Curable resin composition, prepreg, and cured product of said prepreg

Abstract

The purpose of the present invention is to provide a curable resin composition having excellent heat resistance, high elastic modulus, low linear expansion coefficient, and low dielectric tangent, and a cured product thereof. The curable resin composition according to the present invention is composed of a compound represented by formula (1) and a polymer containing a structural unit represented by formula (2). (In formula (1), a plurality of Rs are each independently present and each represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a halogenated alkyl group having 1 to 10 carbon atoms. In the formula, p and r are integers of 0 to 4, q is an integer of 0 to 3, n is an average value of repetition numbers, and 1 < = n < = 20).

Description

Technical Field

[0001] This invention relates to curable resin compositions, prepregs, and cured versions thereof, suitable for applications such as: electrical / electronic components in semiconductor packaging materials, printed circuit boards, and add-on laminates; lightweight, high-strength materials such as carbon fiber reinforced plastics and glass fiber reinforced plastics; and 3D printing applications. Background Technology

[0002] In recent years, as the application fields of laminates carrying electrical / electronic components have expanded, the required characteristics have become more extensive and sophisticated. While the mainstream semiconductor chips are mounted on metal lead frames, high-processing-capability semiconductor chips such as central processing units (hereinafter referred to as "CPUs") are mostly mounted on laminates made of polymer materials.

[0003] The fifth-generation communication system "5G," currently under rapid development, is expected to further advance in terms of high capacity and high-speed communication. The frequencies used in 5G are evolving towards higher frequencies. In achieving high-speed communication using high frequencies, it is crucial to reduce transmission losses, which requires substrate materials to have lower dielectric properties. Transmission losses occurring on printed circuit boards originate from conductor losses and dielectric losses. As described in Non-Patent Document 1, due to dielectric loss α... D It is the relative permittivity ε of the dielectric. r The square root is proportional to the dielectric tangent tanδ, so it can be said that in terms of reducing transmission loss, improving the relative permittivity ε is more effective. r A higher dielectric tangent (tanδ) is considered effective. Materials with low dielectric tangents include thermoplastics such as PTFE (polytetrafluoroethylene), LCP (liquid crystal polymer), and rubber, but they are less formable than thermosetting resins. Furthermore, regarding rubber materials, their high coefficient of linear expansion can lead to cracking when used as substrates due to the difference in linear expansion between them and IC chips with lower coefficients of linear expansion, potentially compromising product reliability. Therefore, it is hoped that thermosetting resins with excellent dielectric properties and compositions containing thermosetting resins can be developed.

[0004] Against this backdrop, the development of thermosetting resins with excellent low dielectric properties and compositions containing thermosetting resins is being reviewed. For example, Patent Document 1 proposes a thermosetting resin composition containing an imide compound having a maleic animide group and a phenolic resin having an aliphatic unsaturated bond. However, because unreacted phenolic hydroxyl groups remain during the curing reaction, the electrical properties are not considered sufficient. Furthermore, Patent Document 2 discloses a biphenylaralkylphenol varnish resin modified with allyl ether, which is formed by the addition of phenolic hydroxyl groups and allyl groups. However, the allyl ether-modified biphenylaralkylphenol varnish resin undergoes a Claisen rearrangement at 190°C, and at the typical substrate molding temperature of 200°C, it generates phenolic hydroxyl groups that do not contribute to the curing reaction, thus failing to meet the electrical property requirements. In addition, in Patent Document 3, in order to provide a resin composition that can obtain a cured material with low dielectric properties and high heat resistance, a composition having a "monofunctional maleic animide compound" and an "olefin-containing polymer" has been proposed, but the dielectric properties are not yet sufficient.

[0005] [Preliminary Technology Documents]

[0006] [Non-patent literature]

[0007] Non-Patent Document 1: "Factors of Signal Loss in High-Speed ​​Signal Transmission on Printed Circuit Boards", 29th Japan Electronic Packaging Association Spring Conference, Communication ID: 16P1-17, 2015.

[0008] [Patent Literature]

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

[0010] Patent Document 2: International Publication No. 2016 / 002704.

[0011] Patent document 3: Japanese Patent No. 7190649. Summary of the Invention

[0012] [The problem the invention aims to solve]

[0013] The present invention was made in view of such circumstances, and its object is to provide a curable resin composition and its cured product with excellent heat resistance, high elastic modulus, low coefficient of linear expansion, and low dielectric tangent.

[0014] [Methods used to solve problems]

[0015] That is, the present invention relates to the following [1] to [9]. In addition, "(numerical value 1) to (numerical value 2)" in this application means that it includes upper and lower limits.

[0016] [1] A curable resin composition comprising: a compound represented by formula (1) below, and a polymer comprising structural units represented by formula (2) below.

[0017]

[0018] In equation (1), there are multiple Rs that exist independently, representing hydrogen atoms, hydrocarbon groups with 1 to 10 carbon atoms, or alkyl halides with 1 to 10 carbon atoms. p and r are integers from 0 to 4, q is an integer from 0 to 3, n is the average of the number of repetitions, and 1 ≤ n ≤ 20.

[0019]

[0020] [2] The curable resin composition described in the preceding item [1] further comprises: the structural unit shown in the following formula (3) of the polymer comprising the aforementioned structural unit shown in formula (2).

[0021]

[0022] In formula (3), R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

[0023] [3] The curable resin composition described in [1] or [2] above further comprises: a polyphenylene ether compound having unsaturated double bonds; and / or a hydrogenated block copolymer composed of "block units of a polymer made of styrene monomers" and "block units of a polymer made of conjugated diene compounds".

[0024] [4] The curable resin composition described in the preceding item [3], wherein the aforementioned polyphenylene ether compound having unsaturated double bonds is as shown in formula (4) or formula (5) below.

[0025]

[0026] In equation (4), n is the average number of repetitions, and 1 < n < 10.

[0027]

[0028] In equation (5), n is the average number of repetitions, and 1 < n < 10.

[0029] [5] The curable resin composition as described in [3] or [4] above, wherein the hydride of the aforementioned block copolymer is a compound represented by the following formula (6).

[0030]

[0031] In equation (6), l, m, and n are the average values ​​of the number of repetitions, representing rational numbers from 1 to 10000. The order of the repetition units enclosed in l, m, and n is not limited, and the bonding pattern can be any of the following: interleaved, block, or random.

[0032] [6] The curable resin composition described in any one of the preceding items [1] to [5] further comprises at least one selected from maleic anhydride compounds, compounds having ethylene unsaturated bonds, cyanate ester resins, polybutadiene and its modified forms, polystyrene and its modified forms, and polyethylene and its modified forms.

[0033] [7] A prepreg having a curable resin composition described in any one of the preceding [1] to [6] in a sheet-like fibrous substrate.

[0034] [8] A hardener is obtained by hardening the hardening resin composition described in any one of the preceding items [1] to [6].

[0035] [9] A hardened material is obtained by hardening the prepreg described in the preceding item [7].

[0036] [Invention Effects]

[0037] According to the present invention, a curable resin composition with excellent heat resistance, high elastic modulus, low coefficient of linear expansion, and low dielectric tangent, and cured products thereof, can be provided. Attached Figure Description

[0038] Figure 1 This is the GPC chart of Synthetic Example 1.

[0039] Figure 2 This is the GPC chart of Synthetic Example 2. Detailed Implementation

[0040] [The compound shown in formula (1)]

[0041] The curable resin composition of this embodiment contains a compound represented by the following formula (1).

