Curable resin composition, resin sheet and cured product thereof

Abstract

The present invention aims to provide a resin composition, a resin sheet, and a cured product thereof that can produce a cured product having high heat resistance and low dielectric properties. A curable resin composition comprises (A) a compound having at least two styrene structures in the molecule, (B) a maleimide compound, and (C) a cyanate ester compound.

Description

Technical Field

[0001] The present invention relates to a curable resin composition, a resin sheet and a cured product thereof. 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] Furthermore, the fifth-generation communication system, "5G," currently under rapid development, is expected to further advance high-capacity and high-speed communications. Demand for materials with low dielectric loss tangents is increasing, with a minimum requirement of 0.005 or less at 10 GHz.

[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] In this context, research is underway on polymer materials that have both high heat resistance and low dielectric properties. For example, Patent Document 1 proposes a composition comprising a maleimide resin and a phenolic resin containing an propylene 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 2 discloses an allyl ether resin that uses allyl groups to replace hydroxyl groups. However, it was shown that Claisen rearrangement occurs at 190°C, and at the general substrate molding temperature of 200°C, phenolic hydroxyl groups that do not contribute to the curing reaction are generated, so the electrical properties cannot be satisfied.

[0007] [Prior art literature]

[0008] [Patent Document]

[0009] Patent Document 1: Japanese Patent Application Laid-Open No. 04-359911

[0010] Patent Document 2: International Publication No. 2016 / 002704 Summary of the Invention

[0011] [Problems to be solved by the invention]

[0012] The present invention has been made in view of the above-mentioned circumstances, and an object of the present invention is to provide a resin composition that can produce a cured product having high heat resistance and low dielectric properties.

[0013] [Technical means to solve the problem]

[0014] The present inventors have conducted intensive studies to solve the above-mentioned problems and have discovered that a cured product of a curable resin composition containing a compound having at least two or more styrene structures in its molecule, a maleimide compound, and a cyanate compound exhibits excellent high heat resistance and low dielectric properties, leading to the completion of the present invention.

[0015] That is, the present invention relates to the following [1] to [8]. In the present invention, "(numerical value 1) to (numerical value 2)" means that the upper and lower limits are included. [1]

[0017] A curable resin composition comprising (A) a compound having at least two styrene structures in a molecule, (B) a maleimide compound, and (C) a cyanate compound. [2]

[0019] The curable resin composition according to the aforementioned item [1], wherein the component (A) is a compound represented by the following formula (1):

[0020] [Chemistry 1]

[0021]

[0022] (In formula (1), a plurality of Rs exist independently and represent a hydrocarbon group or a halogenated alkyl group having 1 to 10 carbon atoms; p and r represent integers of 0 to 4, q represents an integer of 0 to 3, and n is the average value of the number of repetitions, 1≦n≦20) [3]

[0024] The curable resin composition according to the aforementioned item [1] or [2], wherein the component (B) is a compound represented by the following formula (3).

[0025] [Chemistry 2]

[0026]

[0027] (In formula (3), a plurality of Rs exist independently and represent a hydrocarbon group or a halogenated alkyl group having 1 to 10 carbon atoms; p and r represent integers of 0 to 4, q represents an integer of 0 to 3, and n is the average value of the number of repetitions, 1≦n≦20) [4]

[0029] The curable resin composition according to any one of the aforementioned items [1] to [3], further comprising a curing accelerator. [5]

[0031] The curable resin composition according to any one of the above items [1] to [4], further comprising an inorganic filler. [6]

[0033] The curable resin composition according to any one of the aforementioned items [1] to [5], further comprising a polymerization initiator. [7]

[0035] A resin sheet comprising the resin composition according to any one of the above items [1] to [6] and a support. [8]

[0037] A cured product, which is the curable resin composition according to any one of the above items [1] to [6] or the cured product of the resin sheet according to the above item [7].

[0038] [Effects of the Invention]

[0039] According to the present invention, there can be provided a resin composition having high heat resistance and excellent low dielectric properties, a cured product thereof, and a resin sheet comprising the resin composition. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] Figure 1 The GPC chart of Synthesis Example 1 is shown.

[0041] Figure 2 The GPC chart of Synthesis Example 2 is shown.

[0042] Figure 3 Synthesis Example 2 1 H-NMR chart. DETAILED DESCRIPTION

[0043] The curable resin composition of the present invention contains (A) a compound having at least two or more styrene structures in the molecule (hereinafter also referred to as component (A)), (B) a maleimide compound (hereinafter also referred to as component (B)), and (C) a cyanate compound (hereinafter also referred to as component (C)).

