Curable resin composition and cured product thereof

Abstract

To provide a curable resin composition which has excellent storage stability and exhibits a low dielectric loss tangent, and a cured product thereof.SOLUTION: A curable resin composition contains a compound represented by a formula (1) and a compound represented by a formula (2). (In the formula (1), A represents a C1-20 hydrocarbon group; a plurality of R's each independently represents a hydrogen atom, a C1-10 hydrocarbon group, or a C1-10 halogenated alkyl group; and p represents an integer of 0-4 and q represents an integer of 0-3, provided that n1≤n≤20.) (In the formula (2), R1 and R2 each independently represent a C1-20 hydrocarbon group; and n represents an integer of 0-3.)SELECTED DRAWING: Figure 1

Description

[Technical field]

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

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

[0003] The fifth generation communication system "5G", whose development is currently accelerating, is expected to further increase capacity and speed of communication. In 5G, the frequency used will become higher, but in order to realize high-speed communication using high frequencies, it is important to reduce transmission loss, and further reduction in dielectric tangent of the board material will be required. The transmission loss occurring on the printed circuit board is due to conductor loss and dielectric loss. As described in Non-Patent Document 1, since the conductor loss is proportional to the square root of the relative dielectric constant and the dielectric tangent of the dielectric, it can be said that improving the dielectric tangent, which has a higher contribution rate than the relative dielectric constant, is effective in reducing transmission loss. Examples of low-dielectric materials include thermoplastic materials such as PTFE (polytetrafluoroethylene) and LCP (liquid crystal polymer), but they are poor in moldability compared to thermosetting resins. In light of this, the development of thermosetting resins and curable resin compositions that exhibit low dielectric tangent is desired.

[0004] In light of this background, thermosetting resin compositions exhibiting low dielectric tangents have been studied. For example, Patent Document 1 discloses a curable resin composition containing bisvinylphenylethane (BVPE) and a thermosetting polyphenylene ether (Patent Document 1). In this curable resin composition, a polymerization inhibitor is used to improve the storage stability of the resin composition, and 2,5-bis(1,1-dimethylbutyl)hydroquinone is used. In general, when a polymerization inhibitor having a polar group (a substituent containing a heteroatom) in its structure is used, the storage stability improves as the amount of the polymerization inhibitor increases, but on the other hand, the dielectric properties deteriorate, resulting in a trade-off relationship. In addition, when the target compound for which storage stability is to be improved changes, the optimal polymerization inhibitor also changes, making its selection difficult and an important issue. [Prior art documents] [Non-patent literature]

[0005] [Non-Patent Document 1] Signal loss factors in high-speed signal transmission on printed circuit boards (Mitsui Mining & Smelting Co., Ltd.) 29th Japan Institute of Electronics Packaging Spring Conference 16P1-17 [Patent documents]

[0006] [Patent Document 1] JP 2008-115280 A Summary of the Invention [Problem to be solved by the invention]

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

[0008] That is, the present invention relates to the following [1] to [5]. Note that in this application, "(Numerical value 1) to (Numerical value 2)" indicates that the upper and lower limits are included. [1] A curable resin composition comprising a compound represented by the following formula (1) and a compound represented by the following formula (2):

[0009] [ka]

[0010] (In formula (1), A is a hydrocarbon group having 1 to 20 carbon atoms, and each of the multiple R's independently represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a halogenated alkyl group having 1 to 10 carbon atoms. p is an integer of 0 to 4, q is an integer of 0 to 3, n is the average number of repetitions, and 1≦n≦20.)

[0011] [ka]

[0012] (In formula (2), R1 and R2 each independently represent a hydrocarbon group having 1 to 20 carbon atoms, and n represents an integer of 0 to 3.) [2] A curable resin composition comprising a compound represented by the following formula (1-1) and a compound represented by the following formula (2):

[0013] [ka] (In formula (1), each of the multiple R's independently represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a halogenated alkyl group having 1 to 10 carbon atoms. p and r each represent an integer of 0 to 4, q represents an integer of 0 to 3, and n represents the average number of repetitions, and 1≦n≦20.)

[0014] [ka]

[0015] (In formula (2), R1 and R2 each independently represent a hydrocarbon group having 1 to 20 carbon atoms, and n represents an integer of 0 to 3.) [3] The curable resin composition according to item [1] or [2] above, further comprising a polymerization initiator. [4] The curable resin composition according to any one of the preceding items [1] to [3], further comprising at least one selected from the group consisting of a maleimide compound, a polyphenylene ether compound, a compound having an ethylenically unsaturated bond, a cyanate ester resin, polybutadiene and modified products thereof, polystyrene and modified products thereof, and polyethylene and modified products thereof. [5] A cured product obtained by curing the curable resin composition according to any one of the above items [1] to [4]. Effect of the Invention

[0016] The curable resin composition of the present invention and its cured product exhibit a low dielectric tangent. [Brief description of the drawings]

[0017] [Figure 1] 1 shows a GPC chart of Synthesis Example 1. [Diagram 2] 1 shows a GPC chart of Synthesis Example 2. [Diagram 3] 1H-NMR chart of Synthesis Example 2 is shown. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0018] The embodiment of the present invention (hereinafter, also referred to as "the present embodiment") will be described in further detail below. will explain.

[0019] The curable resin composition of the present embodiment contains a compound represented by the following formula (1) as an essential component.

[0020] [ka]

[0021] In formula (1), A is a hydrocarbon group having 1 to 20 carbon atoms, preferably a hydrocarbon group having 2 to 20 carbon atoms, more preferably a hydrocarbon group having 6 to 20 carbon atoms, and particularly preferably a hydrocarbon group having 8 to 20 carbon atoms. The hydrocarbon preferably contains a methylene chain, an alicyclic structure, or an aromatic ring, more preferably a methylene chain or an aromatic ring, and even more preferably contains at least one aromatic ring. By containing an aromatic ring, molecular vibration can be suppressed, resulting in good dielectric properties, and also contributing to improved heat resistance. Each of the multiple R's independently represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a halogenated alkyl group having 1 to 10 carbon atoms, preferably a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and even more preferably a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms. Hydrocarbons having 10 or less carbon atoms are less likely to undergo molecular vibration when exposed to high frequency waves, and therefore have particularly excellent electrical properties.

[0022] In formula (1), p is an integer of 0 to 4, preferably an integer of 0 to 2. q is an integer of 0 to 3, preferably an integer of 0 to 2. n is the average number of repetitions, and is preferably 1≦n≦20, more preferably 1.1≦n≦20, particularly preferably 1.1≦n≦10, and most preferably 1.1≦n≦5. The value of n can be calculated from the value of the number average molecular weight (Mn) obtained by measuring the compound represented by formula (1) by gel permeation chromatography (GPC), etc. 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. If the weight average molecular weight is less than 5000, purification by washing with water becomes easy, and if it is 200 or more, the target compound does not volatilize in the solvent distillation step.

[0023] The compound represented by the above formula (1) is particularly preferably a compound represented by the following formula (1-1).

[0024] [ka]

[0025] In formula (1-1), each of the multiple R's independently represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a halogenated alkyl group having 1 to 10 carbon atoms, preferably a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and more preferably a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms. Hydrocarbons having 10 or less carbon atoms are less likely to undergo molecular vibration when exposed to high frequency waves, and therefore have particularly excellent electrical properties.

[0026] In formula (1-1), p and r are integers of 0 to 4, preferably 0 to 2. q is an integer of 0 to 3, preferably 0 to 2. n is the average number of repeats, and is preferably 1≦n≦20, more preferably 1.1≦n≦20, particularly preferably 1.1≦n≦10, and most preferably 1.1≦n≦5. The value of n can be calculated from the number average molecular weight (Mn) of the compound represented by formula (1-1) measured by gel permeation chromatography (GPC). 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. If the weight average molecular weight is less than 5000, purification by washing with water becomes easy, and if it is 200 or more, the target compound does not volatilize in the solvent distillation step.

[0027] The compound represented by the above formula (1-1) is derived from a compound represented by the following formula (1-2).

[0028] [ka]

[0029] In formula (1-2), the definition of R, and the values ​​of p, r, q, and n, and the preferred ranges thereof are the same as those in formula (1-1). X represents a halogen atom, and from the viewpoints of reactivity and stability of the raw materials, a bromine atom or a chlorine atom is preferable, and a bromine atom is particularly preferable.

[0030] The compound represented by the formula (1-1) can be obtained, for example, by a method of dehydrohalogenating the compound represented by the formula (1-2) in a solvent in the presence of a basic catalyst. Examples of the solvent to be used include, but are not limited to, water-insoluble solvents such as 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 ketone solvents such as methyl isobutyl ketone and cyclopentanone. Two or more of these may be used in combination. In addition to the water-insoluble solvent, an aprotic polar solvent may also be used in combination. Examples include dimethyl sulfone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, and N-methylpyrrolidone, and two or more of these may be used in combination. When an aprotic polar solvent is used, it is preferable to use one having a boiling point higher than that of the water-insoluble solvent to be used in combination. The catalyst is not particularly limited, but examples include basic catalysts such as sodium hydroxide, potassium hydroxide, and potassium carbonate. Since it is difficult to completely proceed with the dehydrohalogenation reaction, the aprotic polar solvent may be used in large excess relative to the substrate, and the dehydrohalogenation reaction may be repeated two or more times. For example, the dehydrohalogenation reaction of the compound represented by the formula (1-2) may be carried out in an organic solvent in the presence of a base catalyst, and the resulting solution may be washed with water and then returned to the reaction vessel, and the base catalyst may be added to cause the reaction again. In this way, the progress of the dehydrohalogenation reaction can be increased. That is, it is possible to reduce the amount of residual halogen contained in the target compound. The amount of residual halogen is preferably 1 to 10,000 ppm in the target product, more preferably 1 to 1,000 ppm, and even more preferably 1 to 750 ppm. If the amount of residual halogen contained in the compound represented by the formula (1-1) is large, molecular vibration occurs when exposed to high frequency, which has a negative effect on electrical properties, particularly dielectric loss tangent.Furthermore, if the amount of residual halogen is large, there is an increased risk of problems such as metal corrosion and ion migration occurring in environmental tests such as HAST tests (High Accelerated Stress Tests), so the above-mentioned halogen content is preferable.