[0042]

[0043] In formula (1), the multiple Rs exist independently and represent hydrogen atoms, hydrocarbon groups with 1 to 10 carbon atoms, or alkyl halides with 1 to 10 carbon atoms. Hydrogen atoms or hydrocarbon groups with 1 to 10 carbon atoms are more preferred, and hydrogen atoms or hydrocarbon groups with 1 to 3 carbon atoms are even more preferred. For hydrocarbons with 10 or fewer carbon atoms, their electrical properties are particularly excellent because they are less prone to molecular vibrations when exposed to high frequencies.

[0044] In formula (1), p and r are integers from 0 to 4, preferably from 0 to 2. q is an integer from 0 to 3, preferably from 0 to 2. n is the average of the number of repetitions, preferably 1 ≤ n ≤ 20, more preferably 1.1 ≤ n ≤ 20, particularly preferably 1.1 ≤ n ≤ 10, and most preferably 1.1 ≤ n ≤ 5. The value of n can be calculated from the number average molecular weight (Mn) value of the compound shown in formula (1) determined by gel permeation chromatography (GPC). The number average molecular weight is preferably 200 or more and less than 5000, more preferably 300 or more and less than 3000, and particularly preferably 400 or more and less than 2000. If the weight average molecular weight is less than 5000, it is easy to purify by washing with water. In addition, if it is 200 or more, the target compound will not volatilize during the solvent distillation step.

[0045] The number of alkenes contained in the compound shown in formula (1) was determined according to the iodine value determination method of JIS K0070. First, weigh 0.096 g of the compound described in formula (1). Add 4 ml of dichloromethane to dissolve it. Add 10 ml of Wijd's reagent and let it stand in the dark for 30 minutes. Measure 8 ml of potassium iodide solution (100 g / L) and 40 ml of water and add them to the sample. Titrate using a 0.1 mol / L sodium thiosulfate aqueous solution with starch solution as an indicator. Regarding the starch reagent, the endpoint is set at the point when the color disappears.

[0046] The iodine value of the compound shown in formula (1) calculated according to this method is preferably 100 to 200, more preferably 110 to 190, and particularly preferably 120 to 180. If the iodine value is greater than 200, the number of olefins is high, which may lead to excessive hardening during the preparation of the prepreg, and there is a concern that the desired molded product may not be obtained. On the other hand, if the iodine value is less than 100, the number of olefins is low, and there is a concern that the heat resistance of the resulting cured product may deteriorate when the composition is hardened. If the iodine value is within the aforementioned range, a cured product whose formability and heat resistance do not deteriorate can be obtained.

[0047] Regarding the amount of the compound shown in formula (1) above, it is more preferably 1 to 99 parts by mass, more preferably 3 to 80 parts by mass, even more preferably 3 to 60 parts by mass, and particularly preferably 5 to 40 parts by mass, out of a total of 100 parts by mass of the curable resin composition. If the amount exceeds the aforementioned range, there is a concern about poor heat resistance. If the amount is less than the aforementioned range, excellent dielectric properties cannot be exhibited. If the amount is within the aforementioned range, both heat resistance and dielectric properties are excellent.

[0048] The compound represented by formula (1) above is derived from the compound represented by formula (1-1) below.

[0049]

[0050] In equation (1-1), R is the same as in equation (1) above. The values ​​and preferred ranges of p, r, q, and n are the same as in equation (1) above. X represents a halogen atom, which is preferably a bromine atom or a chlorine atom from the viewpoint of reactivity and raw material stability, and is particularly preferably a bromine atom.

[0051] The compound represented by formula (1) can be obtained, for example, by "a method for carrying out a dehydrohalogenation reaction of the compound represented by formula (1-1) 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; esters such as ethyl acetate and butyl acetate; and ketones such as methyl isobutyl ketone and cyclopentanone, etc., which are non-aqueous solvents. However, this is not limited to these, and two or more solvents may be used together. In addition to the aforementioned non-aqueous solvents, aprotic polar solvents may also be used. Examples include dimethyl sulfone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidineone, and N-methylpyrrolidone, etc., and two or more solvents may be used together. When using aprotic polar solvents, it is preferable to use a non-aqueous solvent with a boiling point higher than that used. Regarding the catalyst, there are no particular limitations; 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 large excess for the matrix, and the dehydrohalogenation reaction can be repeated two or three times or more. For example, in an organic solvent, in the presence of an alkaline catalyst, the solution obtained after performing the dehydrohalogenation reaction of the compound shown in formula (2) above can be washed with water and then returned to the reaction vessel, where an alkaline catalyst is added to allow it to react again. In this way, the degree of dehydrohalogenation reaction can be increased. That is, the amount of residual halogen contained in the target compound can be reduced. In terms of the amount of residual halogen in the target compound, it is more preferably 1 to 10,000 ppm, more preferably 1 to 1,000 ppm, and even more preferably 1 to 750 ppm. If the amount of residual halogen contained in the compound shown in formula (1) above is high, molecular vibrations will occur when exposed to high frequencies, which will have a particularly adverse effect on the dielectric tangent isoelectric properties. Furthermore, when there is a high residual halogen content, the risk of adverse events such as metal corrosion or ion migration increases during environmental tests such as the HAST test (High Accelerated Stress Test). Therefore, the halogen content mentioned above is preferred.

[0052] There are no particular limitations on the preparation method of the compound shown in formula (1-1). For example, a compound having a (2-bromoethyl)benzene structure and a dihalogenated methyl aryl compound (or a dihydroxymethyl aryl compound, etc.) can be reacted under an acid catalyst such as hydrochloric acid, sulfonic acid, or activated clay. Alternatively, a compound having a (2-bromoethyl)benzene structure can be reacted with a dihydroxymethyl aryl compound under an acid catalyst such as hydrochloric acid, sulfonic acid, or activated clay. When using sulfonic acid as a catalyst, neutralization can be performed using alkali metals such as sodium hydroxide or potassium hydroxide before the extraction step. For the extraction step, aromatic hydrocarbon solvents such as toluene or xylene can be used alone, or non-aromatic hydrocarbons such as cyclohexane or toluene can be used in combination. After extraction, the organic layer is washed with water until the drainage is neutral, and then the solvent and excess compound having a (2-bromoethyl)benzene structure are distilled off using an evaporator or the like. This yields the target compound having at least two or more 2-bromoethylbenzene structures within the molecule.

[0053] Compounds having the (2-bromoethyl)benzene structure include, but are not limited to, (2-bromoethyl)benzene, 1-(2-bromoethyl)-2-methylbenzene, 1-(2-bromoethyl)-3-methylbenzene, 1-(2-bromoethyl)-4-methylbenzene, 1-(2-bromoethyl)-2,3-dimethylbenzene, 1-(2-bromoethyl)-2,4-dimethylbenzene, 1-(2-bromoethyl)-2,5-dimethylbenzene, and 1-(2-bromoethyl)-2,6-dimethylbenzene. These can be used alone or in combination of two or more. While a higher carbon number improves solvent solubility, it also reduces heat resistance. Therefore, unsubstituted or alkyl-substituted compounds with 1 to 3 carbon atoms are preferred, unsubstituted or alkyl-substituted compounds with 1 to 2 carbon atoms are more preferred, and unsubstituted or methyl-substituted compounds are most preferred.