[0044] As component (A), any known component can be used as long as it is a compound having at least two styrene structures in the molecule, and examples thereof include OPE-2St (manufactured by Mitsubishi Gas Chemical Co., Ltd.), oligodivinyl copolymer (ODV),

[0045] (oligo divinyl copolymer, manufactured by Nippon Steel Chemicals & Materials Co., Ltd.), 1,2-bis(vinylphenyl)ethane (1,2-bis(vinylphenyl)ethane) (BVPE: a group of compounds such as 4,4'-ethylene bisphenylene glycol, 3,4'-ethylene bisphenylene glycol, and 3,3'-ethylene bisphenylene glycol), divinylfluorene, divinylbiphenyl, divinylnaphthalene, divinylbenzene, and a compound represented by the following formula (1). Component (A) may be used alone or in combination. Among these, from the viewpoints of heat resistance, dielectric properties, compatibility with other curable resins (epoxy resins or active ester resins, etc.), circuit embedding properties, and the like, a compound represented by the following formula (1) is preferred as component (A).

[0046] [Chemistry 1]

[0047]

[0048] (In formula (1), a plurality of Rs exist independently and represent a hydrocarbon group or a halogenated alkyl group having 1 to 10 carbon atoms; p and r represent integers of 0 to 4, q represents an integer of 0 to 3, and n is the average value of the number of repetitions, 1≦n≦20)

[0049] In the formula (1), p and r are 0 to 4, preferably 0 to 2, and more preferably 0. q is 0 to 3, preferably 0 to 2, and more preferably 0. n is 1≦n≦20, preferably 1.1≦n≦20, more preferably 1.1≦n≦10, and particularly preferably 1.1≦n≦5. The value of n can be calculated based on the value of the number average molecular weight (Mn) determined by gel permeation chromatography (GPC) of the compound of formula (1). The number average molecular weight is preferably 200 or more and less than 5000, more preferably 300 or more and less than 3000, and particularly preferably 400 or more and less than 2000. When the weight average molecular weight is less than 5000, purification by water washing becomes easy, and when it is 200 or more, the target compound does not volatilize in the solvent distillation step.

[0050] In the formula (1), R is a hydrocarbon group having 1 to 10 carbon atoms or a halogenated alkyl group, preferably a hydrocarbon group having 1 to 10 carbon atoms, more preferably a hydrocarbon group having 1 to 5 carbon atoms, and particularly preferably a hydrocarbon group having 1 to 3 carbon atoms. When R is a hydrocarbon group having 3 or fewer carbon atoms, the molecular vibration is less likely to occur when exposed to high frequencies, and thus the electrical properties are particularly excellent.

[0051] The compound represented by the above formula (1) is derived from the compound represented by the following formula (2).

[0052] [Chemistry 2]

[0053]

[0054] (In formula (2), a plurality of Rs exist independently and represent a hydrocarbon group or a halogenated alkyl group having 1 to 10 carbon atoms; p and r represent integers of 0 to 4, q represents an integer of 0 to 3, n is the average value of the number of repetitions, 1≦n≦20; and X represents a halogen atom)

[0055] The preferred ranges of R, p, r, q, and n in formula (2) are the same as those in formula (1). From the viewpoint of reactivity and raw material stability, X is preferably a bromine atom or a chlorine atom, and particularly preferably a bromine atom.

[0056] The compound represented by the formula (1) can be obtained, for example, by subjecting the compound represented by the formula (2) to a dehydrohalogenation reaction in a solvent in the presence of a basic catalyst. 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; and non-water-soluble solvents such as ketone solvents such as methyl isobutyl ketone and cyclopentanone, but are not limited to these, and two or more thereof may be used in combination. In addition, in addition to the 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, and the like, and two or more thereof may be used in combination. When using aprotic polar solvents, it is preferred to use a solvent with a higher boiling point than the non-water-soluble solvent used in combination. The catalyst is not particularly limited, and examples include alkaline catalysts such as sodium hydroxide, potassium hydroxide, and potassium carbonate. Since it is difficult to completely carry out the dehydrohalogenation reaction, a non-protonic polar solvent can be used in great excess relative to the substrate, and the dehydrohalogenation reaction can be repeated two or three times or more. For example, the compound represented by the formula (2) can be subjected to a dehydrohalogenation reaction in an organic solvent in the presence of an alkali catalyst. The solution obtained is washed with water, returned to the reaction vessel again, and an alkali catalyst is added to react it again. Thus, the degree of progress of the dehydrohalogenation reaction can be improved. That is, the amount of residual halogen contained in the target compound can be reduced. As the amount of residual halogen, it is preferably 1ppm to 10000ppm in the target, more preferably 1ppm to 1000ppm, and further preferably 1ppm to 750ppm. If the amount of residual halogen contained in the compound represented by the formula (1) is large, molecular vibration is caused when exposed to high frequency, especially adversely affecting electrical properties such as dielectric loss tangent. Furthermore, when the amount of residual halogen is large, the risk of causing problems such as metal corrosion and ion migration in environmental tests such as HAST tests (High Accelerated Stress Tests) increases, so the above-mentioned halogen content is preferred.

