Compound, curable resin composition, and hardened product thereof

Abstract

The present application provides a kind of compound with excellent low dielectric properties, hardenable resin composition and its hardening.The compound is represented by the following formula (1). (In the formula (1), X represents the hydrocarbon group of carbon number 1-20, A represents the hydrocarbon group represented by the following formula (a) or the following formula (b);In the presence of multiple A, multiple A can be the same, also can be different, and formula (a) and formula (b) can be randomly linked;M represents the integer of 0-20, k represents the integer of 1-3, the average value of m+k (m+k) ave 0 < (m+k) ave =10;n is the average value of repeat number, and 1 = n = 20;R1 represents the hydrocarbon group of carbon number 1-5;l is the integer of 0-2) (In the formula (a), formula (b), represents the bonding position on the benzene ring in formula (1) or the bonding position on the benzene ring in formula (a), formula (b);Multiple R2 respectively independently represent the hydrocarbon group of carbon number 1-5;Multiple p respectively independently are the integer of 0-4.

Description

Technical Field

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

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

[0003] In the currently rapidly developing fifth-generation communication system, "5G (5th Generation Mobile Communication Technology)," it is expected that high-capacity and high-speed communication will be further advanced. The use of higher frequencies in 5G will continue, but to achieve high-speed communication utilizing high frequencies, it is crucial to reduce transmission loss, requiring substrate materials with lower dielectric properties. Transmission loss on printed circuit boards originates from conductor loss and dielectric loss. As described in Non-Patent Document 1, since conductor loss is proportional to the square root of the relative permittivity of the dielectric and the dielectric loss tangent, it can be said that improving the dielectric loss tangent, which is more effective than the relative permittivity in reducing transmission loss, is crucial. Examples of low-dielectric materials include styrene butadiene rubber (SBR) or synthetic rubber materials such as polybutadiene, but these suffer from low reactivity or high viscosity when manufacturing prepregs. Therefore, it is desirable to develop thermosetting resins with excellent low-dielectric properties.

[0004] Against this backdrop, research has focused on polymer materials with excellent low dielectric properties. For example, Patent Document 1 proposes a composition comprising a maleimide resin and a phenolic resin containing propylene groups. However, on the other hand, since phenolic hydroxyl groups that do not participate in the curing reaction remain, the electrical properties cannot be considered sufficient.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 04-359911

[0008] Non-patent literature

[0009] Non-Patent Document 1: "Causes of Signal Loss in High-Speed ​​Signal Transmission on Printed Circuit Boards", 29th Spring Conference of the Electronic Packaging Society, Conference ID: 16P1-17, 2015 Summary of the Invention

[0010] The problem that the invention aims to solve

[0011] The present invention was made in view of this situation, and its object is to provide a compound, a curable resin composition and a cured product thereof having excellent low dielectric properties.

[0012] Technical means to solve the problem

[0013] That is, the present invention relates to the following [1] to

[10] . In addition, in the present invention, "(numerical value 1) to (numerical value 2)" means including upper and lower limits. [1]

[0015] A compound represented by the following formula (1).

[0016] [Chemistry 1]

[0017]

[0018] (In the above formula (1), X represents a hydrocarbon group with 1 to 20 carbon atoms, and A represents the hydrocarbon group represented by formula (a) or formula (b) below; in the case of multiple A's, the multiple A's can be the same or different. In addition, formula (a) and formula (b) can be randomly bonded; m represents an integer from 0 to 20, k represents an integer from 1 to 3, and the average value of m+k is (m+k). ave 0 < (m + k) ave ≦10; n is the average of the number of repetitions, and is 1≦n≦20; R1 represents a hydrocarbon group with 1 to 5 carbon atoms; l is an integer from 0 to 2)

[0019] [Chemistry 2]

[0020]

[0021] (In equations (a) and (b),) The R2 represents the bonding position on the benzene ring in formula (1) or the bonding position on the benzene ring in formula (a) or (b); multiple R2s independently represent hydrocarbon groups with 1 to 5 carbon atoms; multiple ps are independent integers from 0 to 4. [2]

[0023] According to the compound described in the preceding item [1], wherein in the formula (1), n ​​is 1.1≦n≦20. [3]

[0025] According to the compound described in the preceding item [1] or [2], wherein in the formula (1), X is any one or more of (c) to (k) described in the following formula (2).

[0026] [Chemistry 3]

[0027]

[0028] ( (Indicates the location of the bond) [4]

[0030] According to the compound described in the preceding item [3], in the formula (2), X is represented by (d) or (f). [5]

[0032] The compound according to any one of the preceding items [1] to [4] is derived from the compound represented by the following formula (3).

[0033] [Chemistry 4]

[0034]

[0035] (In the above formula (3), X represents a hydrocarbon group with 1 to 20 carbon atoms, and A represents the hydrocarbon group represented by formula (a) or formula (b) below; in the case of multiple A's, the multiple A's can be the same or different. In addition, formula (a) and formula (b) can be randomly bonded; m represents an integer from 0 to 20, k represents an integer from 1 to 3, and the average value of m+k is (m+k). ave 0 < (m + k) ave ≦10; n is the average of the number of repetitions, and is 1≦n≦20; R1 represents a hydrocarbon group with 1 to 5 carbon atoms; l is an integer from 0 to 2; Y represents a halogen atom)

[0036] [Chemistry 5]

[0037]

[0038] (In equations (a) and (b),) The R2 indicates the bonding position on the benzene ring in formula (3) or the bonding position on the benzene ring in formula (a) or formula (b); multiple R2s independently represent hydrocarbon groups with 1 to 5 carbon atoms; multiple ps are independent integers from 0 to 4. [6]

[0040] A curable resin composition comprising any one of the compounds described in any one of the preceding items [1] to [5]. [7]

[0042] The curable resin composition according to the preceding item [6] further comprises at least one selected from curing accelerators, polymerization initiators, epoxy resins, active ester compounds, phenolic resins, polyphenylene ether compounds, amine resins, compounds having vinyl unsaturated bonds, isocyanate resins, polyamide resins, maleimide compounds, cyanate resins, polyimide resins, polybutadiene and its modifications, polystyrene and its modifications, polyethylene and its modifications, and benzoxazine compounds. [8]

[0044] A hardened compound is obtained by hardening a compound according to any one of the preceding items [1] to [5]. [9]

[0046] A hardened material is obtained by hardening the hardening resin composition according to the preceding paragraph [6] or [7].

[10]

[0048] A compound is represented by the following formula (3).

[0049] [Chemistry 6]

[0050]

[0051] (In the above formula (3), X represents a hydrocarbon group with 1 to 20 carbon atoms, and A represents the hydrocarbon group represented by formula (a) or formula (b) below; in the case of multiple A's, the multiple A's can be the same or different. In addition, formula (a) and formula (b) can be randomly bonded; m represents an integer from 0 to 20, k represents an integer from 1 to 3, and the average value of m+k is (m+k). ave 0 < (m + k) ave ≦10; n is the average of the number of repetitions, and is 1≦n≦20; R1 represents a hydrocarbon group with 1 to 5 carbon atoms; l is an integer from 0 to 2; Y represents a halogen atom)

[0052] [Chemistry 7]

[0053]

[0054] (In equations (a) and (b),) The R2 indicates the bonding position on the benzene ring in formula (3) or the bonding position on the benzene ring in formula (a) or formula (b); multiple R2s independently represent hydrocarbon groups with 1 to 5 carbon atoms; multiple ps are independent integers from 0 to 4.

[0055] The effects of the invention

[0056] According to the present invention, a compound and a curable resin composition having excellent low dielectric properties can be provided. Attached Figure Description

[0057] [ Figure 1 [] represents the GPC chart of Synthesis Example 1.

[0058] [ Figure 2 ] indicates the synthesis example 1 1 H-NMR chart.

[0059] [ Figure 3 [] represents the GPC chart of Synthetic Example 2.

[0060] [ Figure 4 ] indicates the synthesis example 2 1 H-NMR chart.

[0061] [ Figure 5 [] indicates the GPC chart of synthetic example 3.

[0062] [ Figure 6 ] indicates the synthesis example 3 1 H-NMR chart.

[0063] [ Figure 7 [] indicates the GPC chart of Synthesis Example 4.

[0064] [ Figure 8 ] indicates the synthesis example 4 1 H-NMR chart. Detailed Implementation

[0065] Hereinafter, embodiments of the present invention (hereinafter also referred to as "this embodiment") will be described in further detail.

[0066] The compound in this embodiment is represented by the following formula (1).

[0067] [Chemistry 8]

[0068]

[0069] In formula (1), X represents a hydrocarbon group with 1 to 20 carbon atoms, and A represents the hydrocarbon group represented by formula (a) or formula (b) below. In the presence of multiple A's, the A's may be the same or different. Furthermore, formula (a) and formula (b) may be randomly bonded. m represents an integer from 0 to 10, k represents an integer from 1 to 3, and the average value of m+k is (m+k). ave 1 < (m + k) ave ≤10. (m+k) aveThe value can be calculated based on the results of gel permeation chromatography (GPC) analysis or nuclear magnetic resonance (NMR) analysis. Alternatively, the values ​​of the raw materials can be referenced. From the viewpoint of adhesion and heat resistance, 0 < (m + K) is preferred. ave ≤7.0, more preferably 1<(m+k) ave ≤5.0. n is the average value of the number of repetitions, and is 1 ≤ n ≤ 20, preferably 1.1 ≤ n ≤ 20, more preferably 1.1 ≤ n ≤ 10, and particularly preferably 1.1 ≤ n ≤ 5. R1 represents a hydrocarbon group with 1 to 5 carbon atoms, preferably a hydrocarbon group with 1 to 3 carbon atoms, and more preferably a methyl group. The value of n can be calculated from the weight average molecular weight (Mw) determined by gel permeation chromatography (GPC) of olefin compounds. l is an integer from 0 to 2.

[0070] [Chemistry 9]

[0071]

[0072] In equations (a) and (b), The term "R2" indicates the bonding position on the benzene ring in formula (1) or on the benzene ring in formulas (a) and (b). Each of the multiple "R2"s independently represents a hydrocarbon group having 1 to 5 carbon atoms, preferably a hydrocarbon group having 1 to 3 carbon atoms, and more preferably a methyl group. If the number of carbon atoms is 5 or less, molecular vibrations are less likely to occur when exposed to high frequencies, resulting in excellent electrical properties. Furthermore, when "R2" is a hydrogen atom, the deterioration of dielectric or hygroscopic properties associated with the formation of polar groups due to the oxidation reaction of alkyl groups during high-temperature storage tests can be suppressed. Each of the multiple "p"s independently represents an integer from 0 to 4, preferably 0.

[0073] The weight-average molecular weight of the compound represented by formula (1), determined by gel permeation chromatography (GPC), 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. The number-average molecular weight is preferably 200 or more and less than 5000, more preferably 250 or more and less than 2000, and particularly preferably 300 or more and less than 1000. If the weight-average molecular weight and number-average molecular weight are less than 5000, purification by washing with water becomes easier; if they are 200 or more, the target compound will not volatilize during the solvent distillation removal process.

[0074] In the formula (1), X is preferably any one or more of (c) to (k) as described in the formula (2) below, and is particularly preferably (d) or (f).