[0054] Examples of dihalogenated methyl aryl compounds include, but are not limited to, o-xylene difluoride, m-xylene difluoride, p-xylene difluoride, o-xylene dichloride, m-xylene dichloride, p-xylene dichloride, o-xylene dibromide, m-xylene dibromide, p-xylene dibromide, o-xylene diiodide, m-xylene diiodide, and p-xylene diiodide. These can be used individually or in combination of two or more. From the viewpoint of the reactivity of the starting materials during synthesis, it is preferable that the chloride, bromide, and iodide are compounds; more preferably, it is preferable that the chloride and bromide are compounds.

[0055] Examples of dihydroxymethyl aryl compounds include, but are not limited to, o-phthalimethanol, iso-phthalimethanol, and terephthalimethanol. These can be used alone or in combination of two or more. The amount of these compounds used is preferably 0.05 to 0.8 parts by mass, more preferably 0.1 to 0.6 parts by mass, relative to 1 part by mass of a compound having a (2-bromoethyl)benzene structure.

[0056] When reacting compounds having a (2-bromoethyl)benzene structure with halogenated methyl aromatic compounds, the catalyst can be selected from hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, Lewis acids such as aluminum chloride and zinc chloride, solid acids such as activated clay, acid clay, white carbon, zeolite, and silica-alumina oxides, and acidic ion exchange resins, depending on the desired reaction. These can be used alone or in combination of two or more. The amount of catalyst used is preferably 0.05 to 0.8 moles, more preferably 0.1 to 0.7 moles, relative to 1 mole of the compound having a (2-bromoethyl)benzene structure. Excessive catalyst usage will result in excessively high viscosity of the reaction solution, making stirring difficult; insufficient catalyst usage will slow down the reaction. The reaction can be carried out using organic solvents such as hexane, cyclohexane, octane, toluene, and xylene, or in a solvent-free manner, depending on the desired reaction. For example, after adding an acidic catalyst to a mixed solution of a compound having a (2-bromoethyl)benzene structure, a halogenated methyl aromatic compound, and a solvent, if the catalyst contains water, the water is removed from the system using azeotropic distillation. Then, the reaction is carried out at 40 to 180°C (preferably 50 to 170°C) for 0.5 to 20 hours. After the reaction is complete, the acidic catalyst can be neutralized with an alkaline aqueous solution, or a water washing step can be performed directly without neutralization. In the water washing step, a non-water-soluble organic solvent is added to the oil layer, and the water washing is repeated until the wastewater becomes neutral.

[0057] The softening point of the compound shown in formula (1-1) is preferably below 80°C, and more preferably below 70°C. If the softening point is below 80°C, the viscosity will be lower when deriving the compound shown in formula (1). Accordingly, it becomes easier to ensure flowability without compromising the impregnation properties of glass cloth or carbon fiber, and it facilitates B-stage processes such as prepreg physicochemical treatment. When the viscosity is reduced by increasing the diluent, there is a possibility that the resin may not be able to adequately adhere to the fibrous material during the impregnation step.

[0058] [Polymers containing the structural units shown in formula (2)]

[0059] The curable resin composition of this embodiment further comprises a polymer containing the structural unit shown in the following formula (2).

[0060]

[0061] The number of olefins in the polymer containing the structural unit shown in formula (2) above is calculated according to the aforementioned iodine value determination method. The iodine value is preferably 50 to 200, more preferably 60 to 180, and particularly preferably 70 to 160. If the iodine value is greater than the aforementioned range, the reactivity will become too high, potentially leading to reduced shelf life or reduced flowability of the cured resin composition. Reduced flowability can result in poor molding conditions such as porosity during molding, potentially compromising the reliability of the wiring board. On the other hand, if the iodine value is less than the aforementioned range, the heat resistance of the cured material may deteriorate. Therefore, if the iodine value is within the aforementioned range, both heat resistance and moldability are excellent.

[0062] The weight-average molecular weight (Mw) of the polymer containing the structural unit shown in formula (2) above is preferably 10,000 to 50,000, more preferably 15,000 to 45,000, and particularly preferably 20,000 to 40,000. If it is less than the aforementioned range, the polymer may become liquid, which may cause adhesion to the surface of the prepreg during production. On the other hand, if it is greater than the aforementioned range, the impregnation of the varnish with the glass cloth will decrease during the production of the prepreg, resulting in deterioration of workability. In addition, the flowability will decrease and the formability will deteriorate during multilayer molding. If it is within the aforementioned range, both workability and formability are excellent.

[0063] In 100 parts by mass of the total amount of the curable resin composition, the amount of polymer containing the structural unit shown in formula (2) is preferably 1 to 99 parts by mass, more preferably 3 to 80 parts by mass, even more preferably 3 to 60 parts by mass, and most preferably 5 to 40 parts by mass. If the amount exceeds the aforementioned range, there is a concern that the low dielectric properties may deteriorate; if the amount is less than the aforementioned range, there is a concern that the heat resistance may deteriorate. By setting the amount within the aforementioned range, both heat resistance and dielectric properties are excellent.

[0064] The polymer containing the structural unit shown in formula (2) above is preferably also containing the structural unit shown in formula (3) below.

[0065]

[0066] In formula (3), R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

[0067] The structural unit shown in equation (3) above can be listed as, for example, the following equations (3-a) to (3-e).

[0068]

[0069] The structural unit shown in formula (3) above is preferably formula (3-a), (3-b) or (3-c), and more preferably (3-a) or (3-c). These may contain only one type or more types.

[0070] [Polyphenylene ether compounds with unsaturated double bonds]

[0071] The curable resin composition of this embodiment may also contain a "polyphenylene ether compound having unsaturated double bonds". Examples of unsaturated double bonds include (meth)acryloyl, styrene, allyl, vinyl, and methalyl, with (meth)acryloyl, styrene, and vinyl being more preferred, (meth)acryloyl and styrene being more preferred, and styrene being particularly preferred. Commercially available polyphenylene ether compounds having unsaturated double bonds include SA-9000-111 (manufactured by Sabic Corporation, a polyphenylene ether compound having a methacryloyl group) as shown in formula (5) below, and OPE-2St-1200 or OPE-2St-2200 (manufactured by Mitsubishi Gas Chemical Corporation, a polyphenylene ether compound having a styrene group) as shown in formula (4) below. In particular, from the viewpoint of reactivity and dielectric properties, compounds shown in formula (4) or formula (5) below are more preferred.

[0072]

[0073] In equation (4), n is the average number of repetitions, and 1 < n < 10.

[0074]

[0075] In equation (5), n is the average number of repetitions, and 1 < n < 10.

[0076] The number average molecular weight (Mn) of polyphenylene ether compounds having unsaturated double bonds is preferably 500 to 5000, more preferably 750 to 4000, and even more preferably 1000 to 3000. A molecular weight of 500 or higher improves the heat resistance of the cured material. A molecular weight below 5000 reduces the melt viscosity, resulting in sufficient fluidity and better formability. Furthermore, increased reactivity shortens the curing time and also improves the heat resistance of the cured material. The number average molecular weight can be determined using methods such as gel permeation chromatography.

[0077] Polyphenylene ether compounds with unsaturated double bonds can be endowed with free radical polymerization properties by reacting them with compounds that have unsaturated double bonds, such as methacryloyl chloride, acryloyl chloride, and chloromethylstyrene.