[0057] The method for preparing the compound represented by the formula (2) is not particularly limited. For example, a compound having a 2-bromoethylbenzene structure can be reacted with a dihalogenated methyl aryl compound (or a bishydroxymethyl aryl compound, etc.) in the presence of an acid catalyst such as hydrochloric acid, sulfonic acid, or activated clay. Alternatively, a compound having a 2-bromoethylbenzene structure can be reacted with a bishydroxymethyl aryl compound in the presence of an acid catalyst such as hydrochloric acid, sulfonic acid, or activated clay. When sulfonic acid or the like is used as a catalyst, the compound can 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 can be used alone, or a non-aromatic hydrocarbon such as cyclohexane or toluene can be used in combination. After extraction, the organic layer is washed with water until the drainage becomes neutral, and the solvent and the compound having excess 2-bromoethylbenzene structure are distilled off using an evaporator, etc., thereby obtaining the target compound having at least two or more 2-bromoethylbenzene structures in the molecule.

[0058] Examples of compounds having a 2-bromoethylbenzene structure include, but are not limited to, 2-bromoethylbenzene, 1-(2-bromoethyl)-2-methylbenzene, 1-(2-bromoethyl)-3-methylbenzene, 1-(2-bromoethyl)-4-methylbenzene, 1-(2-bromoethyl)-2,3-dimethylbenzene, 1-(2-bromoethyl)-2,4-dimethylbenzene, 1-(2-bromoethyl)-2,5-dimethylbenzene, and 1-(2-bromoethyl)-2,6-dimethylbenzene. These compounds may be used alone or in combination of two or more. A large number of carbon atoms improves solvent solubility but reduces heat resistance. Therefore, unsubstituted or substituted with an alkyl group having 1 to 3 carbon atoms is preferred, unsubstituted or substituted with an alkyl group having 1 to 2 carbon atoms is more preferred, and unsubstituted or substituted with a methyl group is most preferred.

[0059] As dihalogenated methyl aryl compound, for example, can be enumerated: o-xylene difluoride, m-xylene difluoride, p-xylene difluoride, o-xylene dichloride, m-xylene dichloride, p-xylene dichloride, o-xylene dibromide, m-xylene dibromide, p-xylene dibromide, o-xylene diiodide, m-xylene diiodide, p-xylene diiodide etc., but are not limited to these.These can be used alone, also can use two or more.With regard to the viewpoint of the reactivity of the raw material during synthesis, preferably chloride-based compound, bromide-based compound, iodide-based compound, more preferably chloride-based compound, bromide-based compound can be enumerated.

[0060] Examples of bishydroxymethylaryl compounds include, but are not limited to, o-phthalic alcohol, m-phthalic alcohol, and p-phthalic alcohol. These may be used alone or in combination of two or more. The amount of these compounds used is preferably 0.05 to 0.8 parts by mass, more preferably 0.1 to 0.6 parts by mass, relative to 1 part by mass of the compound having a 2-bromoethylbenzene structure.

[0061] When a compound having a 2-bromoethylbenzene structure reacts with a halogenated methyl aryl compound, 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 0.05 to 0.8 moles, preferably 0.1 to 0.7 moles, relative to 1 mole of the compound having a 2-bromoethylbenzene structure used. If the amount of catalyst used is too much, the viscosity of the reaction solution is too high, and there is a risk of stirring becoming difficult. If the amount of catalyst used is too little, the reaction is likely to slow down. The reaction can be carried out using an organic solvent such as hexane, cyclohexane, octane, toluene, or xylene, or it can be carried out without a solvent. For example, after adding an acidic catalyst to a mixed solution of a compound having a 2-bromoethylbenzene structure, a methyl aryl halide compound, and a solvent, if the catalyst contains water, the water is removed from the system by azeotropy. The reaction is then carried out at 40°C to 180°C, preferably 50°C to 170°C, for 0.5 to 20 hours. After the reaction is completed, the acidic catalyst can be neutralized with an alkaline aqueous solution, but it can also proceed to a water washing step without neutralization. In the water washing step, a water-insoluble organic solvent is added to the oil layer, and water washing is repeated until the wastewater becomes neutral.

[0062] The softening point of the compound represented by formula (2) is preferably 80°C or lower, more preferably 70°C or lower. If the softening point is 80°C or lower, the viscosity of the compound represented by formula (1) is reduced. This makes it easier to maintain fluidity, does not impair the impregnation properties of glass cloth, carbon fiber, etc., and facilitates B-stage formation such as prepreg. When the viscosity is reduced by adding a diluent solvent, there is a risk that the resin may not sufficiently adhere to the fibrous material during the impregnation step.

[0063] The curable resin composition of the present invention contains a maleimide compound as a component (B). The so-called maleimide compound refers to a compound having one or more maleimide groups in the molecule. As component (B), for example, 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, neophenol (Xyloc) type maleimide compounds (Annilis ( Anilix) maleimide, manufactured by Mitsui Chemicals Fine Chemicals Co., Ltd.), biphenyl aralkyl type maleimide compound (solidified by distilling off 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 and compound represented by the following formula (3)), 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 "Stage (~Continued·Epoxy Resin CAS Numbering Words~Hardener CAS Numbering Memorandum No. 31 Bismaleimide (1)" or "Material Stage (MATERIALSTAGE)" Vol. 19, No. 2 2019 "~Continued·Epoxy Resin CAS Numbering Words~Hardener CAS Numbering Memorandum No. 32 Bismaleimide (2)" are not limited thereto. In addition, these may be used alone or in combination of two or more.