[0075] [Chemistry 10]

[0076]

[0077] ( (Indicates the location of the bond)

[0078] The method for preparing the compound represented by formula (1) is not particularly limited, and it can be obtained by carrying out a dehydrohalogenation reaction of the compound represented by formula (3) in a solvent in the presence of a basic catalyst. Examples of solvents used include: aromatic solvents such as toluene and xylene; aliphatic solvents such as cyclohexane and n-hexane; ethers such as diethyl ether and diisopropyl ether; ester solvents such as ethyl acetate and butyl acetate; and ketone solvents such as methyl isobutyl ketone and cyclopentanone, etc., but are not limited to these, and two or more may be used together. In addition to the aforementioned non-water-soluble solvents, aprotic polar solvents may also be used. Examples include: dimethyl sulfone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolium ketone, N-methylpyrrolidone, etc., and two or more may be used together. When using aprotic polar solvents, it is preferable to use a solvent with a higher boiling point than the non-water-soluble solvent used. The catalyst is not particularly limited, and alkaline catalysts such as sodium hydroxide, potassium hydroxide, and potassium carbonate can be listed. Since the dehydrohalogenation reaction is difficult to complete, aprotic polar solvents can be used in excess relative to the matrix, and the dehydrohalogenation reaction can be repeated two or three times or more. For example, the solution obtained by performing the dehydrohalogenation reaction of the compound represented by formula (1) in an organic solvent in the presence of an alkaline catalyst can be washed with water and then returned to the reaction vessel, and an alkaline catalyst can be added to allow it to react again. This can increase the degree of progress of the dehydrohalogenation reaction. That is, it can reduce the amount of residual halogen contained in the target compound. The amount of residual halogen in the target compound is preferably 1 ppm to 10,000 ppm, more preferably 1 ppm to 1,000 ppm, and even more preferably 1 ppm to 750 ppm. If the amount of residual halogen contained in the compound represented by formula (1) is high, it will cause molecular vibrations when exposed to high frequencies, which will have an adverse effect on electrical properties such as dielectric loss tangent. Furthermore, when the residual halogen content is high, the risk of adverse effects such as metal corrosion or ion migration increases during environmental tests such as the HAST test (High Accelerated Stress Test). Therefore, the halogen content is preferred. The reaction temperature is preferably 0°C to 120°C, more preferably 0°C to 100°C, and even more preferably 0°C to 80°C. If the temperature is above the upper limit, the compound of this embodiment may undergo self-polymerization, potentially leading to gelation. If the temperature is below the lower limit, the reaction may not proceed sufficiently. As a post-reaction treatment, neutralization can be performed using any acid compound. Alternatively, an alcohol compound or water can be added to the reaction solution as needed to recover the target substance in the form of crystals. Alternatively, the obtained reaction solution or crystals can be redissolved in any solvent and an extraction process can be performed.Regarding the extraction process, aromatic hydrocarbon solvents such as toluene or xylene can be used alone, or non-aromatic hydrocarbons such as cyclohexane or methylcyclohexane can be used in combination. After extraction, the organic layer is washed with water until the water becomes neutral, and the solvent is removed by distillation using an evaporator or similar apparatus, thereby obtaining the target compound.

[0079] [Chemistry 11]

[0080]

[0081] In the formula (3), Y represents a halogen atom, which is preferably a bromine atom or a chlorine atom from the viewpoint of reactivity and the stability of the raw materials, and is particularly preferably a bromine atom. The definitions of X, A, R1, the values ​​of k, m, l, n and their preferred ranges are the same as those in the formula (1).

[0082] [Chemistry 12]

[0083]

[0084] In equations (a) and (b), The term "R2" indicates the bonding position on the benzene ring in formula (3) or on the benzene ring in formulas (a) and (b). Each of the multiple R2 groups independently represents a hydrocarbon group with 1 to 5 carbon atoms, preferably a hydrocarbon group with 1 to 3 carbon atoms, and more preferably a methyl group. If the number of carbon atoms is 5 or less, molecular vibrations are less likely to occur when exposed to high frequencies, resulting in excellent electrical properties. Furthermore, in the case of hydrogen atoms, the deterioration of dielectric or hygroscopic properties associated with the formation of polar groups due to the oxidation reaction of alkyl groups during high-temperature storage tests can be suppressed. Each of the multiple p groups independently represents an integer from 0 to 4, preferably 0. The molar ratio of formula (a) to formula (b) is preferably 1:2 to 1:5, and more preferably 1:2 to 1:4.

[0085] The preparation method of the compound represented by formula (3) is not particularly limited. For example, when Y is a bromine atom, the compound having the 2-bromoethylbenzene structure can be self-polymerized under an acid catalyst such as hydrochloric acid or activated clay, and then reacted with a dihalogenated methyl aryl compound. Alternatively, the compound having the 2-bromoethylbenzene structure can be self-polymerized under an acid catalyst such as hydrochloric acid or activated clay, and then reacted with a dihydroxymethyl aryl compound. In addition, the compound having the 2-bromoethylbenzene structure can be reacted with a dihalogenated methyl aryl compound under an acid catalyst such as hydrochloric acid or activated clay, and then the compound having the 2-bromoethylbenzene structure can be reacted with the reaction product. Alternatively, the compound having the 2-bromoethylbenzene structure can be reacted with a dihydroxymethyl aryl compound under an acid catalyst such as hydrochloric acid or activated clay, and then the compound having the 2-bromoethylbenzene structure can be reacted with the reaction product. In the presence of hydrochloric acid as a catalyst, neutralization is performed using alkali metals such as sodium hydroxide or potassium hydroxide, followed by extraction using aromatic hydrocarbon solvents such as toluene or xylene. The mixture is then washed with water until the water is neutralized, and the solvent is removed by distillation using an evaporator or similar apparatus. This process yields a target compound having at least two 2-bromoethylbenzene structures within the molecule.

[0086] Examples of compounds having the 2-bromoethylbenzene structure include: 2-bromoethylbenzene, 1-(2-bromoethyl)-2-methylbenzene, 1-(2-bromoethyl)-3-methylbenzene, 1-(2-bromoethyl)-4-methylbenzene, 1-(2-bromoethyl)-2,3-dimethylbenzene, 1-(2-bromoethyl)-2,4-dimethylbenzene, 1-(2-bromoethyl)-2,5-dimethylbenzene, 1-(2-bromoethyl)-2,6-dimethylbenzene, etc., but are not limited to these. A higher carbon number increases solvent solubility but decreases heat resistance; therefore, unsubstituted or substituted with an alkyl group having 1 to 3 carbons is preferred, more preferably unsubstituted or substituted with an alkyl group having 1 to 2 carbons, and most preferably unsubstituted or substituted with a methyl group.

[0087] Examples of dihalogenated methyl aryl compounds include: difluoro-o-xylene, difluoro-m-xylene, difluoro-p-xylene, dichloro-o-xylene, dichloro-m-xylene, dichloro-p-xylene, dibromo-o-xylene, dibromo-m-xylene, dibromo-p-xylene, diiodo-o-xylene, diiodo-m-xylene, diiodo-p-xylene, 4,4'-difluoromethylene biphenyl, 4,4'-dichloromethylene biphenyl, 4,4'-dibromomethylene biphenyl, 4,4'-diiodomethylene biphenyl, 2, 4-Difluoromethylene biphenyl, 2,4-dichloromethylene biphenyl, 2,4-dibromomethylene biphenyl, 2,4-diiodomethylene biphenyl, 2,2'-difluoromethylene biphenyl, 2,2'-dichloromethylene biphenyl, 2,2'-dibromomethylene biphenyl, 2,2'-diiodomethylene biphenyl, from the viewpoint of the reactivity of the starting materials during synthesis, are preferably chlorine-based compounds, bromine-based compounds, or iodine-based compounds, and more preferably chlorine-based compounds or bromine-based compounds. In addition, other arbitrary halogen compounds may include cyanuric fluoride, cyanuric chloride, cyanuric bromide, cyanuriciodide, etc., but are not limited to these.

[0088] No.

[0089] Examples of dihydroxymethyl aryl compounds include, but are not limited to, o-phthalimethanol, iso-phthalimethanol, terephthalimethanol, 4,4'-dihydroxymethylbiphenyl, 2,4-dihydroxymethylbiphenyl, 2,2'-dihydroxymethylbiphenyl, α,α,α',α'-tetramethyl-1,4-benzenedimethanol, α,α,α',α'-tetramethyl-1,3-benzenedimethanol, and α,α,α',α'-tetramethyl-1,2-benzenedimethanol. These can be used alone or in combination of two or more. The amount of these used is preferably 0.01% to 0.8% by weight, and more preferably 0.05% to 0.6% by weight, relative to 1% by weight of the compound having the 2-bromoethylbenzene structure.

[0090] When synthesizing the compound represented by formula (3), in addition to hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, p-toluenesulfonic acid, and methanesulfonic acid, as needed, Lewis acids such as aluminum chloride and zinc chloride, activated clay, acid clay, white carbon, zeolite, silica alumina, and acidic ion exchange resins can also be used as catalysts. These can be used alone or in combination of two or more. Regarding the amount of catalyst used, it is preferable to add 0.1% to 50% by weight, preferably 1% to 40% by weight, relative to the total weight of the compound represented by formula (3) used. If too much catalyst is used, the viscosity of the reaction solution will be too high, and stirring may become difficult. If too little catalyst is used, the reaction may slow down. The reaction can be carried out using organic solvents such as hexane, cyclohexane, octane, toluene, and xylene, or it can be carried out in a solvent-free environment. For example, after adding an acidic catalyst to a mixed solution of a compound having a 2-bromoethylbenzene structure, a dihalogenated methyl aryl compound, and a solvent (or a solvent-free solution), water is removed from the system by azeotropic extraction if the catalyst contains water. Then, the reaction is carried out at 80°C to 220°C, preferably 100°C to 200°C, for 0.5 to 20 hours. After the reaction, the acidic catalyst can be neutralized with an alkaline aqueous solution, but it can also proceed to a water washing process without neutralization. Regarding the water washing process, a non-water-soluble organic solvent is added to the oil layer, and repeated water washing is performed until the wastewater becomes neutral.

[0091] In addition, regarding the compound represented by formula (3) obtained in the reaction, aromatic hydrocarbon solvents such as toluene or xylene, or non-aromatic hydrocarbon solvents such as cyclohexane or methylcyclohexane, and neutralizing agents such as bases can be added to the solution after the reaction, followed by the addition of non-protic solvents and base catalysts to continuously derive the compound represented by formula (1).

[0092] The compound represented by formula (1) can be cured individually by heating or other means, but its performance can also be improved by adding various materials to form a curable resin composition.

[0093] [Hardening Accelerator]

[0094] The curing properties of the curable resin composition of this embodiment can also be improved by adding a curing accelerator. Preferably, the curing accelerator is an anionic curing accelerator that promotes the curing reaction by generating anions through irradiation or heating with ultraviolet or visible light, or a cationic curing accelerator that promotes the curing reaction by generating cations through irradiation or heating with ultraviolet or visible light.

[0095] Examples of anionic hardening accelerators include: imidazoles such as 2-methylimidazole, 2-ethylimidazole, and 2-ethyl-4-methylimidazole; trialkylamines such as triethylamine and tributylamine; 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo(5,4,0)-undecene, with 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)-undecene being preferred. Other examples include phosphines such as triphenylphosphine, tetrabutylammonium salts, triisopropylmethylammonium salts, trimethyldecylammonium salts, hexadecyltrimethylammonium salts, and hexadecyltrimethylammonium hydroxide, but these are not limited to these. Furthermore, one or more of these can be used together.

[0096] Examples of cationic hardening accelerators include: quaternary phosphonium salts such as triphenylbenzylphosphonium salt, triphenylethylphosphonium salt, and tetrabutylphosphonium salt (the counter ions of quaternary salts are halogens, organic acid anions, hydroxide ions, etc., without specific designation, but organic acid anions and hydroxide ions are particularly preferred), tin octoate, zinc carboxylate (zinc 2-ethylhexanoate, zinc stearate, zinc benzylate, zinc myristate), zinc phosphate esters (zinc octyl phosphate, zinc stearyl phosphate), and transition metal compounds (transition metal salts), but are not limited to these. Furthermore, one or more of these can be used.

[0097] The amount of curing accelerator used is 0.01 to 5.0 parts by weight relative to 100 parts by weight of the curing resin composition.

[0098] [Inorganic filler]

[0099] The curable resin composition of this embodiment may contain inorganic fillers. Examples of inorganic fillers include: fused silica, crystalline silica, porous silica, alumina, zircon, calcium silicate, calcium carbonate, quartz powder, silicon carbide, silicon nitride, boron nitride, zirconium oxide, aluminum nitride, graphite, forsterite, steatite, spinel, mullite, titanium dioxide, talc, clay, iron oxide, asbestos, glass powder, etc., or these can be formed into spherical or fragmented inorganic fillers, but are not limited to these. Furthermore, one or more of these fillers may be used.

[0100] Regarding the inorganic filler, when obtaining a curable resin composition for semiconductor sealing, the amount of inorganic filler used is preferably 80 to 92 parts by weight, and more preferably 83 to 90 parts by weight, out of 100 parts by weight of the curable resin composition. Furthermore, when obtaining a curable resin composition for interlayer insulating layer forming materials, copper laminates or prepregs, RCC and other substrate materials, the amount of the inorganic filler used is preferably 5 to 80 parts by weight, and more preferably 10 to 60 parts by weight, out of 100 parts by weight of the curable resin composition.

