits minimal loss of fluidity and curability even when stored at -25°C to 0°C for more than one week.

[0186] The obtained molded body can be molded into a cured product using a transfer molding machine or a compression molding machine.

[0187] The curable resin composition of the present invention can also be prepared as a varnish-like composition by adding an organic solvent (hereinafter referred to as a varnish). 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, or N-methylpyrrolidone to prepare a varnish, which can then be impregnated into a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, or paper, followed by heat drying. The resulting prepreg can then be hot-pressed to produce a cured product of the curable resin composition of the present invention. The solvent used in this case should constitute 10% to 70% by weight, preferably 15% to 70% by weight, of the mixture of the curable resin composition of the present invention and the solvent. Furthermore, if the composition is in liquid form, the curable resin composition containing carbon fibers can also be obtained directly, for example, by resin transfer molding (RTM).

[0188] The curable resin composition of the present invention can also be used as a modifier for film-type compositions. Specifically, it can be used to improve the flexibility of the B-stage. This film-type resin composition is obtained by preparing the curable resin composition of the present invention into a curable resin composition varnish, applying it to a release film, removing the solvent under heating, and then B-staging it to form a sheet-like adhesive. This sheet-like adhesive can be used as an interlayer insulating layer in multilayer substrates, etc.

[0189] The curable resin composition of the present invention can also be heated and melted, reduced in viscosity, and then impregnated into reinforcing fibers such as glass fibers, carbon fibers, polyester fibers, polyamide fibers, and alumina fibers to produce a prepreg. Specific examples 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. Further examples include inorganic fibers other than glass, and organic fibers such as polyparaphenylene terephthalamide (Kevlar (registered trademark), manufactured by DuPont), wholly aromatic polyamides, polyesters, polyparaphenylene benzoxazole, polyimides, and carbon fibers, but are not particularly limited to these. The shape of the substrate is not particularly limited, and examples include woven fabrics, non-woven fabrics, rovings, and chopped strand mats. Known weaves for woven fabrics include plain weave, basket weave, and twill weave. These weaves can be appropriately selected based on the intended application or performance. Glass fabrics that have been subjected to fiber opening treatment or surface treatment with a silane coupling agent or the like are also preferably used. The thickness of the substrate is not particularly limited, but is preferably approximately 0.01 mm to 0.4 mm. Alternatively, a prepreg can be obtained by impregnating the reinforcing fibers with the varnish and then drying the impregnated fibers under heat.

[0190] In addition, the prepreg can also be used to manufacture a laminate. The laminate is not particularly limited as long as it includes more than one prepreg, and may also have any other layer. As a method for manufacturing a laminate, generally known methods can be appropriately applied without particular limitation. For example, when forming a laminate with a metal foil, a multi-stage press, a multi-stage vacuum press, a continuous forming machine, an autoclave forming machine, etc. can be used, and a laminate can be obtained by stacking the prepregs on each other and performing heating and pressurizing. At this time, the heating temperature is not particularly limited, and is preferably 65°C to 300°C, more preferably 120°C to 270°C. In addition, the pressure of the press is not particularly limited. If the pressure is too high, it is difficult to adjust the solid content of the resin of the laminate, and the quality is unstable. In addition, if the pressure is too low, bubbles or the adhesion between the layers deteriorate. Therefore, it is preferably 2.0MPa to 5.0MPa, and more preferably 2.5MPa to 4.0MPa. Since the laminated plate of this embodiment includes a layer having a metal foil, it can be preferably used as a metal foil-clad laminated plate described later.

[0191] The prepreg is cut into a desired shape and, if necessary, laminated with copper foil or the like. The curable resin composition is then heat-cured while applying pressure to the laminate by press molding, autoclave molding, sheet winding molding, or the like, thereby obtaining an electrical and electronic laminate (printed wiring board) or a carbon fiber reinforced material.