[0064] Among these, 2,2'-bis[4-(4-maleimidephenoxy)phenyl]propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide, and biphenylaralkyl-type maleimide compounds (resin containing maleimide compound (M2) described in Example 4 of JP-A-2009-001783 is removed by distillation under reduced pressure) are preferred from the viewpoints of solvent solubility, dielectric properties, and heat resistance. The present invention relates to a maleimide compound having an indane structure and ...

[0065] [Chemistry 3]

[0066]

[0067] (In formula (3), a plurality of Rs exist independently and represent a hydrocarbon group or a halogenated alkyl group having 1 to 10 carbon atoms; p and r represent integers of 0 to 4, q represents an integer of 0 to 3, and n is the average value of the number of repetitions, 1≦n≦20)

[0068] The preferred ranges of R, p, r, q, and n in formula (3) are the same as those in formula (1).

[0069] The curable resin composition of the present invention contains a cyanate compound as component (C). Component (C) is a compound 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 a compound obtained by converting the hydroxyl group of a phenol-dicyclopentadiene co-condensate into a cyanate group. Specific examples of these compounds include, but are not limited to, dicyanatobenzene, tricyanobenzene, 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 compounds obtained by converting the hydroxyl group of a phenol-dicyclopentadiene co-condensate into a cyanate group. These compounds may be used alone or in combination.

[0070] 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.

[0071] 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.

[0072] The catalyst is preferably used in an amount of 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 total mass of the cyanate resin and components (A) to (C).

[0073] In the curable resin composition of the present invention, the content of component (A) is preferably from 1 part by mass to 300 parts by mass, more preferably from 5 parts by mass to 200 parts by mass, and even more preferably from 10 parts by mass to 150 parts by mass, per 100 parts by mass of the total of component (B) and component (C). If the content of component (A) is less than 1 part by mass, there is a risk of deterioration in dielectric properties or increased water absorption. If the content of component (A) is greater than 100 parts by mass, adhesion to copper foil and the like may be difficult to achieve.

[0074] The amount of component (B) added is preferably 1 to 300 parts by mass, more preferably 5 to 250 parts by mass, and even more preferably 10 to 200 parts by mass, relative to 100 parts by mass of component (A). If the amount of component (B) added is less than 1 part by mass, the copper foil adhesion may be reduced, while if it is more than 300 parts by mass, the curing property or water absorption characteristics may be deteriorated.

[0075] The amount of component (C) added is preferably 1 to 300 parts by mass, more preferably 5 to 250 parts by mass, and even more preferably 10 to 200 parts by mass, relative to 100 parts by mass of component (B). If the amount of component (C) added is less than 1 part by mass, the curability or copper foil adhesion may be reduced, while if it is more than 300 parts by mass, the water absorption characteristics may be deteriorated.

[0076] [Hardening accelerator]

[0077] 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.

[0078] 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, but are not limited to, phosphines such as triphenylphosphine, tetrabutylammonium salts, triisopropylmethylammonium salts, trimethyldecylammonium salts, hexadecyltrimethylammonium salts, and quaternary ammonium salts such as hexadecyltrimethylammonium hydroxide. These accelerators may be used alone or in combination.

[0079] 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.

[0080] When the total amount of the component (B) and the component (C) is 100 parts by mass, the amount of the curing accelerator to be added is 0.01 to 5.0 parts by mass as needed.

[0081] [Inorganic fillers]

[0082] 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, asbestos, glass powder, and other powders, as well as spherical or crushed forms of these inorganic fillers. These fillers may be used alone or in combination.

[0083] 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 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.

[0084] [Polymerization initiator]

[0085] 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.

[0086] 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.

[0087] 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).

[0088] The amount of the polymerization initiator added is preferably 0.01 to 5 parts by mass, particularly preferably 0.01 to 3 parts by mass, relative to 100 parts by mass of the curable resin composition. If the amount of the polymerization initiator used is less than 0.01 parts by mass, the molecular weight may not be sufficiently increased during the polymerization reaction. If it is more than 5 parts by mass, dielectric properties such as the dielectric constant and dielectric loss tangent may be impaired.

[0089] [Polymerization inhibitor]

[0090] 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.

[0091] The polymerization inhibitor may be added during or after the synthesis of component (A). The amount of the polymerization inhibitor used is 0.008 to 1 part by mass, preferably 0.01 to 0.5 parts by mass, per 100 parts by mass of component (A).

[0092] 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.

[0093] 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.

[0094] 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.

[0095] 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.

[0096] 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.