[0101] [Polymerization initiator]

[0102] The curable resin composition of this embodiment can also have its curability improved by adding a polymerization initiator. A polymerization initiator is a compound capable of polymerizing olefin functional groups such as ethylene unsaturated bonds; examples include olefin metathesis polymerization initiators, anionic polymerization initiators, cationic polymerization initiators, and free radical polymerization initiators. Among these, a free radical polymerization initiator with curability and moderate stability is preferred. A free radical polymerization initiator is a compound that generates free radicals and initiates a chain polymerization reaction through irradiation with ultraviolet or visible light or heating. Examples of usable free radical polymerization initiators include organic peroxides, azo compounds, and benzopinnatols. Organic peroxides are preferred because they have minimal impact on curing temperature control, exhaust gas suppression, and the electrical properties of decomposition products.

[0103] Examples of such 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(tert-butylperoxyisopropyl)benzene; peroxy ketals such as tert-butyl peroxide and 1,1-di-tert-butylperoxycyclohexane; α-cumyl peroxyneodecanate, tert-butyl peroxyneodecanate, tert-butyl peroxytrimethylacetate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, and tert-amyl peroxy-2-ethylhexanoate. Alkyl peroxide esters such as tert-butylperoxy-2-ethylhexanoate, tert-pentylperoxy-3,5,5-trimethylhexanoate, tert-butylperoxy-3,5,5-trimethylhexanoate, and tert-pentylperoxybenzoate; peroxide carbonates such as di-2-ethylhexyl peroxide dicarbonate, bis(4-tert-butylcyclohexyl)peroxide dicarbonate, tert-butyl peroxide isopropyl carbonate, and 1,6-bis(tert-butylperoxycarbonyloxy)hexane; and tert-butyl hydroperoxide, cumene hydroperoxide, tert-butyl peroxyoctanoate, and lauroyl peroxide, but not limited to these. Furthermore, one or more of these may be used. Among the organic peroxides, ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, alkyl peroxide esters, and peroxide carbonates are preferred, and dialkyl peroxides are more preferred.

[0104] Examples of the azo compounds include, but are not limited to, azobisisobutyronitrile, 4,4'-azobis(4-cyanopentaic acid), and 2,2'-azobis(2,4-dimethylpentanonitrile). Furthermore, one or more of these compounds may be used.

[0105] The amount of polymerization initiator added is preferably 0.01 to 5 parts by mass relative to 100 parts by mass of the curing resin composition, and particularly preferably 0.01 to 3 parts by mass. If the amount of polymerization initiator used is less than 0.01 parts by mass, there is a possibility that the molecular weight may not be sufficiently elongated during the polymerization reaction; if it is more than 5 parts by mass, there is a possibility that the dielectric constant, dielectric loss tangent, and other dielectric properties may be impaired.

[0106] [Polymerization Inhibitor]

[0107] The curable resin composition of this embodiment may also contain polymerization inhibitors. Containing polymerization inhibitors improves storage stability and allows for control of the reaction initiation temperature. Controlling the reaction initiation temperature facilitates flowability and makes B-stage processes such as prepreg formation easier without compromising impregnation in glass fiber cloth or the like. If the polymerization reaction proceeds excessively during prepreg formation, adverse conditions such as difficulty in lamination can easily occur during the lamination process.

[0108] The polymerization inhibitor may be added during the synthesis of the compound of this embodiment or after synthesis. The amount of polymerization inhibitor used is 0.008 to 1 part by mass relative to 100 parts by mass of the compound of this embodiment, preferably 0.01 to 0.5 parts by mass.

[0109] Examples of polymerization inhibitors include phenolic, sulfur-based, phosphorus-based, hindered amine-based, nitroso-based, and nitryl radical-based inhibitors. Furthermore, one or more polymerization inhibitors may be used. In this embodiment, phenolic, hindered amine-based, nitroso-based, and nitryl radical-based inhibitors are preferred.

[0110] Examples of phenolic polymerization inhibitors include: 2,6-di-tert-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-tert-butyl-p-ethylphenol, stearyl-β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylaniline)-1,3,5-triazine, 2,4-bis[(octylthio)methyl]-o-cresol, and other monophenols, as well as 2,2'-methylenebis(4-methyl 6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 4,4'-butylenebis(3-methyl-6-tert-butylphenol), triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrogenated cinnamamide), 2,2-thio-diethylene... Bisphenols such as bis(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 3,5-di-tert-butyl-4-hydroxybenzyl phosphate-diethyl ester, 3,9-bis[1,1-dimethyl-2-{β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}ethyl]2,4,8,10-tetraoxaspiro[5,5]undecane, and bis(3,5-di-tert-butyl-4-hydroxybenzyl sulfonate ethyl ester) calcium; 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4, 6-Tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tetra-[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane, bis[3,3'-bis-(4'-hydroxy-3'-tert-butylphenyl)butyrate]ethylene glycol ester, tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-tris(3',5'-di-tert-butyl-4'-hydroxybenzyl)-triazine-2,4,6-(1H,3H,5H)trione, tocopherol, and other high molecular weight phenols, but not limited to these.

[0111] Examples of sulfur-based polymerization inhibitors include, but are not limited to, dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, and distearate 3,3'-thiodipropionate.

[0112] Examples of phosphorus-based polymerization inhibitors include: triphenyl phosphite, diphenyl isodecanyl phosphite, phenyl diisodecyl phosphite, tris(nonylphenyl) phosphite, pentaerythritol diisodecyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite, cyclic neopentanetetrayl bis(octadecyl) phosphite, cyclic neopentanetetrayl bis(2,4-di-tert-butylphenyl) phosphite, cyclic neopentanetetrayl bis(2,4-di-tert-butyl-4-methylphenyl) phosphite, bis[2- Phosphites such as tert-butyl-6-methyl-4-{2-(octadecyloxycarbonyl)ethyl}phenyl]hydrophosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(3,5-di-tert-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-decoxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and oxaphosphaphenanthrene oxides, but not limited to these.

[0113] Examples of hindered amine polymerization inhibitors include: Adekastab LA-40MP, Adekastab LA-40Si, Adekastab LA-402AF, Adekastab LA-87, Adekastab LA-82, Adekastab LA-81, Adekastab LA-77Y, Adekastab LA-77G, Adekastab LA-72, Adekastab LA-68, and Adekastab. LA-63P, Adekastab LA-57, Adekastab LA-52, Chimassorb 2020FDL, Chimassorb 944FDL, Chimassorb 944LD, Tinuvin 622SF, Tinuvin PA144, Tinuvin 765, Tinuvin 770DF, Tinuvin XT55FB, Tinuvin 111FDL, Tinuvin 783FDL, Tinuvin 791FB, etc., but not limited to these.

[0114] Examples of nitrosyl polymerization inhibitors include, but are not limited to, p-nitrosophenol, N-nitrosodiphenylamine, ammonium salts of N-nitrosophenylhydroxyamine, and cupferron. Among these, the ammonium salt of N-nitrosophenylhydroxyamine (cupferron) is preferred.

[0115] Examples of nitryl radical polymerization inhibitors include, but are not limited to, di-tert-butyl nitroxide, 2,2,6,6-tetramethylpiperidine-1-oxy, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxy, 4-oxo-2,2,6,6-tetramethylpiperidine-1-oxy, 4-amino-2,2,6,6-tetramethylpiperidine-1-oxy, 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxy, 4-acetoxy-2,2,6,6-tetramethylpiperidine-1-oxy, and 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-1-oxy.

[0116] [Flame retardant]

[0117] The curable resin composition of this embodiment may use a flame retardant. Examples of flame retardants 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.

[0118] The phosphorus-based flame retardant can be either a reactive or additive type. Specific examples include: trimethyl phosphate, triethyl phosphate, trimethylol phosphate, tri(xylyl) phosphate, tolyl diphenyl phosphate, tolyl-2,6-di(xylyl) phosphate, 1,3-phenylenebis(xylyl) phosphate, 1,4-phenylenebis(xylyl) phosphate, 4,4'-biphenyl(xylyl) phosphate, and other phosphate esters; phosphanes such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide; and phosphorus-containing epoxy compounds obtained by reacting epoxy resin with the active hydrogen of the phosphanes, red phosphorus, etc., but are not limited to these. Furthermore, one or more of these substances may be used. Among the exemplary substances, phosphate esters, phosphines, or phosphorus-containing epoxy compounds are preferred, particularly 1,3-phenylenebis(di(xylyl)phosphate), 1,4-phenylenebis(di(xylyl)phosphate), 4,4'-biphenyl(di(xylyl)phosphate), or phosphorus-containing epoxy compounds.

[0119] The flame retardant content is preferably in the range of 0.1 to 0.6 parts by weight relative to 100 parts by weight of the curing resin composition. If it is less than 0.1 parts by weight, the flame retardancy may become insufficient; if it is more than 0.6 parts by weight, it may adversely affect the hygroscopicity and dielectric properties of the cured material.

[0120] [Light stabilizer]

[0121] The curable resin composition of this embodiment may use a light stabilizer. As a light stabilizer, a hindered amine-based light stabilizer is preferred, and a hindered amine light stabilizer (HALS) is particularly preferred. Examples of HALS include: the reaction product of dibutylamine-1,3,5-triazine-N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexamethylenediamine and N-(2,2,6,6-tetramethyl-4-piperidinyl)butylamine, the reaction product of dimethyl-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidinyl succinate, and poly[{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidinyl)imino}hexamethylene{(2,2,6,6-tetramethyl-4-diyl)... Examples of bis(1,2,2,6,6-pentamethyl-4-piperidinyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate, bis(2,2,6,6-tetramethyl-4-piperidinyl)sebaate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)sebaate, bis(1-octoxy-2,2,6,6-tetramethyl-4-piperidinyl)sebaate, 2-(3,5-di-tert-butyl-4-hydroxybenzyl)-2-n-butylmalonate bis(1,2,2,6,6-pentamethyl-4-piperidinyl) ester, etc., but not limited to these. Furthermore, one or more of these may be used.

[0122] The content of light stabilizer is preferably in the range of 0.001 parts by weight to 0.1 parts by weight relative to 100 parts by weight of the curing resin composition. If it is less than 0.001 parts by weight, there is a possibility that the light stabilizing effect will not be sufficient, and if it is more than 0.1 parts by weight, there is a possibility that it will have an adverse effect on the hygroscopicity and dielectric properties of the cured material.

[0123] [Adhesive Resin]

[0124] The curable resin composition of this embodiment may use an adhesive resin. Examples of adhesive resins include, butyral resins, acetal resins, acrylic resins, epoxy-nylon resins, nitrile butadiene rubber (NBR)-phenol resins, epoxy-NBR resins, silicone resins, etc., but are not limited to these. In addition, one or more of these may be used.

[0125] The amount of adhesive resin used is preferably within the range that does not impair the flame retardancy and heat resistance of the cured material. It is preferably 0.05 to 50 parts by weight relative to 100 parts by weight of the curing resin composition, and more preferably 0.05 to 20 parts by weight as needed.

[0126] [additive]

[0127] Additives can be used in the curable resin composition of this embodiment. Examples of additives include modified acrylonitrile copolymers, polyethylene, fluororesins, silicone gels, silicone oils, surface treatment agents for fillers such as silane coupling agents, release agents, carbon black, phthalocyanine blue, phthalocyanine green, and other colorants.

[0128] The amount of additives is preferably 1,000 parts by weight or less, more preferably 700 parts by weight or less, relative to 100 parts by weight of the curing resin composition.

[0129] The curable resin composition of this embodiment can further utilize epoxy resin, reactive ester compound, phenolic resin, polyphenylene ether compound, amine resin, compound having vinyl unsaturated bonds, isocyanate resin, polyamide resin, maleimide compound, cyanate ester resin, polyimide resin, polybutadiene and its modified forms, polystyrene and its modified forms, polyethylene and its modified forms, etc., and one or more of these can be used. Among these compounds, in terms of the balance of heat resistance, adhesion, and dielectric properties, compounds containing polyphenylene ether compound, compound having vinyl unsaturated bonds, cyanate ester resin, polybutadiene and its modified forms, and polystyrene and its modified forms are preferred. By containing these compounds, the brittleness of the cured product can be improved and the adhesion to metals can be enhanced, and cracks in the encapsulation during reflow soldering or reliability tests such as thermal cycling can be suppressed.