[0192] 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 coating the curable resin composition on a support film (support), drying it, and forming a resin composition layer on the support film can be cited. When the curable resin composition of the present invention is used for a resin sheet, it is important that the film softens under the lamination temperature conditions (70°C to 140°C) in the vacuum lamination method, performs lamination of the circuit substrate, and exhibits fluidity (resin flow) that allows the resin to be filled into the through-holes or through-holes present on the circuit substrate. It is preferred to formulate the components so as to exhibit such properties. In addition, in the obtained resin sheet or circuit substrate (copper sheet laminate, etc.), there is no phenomenon such as locally different characteristic values ​​due to phase separation, etc., and a certain performance is exhibited in any part, so uniform appearance is required.

[0193] Here, the through hole of the circuit board has a diameter of 0.1mm to 0.5mm and a depth of 0.1mm to 1.2mm, and is preferably capable of resin filling within the above range. In addition, when laminating both sides of the circuit board, it is ideal to fill about 1 / 2 of the through hole.

[0194] As a specific method for producing the resin sheet, the following method can be cited: after preparing a varnish resin composition by mixing an organic solvent, the varnish resin composition is applied to the surface of a support film (Y), and the organic solvent is dried by heating or hot blowing to form a resin composition layer (X).

[0195] As the organic solvent used here, preferably used are ketones such as acetone, methyl ethyl ketone, and cyclohexanone; acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. In addition, it is preferably used in a ratio of 30% by mass to 60% by mass of the non-volatile component.

[0196] In addition, the thickness of the formed resin composition layer (X) must be greater than the thickness of the conductor layer. The thickness of the conductor layer of the circuit board is in the range of 5 μm to 70 μm, so the thickness of the resin composition layer (X) is preferably 10 μm to 100 μm. In addition, the resin composition layer (X) in the present invention can also be protected by a protective film described later. By protecting with a protective film, dust and the like can be prevented from adhering to the surface of the resin composition layer or from being damaged.

[0197] The support film and the protective film can include polyolefins such as polyethylene, polypropylene, polyvinyl chloride, polyesters such as polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, polyimide, and then release paper or metal foils such as copper foil and aluminum foil. In addition, the support film and the protective film can also be subjected to demoulding treatment in addition to matting treatment and corona treatment. The thickness of the support film is not particularly limited and is 10 μm to 150 μm, preferably used in the range of 25 μm to 50 μm. In addition, the thickness of the protective film is preferably set to 1 μm to 40 μm.

[0198] The support film (Y) is peeled off after being laminated to a circuit board or after being heat-cured to form an insulating layer. Peeling off the support film (Y) after the resin composition layer constituting the resin sheet has been heat-cured can prevent the adhesion of dust and the like during the curing process. When peeling off after curing, the support film is pre-treated for demolding.

[0199] In addition, 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 by a protective film, after peeling these off, the layer (X) of the resin composition is laminated on one side or both sides of the circuit board by, for example, a vacuum lamination method, so that the layer (X) of the resin composition is in direct contact with the circuit board. The lamination method may be a batch method or a continuous method using a roller. In addition, the resin sheet and the circuit board may be heated (preheated) as needed before lamination. Regarding the lamination conditions, it is preferred to set the pressing temperature (lamination temperature) to 70°C to 140°C, and it is preferred to set the pressing pressure to 1kgf / cm 2 ~11kgf / cm 2 (9.8×10 4 N / m 2 ~107.9×10 4 N / m 2 ), preferably lamination is performed under reduced pressure of 20 mmHg (26.7 hPa) or less.

[0200] Furthermore, the curable resin composition of the present invention can be used to manufacture semiconductor devices. Examples of semiconductor devices include dual in-line packages (DIP), quad flat packages (QFP), ball grid arrays (BGA), chip size packages (CSP), small outline packages (SOP), thin small outline packages (TSOP), and thin quad flat packages (TQFP).