[0031] The method for producing the compound represented by the formula (1-2) is not particularly limited, but for example, a compound having a (2-bromoethyl)benzene structure may be reacted with a bishalogenated methylaryl compound (or a bishydroxymethylaryl compound, etc.) under an acid catalyst such as hydrochloric acid, sulfonic acid, or activated clay, or a compound having a (2-bromoethyl)benzene structure may be reacted with a bishydroxymethylaryl compound under an acid catalyst such as hydrochloric acid, sulfonic acid, or activated clay. When sulfonic acid or the like is used as a catalyst, the mixture may be neutralized with an alkali metal such as sodium hydroxide or potassium hydroxide before proceeding to the extraction step. For the extraction step, an aromatic hydrocarbon solvent such as toluene or xylene may be used alone, or a non-aromatic hydrocarbon such as cyclohexane or toluene may be used in combination. After extraction, the organic layer is washed with water until the wastewater becomes neutral, and the solvent and the compound having an excess (2-bromoethyl)benzene structure are distilled off using an evaporator or the like to obtain a compound having at least two or more 2-bromoethyl ethylbenzene structures in the target molecule.

[0032] Examples of compounds having a (2-bromoethyl)benzene structure include (2-bromoethyl)benzene, 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, but are not limited thereto. These may be used alone or in combination of two or more. A large carbon number improves the solvent solubility, but reduces the heat resistance, so that it is preferably unsubstituted or substituted with an alkyl group having 1 to 3 carbon atoms, more preferably unsubstituted or substituted with an alkyl group having 1 to 2 carbon atoms, and most preferably unsubstituted or substituted with a methyl group.

[0033] Examples of the bishalogenated methylaryl compound include, but are not limited to, o-xylylene difluoride, m-xylylene difluoride, p-xylylene difluoride, o-xylylene dichloride, m-xylylene dichloride, p-xylylene dichloride, o-xylylene dibromide, m-xylylene dibromide, p-xylylene dibromide, o-xylylene diiodide, m-xylylene diiodide, and p-xylylene diiodide. These may be used alone or in combination of two or more. From the viewpoint of the reactivity of the raw material during synthesis, chloride-based compounds, bromide-based compounds, and iodide-based compounds are preferred, and chloride-based compounds and bromide-based compounds are more preferred.

[0034] Examples of bishydroxymethylaryl compounds include, but are not limited to, o-benzenedimethanol, m-benzenedimethanol, and p-benzenedimethanol. 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, per part by mass of the compound having a (2-bromoethyl)benzene structure.

[0035] In the reaction of a compound having a (2-bromoethyl)benzene structure with a halogenated methylaryl compound, etc., a catalyst may be used as needed, such as hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, Lewis acids such as aluminum chloride and zinc chloride, activated clay, acidic clay, white carbon, zeolite, solid acids such as silica alumina, acidic ion exchange resins, etc. These may be used alone or in combination of two or more. The amount of catalyst used is 0.05 to 0.8 mol, preferably 0.1 to 0.7 mol, per mol of the compound having a (2-bromoethyl)benzene structure used. If the amount of catalyst used is too large, the viscosity of the reaction solution may be too high, making stirring difficult, and if the amount is too small, the reaction may proceed slowly. The reaction may be carried out using an organic solvent such as hexane, cyclohexane, octane, toluene, or xylene, as necessary, or may be carried out without a solvent. For example, after adding an acid catalyst to a mixed solution of a compound having a (2-bromoethyl)benzene structure, a halogenated methylaryl compound, and a solvent, if the catalyst contains water, the water is removed from the system by azeotropy. Then, the reaction is carried out at 40 to 180°C, preferably 50 to 170°C, for 0.5 to 20 hours. After the reaction is completed, the acid catalyst may be neutralized with an alkaline aqueous solution, but it is also possible to proceed to the water washing step without neutralizing it. 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.

[0036] The softening point of the compound represented by formula (1-2) is preferably 80° C. or lower, more preferably 70° C. or lower. If the softening point is 80° C. or lower, the viscosity when induced into the compound represented by formula (1-1) is low. This makes it easier to ensure fluidity, does not impair the impregnation into glass cloth or carbon fiber, and facilitates B-stage formation such as prepreg formation. If the viscosity is reduced by increasing the dilution solvent, there is a possibility that the resin will not sufficiently adhere to the fibrous material in the impregnation process.

[0037] The curable resin composition of the present embodiment further contains a compound represented by the following formula (2).

[0038] [ka]

[0039] In formula (2), R1 and R2 each independently represent a hydrocarbon group having 1 to 20 carbon atoms, preferably a hydrocarbon group having 1 to 15 carbon atoms, more preferably a hydrocarbon group having 1 to 10 carbon atoms, and even more preferably a hydrocarbon group having 1 to 5 carbon atoms. When R1 and R2 are hydrocarbon groups having more than 20 carbon atoms, the molecules are likely to vibrate when exposed to high frequency waves, and the dielectric properties may deteriorate. When the number of carbon atoms is 20 or less, the equivalent weight of the phenolic hydroxyl group per weight increases, and a sufficient polymerization inhibition effect is obtained. n is an integer of 0 to 3, preferably 0 to 2, more preferably 0 to 1, and particularly preferably 0. When n is small, the equivalent weight of the phenolic hydroxyl group per weight increases, and a sufficient polymerization inhibition effect is obtained, which is more preferable.

[0040] The compound represented by formula (2) has a hydrocarbon group at the ortho position of the phenolic hydroxyl group located at the top of formula (2) and a phenolic hydroxyl group at the para position. The hydrocarbon group donates hydrogen to the phenoxy radical to regenerate the phenolic hydroxyl group, thereby enhancing the polymerization inhibition effect. The phenolic hydroxyl group at the para position increases the electron density of the compound represented by formula (2), thereby improving the radical scavenging performance. In addition, since the polar groups of the compound represented by formula (2) are symmetrically positioned, the dipole moment is small and deterioration of the dielectric properties can be suppressed.

[0041] The compound represented by the formula (2) is preferably 0.0001 to 1 part by mass, more preferably 0.001 to 0.75 parts by mass, further preferably 0.002 to 0.5 parts by mass, and particularly preferably 0.004 to 0.5 parts by mass, relative to 100 parts by mass of the compound represented by the formula (1). If it is less than 0.0001 part by mass, there is a risk that a sufficient polymerization inhibition effect cannot be obtained, and if it is more than 1 part by mass, there is a risk that the dielectric properties are significantly impaired.

[0042] When the curable resin composition of the present embodiment is used for prepreg applications, the drying temperature of a typical prepreg is a maximum of 120°C, so the reaction initiation temperature of the curable resin composition is preferably 120°C or higher. However, since the reaction initiation temperature obtained by DSC is different from the actual temperature because the device is a non-insulating system (Reference: Chemical Explosion Safety Information Database, http: / / www.explosion-safety.jp / INFOMATION / how_to_test_1-3.htm), it is preferable that the heat generation initiation temperature of DSC is at least 170°C or higher. If it is less than 170°C, the reaction proceeds during drying of the prepreg, and there is a risk that the fluidity during molding will not be obtained, making it difficult to create a laminate.

[0043] In addition to the compound represented by formula (1) and the compound represented by formula (2), various materials may be added to the curable resin composition of the present embodiment to improve performance.

[0044] [Polymerization inhibitor] The curable resin composition of the present embodiment may contain other polymerization inhibitors in addition to the compound represented by formula (2). However, when a polymerization inhibitor is used, the amount of the polymerization inhibitor is limited to a range that does not significantly affect the dielectric properties and curing properties of the curable resin composition of the present embodiment.

[0045] Examples of the polymerization inhibitor include phenol-based, sulfur-based, phosphorus-based, hindered amine-based, nitroso-based, and nitroxyl radical-based inhibitors.

[0046] Examples of the phenol-based polymerization inhibitor include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, stearyl-β-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, 2,4-bis[(octylthio)methyl]-o ... Monophenols such as resol, 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol), 4,4'-thiobis(3-methyl-6-t-butylphenol), 4,4'-butylidenebis(3-methyl-6-t-butylphenol), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] , N,N'-Hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, 3,9-bis[1,1-dimethyl-2-{β-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}ethyl]2,4,8,10-tetraoxaspiro[5,5]undecane, bis(3,5-di-t-butyl Bisphenols such as calcium ethyl-4-hydroxybenzylsulfonate, 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, tetrakis-[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methane, bis[3,3'-bis-(4'-hydroxy-3'-t-butylphenyl)butyric acid]glycol ester, tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-tris(3',5'-di-t-butyl-4'-hydroxybenzyl)-S-triazine-2,4,6-(1H,3H,5H)trione, tocopherol and other polymeric phenols are included, but are not limited to these.

[0047] 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.

[0048] Examples of the phosphorus-based polymerization inhibitor include triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, tris(nonylphenyl) phosphite, diisodecyl pentaerythritol phosphite, tris(2,4-di-t-butylphenyl) phosphite, cyclic neopentane tetrayl bis(octadecyl) phosphite, cyclic neopentane tetrayl bi(2,4-di-t-butylphenyl) phosphite, cyclic neopentane tetrayl bi(2,4-di-t-butyl-4-methylphenyl) phosphite, bis[2-t 10-(3,5-di-t-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(3,5-di-t-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and other oxaphosphaphenanthrene oxides, but are not limited to these.

[0049] Examples of the hindered amine polymerization inhibitor include, but are not limited to, Adeka STAB LA-40MP, Adeka STAB LA-40Si, Adeka STAB LA-402AF, Adeka STAB LA-87, Adeka STAB LA-82, Adeka STAB LA-81, Adeka STAB LA-77Y, Adeka STAB LA-77G, Adeka STAB LA-72, Adeka STAB LA-68, Adeka STAB LA-63P, Adeka STAB LA-57, Adeka STAB LA-52, Chimassorb 2020FDL, Chimassorb 944FDL, Chimassorb 944LD, Tinuvin 622SF, Tinuvin PA144, Tinuvin 765, Tinuvin 770DF, Tinuvin XT55FB, Tinuvin 111FDL, Tinuvin 783FDL, Tinuvin 791FB, and the like.