[0078] Regarding polyphenylene ether compounds having unsaturated double bonds, they can be obtained through polymerization or through a redistribution reaction of high molecular weight polyphenylene ether compounds with a weight average molecular weight of 10,000 to 30,000. For example, a redistribution reaction is carried out by heating a high molecular weight polyphenylene ether compound in a solvent such as toluene in the presence of a phenolic compound and a free radical initiator. Polyphenylene ether compounds obtained by such a redistribution reaction are preferred because they possess hydroxyl groups derived from phenolic compounds at the two ends of the molecular chain, which facilitate curing. Furthermore, from the viewpoint of exhibiting excellent flowability, polyphenylene ether compounds obtained through polymerization are preferred.

[0079] Regarding the adjustment of the molecular weight of polyphenylene ether compounds with unsaturated double bonds, if the polyphenylene ether compound is obtained through polymerization, this can be achieved by adjusting the polymerization conditions. Conversely, if the polyphenylene ether compound is obtained through redistribution reactions, the molecular weight can be adjusted by adjusting the conditions of the redistribution reaction. More specifically, adjusting the amount of phenolic compounds used in the redistribution reaction can be considered. That is, the higher the amount of phenolic compounds used, the lower the molecular weight of the resulting polyphenylene ether compound.

[0080] In 100 parts by weight of the total amount of the curable resin composition, the amount of polyphenylene ether compound having unsaturated double bonds is preferably 1 to 80 parts by weight, more preferably 5 to 75 parts by weight, and particularly preferably 10 to 70 parts by weight. If the amount exceeds the above range, the dielectric properties cannot be considered sufficient. If the amount is less than the above range, there is a concern about deterioration in heat resistance. If the amount is within the above range, both heat resistance and dielectric properties are excellent.

[0081] [Hydrogenates of block copolymers composed of block units of polymers made from styrene monomers and block units of polymers made from conjugated diene compounds]

[0082] The curable resin composition of this embodiment may also contain hydrogenated block copolymers, which are composed of "block units of polymers made from styrene monomers" and "block units of polymers made from conjugated diene compounds". The block units of polymers made from styrene monomers are, for example, shown in the following formula (a).

[0083]

[0084] R1 and R2 are preferably each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, particularly preferably a hydrogen atom or a methyl group, and most preferably a hydrogen atom. When the number of carbon atoms is greater than 5, there is a concern that the dielectric tangent may deteriorate due to molecular vibration, and there is also a concern that the heat resistance may decrease. p is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1. q is the average value of the repetitions, representing a rational number from 1 to 10000, q is preferably 1 to 7500, more preferably 1 to 5000, and particularly preferably 1 to 3000.

[0085] The block units of the polymer formed from conjugated diene compounds are obtained by polymerizing "one or more diene compounds selected from chain-like conjugated dienes such as butadiene, isoprene, farnesene, 2,3-dimethyl-1,3-butadiene, and 1,3-cyclopentadiene". From the viewpoint of ease of obtaining raw materials, butadiene, isoprene, and farnesene are more preferred among chain-like conjugated dienes, butadiene and isoprene are more preferred, and isoprene is most preferred.

[0086] The hydride of the block copolymer composed of "block units of polymers made of styrene monomers" and "block units of polymers made of conjugated diene compounds" can be any material known to the public, but is more preferably a compound represented by the following formula (6).

[0087]

[0088] In equation (6), l, m, and n are the average values ​​of the number of repetitions, representing rational numbers from 1 to 10000, more preferably from 1 to 9000, and more preferably from 1 to 8000. The order of the repeating units enclosed in l, m, or n is not limited, and the bonding pattern can be any of staggered, block, or random. The most preferred embodiment is the case where hydrogenated styrene-ethylene / propylene-styrene block copolymer (SEPS) is used.

[0089] Because the compound shown in formula (6) does not have polar groups or unsaturated bonds derived from aliphatic hydrocarbons, it is not easily oxidized even when exposed to semiconductor operating temperatures above 125°C for extended periods. Oxygen, being a polar group, is not easily incorporated into the framework. Therefore, it can mitigate the deterioration of dielectric properties after high-temperature storage tests and also exhibits excellent low water absorption characteristics.

[0090] Of 100 parts by weight of the total curable resin composition, the amount of hydride added to the block copolymer composed of "block units of polymers made from styrene monomers" and "block units of polymers made from conjugated diene compounds" is preferably 1 to 40 parts by weight, more preferably 5 to 35 parts by weight, and particularly preferably 10 to 30 parts by weight. If the amount exceeds the above range, the viscosity of the varnish will be too high, potentially deteriorating the impregnation properties of the glass cloth. If the amount is less than the above range, there is a risk of deterioration in the dielectric properties. If the amount is within the above range, both impregnation properties and dielectric properties are excellent.

[0091] The curable resin composition of this embodiment can be further mixed with various materials shown below for use.

[0092] [Polymerization initiator]

[0093] The curability of the curable resin composition of this embodiment can also be improved by adding a polymerization initiator. A polymerization initiator is a compound that can polymerize olefin functional groups such as ethylene unsaturated bonds, and examples include olefin metathesis polymerization initiators, anionic polymerization initiators, cationic polymerization initiators, and free radical polymerization initiators. Among these, a free radical polymerization initiator that possesses both 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. From the viewpoint of controlling the curing temperature, suppressing gas escape, and minimizing the impact of decomposition products on electrical properties, organic peroxides are preferred.

[0094] Examples of the aforementioned organic peroxides include: ketone peroxides such as methyl ethyl ketone peroxide and acetylacetone peroxide; diacyl peroxides such as benzoyl peroxide; dialkyl peroxides such as diisopropylbenzene peroxide and 1,3-bis-(tert-butylperoxyisopropyl)benzene; peroxy ketals such as tert-butylperoxybenzoate and 1,1-di-tert-butylperoxycyclohexane; and α-isopropylphenylperoxyneodecanate, tert-butylperoxyneodecanate, tert-butylperoxynepentanoate, 1,1,3,3-tetramethylbutylperoxy2-ethylhexanoate, and tert-pentanoate. Alkyl peroxides such as 2-ethylhexanoate, tert-butylperoxy-2-ethylhexanoate, tert-pentylperoxy-3,5,5-trimethylhexanoate, tert-butylperoxy-3,5,5-trimethylhexanoate, and tert-pentylperoxybenzoate; peroxy carbonates such as di-2-ethylhexylperoxydicarbonate, bis(4-tert-butylcyclohexyl)peroxydicarbonate, tert-butylperoxyisopropyl carbonate, and 1,6-bis(tert-butylperoxycarbonyloxy)hexane; tert-butyl hydroperoxide, cumene hydroperoxide, tert-butyl peroxyoctanoate, lauroyl peroxide, etc., but not limited to these. Furthermore, one or more of these can be used. Among the above-mentioned organic peroxides, ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, alkyl peroxides, and peroxy carbonates are more preferred, and dialkyl peroxides are even more preferred.

[0095] Examples of the aforementioned azo compounds include, but are not limited to, azobisisobutyronitrile, 4,4'-azobis(4-cyanopentanoic acid), and 2,2'-azobis(2,4-dimethylpentanonitrile). Furthermore, one or more of these compounds may be used.

[0096] In 100 parts by weight of the curable resin composition, the amount of polymerization initiator added is preferably 0.01 to 5 parts by weight, more preferably 0.01 to 3 parts by weight. If the amount of polymerization initiator used is less than 0.01 parts by weight, there is a concern that the molecular weight will not be sufficiently elongated during the polymerization reaction; if it is more than 5 parts by weight, there is a concern that dielectric properties such as dielectric constant and dielectric tangent will be impaired.