[0130] Regarding the amount of the compound used, unless otherwise specified, it is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and particularly preferably 3 parts by mass or less, relative to the compound of this embodiment. Furthermore, a lower limit of 0.1 parts by mass or more is preferred, more preferably 0.25 parts by mass or more, and more preferably 0.5 parts by mass or more. By setting it within the aforementioned range, the effects of the low dielectric properties of the compound of this embodiment can be effectively utilized, while also incorporating the effects of the added compounds. The following examples illustrate the use of these components.

[0131] [Epoxy Resin]

[0132] The following are examples of preferred epoxy resins, but the use of epoxy resins is not limited to these. Furthermore, the epoxy resin may be in liquid or solid form, and one type or a combination of multiple types may be used.

[0133] Examples of liquid epoxy resins include: bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, phenolic varnish type epoxy resin, alicyclic epoxy resin with ester skeleton, cyclohexane type epoxy resin, cyclohexanediol type epoxy resin, glycidylamine type epoxy resin, and epoxy resin with butadiene structure. Specific examples include: “RE310S”, “RE410S” (manufactured by Nippon Kayaku Co., Ltd., bisphenol A type epoxy resin), “RE303S”, “RE304S”, “RE403S”, “RE404S” (manufactured by Nippon Kayaku Co., Ltd., bisphenol F type epoxy resin), “HP4032”, “HP4032D”, “HP4032SS” (manufactured by DIC Corporation, naphthalene type epoxy resin), “828US”, “jER828EL”, “825”, and “828EL”. (The above are bisphenol A type epoxy resins manufactured by Mitsubishi Chemical Corporation), "jE807", "1750" (the above are bisphenol F type epoxy resins manufactured by Mitsubishi Chemical Corporation), "jER152" (phenolic varnish type epoxy resin manufactured by Mitsubishi Chemical Corporation), "630", "630LSD" (the above are glycidylamine type epoxy resins manufactured by Mitsubishi Chemical Corporation), "ZX1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin manufactured by Nippon Steel & Sumitomo Metal Chemicals Co., Ltd.), "EX-721" (Nagase Chemicals Co., Ltd.) The epoxy resins used include those manufactured by ChemteX (a company specializing in glycidyl ester epoxy resins), Celloxide 2021P (manufactured by Daicel, a cycloaliphatic epoxy resin with an ester backbone), PB-3600 (manufactured by Daicel, an epoxy resin with a butadiene structure), ZX1658, and ZX1658GS (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., liquid 1,4-glycidylcyclohexane epoxy resins). These can be used individually or in combination of two or more.

[0134] As a solid epoxy resin, preferred types include, for example, xylenol-type epoxy resin, naphthalene-type epoxy resin, naphthalene-type tetrafunctional epoxy resin, cresol-phenolic varnish-type epoxy resin, dicyclopentadiene-type epoxy resin, triphenol-type epoxy resin, naphthol-type epoxy resin, biphenyl-type epoxy resin, naphthylene ether-type epoxy resin, anthracene-type epoxy resin, bisphenol A-type epoxy resin, bisphenol AF-type epoxy resin, and tetraphenylethane-type epoxy resin. Examples include naphthol-type epoxy resin, bisphenol AF-type epoxy resin, naphthalene-type epoxy resin, and biphenyl-type epoxy resin.Specific examples include: "HP4032H" (manufactured by DIC, a naphthalene-type epoxy resin), "HP-4700", "HP-4710" (both manufactured by DIC, naphthalene-type tetrafunctional epoxy resins), "N-690" (manufactured by DIC, a cresol-phenolic varnish-type epoxy resin), "N-695" (manufactured by DIC, a cresol-phenolic varnish-type epoxy resin), and "HP-7200" (manufactured by DIC, a dicyclopentadiene-type epoxy resin). "HP-7200", "HP-7200HH", "HP-7200H" (all manufactured by DIC, dicyclopentadiene type epoxy resin), "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP-6000" (all manufactured by DIC, naphthyl ether type epoxy resin), "EPPN-502H" (manufactured by Nippon Kayaku Co., Ltd., pyrrolidone type epoxy resin), "NC-7000L" "NC-7300" (manufactured by Nippon Kayaku Co., Ltd., naphthol-cresin phenolic resin varnish type epoxy resin), "NC-3000H", "NC-3000", "NC-3000L", "NC-3100" (manufactured by Nippon Kayaku Co., Ltd., biphenyl aralkyl type epoxy resin), "XD-1000-2L", "XD-1000-L", "XD-1000-H", "XD-1000-H" (manufactured by Nippon Kayaku Co., Ltd., dicyclopentadiene type epoxy resin), "ESN475V" (Nippon Steel). Sumitomo Chemical Co., Ltd. manufactures naphthol-type epoxy resins), "ESN485" (Nippon Steel & Sumitomo Chemical Co., Ltd. manufactures naphthol-phenolic varnish-type epoxy resins), "YX-4000H", "YX-4000", "YL6121" (all manufactured by Mitsubishi Chemical Co., Ltd., biphenyl-type epoxy resins), "YX-4000HK" (manufactured by Mitsubishi Chemical Co., Ltd., bixylenol-type epoxy resins), "YX-8800" (manufactured by Mitsubishi Chemical Co., Ltd., anthracene-type epoxy resins), "PG-100", "CG-500" (manufactured by Osaka Gas Chemical Co., Ltd.), etc. Gas Chemicals manufactures a variety of epoxy resins, including fluorene-based epoxy resins, "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), etc. These can be used individually or in combination of two or more.

[0135] [Active ester compounds]

[0136] An active ester compound is a compound whose structure contains at least one ester bond and on both sides of the ester bond are aliphatic chains, aliphatic rings, or aromatic rings. Examples of active ester compounds include phenolic esters, thiophenolic esters, N-hydroxyamine esters, and esters of heterocyclic hydroxyl compounds, which are compounds having two or more highly reactive ester groups in one molecule. These compounds can be obtained through a condensation reaction of at least one carboxylic acid compound, acid chloride, or thiocarboxylic acid compound with at least one hydroxyl compound or thiol compound. In particular, from the viewpoint of improving heat resistance, it is preferable to obtain the compound from a carboxylic acid compound or acid chloride and a hydroxyl compound; the hydroxyl compound is preferably a phenolic compound or a naphthol compound. An active ester compound can be used alone or in combination of two or more.

[0137] Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.

[0138] Examples of such acid chlorides include: acetyl chloride, acryloyl chloride, methacryloyl chloride, malonyl chloride, succinyl dichloride, diglycolyl chloride, glutaryl dichloride, octanoyl dichloride, sebacyl dichloride, adipicoyl dichloride, dodecanedioyl dichloride, azelaoyl chloride, 2,5-furandicarbonyl dichloride, phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, trimesoyl chloride, bis(4-chlorocarbonylphenyl) ether, 4,4'-diphenyldicarbonyl chloride, 4,4'-azobisbenzoyl dichloride, etc.

[0139] Examples of the phenolic compounds and naphthol compounds include, for example: hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, acid phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthol, 1,6-dihydroxynaphthol, 2,6-dihydroxynaphthol, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, pyroglucinol, dicyclopentadiene-type diphenol compounds, phenolic varnishes, and phenolic resins described later. Here, "dicyclopentadiene-type diphenol compounds" refers to diphenol compounds obtained by the condensation of two molecules of phenol in one molecule of dicyclopentadiene.

[0140] Preferred examples of active ester compounds include active ester compounds containing a dicyclopentadiene-type diphenol structure, active ester compounds containing a naphthalene structure, active ester compounds containing an acetylated form of phenolic varnish, active ester compounds containing a benzoylated form of phenolic varnish, compounds described in Example 2 of International Publication No. 2020 / 095829, and compounds disclosed in International Publication No. 2020 / 059625. More preferably, active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene-type diphenol structure are preferred. The term "dicyclopentadiene-type diphenol structure" refers to a divalent structural unit containing a phenylene-dicyclopentadiene-phenylene group.

[0141] Commercially available examples of active ester compounds include: "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "HPC-8000H-65TM", "EXB-8000L-65TM", and "EXB-8150-65T" (manufactured by DIC), which are active ester compounds containing a dicyclopentadiene-type diphenol structure; and "EXB9416-70BK" (manufactured by DIC), which is an active ester compound containing a naphthalene structure. "DC808" (manufactured by Mitsubishi Chemical Corporation), an active ester compound containing acetylated compounds of phenolic varnish; "YLH1026", "YLH1030", and "YLH1048" (manufactured by Mitsubishi Chemical Corporation), active ester compounds containing benzoyl compounds of phenolic varnish; "DC808" (manufactured by Mitsubishi Chemical Corporation), an active ester curing agent for acetylated compounds of phenolic varnish; and "EXB-9050L-62M" (manufactured by DIC Corporation), an active ester curing agent containing phosphorus atoms.

[0142] Regarding the formulation ratio of the reactive ester compound and the epoxy resin, the ratio (α / β) of the reactive 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. Outside of these ranges, excess epoxy groups or reactive ester groups may remain in the system, potentially leading to deterioration of properties during high-temperature storage tests (150°C, 1000 hours, etc.) or long-term reliability tests under high-temperature and high-humidity conditions (temperature: 85°C, humidity: 85%, etc.).

[0143] [Phenolic resin]

[0144] Phenolic resins are compounds with two or more phenolic hydroxyl groups within their molecules. Examples of phenolic resins include: reaction products of phenols and aldehydes, reaction products of phenols and dienes, reaction products of phenols and ketones, reaction products of phenols and substituted biphenyls, reaction products of phenols and substituted phenyl compounds, and reaction products of bisphenols and aldehydes, but are not limited to these. Furthermore, one or more of these can be used.

[0145] The following are specific examples of the raw materials, but are not limited to these.

[0146] <Phenolic compounds>

[0147] Phenol, alkyl-substituted phenol, aromatic-substituted phenol, hydroquinone, resorcinol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.

[0148] Aldehydes

[0149] Formaldehyde, acetaldehyde, alkyl aldehydes, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthal, glutaraldehyde, o-phthalaldehyde, crotonaldehyde, cinnamaldehyde, furfural, etc.

[0150] <Diene Compounds>

[0151] Dicyclopentadiene, terpenes, vinylcyclohexene, norbornene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.

[0152] Ketones

[0153] Acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, fluorenone, etc.

[0154] <Substituted biphenyls>

[0155] 4,4'-bis(chloromethyl)-1,1'-biphenyl, 4,4'-bis(methoxymethyl)-1,1'-biphenyl, 4,4'-bis(hydroxymethyl)-1,1'-biphenyl, etc.

[0156] <Substituted Phenyl>

[0157] 1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene, 1,4-bis(hydroxymethyl)benzene, etc.

[0158] [Polyphenylene ether compounds]

[0159] From the viewpoint of heat resistance and electrical properties, polyphenylene ether compounds having vinyl unsaturated bonds are preferred, and more preferably polyphenylene ether compounds having acrylic, methacrylic, or styrene structures. Examples of commercially available products include SA-9000 (manufactured by SABIC, a polyphenylene ether compound having methacrylic groups) and OPE-2St 1200 (manufactured by Mitsubishi Gas Chemical, a polyphenylene ether compound having a styrene structure).

[0160] The number average molecular weight (Mn) of the polyphenylene ether compound is preferably 500 to 5000, more preferably 2000 to 5000, and even more preferably 2000 to 4000. If the molecular weight is less than 500, the heat resistance of the cured product tends to be insufficient. Furthermore, if the molecular weight is greater than 5000, the melt viscosity becomes high, resulting in insufficient flowability and a tendency for poor molding. Additionally, reactivity decreases, the curing reaction requires a longer time, the amount of unreacted material that has not entered the curing system increases, the glass transition temperature of the cured product decreases, and the heat resistance of the cured product tends to decrease.

[0161] If the number-average molecular weight of the polyphenylene ether compound is between 500 and 5000, it can exhibit excellent heat resistance and formability while maintaining excellent dielectric properties. Furthermore, the number-average molecular weight can be specifically determined using methods such as gel permeation chromatography.