[0050] Examples of the nitroso-based polymerization inhibitor include, but are not limited to, p-nitrosophenol, N-nitrosodiphenylamine, ammonium salt of N-nitrosophenylhydroxyamine, (cupferron), etc. Among these, the ammonium salt of N-nitrosophenylhydroxyamine (cupferron) is preferred.

[0051] Examples of the nitroxyl radical polymerization inhibitor include di-tert-butyl nitroxide, 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-amino-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-acetoxy-2,2,6,6-tetramethylpiperidine-1-oxyl, and 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl, but are not limited thereto.

[0052] [Cure accelerator] The curable resin composition of the present embodiment can also have improved curability by adding a curing accelerator. As the curing accelerator, an anionic curing accelerator that accelerates the curing reaction by generating anions upon irradiation with ultraviolet light or visible light or heating, or a cationic curing accelerator that accelerates the curing reaction by generating cations upon irradiation with ultraviolet light or visible light or heating, is preferred.

[0053] Examples of anionic curing accelerators include imidazoles such as 2-methylimidazole, 2-ethylimidazole, and 2-ethyl-4-methylimidazole, trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6,-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo(5,4,0)-undecene, with 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)-undecene being preferred. Other examples include phosphines such as triphenylphosphine, quaternary ammonium salts such as tetrabutylammonium salts, triisopropylmethylammonium salts, trimethyldecanylammonium salts, cetyltrimethylammonium salts, and hexadecyltrimethylammonium hydroxide, but are not limited thereto. These may be used alone or in combination.

[0054] Examples of cationic curing accelerators include quaternary phosphonium salts such as triphenylbenzylphosphonium salt, triphenylethylphosphonium salt, and tetrabutylphosphonium salt (counter ions of quaternary salts are halogen, organic acid ions, hydroxide ions, etc., and are not particularly specified, but organic acid ions and hydroxide ions are particularly preferred), transition metal compounds (transition metal salts) such as tin octylate, zinc carboxylate (zinc 2-ethylhexanoate, zinc stearate, zinc behenate, zinc myristate), and zinc phosphate (zinc octyl phosphate, zinc stearyl phosphate), but are not limited thereto. These may be used alone or in combination.

[0055] The curing accelerator is used in an amount of 0.01 to 5.0 parts by mass based on 100 parts by mass of the curable resin composition, as required.

[0056] [Inorganic filler] The curable resin composition of the present embodiment may contain an inorganic filler. Examples of inorganic fillers include, but are not limited to, powders such as fused silica, crystalline silica, porous silica, alumina, zircon, calcium silicate, calcium carbonate, quartz powder, silicon carbide, silicon nitride, boron nitride, zirconia, aluminum nitride, graphite, forsterite, steatite, spinel, mullite, titania, talc, clay, iron oxide asbestos, and glass powder, or inorganic fillers obtained by making these into a spherical or crushed shape. In addition, these may be used alone or in combination.

[0057] The amount of inorganic filler used in obtaining a curable resin composition for semiconductor encapsulation 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. In addition, in obtaining a curable resin composition for an interlayer insulating layer forming material, a copper-clad laminate, a prepreg, an RCC, or other substrate material, the amount of 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.

[0058] [Polymerization initiator] The curable resin composition of the present embodiment can also improve the curability by adding a polymerization initiator. The polymerization initiator is a compound capable of polymerizing an olefin functional group such as an ethylenically unsaturated bond, and examples of such a polymerization initiator include an olefin metathesis polymerization initiator, an anionic polymerization initiator, a cationic polymerization initiator, and a radical polymerization initiator. Among these, it is preferable to use a radical polymerization initiator having curability and moderate stability. The radical polymerization initiator is a compound that generates radicals by irradiation with ultraviolet light or visible light or by heating, and initiates a chain polymerization reaction. Examples of radical polymerization initiators that can be used include organic peroxides, azo compounds, and benzopinacoles, and it is preferable to use an organic peroxide because it has little effect on curing temperature control, outgassing suppression, and electrical properties of decomposition products.

[0059] Examples of the organic peroxides include ketone peroxides such as methyl ethyl ketone peroxide and acetylacetone peroxide, diacyl peroxides such as benzoyl peroxide, dialkyl peroxides such as dicumyl peroxide and 1,3-bis-(t-butylperoxyisopropyl)-benzene, peroxyketals such as t-butyl peroxybenzoate and 1,1-di-t-butylperoxycyclohexane, α-cumyl peroxyneodecanoate, t-butyl peroxyneodecanoate, t-butyl peroxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-amyl peroxy-2-ethylhex ...amyl peroxy-2-ethylhexanoate, t-butyl peroxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-amyl peroxy-2-ethylhexanoate, t-butyl peroxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-amyl peroxy-2-ethylhexanoate, t-butyl peroxypivalate, 1,1, Examples of the peroxycarbonates include, but are not limited to, alkyl peresters such as t-amyl peroxy-2-ethylhexanoate, t-amyl peroxy-3,5,5-trimethylhexanoate, t-butyl peroxy-3,5,5-trimethylhexanoate, and t-amyl peroxybenzoate, peroxycarbonates such as di-2-ethylhexyl peroxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, t-butyl peroxyisopropyl carbonate, and 1,6-bis(t-butylperoxycarbonyloxy)hexane, t-butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxyoctoate, and lauroyl peroxide. These may be used alone or in combination. Among the above organic peroxides, ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, alkyl peresters, percarbonates, etc. are preferred, and dialkyl peroxides are more preferred.

[0060] Examples of the azo-based compound include, but are not limited to, azobisisobutyronitrile, 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2,4-dimethylvaleronitrile), etc. These may be used alone or in combination.

[0061] The amount of the polymerization initiator added is preferably 0.01 to 5 parts by mass, particularly preferably 0.01 to 3 parts by mass, in 100 parts by mass of the curable resin composition. If the amount of the polymerization initiator used is less than 0.01 part by mass, the molecular weight may not be sufficiently extended during the polymerization reaction, and if it is more than 5 parts by mass, the dielectric properties such as the dielectric constant and the dielectric loss tangent may be impaired.

[0062] [Flame retardant] The curable resin composition of the present embodiment may contain a flame retardant. Examples of the flame retardant include halogen-based flame retardants, inorganic flame retardants (antimony compounds, metal hydroxides, nitrogen compounds, boron compounds, etc.), and phosphorus-based flame retardants. From the viewpoint of achieving halogen-free flame retardancy, phosphorus-based flame retardants are preferred. The phosphorus-based flame retardant may be of reactive type or additive type. Specific examples include phosphoric acid esters such as trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylyleneyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylyleneyl phosphate, 1,3-phenylene bis(dixylyleneyl phosphate), 1,4-phenylene bis(dixylyleneyl phosphate), and 4,4'-biphenyl(dixylyleneyl phosphate), phosphanes such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 10(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, phosphorus-containing epoxy compounds obtained by reacting epoxy resins with active hydrogen of the phosphanes, red phosphorus, etc., but are not limited thereto. Also, these may be used alone or in combination. Of the above-listed substances, phosphates, phosphanes, or phosphorus-containing epoxy compounds are preferred, with 1,3-phenylenebis(dixylilenyl phosphate), 1,4-phenylenebis(dixylilenyl phosphate), 4,4'-biphenyl(dixylilenyl phosphate) or phosphorus-containing epoxy compounds being particularly preferred.

[0063] The content of the flame retardant is preferably in the range of 0.1 to 0.6 parts by mass in 100 parts by mass of the curable resin composition. If the content is less than 0.1 part by mass, the flame retardancy may be insufficient, and if the content is more than 0.6 part by mass, the moisture absorption and dielectric properties of the cured product may be adversely affected.

[0064] [Light stabilizer] The curable resin composition of the present embodiment may contain a light stabilizer. As the light stabilizer, a hindered amine light stabilizer, particularly HALS, etc., is preferable. Examples of HALS include the reaction product of dibutylamine·1,3,5-triazine·N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine and N-(2,2,6,6-tetramethyl-4-piperidyl)butylamine, the reaction product of dimethyl succinate-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, poly[{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidyl)imino}hexamethylene{(2,2,6,6-tetramethyl-4-piperidyl)imino}], bis(1,2 ,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl] butyl malonate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, 2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-n-butyl malonate bis(1,2,2,6,6-pentamethyl-4-piperidyl) and the like, but are not limited thereto. These may be used alone or in combination.

[0065] The content of the light stabilizer is preferably in the range of 0.001 to 0.1 parts by mass in 100 parts by mass of the curable resin composition. If the content is less than 0.001 parts by mass, the light stabilizing effect may be insufficient, and if the content is more than 0.1 parts by mass, the moisture absorption and dielectric properties of the cured product may be adversely affected.

[0066] [Binder resin] The curable resin composition of the present embodiment may use a binder resin. Examples of the binder resin include, but are not limited to, butyral resins, acetal resins, acrylic resins, epoxy-nylon resins, NBR-phenol resins, epoxy-NBR resins, and silicone resins. These may be used alone or in combination.

[0067] The amount of the binder resin is preferably within a range that does not impair the flame retardancy and heat resistance of the cured product, and is preferably 0.05 to 50 parts by mass, and more preferably 0.05 to 20 parts by mass, per 100 parts by mass of the curable resin composition, as needed.

[0068] [Additives] The curable resin composition of the present embodiment may contain additives, such as modified acrylonitrile copolymers, polyethylene, fluororesins, silicone gels, silicone oils, surface treatment agents for fillers such as silane coupling agents, release agents, and colorants such as carbon black, phthalocyanine blue, and phthalocyanine green.

[0069] The amount of the additives to be added is preferably 1,000 parts by mass or less, and more preferably 700 parts by mass or less, based on 100 parts by mass of the curable resin composition.