[0201] 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 for various applications such as molding materials, adhesives, composite materials, and coatings. Because the cured product of the curable resin composition described in the present invention exhibits excellent heat resistance and dielectric properties, it can be preferably used in electrical and electronic parts such as semiconductor element sealing materials, liquid crystal display element sealing materials, organic electroluminescent (EL) element sealing materials, laminated boards (printed wiring boards, ball grid array (BGA) substrates, build-up substrates, etc.), or composite materials for lightweight, high-strength structural materials such as carbon fiber reinforced plastics and glass fiber reinforced plastics, 3D printing, etc.

[0202] Example

[0203] Next, the present invention will be described in more detail by way of examples. Hereinafter, unless otherwise specified, parts are parts by mass. Furthermore, the present invention is not limited to these examples.

[0204] Various analytical methods used in the Examples are described below.

[0205] Gel Permeation Chromatography (GPC)

[0206] The weight average molecular weight (Mw) and the number average molecular weight (Mn) were calculated in terms of polystyrene using a polystyrene standard solution.

[0207] Gel permeation chromatograph (GPC): DGU-20A3R, LC-20AD, SIL-20AHT, RID-20A, SPD-20A, CTO-20A, CBM-20A (all manufactured by Shimadzu Corporation)

[0208] Column: Shodex KF-603, KF-602×2, KF-601×2

[0209] Linking eluent: tetrahydrofuran

[0210] Flow rate: 0.5ml / min.

[0211] Column temperature: 40°C

[0212] Detector: RI (differential refractometer)

[0213] [Example 1]

[0214] While nitrogen was flushed into a flask equipped with a thermometer, a cooling tube, a fractionating tube, and a stirrer, 42.1 parts of octenylsuccinic anhydride, 116 parts of toluene, and 19.8 parts of 4,4'-diaminodiphenylmethane were added and stirring was started. The internal temperature was raised to 112°C over 2 hours and the mixture was allowed to react for 2 hours. 1.0 part of methanesulfonic acid was added, and the mixture was reacted at 113°C to 115°C for 2 hours while the generated water was removed from the system. After cooling, the organic layer was washed with water until the waste liquid became neutral, and then concentrated to obtain 57.4 parts of the compound (A1) represented by the following formula (1-a) as a brown liquid resin. The GPC chart of the obtained compound (A1) is shown in FIG. Figure 1 middle.

[0215]

[0216] [Example 2]

[0217] While nitrogen was flushed into a flask equipped with a thermometer, a cooling tube, a fractionating tube, and a stirrer, 42.0 parts of octenylsuccinic anhydride, 100 parts of xylene, 15 parts of triethylamine, and 15.4 parts of norbornane diamine (manufactured by Mitsui Chemicals Co., Ltd.) were added and stirring was started. The mixture was added dropwise at an internal temperature below 120°C, and the mixture was reacted at 120°C for 1 hour, at 130°C for 2 hours, and at 150°C for 9 hours. The obtained reaction solution was concentrated to obtain 49.9 parts of the compound (A2) represented by the following formula (2-a) as a brown liquid resin. The GPC chart of the obtained compound (A2) is shown in FIG. Figure 2 middle.

[0218]

[0219] [Example 3, Example 4, Comparative Example 1, Comparative Example 2]

[0220] The compounds obtained in Example 1 and Example 2, and the materials described in Table 1 were mixed in the proportions (parts by mass) described in Table 1, and vacuum press molding was performed while sandwiching them with a mirror copper foil (T4X: manufactured by Futian Metal Copper Foil Co., Ltd.), and cured at 220°C for 2 hours. At this time, as a spacer, a buffer paper with a thickness of 250 μm was used, the center of which was dug into 150 mm in length and width. During the evaluation, a laser cutting machine was used to cut the test piece into the desired size as needed, and the evaluation was performed. The evaluation results are shown in Table 1.