[0162] Polyphenylene ether compounds can be obtained through polymerization reactions, or through redistribution reactions of high molecular weight polyphenylene ether compounds with a number average molecular weight of approximately 10,000 to 30,000. Alternatively, they can be given free radical polymerization properties by reacting these compounds with ethylene-unsaturated bonds, such as methacryloyl chloride, acryloyl chloride, and chloromethylstyrene. For example, polyphenylene ether compounds obtained through redistribution reactions can be obtained by heating high molecular weight polyphenylene ether compounds in a solvent such as toluene in the presence of a phenol compound and a free radical initiator. Polyphenylene ether compounds obtained through redistribution reactions thus possess hydroxyl groups derived from phenolic compounds that contribute to curing at both ends of the molecular chain, thus maintaining higher heat resistance. Furthermore, functional groups can be introduced at both ends of the molecular chain after modification with compounds possessing ethylene-unsaturated bonds, which is preferred in this respect. Additionally, polyphenylene ether compounds obtained through polymerization reactions exhibit excellent flowability, which is also preferred in this respect.

[0163] In the case of polyphenylene ether compounds obtained through polymerization, the molecular weight of the polyphenylene ether compound can be adjusted by adjusting the polymerization conditions, etc. Furthermore, in the case of polyphenylene ether compounds obtained through redistribution reactions, the molecular weight of the obtained polyphenylene ether compound can be adjusted by adjusting the conditions of the redistribution reaction, etc. More specifically, this takes into account adjusting the amount of phenolic compounds used in the redistribution reaction, etc. That is, the more phenolic compounds are used, the lower the molecular weight of the obtained polyphenylene ether compound. In this case, poly(2,6-dimethyl-1,4-phenylene ether), etc., can be used as the high molecular weight polyphenylene ether compound subjected to the redistribution reaction. Furthermore, there are no particular limitations on the phenolic compounds used in the redistribution reaction; polyfunctional phenolic compounds having two or more phenolic hydroxyl groups in their molecules, such as bisphenol A, phenolic varnish, cresol varnish, etc., are preferably used. These can be used alone or in combination of two or more.

[0164] The content of the polyphenylene ether compound is not particularly limited, but is preferably 5 to 1000 parts by weight, more preferably 10 to 750 parts by weight, relative to 100 parts by weight of the curing resin composition. If the content of the polyphenylene ether compound is within the aforementioned range, a cured product that not only exhibits excellent heat resistance but also fully utilizes the excellent dielectric properties of the polyphenylene ether compound can be obtained, which is preferred in this respect.

[0165] [Amine resin]

[0166] Amine resins are compounds with two or more amino groups within their molecules. Examples of amine resins include: diaminodiphenylmethane, diaminodiphenyl sulfone, isophorone diamine, naphthyldiamine, aniline phenolic varnish (the product of the reaction of aniline and formalin), N-methylaniline phenolic varnish (the product of the reaction of N-methylaniline and formalin), n-ethylaniline phenolic varnish (the product of the reaction of n-ethylaniline and formalin), 2-methylaniline with formalin, 2,6-diisopropylaniline with formalin, 2,6-diethylaniline with formalin, 2-ethyl-6-ethylaniline with formalin, 2,6-dimethylaniline with formalin, and amine resins produced by the reaction of aniline with dichloroxylene (xylylenec). The aniline resin obtained by reacting with hydroxylamine (Hloride), the reaction products of aniline with substituted biphenyls (such as 4,4'-bis(chloromethyl)-1,1'-biphenyl and 4,4'-bis(methoxymethyl)-1,1'-biphenyl, as described in Japanese Patent No. 6429862, the reaction products of aniline with substituted phenyls (such as 1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene and 1,4-bis(hydroxymethyl)benzene, 4,4'-(1,3-phenylene diisopropylidene)bisaniline, the reaction products of aniline with diisopropylidenebenzene, and dimer diamines, etc., are not limited to these. Furthermore, one or more of these can be used.

[0167] [Compounds containing vinyl unsaturated bonds]

[0168] Compounds containing ethylene unsaturated bonds are those with one or more ethylene unsaturated bonds in their molecule that can be polymerized by heat or light, regardless of whether a polymerization initiator is used.

[0169] Examples of compounds containing vinyl unsaturated bonds include, for instance, the reaction products of the aforementioned phenolic resins with halogen compounds containing vinyl unsaturated bonds (chloromethylstyrene, allyl chloride, methylallyl chloride, acryloyl chloride, methacryloyl chloride, etc.); the reaction products of phenols containing vinyl unsaturated bonds (2-allylphenol, 2-propenylphenol, 4-allylphenol, 4-propenylphenol, eugenol, isoeugenol, etc.) with halogen compounds (1,4-bis(chloromethyl)benzene, 4,4'-bis(chloromethyl)biphenyl, 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-dibromobenzophenone, cyanuric trichloride, etc.); the reaction products of epoxy resins or alcohols with (meth)acrylic acids (acrylic acid, methacrylic acid, etc.); and acid-modified derivatives of these compounds, but are not limited to these. Furthermore, one or more of these compounds may be used.

[0170] [Isocyanate resin]

[0171] Isocyanate resins are compounds having two or more isocyanate groups within their molecules. Examples of isocyanate resins include: aromatic diisocyanates such as terephthalic diisocyanate, isophthalic diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, and naphthalene diisocyanate; aliphatic or alicyclic diisocyanates such as isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, norbornene diisocyanate, and lysine diisocyanate; polyisocyanates such as biuret bodies of one or more isocyanate monomers or isocyanates formed by trimerization of the aforementioned diisocyanate compounds; and polyisocyanates obtained by carbamate reaction of the aforementioned isocyanate compounds with polyol compounds, but are not limited to these examples. In addition, one of these can be used, or multiple can be used together.

[0172] [Polyamide resin]

[0173] Examples of polyamide resins include reaction products of diamines, diisocyanates, oxazolines, and dicarboxylic acids; reaction products of diamines and acid chlorides; and ring-opening polymers of lactam compounds. Furthermore, one or more of these can be used.

[0174] The following are specific examples of the raw materials, but are not limited to these.

[0175] <Diamine>

[0176] Ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decanediamine, undecanediamine, dodecanediamine, tridecanediamine, tetradecanediamine, pentadecanediamine, hexadecanediamine, heptadecananediamine, octadecanediamine, nonadecananediamine, eicosanediamine, 2-methyl-1,5-diaminopentane, 2-methyl-1,8-diaminooctane, dimers Diamine, cyclohexanediamine, bis-(4-aminocyclohexyl)methane, bis(3-methyl-4-aminocyclohexyl)methane, xylenediamine, norbornenediamine, isophoronediamine, bisaminomethyltricyclodecane, phenylenediamine, diethyltoluenediamine, naphthyldiamine, diaminodiphenylmethane, bis(4-amino-3,5-dimethylphenyl)methane, bis(4-amino-3,5-diethylphenyl)methane, 4,4'-methylenebis-o-toluidine, 4,4'-Methylenebis-o-ethylaniline, 4,4'-Methylenebis-2-ethyl-6-methylaniline, 4,4'-Methylenebis-2,6-diisopropylaniline, 4,4-Ethylenediphenylamine, diaminodiphenyl sulfone, diaminodiphenyl ether, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 4,4-bis(4-aminophenoxy)biphenyl, 2,2-bis[4-(4-aminophenoxy) [4-(4-aminophenoxy)phenyl]propane, bis[4-(4-aminophenoxy)phenyl]sulfone, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-(1,3-phenylenediisopropylidene)bisaniline, 4,4'-(1,4-phenylenediisopropylidene)bisaniline, 9,9-bis(4-aminophenyl)fluorene, 2,7-diaminofluorene, aminobenzylamine, diaminobenzophenone, etc.

[0177] <Diisocyanate>

[0178] Benzene diisocyanate, toluene diisocyanate, 1,3-bis(isocyanomethyl)benzene, 1,3-bis(isocyanomethyl)cyclohexane, bis(4-isocyanophenyl)methane, isophorone diisocyanate, 1,3-bis(2-isocyano-2-propyl)benzene, 2,2-bis(4-isocyanophenyl)hexafluoropropane, dicyclohexylmethane-4,4'-diisocyanate, etc.

[0179] <Dicarboxylic acid>

[0180] Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, octanoic acid, azelaic acid, sebacic acid, undecanoic acid, dodecanoic acid, terephthalic acid, isophthalic acid, 5-hydroxyisophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, sodium isophthalic acid-5-sulfonate, hexahydroterephthalic acid, hexahydroisophthalic acid, cyclohexanedicarboxylic acid, biphenyl dicarboxylic acid, naphthalene dicarboxylic acid, benzophenone dicarboxylic acid, furan dicarboxylic acid, 4,4'-dicarboxylic acid diphenyl ether, 4,4'-dicarboxylic acid diphenyl sulfide, etc.

[0181] <Acid Chloride>

[0182] Acetyl chloride, acryloyl chloride, methacryloyl chloride, malonyl chloride, succinyl dichloride, diacetyl oxide, glutaryl dichloride, octanoyl dichloride, sebacyl dichloride, adipyl dichloride, dodecyl dichloride, azelaic chloride, 2,5-furan dicarbonyl dichloride, phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, trimesoyl chloride, bis(4-chlorocarbonylphenyl) ether, 4,4'-diphenyl dicarbonyl chloride, 4,4'-azobisbenzoyl dichloride, etc.

[0183] <lactam>

[0184] ε-caprolactam, ω-undecanolactam, ω-laurolactam, etc.

[0185] [Polyimide resin]

[0186] As polyimide resins, examples include the reaction products of the diamine with the tetracarboxylic dianhydrides exemplified below, but are not limited to these. Furthermore, one or more of these can be used.

[0187] <Tetracarboxylic dianhydride>

[0188] 4,4'-(hexafluoroisopropylidene) phthalic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-cyclohexene-1,2-dicarboxylic anhydride, pyromellitic dianhydride, 1,2,3,4-benzenetetracarboxylic anhydride, 3,3',4,4'-benzophenonetetracarboxylic anhydride, 2,2',3,3'-benzophenonetetracarboxylic anhydride, 3,3',4,4'-biphenyltetracarboxylic anhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic anhydride, 2,2',3,3'-biphenyltetracarboxylic anhydride, methylene-4,4'-phthalic anhydride, 1,1-ethylidene-4,4'-phthalic anhydride, 2,2'-propylidene-4,4'-phthalic anhydride, 1,2-diphenyl... Ethyl-4,4'-diphthalic anhydride, 1,3-trimethylene-4,4'-diphthalic anhydride, 1,4-tetramethylene-4,4'-diphthalic anhydride, 1,5-pentamethylene-4,4'-diphthalic anhydride, 4,4'-oxydiphthalic anhydride, thio-4,4'-diphthalic anhydride, sulfonyl-4,4'-diphthalic anhydride, 1,3-bis(3,4-dicarboxyphenyl)phthalic anhydride, 1,3-bis(3,4-dicarboxyphenoxy)phthalic anhydride, 1,4-bis(3,4-dicarboxyphenoxy)phthalic anhydride, 1,3-bis[2-(3,4-dicarboxyphenyl)-2-propyl]phthalic anhydride, 1,4-bis[2-(3,4-dicarboxyphenyl)-2-propyl]phthalic anhydride [-propyl]phenyl dianhydride, bis[3-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride, bis[4-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride, 2,2-bis[3-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, bis(3,4-dicarboxyphenoxy)dimethylsilane dianhydride, 1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldisiloxane dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, 2,3,6,7-anthracitetetracarboxylic acid dianhydride, 1,2, 7,8-Phenylacetetrate dianhydride, ethylenetetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, 3,3',4,4'-biscyclohexyltetracarboxylic dianhydride, carbonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, methylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,2-ethylidene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,1-ethylidene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 2,2-propylidene-4,4'-bis(cyclohexane-1,4'-dicarboxylic acid)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'-biphenylbis(triphenyltriacrylic acid monoester anhydride), 9,9'-bis(3,4-dicarboxyphenyl)fluorene dihydride, etc.