[0070] The curable resin composition of the present embodiment may further contain epoxy resins, active ester compounds, phenolic resins, polyphenylene ether compounds, amine resins, compounds having ethylenically unsaturated bonds, isocyanate resins, polyamide resins, maleimide compounds, cyanate ester resins, polyimide resins, polybutadiene and modified products thereof, polystyrene and modified products thereof, polyethylene and modified products thereof, etc., which may be used alone or in combination. Among these compounds, it is preferable to contain maleimide compounds, polyphenylene ether compounds, compounds having ethylenically unsaturated bonds, cyanate ester resins, polybutadiene and modified products thereof, polystyrene and modified products thereof, and polyethylene and modified products thereof, in view of the balance of heat resistance, adhesion, and dielectric properties. By containing these compounds, the brittleness of the cured product and adhesion to metals can be improved, and cracks in the package during solder reflow and during reliability tests such as thermal cycles can be suppressed. The total amount of the above compounds used is preferably 10 times by mass or less, more preferably 5 times by mass or less, and particularly preferably 3 times by mass or less, relative to the mixture of the present embodiment, unless otherwise specified. The lower limit is preferably 0.1 times by mass or more, more preferably 0.25 times by mass or more, and even more preferably 0.5 times by mass or more. By being within the above range, the effect of the low dielectric characteristic (low dielectric tangent) of the compound represented by the formula (1) can be utilized while the effect of each compound added can be added. As these components, the following examples can be used.

[0071] [Epoxy resin] Preferred examples of the epoxy resin are shown below, but the epoxy resin is not limited thereto. The epoxy resin may be liquid or solid, and may be used alone or in combination.

[0072] Examples of liquid epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, phenol novolac type epoxy resins, alicyclic epoxy resins having an ester skeleton, cyclohexane type epoxy resins, cyclohexane dimethanol type epoxy resins, glycidyl amine type epoxy resins, and epoxy resins having a butadiene structure. Specific examples include "RE310S", "RE410S" (all manufactured by Nippon Kayaku Co., Ltd., bisphenol A type epoxy resin), "RE303S", "RE304S", "RE403S", "RE404S" (all manufactured by Nippon Kayaku Co., Ltd., bisphenol F type epoxy resin), "HP4032", "HP4032D", "HP4032SS" (all manufactured by DIC Corporation, naphthalene type epoxy resin), "828US", "jER828EL", "825", "828EL" (all manufactured by Mitsubishi Chemical Corporation, bisphenol A type epoxy resin), "jE807", "1750" (all manufactured by Mitsubishi Chemical Corporation, bisphenol F type epoxy resin), "jER152" (manufactured by Mitsubishi Chemical Corporation, phenol Novolac type epoxy resin), "630", "630LSD" (all manufactured by Mitsubishi Chemical Corporation, glycidylamine type epoxy resin), "ZX1059" (manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin), "EX-721" (manufactured by Nagase ChemteX Corporation, glycidyl ester type epoxy resin), "Celloxide 2021P" (manufactured by Daicel Corporation, alicyclic epoxy resin having an ester skeleton), "PB-3600" (manufactured by Daicel Corporation, epoxy resin having a butadiene structure), "ZX1658", "ZX1658GS" (all manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., liquid 1,4-glycidylcyclohexane type epoxy resin), etc. may be mentioned. These may be used alone or in combination of two or more.

[0073] Preferred examples of solid epoxy resins include bixylenol type epoxy resins, naphthalene type epoxy resins, naphthalene type tetrafunctional epoxy resins, cresol novolac type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol type epoxy resins, naphthol type epoxy resins, biphenyl type epoxy resins, naphthylene ether type epoxy resins, anthracene type epoxy resins, bisphenol A type epoxy resins, bisphenol AF type epoxy resins, and tetraphenylethane type epoxy resins, and examples of such solid epoxy resins include naphthol type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, and biphenyl type epoxy resins.Specific examples include "HP4032H" (manufactured by DIC Corporation, naphthalene type epoxy resin), "HP-4700", and "HP-4710" (all manufactured by DIC Corporation, naphthalene type tetrafunctional epoxy resin), "N-690" (manufactured by DIC Corporation, cresol novolac type epoxy resin), "N-695" (manufactured by DIC Corporation, cresol novolac type epoxy resin), "HP-7200" (manufactured by DIC Corporation, dicyclopentadiene type epoxy resin), "HP-7200", "HP-7200HH", and "HP-7200H" (all manufactured by DIC Corporation, dicyclopentadiene type epoxy resin). epoxy resin), "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP-6000" (all manufactured by DIC, naphthylene ether type epoxy resin), "EPPN-502H" (manufactured by Nippon Kayaku Co., Ltd., trisphenol type epoxy resin), "NC-7000L", "NC-7300" (all manufactured by Nippon Kayaku Co., Ltd., naphthol-cresol novolac type epoxy resin), "NC-3000H", "NC-3000", "NC-3000L", "NC-3100" (all manufactured by Nippon Kayaku Co., Ltd., biphenyl ether type epoxy resin). arylalkyl type epoxy resin), "XD-1000-2L", "XD-1000-L", "XD-1000-H", "XD-1000-H" (all manufactured by Nippon Kayaku Co., Ltd., dicyclopentadiene type epoxy resin), "ESN475V" (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., naphthol type epoxy resin), "ESN485" (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., naphthol novolac type epoxy resin), "YX-4000H", "YX-4000", "YL6121" (all manufactured by Mitsubishi Chemical Corporation, biphenyl type epoxy resin), "YX-4000HK" (manufactured by Mitsubishi Chemical Corporation, bixyl Examples of epoxy resins that can be used include "YX-8800" (manufactured by Mitsubishi Chemical Corporation, anthracene type epoxy resin), "PG-100", "CG-500" (manufactured by Osaka Gas Chemical Co., Ltd., fluorene type epoxy resin), "YL-7760" (manufactured by Mitsubishi Chemical Corporation, bisphenol AF type epoxy resin), "YL-7800" (manufactured by Mitsubishi Chemical Corporation, fluorene type epoxy resin), "jER1010" (manufactured by Mitsubishi Chemical Corporation, solid bisphenol A type epoxy resin), and "jER1031S" (manufactured by Mitsubishi Chemical Corporation, tetraphenylethane type epoxy resin).These may be used alone or in combination of two or more.

[0074] [Active ester compounds] The active ester compound refers to a compound that contains at least one ester bond in the structure and has an aliphatic chain, an aliphatic ring, or an aromatic ring bonded to both sides of the ester bond. Examples of the active ester compound include compounds having two or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, and are obtained by a condensation reaction between at least one compound of a carboxylic acid compound, an acid chloride, or a thiocarboxylic acid compound and at least one compound of a hydroxy compound or a thiol compound. In particular, from the viewpoint of improving heat resistance, it is preferable to obtain it from a carboxylic acid compound or an acid chloride and a hydroxy compound, and the hydroxy compound is preferably a phenol compound or a naphthol compound. The active ester compound may be used alone or in combination of two or more types.

[0075] 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.

[0076] Examples of the acid chloride include acetyl chloride, acrylic acid chloride, methacrylic acid chloride, malonyl chloride, succinic acid dichloride, diglycolyl chloride, glutaric acid dichloride, suberic acid dichloride, sebacic acid dichloride, adipic acid dichloride, dodecandioyl dichloride, azelaic acid chloride, 2,5-furandicarbonyl dichloride, phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, trimesic acid chloride, bis(4-chlorocarbonylphenyl) ether, 4,4'-diphenyldicarbonyl chloride, and 4,4'-azodibenzoyl dichloride.

[0077] Examples of the phenol compounds and naphthol compounds include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene-type diphenol compounds, phenol novolac, and phenol resins described below. Here, the term "dicyclopentadiene-type diphenol compounds" refers to diphenol compounds obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.

[0078] Preferred specific examples of the active ester compound include an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, an active ester compound containing a benzoylated product of phenol novolac, a compound described in Example 2 of International Publication No. 2020 / 095829, and a compound disclosed in International Publication No. 2020 / 059625. Among them, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene-type diphenol structure are more preferred. The dicyclopentadiene-type diphenol structure refers to a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

[0079] Commercially available active ester compounds include, for example, "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "HPC-8000H-65TM", "EXB-8000L-65TM", and "EXB-8150-65T" (manufactured by DIC Corporation) as active ester compounds containing a dicyclopentadiene-type diphenol structure, "EXB9416-70BK" (manufactured by DIC Corporation) as an active ester compound containing a naphthalene structure, and "phenolnoxamine" (manufactured by DIC Corporation). Examples of active ester compounds containing acetylated phenol novolac include "DC808" (manufactured by Mitsubishi Chemical Corporation); active ester compounds containing benzoylated phenol novolac include "YLH1026," "YLH1030," and "YLH1048" (manufactured by Mitsubishi Chemical Corporation); "DC808" (manufactured by Mitsubishi Chemical Corporation) is an active ester curing agent which is an acetylated phenol novolac; and "EXB-9050L-62M" (manufactured by DIC Corporation) is an active ester curing agent containing a phosphorus atom.

[0080] Regarding the compounding ratio of the active ester compound and the epoxy resin, the ratio (α / β) of the active ester equivalent (α) to the epoxy equivalent (β) is preferably 0.5 to 1.5, more preferably 0.8 to 1.2, and even more preferably 0.90 to 1.10. If it is out of the above range, there is a risk that excess epoxy groups or active ester groups will remain in the system, and the characteristics may deteriorate in a high-temperature storage test (e.g., 150°C, 1000 hours) or a long-term reliability test under high-temperature and high-humidity conditions (e.g., temperature: 85°C, humidity: 85%).