[0097] Examples of the nitroso polymerization inhibitor include, but are not limited to, p-nitrosophenol, N-nitrosodiphenylamine, ammonium salts of N-nitrosophenylhydroxylamine, and cupferron. Among these, ammonium salts of N-nitrosophenylhydroxylamine (cupferron) are preferred.

[0098] 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.

[0099] [Flame retardant]

[0100] 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.

[0101] The phosphorus-based flame retardant may be a reactive phosphorus-based flame retardant or an additive phosphorus-based flame retardant. Specific examples include: 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), 4,4'-biphenyl(dixyl phosphate); phosphanes such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide; and phosphorus-containing epoxy compounds obtained by reacting epoxy resins with active hydrogen of the phosphanes, red phosphorus, and the like, but are not limited thereto. These may be used alone or in combination. Among the 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.

[0102] [Flame retardant]

[0103] The content of the flame retardant is preferably in the range of 0.1 to 0.6 parts by mass, based on 100 parts by mass of the total of components (A) to (C). If the content is less than 0.1 parts by mass, the flame retardancy may be insufficient, while if the content is more than 0.6 parts by mass, the hygroscopicity and dielectric properties of the cured product may be adversely affected.

[0104] [Light stabilizer]

[0105] 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.

[0106] The content of the light stabilizer is preferably in the range of 0.001 to 0.1 parts by mass based on 100 parts by mass of the total of components (A) to (C). If the content is less than 0.001 parts by mass, the light stabilization effect may be insufficient, while if the content is more than 0.1 parts by mass, the hygroscopicity and dielectric properties of the cured product may be adversely affected.

[0107] [Binder resin]

[0108] 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.

[0109] 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, and more preferably 0.05 to 20 parts by mass, based on 100 parts by mass of the total of components (A) to (C).

[0110] [additive]

[0111] 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.

[0112] The amount of the additives added is preferably 1,000 parts by mass or less, more preferably 700 parts by mass or less, relative to 100 parts by mass of the curable resin composition.

[0113] The curable resin composition of the present invention may further include epoxy resins, active ester compounds, phenol resins, polyphenylene ether compounds, amine resins, compounds having ethylenically unsaturated bonds, isocyanate resins, polyamide resins, polyimide resins, polybutadiene and its modified products, polystyrene and its modified products, and the like. These may be used singly or in combination. Among these compounds, polyphenylene ether compounds, compounds having ethylenically unsaturated bonds, cyanate resins, polybutadiene and its modified products, polystyrene and its modified products are preferably included in order to achieve a balance between heat resistance, adhesion, and dielectric properties. By including these compounds, the brittleness of the cured product can be improved, the adhesion to metal can be enhanced, and cracking of the package during reflow soldering or thermal cycling reliability testing can be suppressed.

[0114] About the usage amount of the compound, when not otherwise specified, relative to the composition (A), preferably less than 10 mass parts, and then preferably less than 5 mass parts, particularly preferably less than 3 mass parts. 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 to within the scope of the invention, the effect of each compound added can be added while effectively utilizing the effect of the heat resistance or dielectric properties of the composition (A). About these compositions, the composition exemplified below can be used.

[0115] [Epoxy resin]

[0116] 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.

[0117] 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.

[0118] 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.

[0119] [Active ester compound]

[0120] 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 reactive high ester groups in one molecule, can be enumerated. The active ester compound can be obtained by the condensation reaction of at least one compound of a carboxylic acid compound, an acid chloride or a thiocarboxylic acid compound with at least one compound of a hydroxy compound or a thiol compound. Particularly, with regard to the viewpoint of improving heat resistance, when preferably obtaining from a carboxylic acid compound or an acid chloride and a hydroxy compound, as a hydroxy compound, it is preferably a phenolic compound or a naphthol compound. Active ester compound can be used alone or in combination with two or more.

[0121] 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.

[0122] 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, azelayl 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.

[0123] 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.

[0124] 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.

[0125] 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.

[0126] [Phenolic resin]

[0127] 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.

[0128] Specific examples of the raw materials are shown below, but the raw materials are not limited to these.

[0129] <Phenols>

[0130] Phenol, alkyl-substituted phenol, aromatic-substituted phenol, hydroquinone, resorcinol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.

[0131] <Aldehydes>

[0132] Formaldehyde, acetaldehyde, alkyl aldehydes, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, o-phthalaldehyde, crotonaldehyde, cinnamaldehyde, furfural, etc.

[0133] <Diene compounds>

[0134] Dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.

[0135] Ketones

[0136] Acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, fluorenone, etc.

[0137] Substituted biphenyls

[0138] 4,4'-bis(chloromethyl)-1,1'-biphenyl, 4,4'-bis(methoxymethyl)-1,1'-biphenyl, 4,4'-bis(hydroxymethyl)-1,1'-biphenyl, etc.

[0139] <Substituted phenyl groups>

[0140] 1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene, 1,4-bis(hydroxymethyl)benzene, etc.

[0141] [Polyphenylene ether compound]

[0142] 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.).