[0189] [Maleimide compounds]

[0190] The curable resin composition of this embodiment may also contain a maleimide compound. A maleimide compound is a compound having one or more maleimide groups within its molecule. Examples of maleimide compounds include: 4,4'-diphenylmethane bismaleimide, polyphenylmethane maleimide, m-phenylene bismaleimide, 2,2'-bis[4-(4-maleimidephenoxy)phenyl]propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 4,4'-diphenyl ether bismaleimide, 4,4'-diphenyl sulfone bismaleimide, 1,3-bis(3-maleimidephenoxy)benzene, 1,3-bis(4-maleimidephenoxy)benzene, and Xyloc type maleimide compounds. Anilix maleimide (manufactured by Mitsui Chemicals Fine Chemicals Co., Ltd.), biphenyl aralkyl type maleimide compounds (substances solidified by solvent distillation of a resin solution containing maleimide compound (M2) described in Example 4 of Japanese Patent Application Publication No. 2009-001783 under reduced pressure), diaminocumylbenzene type maleimide (maleimide compound described in International Publication No. 2020 / 054601), maleimide compounds having an indane structure described in Japanese Patent No. 6629692 or International Publication No. 2020 / 217679, "Material Stage" The maleimide compounds described in “~Continued·Epoxy Resin CAS Number Story~ Hardener CAS Number Memorandum No. 31 Bismaleimide (1)” or “Material Stage” Vol. 19, No. 2, 2019 “~Continued·Epoxy Resin CAS Number Story~ Hardener CAS Number Memorandum No. 32 Bismaleimide (2)” are not limited to these. In addition, one or more of these may be used.

[0191] [Cyanate ester resin]

[0192] Cyanate ester resins are cyanate ester compounds obtained by reacting phenolic resins with cyanide halides. Specific examples include: dicyanatobenzene, tricyanoxybenzene, dicyanoxynaphthalene, dicyanoxybiphenyl, 2,2'-bis(4-cyanoxyphenyl)propane, bis(4-cyanoxyphenyl)methane, bis(3,5-dimethyl-4-cyanoxyphenyl)methane, 2,2'-bis(3,5-dimethyl-4-cyanoxyphenyl)propane, 2,2'-bis(4-cyanoxyphenyl)ethane, 2,2'-bis(4-cyanoxyphenyl)hexafluoropropane, bis(4-cyanoxyphenyl)sulfone, bis(4-cyanoxyphenyl) sulfide, phenolic phenolic varnish cyanate ester, and compounds by converting the hydroxyl groups of phenol-dicyclopentadiene cocondensates to cyanate ester groups, etc., but are not limited to these. Furthermore, one or more of these can be used.

[0193] Furthermore, the cyanate ester compound described in Japanese Patent Application Publication No. 2005-264154 is particularly preferred as a cyanate ester compound due to its excellent low hygroscopicity, flame retardancy, and dielectric properties.

[0194] To facilitate the trimerization of cyanate groups to form a sym-triazine ring as needed, cyanate ester resins may also contain catalysts such as zinc naphthenate, cobalt naphthenate, copper naphthenate, lead naphthenate, zinc octanoate, tin octanoate, lead acetylacetone, and dibutyltin maleate.

[0195] The catalyst is preferably used in amounts of 0.0001 to 0.10 parts by weight, more preferably 0.00015 to 0.0015 parts by weight, relative to 100 parts by weight of the cyanate resin and the curing resin composition.

[0196] Polybutadiene and its modified forms

[0197] Polybutadiene and its modified forms are compounds that have a polybutadiene structure or a structure derived from polybutadiene within their molecules. Structures derived from polybutadiene can be hydrogenated to convert some or all of the unsaturated bonds into single bonds.

[0198] Examples of polybutadiene and its modified forms include, but are not limited to, polybutadiene, hydroxyl-terminated polybutadiene, terminal (meth)acrylated polybutadiene, carboxylic acid-terminated polybutadiene, amine-terminated polybutadiene, and styrene-butadiene rubber. Furthermore, one or more of these can be used. From the viewpoint of dielectric properties, polybutadiene or styrene-butadiene rubber is preferred. Examples of styrene-butadiene rubber (SBR) include, for example, RICON-100, RICON-181, RICON-184 (all manufactured by Cray Valley Corporation), and 1,2-SBS (manufactured by Nippon Soda Corporation). Examples of polybutadiene include, for example, B-1000, B-2000, and B-3000 (all manufactured by Nippon Soda Corporation). The molecular weight of polybutadiene and styrene-butadiene rubber is preferably 500 to 10,000 by weight average, more preferably 750 to 7,500, and even more preferably 1,000 to 5,000. Below the lower limit of this range, the volatile content is high, making it difficult to adjust the solid composition during prepreg production; above the upper limit of this range, compatibility with other curing resins deteriorates. Generally, in the case of compounds containing heteroatoms such as oxygen or nitrogen, such as bismaleimide or polymaleimide, compatibility with low-polarity compounds such as compounds mainly containing hydrocarbons or compounds containing only hydrocarbons is difficult to ensure due to their polarity. On the other hand, the compounds of this embodiment, because they are not designed to actively introduce heteroatoms such as oxygen or nitrogen into the skeleton, exhibit excellent compatibility with materials having low polarity and low dielectric properties, or compounds containing only hydrocarbons.

[0199] Polystyrene and its modified forms

[0200] Polystyrene and its modified products are compounds that have a structure of polystyrene or derived from polystyrene within their molecules.

[0201] Examples of polystyrene and its modified forms include: polystyrene, styrene-2-isopropenyl-2-oxazoline copolymers (Epocros RPS-1005 and RP-61, both manufactured by Nippon Catalyst Co., Ltd.), SEP (styrene-ethylene-propylene copolymer: Septon 1020, manufactured by Kuraray Co., Ltd.), and SEPS (styrene-ethylene-propylene-styrene copolymers: Septon 2002, Septon 2004F, Septon 2005, Septon 2006, Septon 2063, and Septon 2104). All are manufactured by Kuraray Corporation. SEEPS (styrene-ethylene / ethylene-propylene-styrene block copolymers: Septon 4003, Septon 4044, Septon 4055, Septon 4077, Septon 4099, all manufactured by Kuraray Corporation), SEBS (styrene-ethylene-butene-styrene block copolymers: Septon 8004, Septon 8006, Septon 8007L, all manufactured by Kuraray Corporation), SEEPS-ОH (a compound with hydroxyl groups at the end of the styrene-ethylene / ethylene-propylene-styrene block copolymer: Septon HG252) Polystyrene and its modified forms include, but are not limited to, polystyrene (manufactured by Kuraray Corporation), SIS (styrene-isoprene-styrene block copolymers: Septon 5125 and Septon 5127, both manufactured by Kuraray Corporation), hydrogenated SIS (hydrogenated styrene-isoprene-styrene block copolymers: Hybrar 7125F and Hybrar 7311F, both manufactured by Kuraray Corporation), SIBS (styrene-isobutylene-styrene block copolymers: SIBSTAR073T, SIBSTAR102T, and SIBSTAR103T, all manufactured by Kaneka Corporation, and Septon V9827, manufactured by Kuraray Corporation), and others. Furthermore, one or more of these can be used. Polystyrene and its modified forms have higher heat resistance and are less prone to oxidative degradation; therefore, the absence of unsaturated bonds is preferred.In addition, there are no particular restrictions on the weight average molecular weight of polystyrene and its modified products if it is 10,000 or more. However, if it is too large, the compatibility with low molecular weight components with a weight average molecular weight of about 50 to 1,000 and oligomer components with a weight average molecular weight of about 1,000 to 5,000 will become poor, except for polyphenylene ether compounds. It will be difficult to ensure the stability of mixing and solvents. Therefore, it is preferred to be about 10,000 to 300,000.

[0202] Polyethylene and its modified forms

[0203] Polyethylene and its modified forms refer to compounds that have a polyethylene or polyethylene-derived structure within their molecules. Examples of polyethylene and its modified forms include: ethylene-propylene copolymers, ethylene-styrene copolymers, ethylene-propylene-ethylene norbornene copolymers (such as EBT: K-8370EM, K-9330M manufactured by Mitsui Chemicals), ethylene-propylene-vinyl norbornene copolymers (such as VNB-EPT: PX-006M, PX-008M, PX-009M manufactured by Mitsui Chemicals), ethylene-vinyl alcohol copolymers, and ethylene-vinyl acetate copolymers, but are not limited to these. From the viewpoint of improving heat resistance, ethylene-propylene-ethylene norbornene copolymers and ethylene-propylene-vinyl norbornene copolymers containing crosslinking structures are preferred. Furthermore, one or more of these can be used. There are no particular restrictions if the weight average molecular weight of polyethylene and its modified products is above 10,000. However, if the weight average molecular weight of polyethylene and its modified products is too large, in addition to the deterioration of compatibility with polyphenylene ether compounds, the compatibility with low molecular weight components with a weight average molecular weight of about 50 to 1,000 and oligomer components with a weight average molecular weight of about 1,000 to 5,000 will also deteriorate, making it difficult to mix and ensure solvent stability. Therefore, a weight average molecular weight of about 10,000 to 300,000 is preferred.

[0204] [Benzoxazine compounds]

[0205] As benzoxazine compounds, any compound having a phenolic hydroxyl group, an amino group, or an aldehyde group can be used to generate the compound. There are no particular limitations on compounds having a phenolic hydroxyl group; for example, the aforementioned phenolic resins, phenol (which may have substituents such as alkenyl or alkyl groups), and bisphenols can be used. There are no particular limitations on compounds having an amino group, but the aforementioned amine resins, diamines, and anilines (which may have substituents such as alkenyl or alkyl groups) can be used. As aldehyde compounds, for example, the aforementioned aldehydes can be used, with formaldehyde being preferred. Commercially available products can be used, such as benzoxazine Pd, Fa, ALP-d (manufactured by Shikoku Chemical Co., Ltd.), JBZ-BA100N, JBZ-FA100N, JBZ-DP100N, JBZ-OP100N, JBZ-OP100D, JBZ-OP100I (manufactured by JFE Chemical Co., Ltd.), BTBz (manufactured by Nippon Materials Technology Co., Ltd.), etc.

[0206] The curable resin composition of this embodiment can be obtained by preparing the components in a prescribed ratio, pre-curing it at 130°C to 180°C for 30 to 500 seconds, and then post-curing it at 150°C to 200°C for 2 to 15 hours to achieve a sufficient curing reaction and obtain the cured product of this embodiment. Alternatively, the components of the curable resin composition can be uniformly dispersed or dissolved in a solvent or the like, and then cured after removing the solvent.

[0207] The preparation method of the curable resin composition of this embodiment is not particularly limited; the components may simply be mixed uniformly, or prepolymerization may be performed. For example, prepolymerization can be performed by heating a mixture containing the compounds of this embodiment in the presence or absence of a curing accelerator or polymerization initiator, and in the presence or absence of a solvent. Similarly, prepolymerization may be performed by adding amine compounds, compounds having ethylene unsaturated bonds, maleimide compounds, cyanate ester compounds, polybutadiene and its modified forms, polystyrene and its modified forms, inorganic fillers, and other additives. Regarding the mixing or prepolymerization of the components, an extruder, kneader, roller, etc., may be used in the absence of a solvent, while a reaction vessel equipped with a stirring device may be used in the presence of a solvent.

[0208] As a method for uniform mixing, the resin composition is prepared by mixing using devices such as kneaders, rollers, or planetary mixers at a temperature ranging from 50°C to 100°C. The obtained resin composition can also be pulverized and molded into cylindrical ingots, granular powders, or powdered molded bodies using a tablet machine or similar molding machine. Alternatively, these compositions can be melted onto a surface support to form sheets with a thickness of 0.05 mm to 10 mm, thus creating a curable resin composition molded body. The resulting molded body is non-sticky at 0°C to 20°C and maintains almost no decrease in fluidity or curability even after storage at -25°C to 0°C for more than one week.

[0209] The obtained molded body can be molded into a hardened material using a transfer molding machine or a compression molding machine.

[0210] The curable resin composition of this embodiment can also be configured as a varnish-like composition (hereinafter referred to as varnish) by adding an organic solvent. The curable resin composition of this embodiment can be dissolved in solvents such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone to prepare a varnish. This varnish is then impregnated in a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, or paper and dried by heating. The resulting prepreg is then hot-pressed to produce a cured product of the curable resin composition of this embodiment. The solvent used in this case accounts for 10% to 70% by weight, preferably 15% to 70% by weight, in the mixture of the curable resin composition of this embodiment and the solvent. Alternatively, if it is a liquid composition, a curable resin composition containing carbon fibers can be obtained directly, for example, by resin transfer molding (RTM).