[0097] [Hardening Accelerator]

[0098] 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 generates anions by irradiation with ultraviolet or visible light or by heating, thereby promoting the curing reaction; or, a cationic curing accelerator that generates cations by irradiation with ultraviolet or visible light or by heating, thereby promoting the curing reaction.

[0099] 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 more preferred. Other examples include: phosphines such as triphenylphosphine; quaternary ammonium salts such as tetrabutylammonium salt, triisopropylmethylammonium salt, trimethyldecylammonium salt, hexadecyltrimethylammonium salt, and hexadecyltrimethylammonium hydroxide, but these are not limited to these. Furthermore, one or more of these can be used.

[0100] Cationic hardening accelerators can include, but are not limited to, quaternary phosphonium salts such as triphenylbenzylphosphonium salt, triphenylethylphosphonium salt, and tetrabutylphosphonium salt (the relative ions of quaternary salts are halogen ions, organic acid ions, hydroxide ions, etc., without special specification, but organic acid ions and hydroxide ions are particularly preferred), transition metal compounds (transition metal salts) such as tin octoate, zinc carboxylate (zinc 2-ethylhexanoate, zinc stearate, zinc docosinate, zinc myristate), and zinc phosphate esters (zinc octyl phosphate, zinc stearyl phosphate), etc. Furthermore, one or more of these can be used.

[0101] In 100 parts by weight of the curing resin composition, the amount of curing accelerator may be 0.01 to 5.0 parts by weight as needed.

[0102] [Inorganic filler]

[0103] The curable resin composition of this embodiment may also 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, soapstone, spinel, mullite, titanium dioxide, talc, clay, iron oxide asbestos, glass powder, etc., or inorganic fillers formed into spherical or fragmented shapes, but are not limited to these. Furthermore, one or more of these fillers may be used.

[0104] When obtaining a curable resin composition for semiconductor sealing, the amount of inorganic filler used in 100 parts by weight of the curable resin composition is preferably 80 to 92 parts by weight, more preferably 83 to 90 parts by weight. Furthermore, when obtaining a curable resin composition for interlayer insulating layer forming materials, copper-clad laminates, prepregs, RCC and other substrate materials, the amount of the aforementioned inorganic filler used in 100 parts by weight of the curable resin composition is preferably 5 to 80 parts by weight, more preferably 10 to 60 parts by weight.

[0105] [Polymerization Inhibitor]

[0106] The curable resin composition of this embodiment may also contain polymerization inhibitors. By containing polymerization inhibitors, storage stability can be improved, and the reaction initiation temperature can be controlled. Controlling the reaction initiation temperature makes it easy to ensure flowability without compromising impregnation of glass cloth, etc., and facilitates B-stage processes such as prepreg conditioning. If the polymerization reaction is excessively carried out during prepreg conditioning, adverse conditions such as difficulty in lamination can easily occur in the lamination step.

[0107] Regarding the polymerization inhibitor, it can be added during the synthesis of the compound shown in formula (1) above, or it can be added after synthesis. In 100 parts by weight of the compound shown in formula (1) above, the amount of polymerization inhibitor used is 0.008 to 1 part by weight, more preferably 0.01 to 0.5 parts by weight.

[0108] Examples of polymerization inhibitors include phenolic, sulfur-based, phosphorus-based, hindered amine-based, nitroso-based, and nitroacyl radical-based inhibitors. Furthermore, one or more polymerization inhibitors may be used. In this embodiment, phenolic, hindered amine, nitroso, and nitroacyl radical-based inhibitors are preferred.

[0109] Examples of phenolic polymerization inhibitors include: 2,6-di-tert-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-tert-butyl-p-ethylphenol, stearate β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, isooctyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylaniline)-1,3,5-triazine, and monophenols such as 2,4-bis[(octylthio)methyl]o-cresol; 2,2'-methylenebis(4-methyl-6-tert-butyl) phenol), 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-cinnamicamide), 2,2-thio-divinylbis[3-( Bisphenols such as 3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate-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-hydroxybenzylsulfonic acid ethyl)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]glycol, tris(3,5-di-tert-butyl-4-hydroxybenzyl)-triisocyanate, 1,3,5-tris(3',5'-di-tert-butyl-4'-hydroxybenzyl)-S-triazine-2,4,6-(1H,3H,5H)trione, tocopherol, and other high molecular weight phenols, but not limited to these.

[0110] Examples of sulfur-based polymerization inhibitors include, but are not limited to, dilaurate 3,3'-thiodipropionate, dimyristic 3,3'-thiodipropionate, and distearate 3,3'-thiodipropionate.

[0111] Examples of phosphorus-based polymerization inhibitors include: triphenyl phosphite, diphenyl isodecanyl phosphite, phenyl diisodecyl phosphite, tri(nonylphenyl) phosphite, diisodecyl pentaerythritol 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, and bis[2-tert-butyl] Phosphites such as 6-methyl-4-{2-(octadecyloxycarbonyl)ethyl}phenyl]hydrophosphite; oxaphosphazene oxides such as 9,10-dihydro-9-oxa-10-phosphazene 10-oxide, 10-(3,5-di-tert-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphazene 10-oxide, and 10-decoxy-9,10-dihydro-9-oxa-10-phosphazene 10-oxide, but not limited to these.

[0112] Examples of hindered amine polymerization inhibitors mentioned above include: ADKSTAB (registered trademark) LA-40MP, ADKSTAB LA-40Si, ADKSTAB LA-402AF, ADKSTAB LA-87, ADKSTAB LA-82, ADKSTAB LA-81, ADKSTAB LA-77Y, ADKSTAB LA-77G, ADKSTAB LA-72, ADKSTAB LA-68, ADKSTAB LA-63P, ADKSTAB LA-57, and ADKSTAB LA-52 (all manufactured by ADEKA Inc.); Chimassorb (registered trademark) 2020FDL, Chimassorb 944FDL, and Chimassorb... 944LD, Tinuvin (registered trademark) 622SF, Tinuvin PA144, Tinuvin 765, Tinuvin 770DF, Tinuvin XT55FB, Tinuvin 111FDL, Tinuvin 783FDL, Tinuvin 791FB (all of which are manufactured by BASF), etc., but not limited to these.

[0113] Examples of nitrosyl polymerization inhibitors include, but are not limited to, ammonium salts of p-nitrosophenol, N-nitrosodiphenylamine, and N-nitrosophenylhydroxylamine (Cupferron). Among these, the ammonium salt of N-nitrosophenylhydroxylamine (Cupferron) is preferred.

[0114] Examples of nitryl radical polymerization inhibitors include, but are not limited to, di-tert-butyl nitroxide radical, 2,2,6,6-tetramethylpiperidine-1-oxy, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxy, 4-sideoxy-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.

[0115] [Flame retardant]

[0116] Flame retardants may also be used in the curable resin composition of this embodiment. Examples of flame retardants include halogenated 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.