[0143] 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.

[0144] 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.

[0145] The polyphenylene ether compound may be a polyphenylene ether compound obtained by polymerization reaction, or a polyphenylene ether compound obtained by redistributing 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 may be imparted by reacting these compounds with compounds having ethylenically unsaturated bonds such as methacryloyl chloride, acryloyl chloride, and chloromethylstyrene using these compounds as raw materials. The polyphenylene ether compound obtained by redistribution reaction may 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 thus has hydroxyl groups at both ends of the molecular chain that are derived from phenolic compounds that contribute to hardening, and therefore not only can maintain higher heat resistance, but also can 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 exhibits excellent fluidity, which is preferred in terms of the above aspect.

[0146] 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.

[0147] The content of the polyphenylene ether compound is not particularly limited, but is preferably 5 to 1000 parts by mass, more preferably 10 to 750 parts by mass, based on 100 parts by mass of the total mass of components (A) to (C). When the content of the polyphenylene ether compound is within this range, a cured product having excellent heat resistance and the like and fully utilizing the excellent dielectric properties of the polyphenylene ether compound can be obtained, which is preferred from this perspective.

[0148] [Amine resin]

[0149] 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.

[0150] [Compounds containing ethylenically unsaturated bonds]

[0151] 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.

[0152] 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.

[0153] [Isocyanate resin]

[0154] 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.

[0155] [Polyamide resin]

[0156] 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.

[0157] Specific examples of the raw materials are shown below, but the raw materials are not limited to these.

[0158] <Diamine>

[0159] 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.

[0160] <Diisocyanate>

[0161] 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.

[0162] <Dicarboxylic acid>

[0163] 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.

[0164] <Lactam>

[0165] ε-caprolactam, ω-undecanolactam, ω-laurolactam, etc.

[0166] [Polyimide resin]

[0167] 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.

[0168] <Tetracarboxylic dianhydride>

[0169] 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.

[0170] [Polybutadiene and its modified products]

[0171] 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.

[0172] 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, and it is difficult to adjust the solid content when the prepreg is made. 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, component (A) of the present invention is also excellent in compatibility with materials with low polarity and low dielectric properties, or compounds containing only hydrocarbons, because it is not itself actively designed to introduce heteroatoms such as oxygen or nitrogen.

[0173] [Polystyrene and its modified products]

[0174] Polystyrene and its modified products are compounds having a structure of polystyrene or a structure derived from polystyrene in the molecule.

[0175] Examples of polystyrene and modified products thereof include polystyrene, styrene-2-isopropenyl-2-oxazoline copolymer (Epocros RPS-1005 and RP-61 are both manufactured by Nippon Catalyst Co., Ltd.), SEP (styrene-ethylene-propylene copolymer: Septon 1020 manufactured by Kuraray), SEPS (styrene-ethylene-propylene-styrene copolymer: 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, Septon 5127 are all manufactured by Kuraray) y) company), hydrogenated SIS (hydrogenated styrene-isoprene-styrene block copolymer: Hybrar 7125F, Hybrar 7311F are both manufactured by Kuraray), SIBS (styrene-isobutylene-styrene block copolymer: SIBSTAR073T, SIBSTAR102T, SIBSTAR103T (all manufactured by Kaneka Chemical Co., Ltd.), 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.

[0176] 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.

[0177] The method for preparing the curable resin composition of the present invention is not particularly limited, and the components may be simply mixed uniformly, or prepolymerized. For example, prepolymerization can be performed by heating a mixture containing components (A) to (C) in the presence or absence of a curing accelerator or a polymerization initiator, and in the presence or absence of a solvent. Similarly, prepolymerization can be performed 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. For mixing or prepolymerization of the components, an extruder, kneader, roller, etc., is used in the absence of a solvent, and a reactor equipped with a stirring device is used in the presence of a solvent.

[0178] 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.

[0179] The obtained molded body can be molded into a cured product using a transfer molding machine or a compression molding machine.

[0180] 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).

[0181] 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.

[0182] 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. In addition, known weaves for woven fabrics include plain weave, basket weave, and twill weave. These weaves can be appropriately selected from these known weaves depending on the intended use or performance. Furthermore, woven fabrics subjected to fiber opening treatment or glass fabrics surface-treated with a silane coupling agent or the like can be 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 varnish into reinforcing fibers and then heating and drying the resulting fibers.

[0183] In addition, the prepreg can also be used to manufacture a laminate. The laminate is not particularly limited as long as it is a laminate comprising 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, and 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.

[0184] 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.

[0185] 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.

[0186] 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.

[0187] 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).

[0188] 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.

[0189] 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.

[0190] 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.

[0191] 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.

[0192] 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.

[0193] 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).

[0194] 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. Since 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 for electrical and electronic parts such as semiconductor element sealing materials, liquid crystal display element sealing materials, organic electroluminescent (EL) element sealing materials, laminates (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, three-dimensional (3D) printing, etc.