[0211] Alternatively, the curable resin composition of this embodiment can also be used as a modifier for film-type compositions. Specifically, it can be used to improve the flexibility of the B-stage, etc. This type of film-type resin composition is obtained by preparing a varnish from the curable resin composition of this embodiment, coating it onto a release film, removing the solvent under heat, and then performing B-stage curing, thereby obtaining a sheet-like adhesive. This sheet-like adhesive can be used as an interlayer insulating layer in multilayer substrates, etc.

[0212] The curable resin composition of this embodiment can also be heated, melted, and reduced in viscosity to impregnate reinforcing fibers such as glass fibers, carbon fibers, polyester fibers, polyamide fibers, and alumina fibers, thereby obtaining a prepreg. Specific examples include glass fibers such as E-glass cloth, D-glass cloth, S-glass cloth, Q-glass cloth, spherical glass cloth, NE-glass cloth, and T-glass cloth. Further examples include inorganic fibers other than glass, or organic fibers such as polyparaphenylene terephthalamide (Kevlar, a registered trademark, manufactured by DuPont), fully aromatic polyamides, polyesters, polyparaphenylene benzoxazole, polyimides, and carbon fibers, but these are not particularly limited. The shape of the substrate is not particularly limited; examples include woven fabrics, non-woven fabrics, roving, and chopped strand mat. In addition, known weaving methods include plain weave, basket weave, and twill weave, and these known weaving methods can be appropriately selected according to the target application or performance. Furthermore, glass fabrics that have undergone fiber opening treatment or surface treatment using silane coupling agents are preferably used. The thickness of the substrate is not particularly limited, but is preferably around 0.01 mm to 0.4 mm. Alternatively, the prepreg can be obtained by impregnating the varnish in reinforcing fibers and then heating and drying it.

[0213] Alternatively, the prepreg can also be used to manufacture laminates. There is no particular limitation as long as the laminate includes one or more prepregs, and it may also have any other layers. As for the manufacturing method of the laminate, generally known methods can be appropriately applied, and there are no particular limitations. For example, in forming a laminate with metal foil, a multi-stage press, a multi-stage vacuum press, a continuous forming machine, an autoclave forming machine, etc., can be used. The laminate can be obtained by stacking the prepregs together and heating and pressurizing them. In this case, the heating temperature is not particularly limited, but is preferably 65°C to 300°C, more preferably 120°C to 270°C. Furthermore, the pressure applied is not particularly limited. If the pressure is too high, it is difficult to adjust the solid composition of the resin in the laminate, resulting in unstable quality. Conversely, if the pressure is too low, air bubbles or poor adhesion between layers will occur. Therefore, 2.0 MPa to 5.0 MPa is preferred, and more preferably 2.5 MPa to 4.0 MPa. The laminate of this embodiment, by including a layer having metal foil, can preferably be used as the metal foil-coated laminate described later.

[0214] The prepreg is cut into the desired shape and, as needed, laminated with copper foil, etc., while applying pressure to the laminate using pressing, autoclave forming, sheet winding, etc., and heating and curing the curable resin composition, thereby obtaining an electrical and electronic laminate (printed wiring board) or carbon fiber reinforced material.

[0215] 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 can be described by coating the curable resin composition onto a support film (support body), drying it, and forming a resin composition layer on the support film. When using the curable resin composition of this embodiment for a resin sheet, it is important that the film softens under the lamination temperature conditions (70°C to 140°C) in a vacuum lamination process, and that the lamination of the circuit board exhibits fluidity (resin flow) capable of filling the through-holes or vias present on the circuit board. It is preferable to formulate the components to exhibit this characteristic. Furthermore, in the obtained resin sheet or circuit board (copper laminate, etc.), phenomena such as locally different characteristic values ​​due to phase separation or the like do not occur; certain properties are exhibited in any location, therefore, uniform appearance is required.

[0216] Here, the diameter of the through-hole in the circuit board is 0.1 mm to 0.5 mm, and the depth is 0.1 mm to 1.2 mm, preferably within the range where resin filling is possible. Furthermore, when laminating both sides of the circuit board, it is ideal to fill approximately half of the through-hole.

[0217] As a specific method for manufacturing the resin sheet, the following method can be listed: after preparing a varnished resin composition by mixing an organic solvent, the varnished resin composition is coated on the surface of a support film (Y), and then the organic solvent is dried by heating or hot air blowing to form a resin composition layer (X).

[0218] The preferred organic solvents used here are ketones such as acetone, methyl ethyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, cellolytic acetate, propylene glycol monomethyl ether acetate, carbitol acetate, etc.; cellolytic agents, carbitols such as butyl carbitol; aromatic hydrocarbons such as toluene and xylene; dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. In addition, it is preferred to use the organic solvent in a proportion of 30% to 60% by mass of the non-volatile components as a whole.

[0219] Furthermore, the thickness of the formed resin composition layer (X) must be greater than or equal to the thickness of the conductor layer of the circuit board on which the resin composition layer (X) is laminated. The thickness of the conductor layer of the circuit board is in the range of 5 μm to 70 μm; therefore, the thickness of the resin composition layer (X) is preferably 10 μm to 100 μm. Additionally, the resin composition layer (X) in this embodiment can also be protected using the protective film described later. By using the protective film, dust or other contaminants can be prevented from adhering to the surface of the resin composition layer (X), or damage can occur.

[0220] The supporting film and protective film can be made of various materials, including polyethylene, polypropylene, polyvinyl chloride and other polyolefins, polyethylene terephthalate (PET), polyethylene naphthalate and other polyesters, polycarbonate, polyimide, and release paper or metal foils such as copper foil and aluminum foil. In addition to matte treatment and corona treatment, the supporting film and protective film can also undergo a release treatment. The thickness of the supporting film is not particularly limited, ranging from 10 μm to 150 μm, preferably in the range of 25 μm to 50 μm. The thickness of the protective film is preferably set to 1 μm to 40 μm.

[0221] The support film (Y) is peeled off after the resin composition layer (X) is laminated onto the circuit board, or after an insulating layer is formed by heat curing the resin composition layer (X). If the support film (Y) is peeled off after the resin composition layer (X) constituting the resin sheet has been heat-cured, the adhesion of dust and the like during the curing process can be prevented. In the case of peeling off the support film (Y) after the resin composition layer (X) has been cured, a demolding treatment is performed on the support film (Y) beforehand.

[0222] Furthermore, multilayer printed circuit boards can be manufactured from the resin sheet obtained as described above. For example, when the resin composition layer (X) is protected by a protective film, after peeling off the protective film, the resin composition layer (X) is laminated onto one or both sides of the circuit board by, for example, vacuum lamination, so that the resin composition layer (X) is in direct contact with the circuit board. The lamination method can be batch or continuous using rollers. Additionally, the resin sheet and circuit board can be heated (preheated) as needed before lamination. Regarding the lamination conditions, it is preferable to set the pressing temperature (lamination temperature) to 70°C to 140°C, and preferably to set the pressing pressure to 1 kgf / cm². 2 ~11 kgf / cm 2 (9.8×10) 4 N / m 2 ~107.9×10 4 N / m 2The lamination is preferably carried out under reduced pressure of 20 mmHg (26.7 hPa) or less.

[0223] Furthermore, the curable resin composition of this embodiment can be used to manufacture semiconductor devices. Examples of semiconductor devices include: dual in-line package (DIP), quad flat package (QFP), ball grid array (BGA), chip size package (CSP), small outline package (SOP), thin small outline package (TSOP), and thin quad flat package (TQFP).

[0224] The curable resin composition and its cured product of this embodiment 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 coatings. Since the cured product of the curable resin composition described in this embodiment exhibits excellent heat resistance and dielectric properties, it is preferably used in sealing materials for semiconductor components, sealing materials for liquid crystal display components, sealing materials for organic electroluminescent (EL) components, electrical and electronic components such as laminates (printed wiring boards, ball grid array (BGA) substrates, build-up substrates, etc.), composite materials for lightweight, high-strength structural materials such as carbon fiber reinforced plastics and glass fiber reinforced plastics, 3D printing, etc.

[0225] Example

[0226] The present invention will now be described in more detail through embodiments. Unless otherwise specified, parts refer to parts by weight. Furthermore, this embodiment is not limited to these embodiments.

[0227] The following describes the various analytical methods used in the examples.

[0228] <Number average molecular weight (Mn), weight average molecular weight (Mw)>

[0229] The value is calculated using a polystyrene standard solution and a polystyrene conversion.

[0230] Gel permeation chromatograph (GPC): DGU-20A3R, LC-20AD, SIL-20AHT, RID-20A, SPD-20A, CTO-20A, CBM-20A (all manufactured by Shimadzu Corporation)

[0231] Tubing: Shodex KF-603, KF-602×2, KF-601×2

[0232] Eluent: Tetrahydrofuran

[0233] Flow rate: 0.5 ml / min.

[0234] Column temperature: 40℃

[0235] Detector: RI (Differential Refraction Detector)

[0236] [Synthesis example 1]

[0237] While purging the flask equipped with a thermometer, cooling pipe, and stirrer with nitrogen, 253.6 parts of 2-bromoethylbenzene (manufactured by Tokyo Chemical Co., Ltd.) and 25.4 parts of methanesulfonic acid (manufactured by Tokyo Chemical Co., Ltd.) were added, and the reaction was carried out at 170°C for 5 hours. Then, the internal temperature was cooled to 80°C, and 43.8 parts of α,α'-dichloro-p-xylene (manufactured by Tokyo Chemical Co., Ltd.) were added, and the reaction was carried out at 100°C for 2 hours, followed by a reaction at 130°C for 4 hours. Then, the internal temperature was cooled to 60°C, and extraction was performed using 220.0 parts of toluene. 34.8 parts of a 30% sodium hydroxide aqueous solution were added for neutralization, and the organic layer was washed five times with 100 parts of water. The mixture was placed under reduced pressure and the toluene was recovered, thereby obtaining 192.4 parts of an olefin resin precursor (b-1) as a liquid resin (Mn: 528, Mw: 737). The GPC diagram of the obtained compound is shown below. Figure 1 The following formula (b-1) is calculated based on the area percentage of each peak, where (m+k) is the sum of its components. ave The value is 1.41. The obtained compound... 1 H-NMR ( 1 H-nuclear magnetic resonance, 1 H-NMR data (deuterated chloroform) are shown in Figure 2 .exist 1Signals from ethylene crosslinked hydrogen (BCH) derived from formula (b-2) were observed at 2.80 ppm–3.00 ppm in the H-NMR chart, and signals from methylene crosslinked hydrogen (BCH) derived from formula (b-3) were observed at 4.00 ppm–4.30 ppm. The integral value of the peak value from ethylene crosslinked hydrogen was 11.6, and the integral value of the peak value from methylene crosslinked hydrogen was 1.0. Therefore, the ratio of (b-2) to (b-3) in X in formula (b-1) was calculated to be 1:2.9. Furthermore, signals from bromoethyl hydrogen (BCH) derived from formula (b-1) were observed at 3.00 ppm–3.70 ppm, and signals from methylene crosslinked hydrogen (BCH) were observed at 3.80 ppm–4.10 ppm. The integral value of the peak value from bromoethyl hydrogen was 15.7, and the integral value of the peak value from methylene crosslinked hydrogen (BCH) was 8.7. Therefore, the value of n in formula (b-1) was calculated to be 1.2.

[0238] [Chemistry 13]

[0239]

[0240] In formula (b-1), A represents the hydrocarbon group represented by formula (b-2) or formula (b-3) below.

[0241] [Chemistry 14]

[0242]

[0243] In equations (b-2) and (b-3), This indicates the bonding position on the benzene ring in formula (b-1) or on the benzene ring in formulas (b-2) and (b-3).