[0117] The aforementioned phosphorus-based flame retardants can be reactive or additive. Specific examples include phosphate esters such as trimethyl phosphate, triethyl phosphate, tricresyl phosphate, tri(xylenol) phosphate, cresyl diphenyl phosphate, cresyl-2,6-di(xylenol) phosphate, 1,3-epoxyphenylbis(xylenol) phosphate, 1,4-epoxyphenylbis(xylenol) phosphate, and 4,4'-biphenyl(xylenol) phosphate; and phosphine derivatives such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 10(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide. Examples also include phosphorus-containing epoxy compounds obtained by reacting epoxy resin with the active hydrogen of the aforementioned phosphine derivatives, and red phosphorus, but these are not limited to these. Furthermore, one or more of these can be used. Among the above-described substances, phosphate esters, phosphine derivatives, or phosphorus-containing epoxy compounds are particularly preferred, and 1,3-epoxyphenylbis(di-dimethylphosphide), 1,4-epoxyphenylbis(di-dimethylphosphide), 4,4'-biphenyl(di-dimethylphosphide), or phosphorus-containing epoxy compounds are more preferred.

[0118] In 100 parts by weight of the curable resin composition, the content of flame retardant is preferably in the range of 0.1 to 0.6 parts by weight. If it is less than 0.1 parts by weight, there is a concern that the flame retardancy will be insufficient; if it is more than 0.6 parts by weight, there is a concern that it will adversely affect the hygroscopicity and dielectric properties of the cured material.

[0119] [Light stabilizer]

[0120] Light stabilizers may also be used in the curable resin composition of this embodiment. Hindered amine light stabilizers (HALS) are preferred. Examples of HALS include: a reaction product of dibutylamine / 1,3,5-triazine / N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl-1,6-hexamethylenediamine and N-(2,2,6,6-tetramethyl-4-piperidinyl)butylamine, a reaction product of dimethyl-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-piperidinyl)imino}] 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)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate, bis(1-octoxy-2,2,6,6-tetramethyl-4-piperidinyl)sebacate, 2-(3,5-di-tert-butyl-4-hydroxybenzyl)-2-n-butylmalonate bis(1,2,2,6,6-pentamethyl-4-piperidinyl), etc., but not limited to these. Furthermore, one or more of these can be used.

[0121] In 100 parts by weight of the curable resin composition, the content of the light stabilizer is preferably in the range of 0.001 to 0.1 parts by weight. If it is less than 0.001 parts by weight, there is a concern that the light stabilizing effect may not be fully manifested. In addition, if it is more than 0.1 parts by weight, there is a concern that it may adversely affect the hygroscopicity and dielectric properties of the cured material.

[0122] [Adhesive Resin]

[0123] The curable resin composition of this embodiment may also use a binder resin. Examples of binder resins include, butyral resins, acetal resins, acrylic resins, epoxy-nylon resins, NBR-phenol resins, epoxy-NBR resins, and silicone resins, but are not limited to these. Furthermore, one or more of these resins may be used.

[0124] Regarding the amount of binder resin, it is preferred to use within a range that does not impair the flame retardancy and heat resistance of the cured product. In 100 parts by weight of the cured resin composition, it is more preferably used to use 0.05 to 50 parts by weight, and more preferably to use 0.05 to 20 parts by weight, depending on the need.

[0125] [additive]

[0126] Additives may also be used in the curable resin composition of this embodiment. Examples of additives include, for instance, modified acrylonitrile copolymers, polyethylene, fluororesins, polysiloxane gels, polysiloxane oils, silane coupling agents, and other filler surface treatment agents, mold release agents, carbon black, phthalocyanine blue, phthalocyanine green, and other colorants.

[0127] In 100 parts by weight of the curable resin composition, the amount of additive is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, and particularly preferably 10 parts by weight or less.

[0128] The curable resin composition of this embodiment may further include, for example, epoxy resin, reactive ester compound, phenolic resin, polyphenylene ether compound without unsaturated double bonds, amine resin, compound with vinyl unsaturated bonds, isocyanate resin, polyamide resin, maleic anhydride compound, cyanate resin, polyimide resin, polybutadiene and its modified forms, polystyrene and its modified forms, polyethylene and its modified forms, etc. One or more of these compounds may be used. From the viewpoint of balancing heat resistance, adhesion, and dielectric properties, it is preferable to include: maleic anhydride compound, polyphenylene ether compound without unsaturated double bonds, amine resin, compound with vinyl unsaturated bonds, isocyanate resin, polyamide resin, compound with vinyl unsaturated bonds, cyanate resin, polybutadiene and its modified forms, polystyrene and its modified forms, and polyethylene and its modified forms. By including these compounds, the brittleness of the hardened material and the adhesion to the metal can be improved, and the cracking of the package can be suppressed during solder reflow or reliability tests such as thermal cycling. Regarding the total amount of the aforementioned compounds, unless otherwise stated, it is preferably 10 times or less by mass relative to the compound shown in formula (1), more preferably 5 times or less by mass, and particularly preferably 3 times or less by mass. Furthermore, the lower limit is preferably 0.1 times or more by mass, more preferably 0.25 times or more by mass, and particularly preferably 0.5 times or more by mass. By setting it within the aforementioned range, the low dielectric properties of the compound shown in formula (1) can be utilized, and the effects of each of the known compounds can be added. Examples of these components are shown below.

[0129] [Epoxy Resin]

[0130] Regarding epoxy resins, the following are examples of preferred formulations, but the use is not limited to these. Furthermore, epoxy resins can be in liquid or solid form, and one type or multiple types can be used.

[0131] 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, phenol novolac 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, etc. Specific examples include: "RE310S", "RE410S" (all manufactured by Nippon Kayaku Co., Ltd., bisphenol A type epoxy resin); "RE303S", "RE304S", "RE403S", "RE404S" (all manufactured by Nippon Kayaku Co., Ltd., bisphenol F type epoxy resin); "HP4032", "HP4032D", "HP4032SS" (all manufactured by DIC Corporation, naphthalene type epoxy resin); "828US", "jER (registered trademark) 828EL", "825", "828" "EL" (all of the above are bisphenol A type epoxy resins manufactured by Mitsubishi Chemical Corporation); "jE807" and "1750" (all of the above are bisphenol F type epoxy resins manufactured by Mitsubishi Chemical Corporation); "jER152" (phenolic aldehyde varnish type epoxy resin manufactured by Mitsubishi Chemical Corporation), "630" and "630LSD" (all of 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) ChemteX (glycidyl ester type epoxy resin); Celloxide 2021P (Daicel Corporation, alicyclic epoxy resin with an ester backbone); PB-3600 (Daicel Corporation, an epoxy resin with a butadiene structure); ZX1658 and ZX1658GS (both manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., liquid 1,4-epoxypropylcyclohexane type epoxy resins), etc. These can be used individually or in combination of two or more.