[0195] [Example]

[0196] 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.

[0197] Various analytical methods used in the Examples are described below.

[0198] <Weight average molecular weight (Mw), number average molecular weight (Mn)>

[0199] Calculate the amount by polystyrene conversion using a polystyrene standard solution.

[0200] Gel permeation chromatograph (GPC): DGU-20A3R, LC-20AD, SIL-20AHT, RID-20A, SPD-20A, CTO-20A, CBM-20A (all manufactured by Shimadzu Corporation)

[0201] Column: Shodex KF-603, KF-602×2, KF-601×2

[0202] Linking eluent: tetrahydrofuran

[0203] Flow rate: 0.5ml / min.

[0204] Column temperature: 40°C

[0205] Detector: RI (differential refractometer)

[0206] [Synthesis example 1]

[0207] An aspirator and an alkali trap were set in a flask equipped with a thermometer, a cooling tube, and a stirrer. 370.1 parts of 2-bromoethylbenzene (manufactured by Tokyo Chemical Industry Co., Ltd.), 175.1 parts of α,α'-dichloroparaxylene (manufactured by Tokyo Chemical Industry Co., Ltd.), and 27.3 parts of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were placed in the flask, and the reaction was carried out at 130°C for 6 hours while the generated hydrogen chloride was captured by the alkali trap. 100 parts of toluene and 600 parts of cyclohexane were added and extracted, and the organic layer was washed 5 times with 100 parts of water. The solvent and excess 2-bromoethylbenzene were distilled off under heating and reduced pressure to obtain 380 parts of a compound (BEB-1) having a 2-bromoethylbenzene structure represented by the following formula (4) as a liquid resin (Mn: 938, Mw: 1290). The GPC chart of the obtained compound is shown in FIG. Figure 1 The average value n of the repeating units calculated from the area % of the GPC chart was 2.2.

[0208] [Chemistry 5]

[0209]

[0210] [Synthesis example 2]

[0211] In a flask equipped with a thermometer, a cooling tube, and a stirrer, 300 parts of BEB-1 obtained in Synthesis Example 1, 245 parts of toluene, 735 parts of dimethyl sulfoxide, 0.15 parts of 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl free radical, and 146.4 parts of a 50 wt% sodium hydroxide aqueous solution were added, and the reaction was continued at 40°C for 6 hours. 100 parts of water were added, and after washing the organic layer, the organic layer was returned to the reaction vessel. 735 parts of dimethyl sulfoxide and 9.8 parts of a 50 wt% sodium hydroxide aqueous solution were added, and the reaction was again carried out at 40°C for 1 hour. 300 parts of toluene were added, and the organic layer was repeatedly washed with 100 parts of water until the drainage became neutral. The mixture was concentrated under reduced pressure using an evaporator to obtain 180 parts of a compound (O-1) represented by the following formula (5) having two or more styrene structures in the molecule. The GPC chart of the obtained compound is shown in FIG. Figure 2 In addition, the obtained compound 1 H-NMR ( 1 H-nuclear magnetic resonance, 1 H-NMR) data (heavy chloroform) are shown in Figure 3 In. 1 Signals derived from vinyl groups were observed at 5.10-5.30 ppm, 5.50-5.85 ppm, and 6.60-6.80 ppm in the H-NMR chart. The average value n of the repeating units calculated from the area % of the GPC chart was 2.2 (molecular weight of the resin component: Mn: 797, Mw: 1187).

[0212] [Chemistry 6]

[0213]

[0214] [Synthesis example 3]

[0215] A resin solution containing a maleimide compound represented by the following formula (6) synthesized according to the method described in International Publication No. 2020 / 054601 was concentrated under reduced pressure and heating to obtain a solidified maleimide compound (M-1).

[0216] [Chemistry 7]

[0217]

[0218] [Example 1, Comparative Example 1]

[0219] The materials listed in Table 1 were dissolved and mixed in acetone to a solids content of 66% by mass. The mixture was then applied to a mirror-finished copper foil to a wet film thickness of 200 μm. The film was pre-dried in a vacuum oven at 60°C for 30 minutes and then cured at 220°C for 1 hour. After curing, the copper foil was etched with ferric chloride to obtain a cured film (for Comparative Example 1, the film was cured at 175°C for 2 hours). For evaluation, test pieces were cut to the desired size using a laser cutter, as needed.

[0220] <Dielectric constant test / dielectric loss tangent test>

[0221] The test was conducted using a 10 GHz cavity resonator manufactured by ATE Co., Ltd. The cavity resonator perturbation method was used. The test sample size was 1.7 mm wide x 100 mm long and 0.1 mm thick.

[0222] <Heat resistance (differential scanning calorimeter (DSC))>

[0223] Differential scanning calorimeter: DSC6220 (manufactured by SII NanoTechnology)

[0224] Measuring temperature range: 30℃~330℃

[0225] Heating rate: 10℃ / min

[0226] Environment: Nitrogen (30 mL / min)

[0227] Sample size: 5 mg

[0228] Tg: The inflection point of the DSC chart is set as Tg.