[0244] [Synthesis example 2]

[0245] While purging the flask equipped with a thermometer, cooling pipe, and stirrer with nitrogen, 80.0 parts of (b-1) obtained in Synthesis Example 1, 100 parts of toluene, 300 parts of dimethyl sulfoxide, 0.04 parts of 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxy (free radical), and 27.7 parts of 48% sodium hydroxide aqueous solution were added, and the reaction was continued at 40°C for 7 hours. 26 parts of water were added, and after the aqueous layer was removed, 280 parts of toluene were added. The organic layer was repeatedly washed with 26 parts of water until the drainage was neutral. The mixture was concentrated under reduced pressure using an evaporator to obtain 49 parts of the olefin resin (Mn: 431, Mw: 789) represented by the following formula (b-4). The GPC diagram of the obtained compound is shown in [image / image / description]. Figure 3 The obtained compound 1 H-NMR data (deuterated chloroform) are shown in Figure 4 .exist 1Signals from ethylene crosslinked hydrogen (BH2NMR) originating from formula (b-5) were observed at 2.60 ppm–3.20 ppm, and signals from methylene crosslinked hydrogen (BH2NMR) originating from formula (b-6) were observed at 4.10 ppm–4.30 ppm. The integral value of the peak value from ethylene crosslinked hydrogen was 12.7, and the integral value of the peak value from methylene crosslinked hydrogen was 1.0. Therefore, the ratio of (b-5) to (b-6) in A of formula (b-4) was calculated to be 1:3.2. Furthermore, signals from vinyl terminal hydrogen (BH2NMR) originating from formula (b-4) were observed at 5.00 ppm–6.00 ppm, and signals from methylene crosslinked hydrogen (BH2NMR) were observed at 3.60 ppm–4.10 ppm. The integral value of the peak value from vinyl terminal hydrogen was 7.9, and the integral value of the peak value from methylene crosslinked hydrogen (BH2NMR) was 9.1. Therefore, the value of n in formula (b-4) was calculated to be 1.2.

[0246] [Chemistry 15]

[0247]

[0248] In formula (b-4), A represents the hydrocarbon group represented by formula (b-5) or formula (b-6) below.

[0249] [Chemistry 16]

[0250]

[0251] In equations (b-5) and (b-6), This indicates the bonding position on the benzene ring in formula (b-4) or on the benzene ring in formulas (b-5) and (b-6).

[0252] [Synthesis example 3]

[0253] While purging the flask equipped with a thermometer, cooling pipe, and stirrer with nitrogen, 152.3 parts of 2-bromoethylbenzene (manufactured by Tokyo Chemical Co., Ltd.) and 15.2 parts of methanesulfonic acid (manufactured by Tokyo Chemical Co., Ltd.) were added, and the reaction was carried out at 170°C for 5 hours. Then, the internal temperature was cooled to 80°C, and 37.7 parts of 4,4'-bis(chloromethyl)biphenyl (manufactured by Tokyo Chemical Co., Ltd.) were added, and the reaction was carried out at 80°C for 3 hours, at 100°C for 8 hours, and at 130°C for 4 hours. Then, the internal temperature was cooled to 60°C, and extraction was performed using 440.0 parts of toluene. 20.9 parts of a 30% sodium hydroxide aqueous solution were added for neutralization, and the organic layer was washed five times with 50 parts of water. The mixture was placed under reduced pressure and the toluene was recovered, thereby obtaining 121.3 parts of an olefin resin precursor (b-7) as a liquid resin (Mn: 181, Mw: 3496). The GPC diagram of the obtained compound is shown below. Figure 5The following formula (b-7) (m+k) is calculated based on the area percentage of each peak. ave The value is 1.45. The obtained compound... 1 H-NMR data (deuterated chloroform) are shown in Figure 6 .exist 1 Signals from ethylene crosslinked hydrogen (BCH) derived from formula (b-8) were observed at 3.00 ppm–3.60 ppm in the H-NMR chart, and signals from methylene crosslinked hydrogen (BCH) derived from formula (b-9) were observed at 4.00 ppm–4.30 ppm. The integral value of the peak value from ethylene crosslinked hydrogen was 5.9, and the integral value of the peak value from methylene crosslinked hydrogen was 1.0. Therefore, the ratio of (b-8) to (b-9) in A of formula (b-7) was calculated to be 1:1.5. Furthermore, signals from bromoethyl hydrogen (BCH) derived from formula (b-7) were observed at 3.00 ppm–3.70 ppm, and signals from methylene crosslinked hydrogen (BCH) were observed at 3.80 ppm–4.10 ppm. The integral value of the peak value from bromoethyl hydrogen was 9.3, and the integral value of the peak value from methylene crosslinked hydrogen (BCH) was 3.2. Therefore, the value of n in formula (b-7) was calculated to be 1.5.

[0254] [Chemistry 17]

[0255]

[0256] In formula (b-7), A represents the hydrocarbon group represented by formula (b-8) or formula (b-9) below.

[0257] [Chemistry 18]

[0258]

[0259] In equations (b-8) and (b-9), This indicates the bonding position on the benzene ring in formula (b-7) or on the benzene ring in formulas (b-8) and (b-9).

[0260] [Synthesis Example 4]

[0261] While purging the flask equipped with a thermometer, cooling pipe, and stirrer with nitrogen, 50.0 parts of (b-1) obtained in Synthesis Example 1, 87.5 parts of toluene, 162.5 parts of dimethyl sulfoxide, 0.03 parts of 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxy (free radical), and 19.0 parts of 48% sodium hydroxide aqueous solution were added, and the reaction was continued at 40°C for 7 hours. 26 parts of water were added, and after the aqueous layer was removed, 175 parts of toluene were added. The organic layer was repeatedly washed with 17 parts of water until the drainage was neutral. The mixture was concentrated under reduced pressure using an evaporator to obtain 26 parts of the olefin resin (Mn: 544, Mw: 4438) represented by the following formula (b-10). The GPC diagram of the obtained compound is shown below. Figure 7 The obtained compound 1 H-NMR data (deuterated chloroform) are shown in Figure 8 .exist 1 Signals from ethylene crosslinked hydrogen (BCH) derived from formula (b-11) were observed at 2.30 ppm–3.00 ppm in the H-NMR chart, while signals from methylene crosslinked hydrogen (BCH) derived from formula (b-12) were observed at 4.10 ppm–4.30 ppm. The integral value of the peak value from ethylene crosslinked hydrogen was 5.5, and the integral value of the peak value from methylene crosslinked hydrogen was 1.0. Therefore, the ratio of (b-11) to (b-12) in formula (b-10) was calculated to be 1:1.4. Furthermore, signals from vinyl terminal hydrogen (BCH) derived from formula (b-10) were observed at 5.00 ppm–6.80 ppm, while signals from methylene crosslinked hydrogen (BCH) were observed at 3.80 ppm–4.10 ppm. The integral value of the peak value from vinyl terminal hydrogen was 1.9, and the integral value of the peak value from methylene crosslinked hydrogen (BCH) was 3.0. Therefore, the value of n in formula (b-10) was calculated to be 1.6.

[0262] [Chemistry 19]

[0263]

[0264] In formula (b-10), A represents the hydrocarbon group represented by formula (b-11) or formula (b-12) below.

[0265] [Chemistry 20]

[0266]

[0267] In equations (b-11) and (b-12), This indicates the bonding position on the benzene ring in formula (b-10) or on the benzene ring in formulas (b-11) and (b-12).

[0268] [Example 1, Example 2, Comparative Example 1]

[0269] Using the amounts of compound (b-4) obtained in Synthesis Example 2, compound (b-10) obtained in Synthesis Example 4, and OPE-2St (manufactured by Mitsubishi Gas Chemical Co., Ltd., a polyphenylene ether compound), as shown in Table 1, the samples were vacuum-pressed while being sandwiched in mirror copper foil (T4X: manufactured by Fukuda Metal Copper Foil Co., Ltd.), and then cured at 220°C for 2 hours. At this time, as spacers, spacers with a central cutout of 150 mm in length and width were used from a 250 μm thick buffer paper. For evaluation, the test pieces were cut to the desired dimensions using a laser cutter as needed.

[0270] <Dielectric Loss Tangent Test>

[0271] A 10 GHz cavity resonator manufactured by AET Corporation was used for testing at 25°C using the cavity resonator perturbation method. The sample dimensions were set to 1.7 mm width × 100 mm length and 0.3 mm thickness. The evaluation results are shown in Table 1.

[0272] [Table 1]

[0273]

[0274] Based on the results in Table 1, the low dielectric properties of the compounds of the present invention are confirmed to be excellent.

[0275] Industrial availability

[0276] The compounds of the present invention can be preferably used in electrical and electronic components such as semiconductor sealing materials, printed wiring substrates, and multilayer laminates.

Claims

1. A compound represented by the following formula (1); [Chemistry 1] (In the above formula (1), X represents a hydrocarbon group with 1 to 20 carbon atoms, and A represents the hydrocarbon group represented by formula (a) or formula (b) below; in the case of multiple A's, the multiple A's can be the same or different. In addition, formula (a) and formula (b) can be randomly bonded; m represents an integer from 0 to 20, k represents an integer from 1 to 3, and the average value of m+k is (m+k). ave 0 < (m + k) ave ≦10; n is the average of the number of repetitions, and is 1≦n≦20; R1 represents a hydrocarbon group with 1 to 5 carbon atoms; l is an integer from 0 to 2) [Chemistry 2] (In equations (a) and (b),) The position of the bond on the benzene ring in formula (1) or in formula (a) or (b) is indicated; multiple R2s independently represent hydrocarbon groups with 1 to 5 carbon atoms; multiple ps are independent integers from 0 to 4.

2. The compound according to claim 1, wherein, In the above formula (1), n ​​is 1.1≦n≦20.

3. The compound according to claim 1, wherein, In the above formula (1), X is any one or more of (c) to (k) as described in the following formula (2); [Chemistry 3] ( (Indicates the location of the bond).

4. The compound according to claim 3, wherein, In the above formula (2), X is represented by (d) or (f).

5. The compound according to claim 1 is derived from a compound represented by the following formula (3); [Chemistry 4] (In the above formula (3), X represents a hydrocarbon group with 1 to 20 carbon atoms, and A represents the hydrocarbon group represented by formula (a) or formula (b) below; in the case of multiple A's, the multiple A's can be the same or different. In addition, formula (a) and formula (b) can be randomly bonded; m represents an integer from 0 to 20, k represents an integer from 1 to 3, and the average value of m+k is (m+k). ave 0 < (m + k) ave ≦10; n is the average of the number of repetitions, and is 1≦n≦20; R1 represents a hydrocarbon group with 1 to 5 carbon atoms; l is an integer from 0 to 2; Y represents a halogen atom) [Chemistry 5] (In equations (a) and (b),) The R2 indicates the bonding position on the benzene ring in formula (3) or the bonding position on the benzene ring in formula (a) or formula (b); multiple R2s independently represent hydrocarbon groups with 1 to 5 carbon atoms; multiple ps are independent integers from 0 to 4.

6. A curable resin composition comprising the compound as described in any one of claims 1 to 5.

7. The curable resin composition according to claim 6, further comprising at least one selected from curing accelerators, polymerization initiators, epoxy resins, reactive ester compounds, phenolic resins, polyphenylene ether compounds, amine resins, compounds having vinyl unsaturated bonds, isocyanate resins, polyamide resins, maleimide compounds, cyanate resins, polyimide resins, polybutadiene and its modifications, polystyrene and its modifications, polyethylene and its modifications, and benzoxazine compounds.

8. A hardened compound obtained by hardening the compound as described in any one of claims 1 to 5.

9. A cured material obtained by curing the curable resin composition as described in claim 6.

10. A compound represented by the following formula (3); [Chemistry 6] (In the above formula (3), X represents a hydrocarbon group with 1 to 20 carbon atoms, and A represents the hydrocarbon group represented by formula (a) or formula (b) below; in the case of multiple A's, the multiple A's can be the same or different. In addition, formula (a) and formula (b) can be randomly bonded; m represents an integer from 0 to 20, k represents an integer from 1 to 3, and the average value of m+k is (m+k). ave 0 < (m + k) ave ≦10; n is the average of the number of repetitions, and is 1≦n≦20; R1 represents a hydrocarbon group with 1 to 5 carbon atoms; l is an integer from 0 to 2; Y represents a halogen atom) [Chemistry 7] (In equations (a) and (b),) The R2 indicates the bonding position on the benzene ring in formula (3) or the bonding position on the benzene ring in formula (a) or formula (b); multiple R2s independently represent hydrocarbon groups with 1 to 5 carbon atoms; multiple ps are independent integers from 0 to 4.

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