[0081] [Phenol resin] A phenolic resin is a compound having two or more phenolic hydroxyl groups in a molecule. Examples of phenolic resins include, but are not limited to, reaction products of phenols and aldehydes, reaction products of phenols and diene compounds, reaction products of phenols and ketones, reaction products of phenols and substituted biphenyls, reaction products of phenols and substituted phenyls, and reaction products of bisphenols and aldehydes. These may be used alone or in combination. Specific examples of the above-mentioned raw materials are given below, but the raw materials are not limited thereto. <Phenols> Phenol, alkyl-substituted phenol, aromatic-substituted phenol, hydroquinone, resorcin, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc. <Aldehydes> Formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, furfural, and the like. <Diene compounds> Dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, and the like. <Ketones> Acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, fluorenone, etc. <Substituted biphenyls> 4,4'-bis(chloromethyl)-1,1'-biphenyl, 4,4'-bis(methoxymethyl)-1,1'-biphenyl, 4,4'-bis(hydroxymethyl)-1,1'-biphenyl and the like. <Substituted phenyls> 1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene, 1,4-bis(hydroxymethyl)benzene and the like.

[0082] [Polyphenylene ether compounds] From the viewpoint of heat resistance and electrical properties, the polyphenylene ether compound is preferably a polyphenylene ether compound having an ethylenically unsaturated bond, and more preferably a polyphenylene ether compound having an acrylic group, a methacrylic group, or a styrene structure. Commercially available products include SA-9000 (manufactured by SABIC, a polyphenylene ether compound having a methacrylic group) and OPE-2St 1200 (manufactured by Mitsubishi Gas Chemical, a polyphenylene ether compound having a styrene structure). The number average molecular weight (Mn) of the polyphenylene ether compound is preferably 500 to 5000, more preferably 2000 to 5000, and more preferably 2000 to 4000. If the molecular weight is less than 500, the heat resistance of the cured product tends to be insufficient. If the molecular weight is more than 5000, the melt viscosity increases and sufficient fluidity cannot be obtained, which tends to lead to molding defects. In addition, the reactivity decreases, the curing reaction takes a long time, and the amount of unreacted material that is not incorporated into the curing system increases, which decreases the glass transition temperature of the cured product and tends to decrease the heat resistance of the cured product. If the number average molecular weight of the polyphenylene ether compound is 500 to 5000, it is possible to exhibit excellent heat resistance, moldability, etc. while maintaining excellent dielectric properties. The number average molecular weight here can be specifically measured using gel permeation chromatography, etc.

[0083] The polyphenylene ether compound may be one obtained by a polymerization reaction, or one obtained by a redistribution reaction of a high molecular weight polyphenylene ether compound having a number average molecular weight of about 10,000 to 30,000. In addition, these may be used as raw materials and reacted with a compound having an ethylenically unsaturated bond, such as methacryl chloride, acrylic chloride, or chloromethylstyrene, to impart radical polymerizability. The polyphenylene ether compound obtained by the redistribution reaction is obtained, for example, by heating a high molecular weight polyphenylene ether compound in a solvent such as toluene in the presence of a phenolic compound and a radical initiator to cause a redistribution reaction. The polyphenylene ether compound obtained by the redistribution reaction in this way has hydroxyl groups derived from a phenolic compound that contributes to curing at both ends of the molecular chain, and is therefore preferable in that it can maintain even higher heat resistance, and that functional groups can be introduced at both ends of the molecular chain even after modification with a compound having an ethylenically unsaturated bond. In addition, the polyphenylene ether compound obtained by the polymerization reaction is preferable in that it exhibits excellent fluidity.

[0084] The molecular weight of the polyphenylene ether compound can be adjusted by adjusting the polymerization conditions, etc., in the case of a polyphenylene ether compound obtained by a polymerization reaction. In addition, in the case of a polyphenylene ether compound obtained by a redistribution reaction, the molecular weight of the obtained polyphenylene ether compound can be adjusted by adjusting the conditions of the redistribution reaction, etc. More specifically, it is possible to adjust the amount of the phenolic compound used in the redistribution reaction. That is, the greater the amount of the phenolic compound, the lower the molecular weight of the obtained polyphenylene ether compound. In this case, poly(2,6-dimethyl-1,4-phenylene ether) and the like can be used as the high molecular weight polyphenylene ether compound that undergoes the redistribution reaction. In addition, the phenolic compound used in the redistribution reaction is not particularly limited, but for example, a multifunctional phenolic compound having two or more phenolic hydroxyl groups in the molecule, such as bisphenol A, phenol novolac, cresol novolac, etc., is preferably used. These may be used alone or in combination of two or more.

[0085] [Amine resin] Amine resins are compounds having two or more amino groups in the molecule. Examples of amine resins include diaminodiphenylmethane, diaminodiphenylsulfone, isophoronediamine, naphthalenediamine, aniline novolac (a reaction product of aniline and formalin), N-methylaniline novolac (a reaction product of N-methylaniline and formalin), orthoethylaniline novolac (a reaction product of orthoethylaniline and formalin), a reaction product of 2-methylaniline and formalin, a reaction product of 2,6-diisopropylaniline and formalin, a reaction product of 2,6-diethylaniline and formalin, a reaction product of 2-ethyl-6-ethylaniline and formalin, a reaction product of 2,6-dimethylaniline and formalin, and a reaction product obtained by reacting aniline and xylylene chloride. Examples of the aniline resin include, but are not limited to, the aniline resin disclosed in Japanese Patent No. 6429862, a reaction product of aniline and a substituted biphenyl (4,4'-bis(chloromethyl)-1,1'-biphenyl, 4,4'-bis(methoxymethyl)-1,1'-biphenyl, etc.), a reaction product of aniline and a substituted phenyl (1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene, 1,4-bis(hydroxymethyl)benzene, etc.), 4,4'-(1,3-phenylenediisopropylidene)bisaniline, 4,4'-(1,4-phenylenediisopropylidene)bisaniline, a reaction product of aniline and diisopropenylbenzene, dimer diamine, etc. Furthermore, these may be used alone or in combination.

[0086] [Compounds containing ethylenically unsaturated bonds] The compound containing an ethylenically unsaturated bond is a compound having an ethylenically unsaturated bond which can be polymerized by heat or light. Examples of compounds containing ethylenically unsaturated bonds include, but are not limited to, reaction products of the above-mentioned phenol resins and halogen-based compounds containing ethylenically unsaturated bonds (chloromethylstyrene, allyl chloride, methallyl chloride, acrylic acid chloride, methacrylic acid chloride, etc.), reaction products of phenols containing ethylenically unsaturated bonds (2-allylphenol, 2-propenylphenol, 4-allylphenol, 4-propenylphenol, eugenol, isoeugenol, etc.) and halogen-based compounds (1,4-bis(chloromethyl)benzene, 4,4'-bis(chloromethyl)biphenyl, 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-dibromobenzophenone, cyanuric chloride, etc.), reaction products of epoxy resins or alcohols and (meth)acrylic acids (acrylic acid, methacrylic acid, etc.), and acid-modified products thereof. In addition, these may be used alone or in combination.

[0087] [Isocyanate resin] An isocyanate resin is a compound that has two or more isocyanate groups in its molecule. Examples of the isocyanate resin include aromatic diisocyanates such as p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and naphthalene diisocyanate; aliphatic or alicyclic diisocyanates such as isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, norbornene diisocyanate, and lysine diisocyanate; polyisocyanates such as one or more biuret forms of isocyanate monomers or isocyanate forms obtained by trimerizing the above diisocyanate compounds; and polyisocyanates obtained by a urethanization reaction between the above isocyanate compounds and polyol compounds, but are not limited thereto. These may be used alone or in combination.

[0088] [Polyamide resin] Examples of polyamide resins include reaction products of one or more of diamines, diisocyanates, and oxazolines with dicarboxylic acids, reaction products of diamines with acid chlorides, and ring-opening polymers of lactam compounds. These may be used alone or in combination. Specific examples of the above-mentioned raw materials are given below, but the raw materials are not limited thereto. <Diamine> Ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decanediamine, undecanediamine, dodecanediamine, tridecanediamine, tetradecanediamine, pentadecanediamine, hexadecanediamine, heptadecanediamine, octadecanediamine, nonadecanediamine, eicosanediamine, 2-methyl-1,5-diaminopentane, 2-methyl 1,8-diaminooctane, dimer diamine, cyclohexane diamine, bis-(4-aminocyclohexyl)methane, bis(3-methyl-4-aminocyclohexyl)methane, xylylene diamine, norbornane diamine, isophorone diamine, bisaminomethyltricyclodecane, phenylenediamine, diethyltoluenediamine, naphthalenediamine, diaminodiphenylmethane, bis(4-amino-3,5-dimethylphenyl)methane, bis(4-amino-3,5-diethylphenyl)methane , 4,4'-methylenebis-o-toluidine, 4,4'-methylenebis-o-ethylaniline, 4,4'-methylenebis-2-ethyl-6-methylaniline, 4,4'-methylenebis-2,6-diisopropylaniline, 4,4-ethylenedianiline, diaminodiphenyl sulfone, diaminodiphenyl ether, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 4,4-bis(4-aminophenoxy)biphenyl, 2,2-bis[4-(4-amino 4,4'-(1,3-phenylenediisopropylidene)bisaniline, 4,4'-(1,4-phenylenediisopropylidene)bisaniline, 9,9-bis(4-aminophenyl)fluorene, 2,7-diaminofluorene, aminobenzylamine, diaminobenzophenone, and the like. <Diisocyanate> Benzene diisocyanate, toluene diisocyanate, 1,3-bis(isocyanatomethyl)benzene, 1,3-bis(isocyanatomethyl)cyclohexane, bis(4-isocyanatophenyl)methane, isophorone diisocyanate, 1,3-bis(2-isocyanato-2-propyl)benzene, 2,2-bis(4-isocyanatophenyl)hexafluoropropane, dicyclohexylmethane-4,4'-diisocyanate, and the like. <Dicarboxylic acid> Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, 5-hydroxyisophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, cyclohexanedicarboxylic acid, biphenyldicarboxylic acid, naphthalenedicarboxylic acid, benzophenonedicarboxylic acid, furandicarboxylic acid, 4,4'-dicarboxydiphenyl ether, 4,4'-dicarboxydiphenyl sulfide, etc. <Acid chloride> Acetyl chloride, acrylic acid chloride, methacrylic acid chloride, malonyl chloride, succinic acid dichloride, diglycolyl chloride, glutaric acid dichloride, suberic acid dichloride, sebacic acid dichloride, adipic acid dichloride, dodecandioyl dichloride, azelaic acid chloride, 2,5-furandicarbonyl dichloride, phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, trimesic acid chloride, bis(4-chlorocarbonylphenyl) ether, 4,4'-diphenyldicarbonyl chloride, 4,4'-azodibenzoyl dichloride, and the like. <Lactam> ε-caprolactam, ω-undecanelactam, ω-laurolactam, and the like.