[0132] Solid epoxy resins are preferably, 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, naphthyl ether-type epoxy resin, anthracene-type epoxy resin, bisphenol A-type epoxy resin, bisphenol AF-type epoxy resin, tetraphenylethane-type epoxy resin, and 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, naphthalene-type epoxy resin); "HP-4700" and "HP-4710" (both manufactured by DIC, naphthalene-type tetrafunctional epoxy resins); "N-690" (manufactured by DIC, cresol-phenolic varnish-type epoxy resin); "N-695" (manufactured by DIC, cresol-phenolic varnish-type epoxy resin); "HP-7200" (manufactured by DIC, dicyclopentadiene-type epoxy resin); "HP-7200" and "HP-7200" "HH", "HP-7200H" (all manufactured by DIC Corporation, dicyclopentadiene type epoxy resin); "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP-6000" (all manufactured by DIC Corporation, naphthyl ether type epoxy resin); "EPPN-502H" (manufactured by Nippon Kayaku Co., Ltd., pyrrolidone type epoxy resin); "NC-7000L", "NC-7300" (all manufactured by Nippon Kayaku Co., Ltd., pyrrolidone type epoxy resin); This company manufactures naphthol-cresyl phenolic epoxy resins; "NC-3000H", "NC-3000", "NC-3000L", "NC-3100" (all manufactured by Nippon Chemical Co., Ltd., biphenyl aralkyl type epoxy resins); "XD-1000-2L", "XD-1000-L", "XD-1000-H", "XD-1000-H" (all manufactured by Nippon Chemical Co., Ltd., dicyclopentadiene type epoxy resins); "ESN475V" (Nippon Steel & Sumitomo Metal Chemicals). Nippon Steel & Sumitomo Chemical Co., Ltd. (manufactured naphthol-type epoxy resin); "ESN485" (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., naphthol phenolic varnish type epoxy resin); "YX-4000H", "YX-4000", "YL6121" (all manufactured by Mitsubishi Chemical Co., Ltd., biphenyl-type epoxy resin); "YX-4000HK" (manufactured by Mitsubishi Chemical Co., Ltd., bixylenol-type epoxy resin); "YX-8800" (manufactured by Mitsubishi Chemical Co., Ltd., anthracene-type epoxy resin); "PG-100", "CG-500" (Osaka Gas Chemicals manufactures fluorene-based epoxy resins; "YL-7760" (Mitsubishi Chemical Corporation manufactures bisphenol AF type epoxy resin), "YL-7800" (Mitsubishi Chemical Corporation manufactures fluorene type epoxy resin), "jER1010" (Mitsubishi Chemical Corporation manufactures solid bisphenol A type epoxy resin), "jER1031S" (Mitsubishi Chemical Corporation manufactures tetraphenylethane type epoxy resin), etc. These can be used individually or in combination of two or more.

[0133] [Active Ester Compound]

[0134] The term "reactive ester compound" refers to a compound containing at least one ester bond in its structure, with aliphatic chains, aliphatic rings, or aromatic rings bonded to both sides of the ester bond. Examples of reactive ester compounds include phenolic esters, thiophenolic esters, N-hydroxyamine esters, and heterocyclic hydroxyl esters, which are compounds with two or more highly reactive ester groups in one molecule. They are obtained by a condensation reaction of "at least one of a carboxylic acid compound, acyl chloride, or thiocarboxylic acid compound" with "at least one of a hydroxyl compound or thiol compound." Particularly from the viewpoint of improving heat resistance, it is preferable to obtain a compound from a carboxylic acid compound or acyl chloride and a hydroxyl compound; the hydroxyl compound is preferably a phenolic compound or a naphthol compound. Reactive ester compounds can be used alone or in combination of two or more.

[0135] Examples of the aforementioned carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, isophthalic acid, p-phthalic acid, and pyromellitic acid.

[0136] Examples of the aforementioned acyl chlorides include: acetyl chloride, acryloyl chloride, methacryloyl chloride, malonyl chloride, succinoyl dichloride, diglycyl chloride, glutaric acid dichloride, suberic acid dichloride, sebacic acid dichloride, adipic acid dichloride, dodecanedioyl dichloride, azelaoyl dichloride, 2,5-furandicarbonyl dichloride, phthaloyl chloride, isophthaloyl chloride, p-phthaloyl chloride, trimesoyl chloride, bis(4-chlorocarbonylphenyl) ether, 4,4'-diphenyldicarbonyl chloride, 4,4'-azodibenzoyl dichloride, etc.

[0137] Examples of the aforementioned phenolic compounds and naphthol compounds include: hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, 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, phloroglucinol, 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 one molecule of dicyclopentadiene and two molecules of phenol.

[0138] 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 benzoyl form of phenolic varnish, the compound described in Example 2 of International Publication No. 2020 / 095829, and the compound disclosed in International Publication No. 2020 / 059625. More preferred are active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene-type diphenol structure. The term "dicyclopentadiene-type diphenol structure" refers to a divalent structural unit composed of exenylphenyl-exenyldicyclopentyl-exenylphenyl.

[0139] Commercially available reactive ester compounds include, for example, reactive ester compounds containing a dicyclopentadiene-type diphenol structure such as "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "HPC-8000H-65TM", "EXB-8000L-65TM", and "EXB-8150-65T" (manufactured by DIC Corporation); and reactive ester compounds containing a naphthalene structure such as "EXB9416-70BK" (manufactured by DIC Corporation). The active ester compounds containing phenolic varnishes that are acetylated can be listed as "DC808" (manufactured by Mitsubishi Chemical Corporation). The active ester compounds containing phenolic varnishes that are benzoylated can be listed as "YLH1026", "YLH1030", and "YLH1048" (manufactured by Mitsubishi Chemical Corporation). The active ester compounds containing phenolic varnishes that are acetylated and used as curing agents can be listed as "DC808" (manufactured by Mitsubishi Chemical Corporation). The active ester compounds containing phosphorus atoms that are used as curing agents can be listed as "EXB-9050L-62M" manufactured by DIC Corporation, etc.

[0140] Regarding the blending ratio of the reactive ester compound to 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 particularly preferably 0.90 to 1.10. If the above range is not met, there is a concern that excess epoxy groups or reactive ester groups may remain in the system, which could lead 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.).

[0141] [Phenolic resin]

[0142] Phenolic resins refer to compounds with two or more phenolic hydroxyl groups within their molecules. Examples of phenolic resins include, but are not limited to, reactants of phenols with aldehydes, reactants of phenols with dienes, reactants of phenols with ketones, reactants of phenols with substituted biphenyls, reactants of phenols with substituted phenyl compounds, and reactants of bisphenols with aldehydes. Furthermore, one or more of these can be used.

[0143] Specific examples of the above-mentioned raw materials are shown below, but are not limited to these.

[0144] <Phenolic compounds>

[0145] Phenols, alkyl-substituted phenols, aromatic-substituted phenols, hydroquinone, resorcinol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.

[0146] Aldehydes

[0147] Formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, furfural, etc.

[0148] <Diene Compounds>

[0149] Dicyclopentadiene, terpenes, vinylcyclohexene, nordiene, vinyl nordiene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.

[0150] Ketones

[0151] Acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, diphenyl ketone, fluorene ketone, etc.

[0152] <Substituted biphenyls>

[0153] 4,4'-bis(chloromethyl)-1,1'-biphenyl, 4,4'-bis(methoxymethyl)-1,1'-biphenyl, 4,4'-bis(hydroxymethyl)-1,1'-biphenyl, etc.

[0154] <Substituted phenyl compounds>

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

[0156] [Polyphenylene ether compounds without unsaturated double bonds]

[0157] The term "polyphenylene ether compound without unsaturated double bonds" refers to polyphenylene ether compounds other than those with unsaturated double bonds. The number average molecular weight (Mn) of the polyphenylene ether compound without unsaturated double bonds 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 cured material tends to lack sufficient heat resistance. 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, there is a tendency for decreased reactivity, longer curing time, increased unreacted substances not introduced into the curing system, lower glass transition temperature of the cured material, and reduced heat resistance of the cured material.

[0158] 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, this number average molecular weight can be specifically determined using methods such as gel permeation chromatography.