[0229] [Table 1]

[0230]

[0231] CYTESTER TA: Bisphenol A cyanate ester compound (manufactured by Mitsubishi Gas Chemical Co., Ltd.)

[0232] NC-3000-L: Biphenyl aralkyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd.)

[0233] 18% Octope Zn: Zinc 2-ethylhexanoate (hardening accelerator, manufactured by Hope Pharmaceuticals)

[0234] TPP-K: Tetraphenylphosphonium tetraphenylborate (hardening accelerator, manufactured by Beixing Chemical Co., Ltd.)

[0235] 2E4MZ: 2-ethyl-4-methylimidazole (hardening accelerator, manufactured by Shikoku Chemical Co., Ltd.)

[0236] From the results in Table 1, it was confirmed that Example 1 was superior in high heat resistance and low dielectric properties compared to the epoxy resin composition used in the past.

[0237] [Example 2]

[0238] The materials listed in Table 2 were dissolved and mixed in acetone to a solids content of 66% by mass. The mixture was then applied to a mirror-finished copper foil to a wet film thickness of 200 μm. The mixture was pre-dried in a vacuum oven at 60°C for 30 minutes and then cured at 220°C for 1 hour. After curing, the copper foil was etched with ferric chloride to obtain a cured film.

[0239] Compatibility test

[0240] Table 2 shows the results of evaluation based on the following criteria.

[0241] The materials were mixed in a polybottle (I-boy, manufactured by ASONE) at the ratios shown in Table 2. The mixture was stirred at 100 rpm at 25°C for 1 hour using a roll mixer (MIX-ROTAR VMR-5, manufactured by ASONE). The mixture was then evaluated based on the following criteria. The results are shown in Table 2.

[0242] · When each material except the inorganic filler is prepared into a resin solution, a uniform solution is obtained: ○

[0243] · When materials other than the inorganic filler are prepared into a resin solution, a uniform solution cannot be obtained: ×

[0244] <Film forming test>

[0245] Table 2 shows the results of evaluation based on the following criteria.

[0246] · When no cracks or fissures occur in the cured film after etching: ○

[0247] · If cracks or fissures occur in the hardened film after etching: ×

[0248] [Table 2]

[0249]

[0250] CYTESTER TA: Bisphenol A cyanate ester compound (manufactured by Mitsubishi Gas Chemical Co., Ltd.)

[0251] 18% Octope Zn: Zinc 2-ethylhexanoate (hardening accelerator, manufactured by Hope Pharmaceuticals)

[0252] TPP-K: Tetraphenylphosphonium tetraphenylborate (hardening accelerator, manufactured by Beixing Chemical Co., Ltd.)

[0253] DCP: dicumyl peroxide (manufactured by Kayaku Akzo Chemicals)

[0254] MSR-2212: Silica filler (manufactured by Longsen Corporation)

[0255] From the results in Table 2, it was confirmed that Example 2 had excellent compatibility and sufficient flexibility for film formation.

[0256] The curable resin composition, resin sheet, and cured product thereof of the present invention can be preferably used in electrical and electronic parts such as semiconductor sealing materials, printed wiring boards, and build-up laminates.

Claims

1. A curable resin composition comprising (A) a compound having at least two styrene structures in a molecule, (B) a maleimide compound, and (C) a cyanate compound. in, The component (A) is one or more selected from the group consisting of oligomeric divinyl copolymers, 4,4'-ethylenebisstyrene, 3,4'-ethylenebisstyrene, 3,3'-ethylenebisstyrene, divinylfluorene, divinylbiphenyl, divinylnaphthalene, divinylbenzene, and a compound represented by the following formula (1). [Chemistry 1] In formula (1), multiple Rs exist independently and represent a hydrocarbon group having 1 to 10 carbon atoms or a halogenated alkyl group having 1 to 10 carbon atoms; p and r represent integers of 0 to 4, q represents an integer of 0 to 3, and n is the average value of the repetition number, 1≦n≦20.

2. The curable resin composition according to claim 1, wherein The component (A) is a compound represented by the formula (1).

3. The curable resin composition according to claim 1 or 2, wherein The component (B) is a compound represented by the following formula (3); [Chemistry 2] In formula (3), multiple Rs exist independently and represent a hydrocarbon group with 1 to 10 carbon atoms or a halogenated alkyl group with 1 to 10 carbon atoms; p and r represent integers of 0 to 4, q represents an integer of 0 to 3, and n is the average value of the repetition number, 1≦n≦20. The curable resin composition according to claim 1 or 2, further comprising a curing accelerator. The curable resin composition according to claim 1 or 2, further comprising an inorganic filler. The curable resin composition according to claim 1 or 2, further comprising a polymerization initiator. 7 . A resin sheet comprising the resin composition according to claim 1 and a support. 8 . A cured product, which is the cured product of the curable resin composition according to claim 1 or the resin sheet according to claim 7 .

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