[0089] [Polyimide resin] Examples of polyimide resins include, but are not limited to, reaction products of the diamines and the tetracarboxylic dianhydrides shown below. These may be used alone or in combination. <Tetracarboxylic acid dianhydride> 4,4'-(Hexafluoroisopropylidene)diphthalic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-cyclohexene-1,2 dicarboxylic anhydride, pyromellitic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 2,2',3, 3'-Biphenyltetracarboxylic dianhydride, methylene-4,4'-diphthalic dianhydride, 1,1-ethylidene-4,4'-diphthalic dianhydride, 2,2'-propylidene-4,4'-diphthalic dianhydride, 1,2-ethylene-4,4'-diphthalic dianhydride, 1,3-trimethylene-4,4'-diphthalic dianhydride, 1,4-tetramethylene-4,4'-diphthalic dianhydride, 1,5-pentamethylene-4,4'-diphthalic dianhydride, 4,4'-oxydiphthalic dianhydride, thio-4,4'-diphthalic dianhydride, sulfonyl-4,4'-diphthalic acid Dianhydride, 1,3-bis(3,4-dicarboxyphenyl)benzene dianhydride, 1,3-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 1,3-bis[2-(3,4-dicarboxyphenyl)-2-propyl]benzene dianhydride, 1,4-bis[2-(3,4-dicarboxyphenyl)-2-propyl]benzene dianhydride, bis[3-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride, bis[4-(3,4-dicarboxyphenoxy)phenyl]methane 2,2-bis[3-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, bis(3,4-dicarboxyphenoxy)dimethylsilane dianhydride, 1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldisiloxane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3,4,9,10-Perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, ethylenetetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride tetracarboxylic dianhydride, 3,3',4,4'-bicyclohexyltetracarboxylic dianhydride, carbonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic) dianhydride, methylene-4,4'-bis(cyclohexane-1,2-dicarboxylic) dianhydride, 1,2-ethylene-4,4'-bis(cyclohexane-1,2-dicarboxylic) dianhydride, 1,1-ethylidene-4,4'-bis(cyclohexane-1,2-dicarboxylic) dianhydride, 2,2-propylidene -4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, oxy-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, thio-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, sulfonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, rel-[1S,5R,6R]-3-oxabicyclo[3,2 ,1]Octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, ethylene glycol-bis-(3,4-dicarboxylic anhydride phenyl) ether, 4,4'-biphenyl bis(trimellitic acid monoester acid anhydride), 9,9'-bis(3,4-dicarboxyphenyl)fluorene dianhydride, etc.,

[0090] [Maleimide compounds] The curable resin composition of the present embodiment may contain a maleimide compound, and examples of such compounds include 4,4'-diphenylmethane bismaleimide, polyphenylmethane maleimide, m-phenylene bismaleimide, 2,2'-bis[4-(4-maleimidophenoxy)phenyl]propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 4,4'-diphenylether bismaleimide, 4,4'-diphenylsulfone bismaleimide, 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene), and Xylox-type maleimide compounds (anilix). Maleimide, manufactured by Mitsui Chemicals Fine Co., Ltd.), biphenylaralkyl-type maleimide compound (solidified by distilling off the solvent under reduced pressure from a resin solution containing the maleimide compound (M2) described in Example 4 of JP 2009-001783 A), bisaminocumylbenzene-type maleimide (maleimide compound described in WO 2020 / 054601 A), maleimide compounds having an indane structure described in Japanese Patent No. 6629692 or WO 2020 / 217679, MATERIAL STAGE Vol. 18, No. 12 2019 ``~Continued Epoxy Resin CAS Number Story~ Hardener CAS Number Memorandum No. 31 Bismaleimide (1)'' and MATERIAL STAGE Vol. 19, No. 2 2019 ``~Continued Epoxy Resin CAS Number Story~ Hardener CAS Number Memorandum No. 32 Bismaleimide (2) and the like can be used, but are not limited thereto. These can be used alone or in combination.

[0091] [Cyanate ester resin] Cyanate ester resins are cyanate ester compounds obtained by reacting phenolic resins with cyanogen halides, and specific examples include dicyanatobenzene, tricyanatobenzene, dicyanatonaphthalene, dicyanatobiphenyl, 2,2'-bis(4-cyanatophenyl)propane, bis(4-cyanatophenyl)methane, bis(3,5-dimethyl-4-cyanatophenyl)methane, 2,2'-bis(3,5-dimethyl-4-cyanatophenyl)propane, 2,2'-bis(4-cyanatophenyl)ethane, 2,2'-bis(4-cyanatophenyl)hexafluoropropane, bis(4-cyanatophenyl)sulfone, bis(4-cyanatophenyl)thioether, phenol novolac cyanate, and phenol-dicyclopentadiene co-condensates in which the hydroxyl groups have been converted to cyanate groups, but are not limited thereto. These may be used alone or in combination. Furthermore, the cyanate ester compound, the synthesis method of which is described in JP-A-2005-264154, is particularly preferred as the cyanate ester compound because it has low moisture absorption, excellent flame retardancy, and excellent dielectric properties. The cyanate ester resins can optionally contain a catalyst, such as zinc naphthenate, cobalt naphthenate, copper naphthenate, lead naphthenate, zinc octoate, tin octoate, lead acetylacetonate, or dibutyltin maleate, to trimerize the cyanate groups to form sym-triazine rings.

[0092] The catalyst is preferably used in an amount of 0.0001 to 0.10 parts by mass, and more preferably 0.00015 to 0.0015 parts by mass, based on 100 parts by mass of the cyanate ester resin and the curable resin composition.

[0093] [Polybutadiene and its modified products] The polybutadiene and its modified products are polybutadiene or compounds having a structure derived from polybutadiene in the molecule. The unsaturated bonds in the polybutadiene-derived structure may be partially or entirely converted to single bonds by hydrogenation. Examples of polybutadiene and modified products thereof include, but are not limited to, polybutadiene, hydroxyl-terminated polybutadiene, (meth)acrylate-terminated polybutadiene, carboxylic acid-terminated polybutadiene, amine-terminated polybutadiene, styrene-butadiene rubber, and the like. These may be used alone or in combination. Among these, polybutadiene or styrene-butadiene rubber is preferred from the viewpoint of dielectric properties. Examples of styrene-butadiene rubber (SBR) include RICON-100, RICON-181, RICON-184 (all manufactured by Cray Valley), 1,2-SBS (manufactured by Nippon Soda Co., Ltd.), and examples of polybutadiene include B-1000, B-2000, B-3000 (all manufactured by Nippon Soda Co., Ltd.). The molecular weight of polybutadiene and styrene-butadiene rubber is preferably a weight average molecular weight of 500 to 10,000, more preferably 750 to 7,500, and even more preferably 1,000 to 5,000. Below the lower limit of the above range, the amount of volatilization is large, making it difficult to adjust the solid content when preparing the prepreg, and above the upper limit of the above range, the compatibility with other curable resins is deteriorated. In general, in the case of compounds containing heteroatoms such as oxygen and nitrogen, such as bismaleimide and polymaleimide, it is difficult to ensure compatibility with low-polarity compounds such as compounds mainly composed of hydrocarbons or compounds composed only of hydrocarbons due to their polarity. On the other hand, the compound of the present embodiment is excellent in compatibility with materials exhibiting low polarity and low dielectric tangent and compounds composed only of hydrocarbons, due to the fact that the compound itself does not have a skeleton design in which heteroatoms such as oxygen and nitrogen are actively introduced.

[0094] [Polystyrene and its modified products] Polystyrene and modified products thereof are polystyrene or compounds having a structure derived from polystyrene in the molecule. Examples of polystyrene and modified products thereof include polystyrene, styrene-2-isopropenyl-2-oxazoline copolymers (Epocross RPS-1005, RP-61, both manufactured by Nippon Shokubai Co., Ltd.), SEP (styrene-ethylene-propylene copolymer: Septon 1020, manufactured by Kuraray Co., Ltd.), SEPS (styrene-ethylene-propylene-styrene copolymer: Septon 2002, Septon 2004F, Septon 2005, Septon 2006, Septon 2063, Septon 2104, all manufactured by Kuraray Co., Ltd.), SEEPS (styrene-ethylene / ethylene-propylene-styrene block copolymer: Septon 4003, Septon 4044, Septon 4055, Septon 4077, Septon 4099, all manufactured by Kuraray Co., Ltd.), SEBS (styrene-ethylene-butylene-styrene block copolymer: Septon 4003, Septon 4044, Septon 4055, Septon 4077, Septon 4099, all manufactured by Kuraray Co., Ltd.), Examples of the block copolymer include Septon 8004, Septon 8006, and Septon 8007L (all manufactured by Kuraray Co., Ltd.), SEEPS-OH (a compound having a hydroxyl group at the end of a styrene-ethylene / ethylene-propylene-styrene block copolymer: Septon HG252 manufactured by Kuraray Co., Ltd.), SIS (styrene-isoprene-styrene block copolymer: Septon 5125 and Septon 5127 manufactured by Kuraray Co., Ltd.), hydrogenated SIS (hydrogenated styrene-isoprene-styrene block copolymer: Hybler 7125F and Hybler 7311F manufactured by Kuraray Co., Ltd.), SIBS (styrene-isobutylene-styrene block copolymer: SIBSTAR073T, SIBSTAR102T, and SIBSTAR103T (all manufactured by Kaneka Co., Ltd.), and Septon V9827 (manufactured by Kuraray Co., Ltd.)), but are not limited thereto. These may be used alone or in combination. Polystyrene and its modified products are preferably those that do not have unsaturated bonds, since they have higher heat resistance and are less susceptible to oxidation deterioration. The weight-average molecular weight of polystyrene and its modified products is not particularly limited as long as it is 10,000 or more, but if it is too large, the compatibility with not only polyphenylene ether compounds, but also low molecular weight components with weight-average molecular weights of about 50 to 1,000 and oligomer components with weight-average molecular weights of about 1,000 to 5,000 deteriorates, making it difficult to ensure mixing and solvent stability, so it is preferably about 10,000 to 300,000.