[0221] <Heat resistance (Dynamic Mechanical Analysis, DMA)>

[0222] Dynamic viscoelasticity tester: TA-instruments, DMA-2980

[0223] Measuring temperature range: -30℃~280℃

[0224] Heating rate: 2℃ / min

[0225] Frequency: 10Hz

[0226] Measurement mode: Tensile

[0227] Test piece size: Use cut into 5mm x 50mm (thickness 0.2mm)

[0228] Tg: The peak point of tan δ (= loss modulus / storage modulus) is defined as Tg

[0229] <Dielectric constant test / dielectric loss tangent test>

[0230] The test was conducted using a 10 GHz cavity resonator manufactured by ATE Co., Ltd. using the cavity resonator perturbation method at 25° C. The test was conducted using a sample size of 1.7 mm in width × 100 mm in length and 0.3 mm in thickness.

[0231] [Table 1]

[0232]

[0233] MI: A resin solution containing a maleimide compound (M2) described in Example 4 of Japanese Patent Application Laid-Open No. 2009-001783 was solidified by distilling off the solvent under reduced pressure.

[0234] SA-9000: Terminal methacrylated polyphenylene ether compound (manufactured by Saudi Basic Industries (SABIC))

[0235] DCP: dicumyl peroxide (manufactured by Kayaku Akzo Chemicals)

[0236] 2E4MZ: 2-ethyl-4-methylimidazole (hardening accelerator, manufactured by Shikoku Chemical Co., Ltd.)

[0237] The results of Comparative Example 1 show that when the maleimide compound was radically polymerized alone (Comparative Example 1), heat resistance was good but the dielectric loss tangent was poor. On the other hand, Examples 3 and 4, which incorporated the compound of the present invention, demonstrated a dielectric loss tangent of 32.4%, which was superior to that of Comparative Example 1. Meanwhile, Comparative Example 2, which incorporated a polyphenylene ether compound, exhibited heat resistance comparable to that of Examples 3 and 4, but exhibited a dielectric loss tangent of 14.7%, which was superior to that of Comparative Example 1.

[0238] [Example 5, Example 6, Comparative Example 3]

[0239] <Solvent solubility test>

[0240] In a 5 mL glass sample bottle, 1.0 g each of A1, A2, and phenylmethanemaleimide (abbreviated as PMMI, CAS No.: 67784-74-1) and 1.0 g each of toluene were mixed. The mixture was stirred at 100 rpm using a roll mixer (MIX-ROTAR VMR-5, manufactured by ASONE) at 25°C for 1 hour to prepare a toluene solution containing each compound at a solids content of 50 wt%. The resulting solutions were visually observed and evaluated based on the following criteria. The results are shown in Table 2.

[0241] In case a uniform solution can be obtained: ○

[0242] In the case where a uniform solution is not obtained: ×

[0243] [Table 2]

[0244]

[0245] The results in Table 2 indicate that the compound of the present invention exhibits solvent solubility that cannot be achieved with a maleimide group by introducing an alkenyl group and a succinimide structure into the molecule to reduce intermolecular interactions and lower crystallinity.

[0246] Industrial applicability

[0247] The curable resin composition, resin sheet, and cured product thereof of the present invention can be preferably used not only for semiconductor encapsulating materials, printed wiring boards, and electric / electronic components such as build-up laminates, but also for lightweight, high-strength materials such as carbon fiber reinforced plastics and glass fiber reinforced plastics, and for 3D printing applications.

Claims

1. A compound represented by the following formula (b); In the formula (b), a plurality of Ys each independently represent a hydrocarbon group having 1 to 20 carbon atoms, and X represents one or more of the following formulas (A) to (T). In the formulas (A) to (T), R represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, a represents an integer of 1 to 4; p and n are repeating numbers, representing numbers of 1 to 20; and * represents the bonding position to the nitrogen atom in formula (2).

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

3. The curable resin composition according to claim 2, further comprising a radical polymerization initiator.

4. The curable resin composition according to claim 2, further comprising a maleimide compound.

5. A cured product obtained by curing the curable resin composition according to any one of claims 2 to 4.

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