[0095] [Polyethylene and its modified products] Polyethylene and its modified products are compounds having polyethylene or a structure derived from polyethylene in the molecule. Examples of polyethylene and its modified products include ethylene-propylene copolymers, ethylene-styrene copolymers, ethylene-propylene-ethylidenenorbornene copolymers (EBT: K-8370EM, K-9330M, etc., manufactured by Mitsui Chemicals), ethylene-propylene-vinylnorbornene copolymers (VNB-EPT: PX-006M, PX-008M, PX-009M, etc., manufactured by Mitsui Chemicals), ethylene-vinyl alcohol copolymers, ethylene-vinyl acetate copolymers, etc., but are not limited thereto. From the viewpoint of improving heat resistance, it is preferable to use ethylene-propylene-ethylidenenorbornene copolymers and ethylene-propylene-vinylnorbornene copolymers containing a crosslinkable structure. In addition, these may be used alone or in combination. There are no particular limitations on the weight-average molecular weight of polyethylene and modified products thereof as long as it is 10,000 or more. However, if it is too large, compatibility with not only polyphenylene ether compounds but also low molecular weight components having a weight-average molecular weight of about 50 to 1,000 and oligomer components having a weight-average molecular weight of about 1,000 to 5,000 deteriorates, making it difficult to ensure mixing and solvent stability. Therefore, it is preferably about 10,000 to 300,000.

[0096] The curable resin composition of the present embodiment is obtained by preparing the above-mentioned components in a predetermined ratio, pre-curing at 130 to 180° C. for 30 to 500 seconds, and further post-curing at 150 to 200° C. for 2 to 15 hours, whereby a sufficient curing reaction proceeds to obtain a cured product of the present embodiment. Alternatively, the components of the curable resin composition may be uniformly dispersed or dissolved in a solvent or the like, and cured after removing the solvent.

[0097] The method for preparing the curable resin composition of the present embodiment is not particularly limited, but each component may be mixed uniformly or may be prepolymerized. For example, a mixture containing the compound of the present embodiment is heated in the presence or absence of a curing accelerator or a polymerization initiator, and in the presence or absence of a solvent to form a prepolymer. Similarly, an amine compound, a compound having an ethylenically unsaturated bond, a maleimide compound, a cyanate ester compound, polybutadiene and its modified products, polystyrene and its modified products, inorganic fillers, and other additives may be added to form a prepolymer. The mixing or prepolymerization of each component is carried out using, for example, an extruder, a kneader, a roll, or the like in the absence of a solvent, and a reaction kettle with a stirrer in the presence of a solvent.

[0098] As a method of uniformly mixing, the mixture is kneaded at a temperature in the range of 50 to 100°C using a device such as a kneader, roll, or planetary mixer to obtain a uniform resin composition. The obtained resin composition is crushed and then molded into a cylindrical tablet shape using a molding machine such as a tablet machine, or into a granular powder or powder molded body, or these compositions can be melted on a surface support and molded into a sheet with a thickness of 0.05 mm to 10 mm to obtain a molded curable resin composition. The obtained molded body is a non-sticky molded body at 0 to 20°C, and even if stored at -25 to 0°C for one week or more, the flowability and curability are hardly reduced. The obtained molded article can be molded into a cured product using a transfer molding machine or a compression molding machine.

[0099] The curable resin composition of the present embodiment can be made into a varnish-like composition (hereinafter, simply referred to as varnish) by adding an organic solvent. The curable resin composition of the present embodiment can be dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, or N-methylpyrrolidone as necessary to obtain a varnish, which can be impregnated into a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, or paper, and dried by heating to obtain a prepreg. The prepreg can be hot-press molded to obtain a cured product of the curable resin composition of the present embodiment. The solvent used in this case is in an amount of 10 to 70% by weight, preferably 15 to 70% by weight, in the mixture of the curable resin composition of the present embodiment and the solvent. In addition, if the composition is in a liquid state, a cured product of the curable resin containing carbon fiber can be obtained as it is, for example, by the RTM method.

[0100] The curable composition of the present embodiment can also be used as a modifier for a film-type composition. Specifically, it can be used to improve flexibility in the B-stage. Such a film-type resin composition is obtained as a sheet-like adhesive by applying the curable resin composition of the present embodiment as the curable resin composition varnish onto a release film, removing the solvent under heating, and then performing B-stage formation. This sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like.

[0101] The curable resin composition of the present embodiment can be heated and melted to reduce the viscosity, and impregnated into reinforcement fibers such as glass fibers, carbon fibers, polyester fibers, polyamide fibers, and alumina fibers to obtain a prepreg. Specific examples thereof include glass fibers such as E glass cloth, D glass cloth, S glass cloth, Q glass cloth, spherical glass cloth, NE glass cloth, and T glass cloth, inorganic fibers other than glass, and organic fibers such as polyparaphenylene terephthalamide (Kevlar (registered trademark), manufactured by DuPont), wholly aromatic polyamide, polyester, polyparaphenylene benzoxazole, polyimide, and carbon fibers, but are not particularly limited thereto. The shape of the substrate is not particularly limited, but examples thereof include woven fabric, nonwoven fabric, roving, chopped strand mat, and the like. In addition, as the weaving method of the woven fabric, plain weave, saddle weave, twill weave, and the like are known, and these known weaves can be appropriately selected and used depending on the intended use and performance. In addition, woven fabrics that have been subjected to fiber opening treatment and glass woven fabrics that have been surface-treated with a silane coupling agent or the like are preferably used. The thickness of the substrate is not particularly limited, but is preferably about 0.01 to 0.4 mm. A prepreg can also be obtained by impregnating reinforcing fibers with the varnish and drying the fibers by heating.

[0102] The prepreg can also be used to manufacture a laminate. The laminate is not particularly limited as long as it has one or more prepregs, and may have any other layers. The method for manufacturing the laminate can be appropriately applied by a generally known method, and is not particularly limited. For example, a multi-stage press machine, a multi-stage vacuum press machine, a continuous molding machine, an autoclave molding machine, etc. can be used when molding a metal foil-clad laminate, and the prepregs are laminated together and heated and pressurized to obtain a laminate. At this time, the heating temperature is not particularly limited, but is preferably 65 to 300 ° C, and more preferably 120 to 270 ° C. In addition, the pressure to be applied is not particularly limited, but if the pressure is too high, it is difficult to adjust the solid content of the resin in the laminate, and the quality is not stable, and if the pressure is too low, air bubbles and adhesion between the laminates are deteriorated, so that the pressure is preferably 2.0 to 5.0 MPa, and more preferably 2.5 to 4.0 MPa. The laminate of this embodiment can be suitably used as a metal foil-clad laminate described later by providing a layer made of metal foil. The prepreg is cut into a desired shape and laminated with copper foil or the like if necessary. The laminate is then heated and cured while applying pressure thereto by press molding, autoclave molding, sheet winding molding, or the like, to obtain an electrical and electronic laminate (printed wiring board) or a carbon fiber reinforced material.

[0103] The curable resin composition of this embodiment can also be made into a resin sheet. As a method for obtaining a resin sheet from the curable resin composition of this embodiment, for example, a method of applying the curable resin composition onto a support film (support), drying it, and forming a resin composition layer on the support film can be mentioned. When the curable resin composition of this embodiment is used for a resin sheet, it is essential that the film softens under the temperature conditions (70°C to 140°C) for lamination in the vacuum lamination method, and exhibits a fluidity (resin flow) that allows resin filling in via holes or through holes present in the circuit board at the same time as laminating the circuit board, and it is preferable to mix each of the above components so as to express such characteristics. In addition, in the obtained resin sheet or circuit board (copper-clad laminate, etc.), a phenomenon that locally different characteristic values ​​are exhibited due to phase separation or the like does not occur, and a certain performance is expressed at any part, so that a uniform appearance is required.

[0104] Here, the through-holes in the circuit board have a diameter of 0.1 to 0.5 mm and a depth of 0.1 to 1.2 mm, and it is preferable that the resin be filled within this range. When laminating both sides of the circuit board, it is preferable that about half of the through-holes are filled.

[0105] A specific method for producing the resin sheet includes preparing a resin composition varnished by blending an organic solvent, applying the varnished resin composition to the surface of a support film (Y), and then drying the organic solvent by heating or blowing hot air or the like to form a resin composition layer (X).

[0106] The organic solvent used here preferably includes, for example, ketones such as acetone, methyl ethyl ketone, cyclohexanone, etc., acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, etc., carbitols such as cellosolve, butyl carbitol, etc., aromatic hydrocarbons such as toluene, xylene, etc., dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc., and it is preferable to use the organic solvent in a proportion such that the nonvolatile content is 30 to 60 mass%.

[0107] The thickness of the resin composition layer (X) formed must be equal to or greater than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is in the range of 5 to 70 μm, the thickness of the resin composition layer (X) is preferably 10 to 100 μm. The resin composition layer (X) in this embodiment may be protected with a protective film described below. By protecting the resin composition layer with a protective film, adhesion of dirt and the like to the surface of the resin composition layer and scratches can be prevented.

[0108] The support film and the protective film may be made of polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate, polycarbonate, polyimide, and even release paper and metal foils such as copper foil and aluminum foil. The support film and the protective film may be subjected to a release treatment in addition to a mud treatment and a corona treatment. The thickness of the support film is not particularly limited, but is in the range of 10 to 150 μm, and preferably 25 to 50 μm. The thickness of the protective film is preferably 1 to 40 μm.

[0109] The support film (Y) is peeled off after laminating it onto a circuit board or after forming an insulating layer by heat curing. If the support film (Y) is peeled off after the resin composition layer constituting the resin sheet is heat cured, adhesion of dust and the like during the curing process can be prevented. When peeling off after curing, the support film is previously subjected to a release treatment.

[0110] 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, the film is peeled off, and then the resin composition layer (X) is laminated on one or both sides of the circuit board so as to be in direct contact with the circuit board, for example, by a vacuum lamination method. The lamination method may be a batch method or a continuous method using a roll. If necessary, the resin sheet and the circuit board may be heated (preheated) before lamination. The lamination conditions are preferably a pressure bonding temperature (lamination temperature) of 70 to 140°C and a pressure bonding pressure of 1 to 11 kgf / cm. 2 (9.8×10 4 ~107.9×10 4 N / m 2 ), and lamination is preferably performed under reduced air pressure of 20 mmHg (26.7 hPa) or less.

[0111] The curable resin composition of the present embodiment can be used to manufacture a semiconductor device, such as a DIP (dual in-line package), a QFP (quad flat package), a BGA (ball grid array), a CSP (chip size package), a SOP (small outline package), a TSOP (thin small outline package), or a TQFP (thin quad flat package).

[0112] The curable resin composition of the present embodiment and its cured product can be used in a wide range of fields. Specifically, it can be used in various applications such as molding materials, adhesives, composite materials, and paints. The cured product of the curable resin composition described in the present embodiment exhibits excellent heat resistance and dielectric properties, and is therefore suitable for use in electrical and electronic components such as encapsulants for semiconductor elements, encapsulants for liquid crystal display elements, encapsulants for organic EL elements, laminates (printed wiring boards, BGA substrates, build-up substrates, etc.), composite materials for lightweight and high-strength structural materials such as carbon fiber reinforced plastics and glass fiber reinforced plastics, 3D printing, etc. EXAMPLES

[0113] The present invention will now be described in more detail with reference to examples. Unless otherwise specified, all parts are by weight. However, the present invention is not limited to these examples.

[0114] Various analytical methods used in the examples are described below. ·GPC (gel permeation chromatography) analysis Columns: SHODEX GPC KF-601 (2 columns), KF-602, KF-602.5, KF-603 Flow rate: 1.5ml / min. Column temperature: 40℃ Solvent used: THF (tetrahydrofuran) Detector: RI (Differential Refraction Detector)

[0115] [Synthesis Example 1] A flask equipped with a thermometer, a condenser, and a stirrer was equipped with an aspirator and a base trap. 370.1 parts of 2-bromoethylbenzene (Tokyo Chemical Industry Co., Ltd.), 175.1 parts of α,α'-dichloro-p-xylene (Tokyo Chemical Industry Co., Ltd.), and 27.3 parts of methanesulfonic acid (Tokyo Chemical Industry Co., Ltd.) were charged into the flask, and the reaction was carried out at 130°C for 6 hours while collecting the generated hydrogen chloride with a base trap. 100 parts of toluene and 600 parts of cyclohexane were added for extraction, and the organic layer was washed five 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 (3) as a liquid resin (Mn: 938, Mw: 1290). The GPC chart of the obtained compound is shown in Figure 1. The average value n of the repeating units calculated from the area % of the GPC chart was 2.2.

[0116] [ka]

[0117] [Synthesis Example 2] 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-tetramethylpiperidine-1-oxyl free radical, and 146.4 parts of 50 wt% aqueous sodium hydroxide solution were added, and the reaction was continued at 40 ° C. for 6 hours. 100 parts of water was added, the organic layer was washed, and the organic layer was returned to the reaction vessel. 735 parts of dimethyl sulfoxide and 9.8 parts of 50 wt% aqueous sodium hydroxide solution were added, and the reaction was continued again 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 wastewater became neutral. The mixture was concentrated under reduced pressure using an evaporator, and 180 parts of a compound (O-1) having two or more styrene structures in the molecule represented by the following formula (4) was obtained. The GPC chart of the obtained compound is shown in Figure 2. In addition, 1 H-NMR data (deuterated chloroform) is shown in Figure 3. 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 (the molecular weight of the resin component was Mn: 797, Mw: 1187).

[0118] [ka]

[0119] [Example 1, Reference Example 1, Comparative Examples 1 to 7] Each polymerization inhibitor and compound (O-1) obtained in Synthesis Example 2 were mixed in the amounts shown in Table 1 to prepare a toluene solution with a solid content of 60 wt%. Each solution was stored in a 5 mL glass sample bottle at 40°C for 50 days, and gelation confirmed by visual inspection was marked with an X, and no change in properties was noted with an O. The results are shown in Table 1.

[0120] [Table 1]

[0121] MHQ: Methylhydroquinone (Seiko Chemical Co., Ltd.) TBC: 4-tert-butylcatechol (TCI) HQ: Hydroquinone (TCI) Chimass® rb944FDL: Hindered amine light stabilizer (manufactured by BASF) TEMPOL Free Radical: 4-Hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical (TCI) Q-1301: Ammónium N-Nitrоsоphenylhydrоxylamine AО-60: Pentaerythritоl tetrakis [3-(3,5-di-tert-butyl-4-hydrоxyphenyl)propionate] (manufactured by ADEKA) Irganоx-1010: Pentaerythritоl tetrakis(3-(3,5-di-tert-butyl-4-hydrоxyphenyl)propionate)(manufactured by BASF) PEP-36:3,9-Bis(2,6-di-tert-butyl-4-methylphenоxy)-2,4,8,10-tetraоxa-3,9-diphosphaspirо[5.5]undecane (manufactured by ADEKA) AО-412S:2,2-Bis{[3-(dоdecylthiо)-1-оxоprоpоxy]methyl}propane-1,3-diyl bis[3-(dоdecylthiо)prоpоnate] (manufactured by ADEKA)

[0122] From the results in Table 1, it was confirmed that the curable resin composition using MHQ, which has a structure in which two phenol groups and an alkyl group are substituted on one benzene ring, and TBC, has excellent storage stability.

[0123] [Example 2, Comparative Examples 8 and 9] The compound (O-1) obtained in Synthesis Example 2 and the polymerization inhibitor were used in the amounts shown in Table 2, sandwiched between mirror-finished copper foil (T4X: manufactured by Fukuda Metal Copper Foil Co., Ltd.), vacuum-press molded, and cured at 220°C for 2 hours. At this time, a piece of cushion paper with a thickness of 250 μm, with the center cut out to 150 mm length and width, was used as a spacer. For evaluation, a test piece of the desired size was cut out using a laser cutter as necessary, and evaluation was performed.

[0124] <Dielectric constant test / dielectric loss test> The test was performed at 25°C using a 10GHz cavity resonator manufactured by AET Co., Ltd., using a cavity resonator perturbation method. The sample size was 1.7mm wide x 100mm long, and the thickness was 0.1mm. The evaluation results are shown in Table 2.

[0125] [Table 2]

[0126] The results in Table 2 confirm that MHQ has little effect on the dielectric properties. On the other hand, it was confirmed that TBC deteriorates the dielectric properties. It is believed that because MHQ has symmetrically positioned phenol groups, the dipole moment is small, which prevents deterioration of the dielectric properties.

[0127] [Examples 3 to 5, Comparative Examples 10 to 13] Differential scanning calorimetry (DSC) was carried out using the compound (O-1) obtained in Synthesis Example 2 and the polymerization inhibitor in the amounts shown in Table 3.

[0128] <Differential Scanning Calorimetry (DSC)> The test was performed using a Chip-DSC1 manufactured by LINSEIS. The measurement temperature range was 30°C-300°C, the heating rate was 20°C / min, and the gas flow rate was 150mL / min of nitrogen gas. The onset temperature (exothermic start temperature) of the exothermic peak is shown in Table 3.

[0129] [Table 3]

[0130] TBHQ: tert-butyl hydroquinone (TCI) DMHQ: 2,6-dimethylhydroquinone (TCI) O-Cresol: TCI

[0131] From the results in Table 3, it was confirmed that the curable resin composition of the present invention had a DSC heat generation onset temperature of 170° C. or higher. [Industrial Applicability]

[0132] The curable resin composition of the present invention is suitably used for electric and electronic parts such as semiconductor encapsulants, printed wiring boards, and build-up laminates.

Claims

1. A curable resin composition comprising a compound represented by the following formula (1) and a compound represented by the following formula (2): [Case 1] (In formula (1), A is a hydrocarbon group having 1 to 20 carbon atoms, and each of the multiple R's independently represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a halogenated alkyl group having 1 to 10 carbon atoms. p is an integer of 0 to 4, q is an integer of 0 to 3, and n is the average number of repetitions, and 1≦n≦20.) [Case 2] (In formula (2), R １ and R ２ each independently represents a hydrocarbon group having 1 to 20 carbon atoms, and n represents an integer of 0 to 3.

2. A curable resin composition containing a compound represented by the following formula (1-1) and a compound represented by the following formula (2): [C3] (In formula (1), each of the multiple R's independently represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a halogenated alkyl group having 1 to 10 carbon atoms; p and r each represent an integer of 0 to 4; q represents an integer of 0 to 3; n represents the average number of repetitions, and 1≦n≦20.) [C4] (In formula (2), R １ and R ２ each independently represents a hydrocarbon group having 1 to 20 carbon atoms, and n represents an integer of 0 to 3.

3. The curable resin composition according to claim 1 , further comprising a polymerization initiator.

4. The curable resin composition according to claim 1, further comprising at least one selected from the group consisting of a maleimide compound, a polyphenylene ether compound, a compound having an ethylenically unsaturated bond, a cyanate ester resin, polybutadiene and modified products thereof, polystyrene and modified products thereof, and polyethylene and modified products thereof.

5. A cured product obtained by curing the curable resin composition according to any one of claims 1 to 4.

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