[0159] For polyphenylene ether compounds without unsaturated double bonds, they can be obtained through polymerization or through a redistribution reaction of high molecular weight polyphenylene ether compounds with a number average molecular weight of about 10,000 to 30,000. Polyphenylene ether compounds obtained through redistribution reactions are, for example, obtained by heating a high molecular weight polyphenylene ether compound in a solvent such as toluene in the presence of a phenolic compound and a free radical initiator, followed by a redistribution reaction. Accordingly, polyphenylene ether compounds obtained through redistribution reactions are preferred because they have hydroxyl groups derived from phenolic compounds that contribute to curing at the two ends of the molecular chain, thus maintaining higher heat resistance. Furthermore, functional groups can still be introduced to the two ends of the molecular chain after modification with compounds having vinyl unsaturated bonds. Additionally, from the viewpoint of exhibiting excellent flowability, polyphenylene ether compounds without unsaturated double bonds obtained through polymerization reactions are preferred.

[0160] Regarding the adjustment of the molecular weight of polyphenylene ether compounds without unsaturated double bonds, if the polyphenylene ether compound is obtained through polymerization, this can be achieved by adjusting the polymerization conditions, etc. Alternatively, if the polyphenylene ether compound is obtained through redistribution, the molecular weight can be adjusted by adjusting the conditions of the redistribution reaction, etc. More specifically, the amount of phenolic compound used in the redistribution reaction can be adjusted. That is, the more phenolic compound used, the lower the molecular weight of the obtained polyphenylene ether compound. In this case, poly(2,6-dimethyl-1,4-phenylene ether) and the like can be used as the high molecular weight polyphenylene ether compound undergoing the redistribution reaction. Furthermore, there are no particular limitations on the phenolic compound used in the aforementioned redistribution reaction; for example, polyfunctional phenolic compounds with two or more phenolic hydroxyl groups in their molecules, such as bisphenol A, phenolic varnish, and cresol varnish, are preferred. One of these can be used alone, or two or more can be used in combination.

[0161] [Amine resin]

[0162] Amine resins are compounds containing two or more amine groups within their molecules. Examples of amine resins include: diaminodiphenylmethane, diaminodiphenyl sulfone, isophorone diamine, naphthyldiamine, aniline-phenolic varnish (a product of the reaction of aniline and formalin), N-methylaniline-phenolic varnish (a product of the reaction of N-methylaniline and formalin), o-ethylaniline-phenolic varnish (a product of the reaction of o-ethylaniline and formalin), 2-methylaniline reacting with formalin, 2,6-diisopropylaniline reacting with formalin, 2,6-diethylaniline reacting with formalin, 2-ethyl-6-ethylaniline reacting with formalin, 2,6-dimethylaniline reacting with formalin, and resins obtained from the reaction of aniline with dichloroxylene. Aniline resins; reactants 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); reactants of aniline with substituted phenyls (such as 1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene and 1,4-bis(hydroxymethyl)benzene, etc.); 4,4'-(1,3-epenylphenyldiisopropylidene)bisaniline and 4,4'-(1,4-epenylphenyldiisopropylidene)bisaniline; reactants of aniline with diisopropylbenzene; dimerized diamines, etc., but not limited to these. Furthermore, one or more of these may be used.

[0163] [Compounds containing ethylene-like unsaturated bonds]

[0164] Compounds with ethylene unsaturated bonds are those that can be polymerized by heat or light regardless of the use of a polymerization initiator, and that have one or more ethylene unsaturated bonds in their molecules.

[0165] Examples of compounds containing vinyl unsaturated bonds include: reactants of the aforementioned phenolic resins with halogenated compounds containing vinyl unsaturated bonds (chloromethylstyrene, allyl chloride, methylallyl chloride, acryloyl chloride, methacryloyl chloride, etc.); reactants of phenols containing vinyl unsaturated bonds (2-allylphenol, 2-propenylphenol, 4-allylphenol, 4-propenylphenol, eugenol, isoeugenol, etc.) with halogenated compounds (1,4-bis(chloromethyl)benzene, 4,4'-bis(chloromethyl)biphenyl, 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-dibromobenzophenone, cyanuric trichloroethylene, etc.); reactants of epoxy resins or alcohols with (meth)acrylic acids (acrylic acid, methacrylic acid, etc.) and their acid-modified derivatives, but are not limited to these. Furthermore, one or more of these compounds may be used.

[0166] [Isocyanate resin]

[0167] Isocyanate resins refer to 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, northocyanide diisocyanate, and lysine diisocyanate; polyisocyanates such as one or more biuret forms of isocyanate monomers, or isocyanates formed by trimerizing the above diisocyanate compounds; and polyisocyanates obtained by the aminoformation reaction of the above isocyanate compounds with polyol compounds, but are not limited to these. In addition, one type of these can be used, or multiple types can be used together.

[0168] [Polyamide resin]

[0169] Examples of polyamide resins include: reactants of diamines, diisocyanates, and oxazolines with dicarboxylic acids; reactants of diamines with acyl chlorides; and ring-opening polymers of lactam compounds. Furthermore, one or more of these may be used.

[0170] Specific examples of the above-mentioned raw materials are shown below, but are not limited to these.

[0171] <Diamine>

[0172] 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, di... Polymeric diamine, cyclohexane diamine, bis(4-aminocyclohexyl)methane, bis(3-methyl-4-aminocyclohexyl)methane, xylene diamine, northane diamine, isophorone diamine, diaminomethyltricyclodecane, phenylenediamine, diethyltoluene diamine, naphthyl diamine, diaminodiphenylmethane, bis(4-amino-3,5-dimethylphenyl)methane, bis(4-amino-3,5-diethylphenyl)methane, 4,4'-methylenebis(o-toluene) Amines, 4,4'-methylenebis-o-ethylaniline, 4,4'-methylenebis-2-ethyl-6-methylaniline, 4,4'-methylenebis-2,6-diisopropylaniline, 4,4-vinyldiphenylamine, 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-aminophenyl) [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-aminophenyldiisopropylidene)bisaniline, 4,4'-(1,4-aminophenyldiisopropylidene)bisaniline, 9,9-bis(4-aminophenyl)fluorene, 2,7-diaminofluorene, aminobenzylamine, diaminobenzophenone, etc.

[0173] Diisocyanate

[0174] 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.

[0175] Dicarboxylic acid

[0176] Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, octanoic acid, azelaic acid, sebacic acid, undecanoic acid, dodecanoic acid, p-phthalic acid, isophthalic acid, 5-hydroxyisophthalic acid, 2-chlorop-phthalic acid, 2-methylp-phthalic acid, 5-methylisophthalic acid, sodium 5-sulfoisophthalate, hexahydrop-phthalic acid, hexahydroisophthalic acid, cyclohexanedicarboxylic acid, biphenyldicarboxylic acid, naphthalenedicarboxylic acid, diphenyl ketonedicarboxylic acid, furandicarboxylic acid, 4,4'-dicarboxylic acid diphenyl ether, 4,4'-dicarboxylic acid diphenyl sulfide, etc.

[0177] <Acyl chloride>

[0178] Acetyl chloride, acryloyl chloride, methacryloyl chloride, malonyl chloride, succinyl dichloride, diglycyl chloride, glutaryl dichloride, octyl dichloride, sebacyl dichloride, adipicoyl dichloride, dodecyl dichloride, azelaic dichloride, 2,5-furandicarboxyl dichloride, phthaloyl chloride, isophthaloyl chloride, p-phthaloyl chloride, pyromellitic tricarboxylic acid chloride, bis(4-chlorocarbonylphenyl) ether, 4,4'-diphenyldicarbonyl chloride, 4,4'-azobisbenzoyl dichloride, etc.

[0179] <lactam>

[0180] ε-caprolactam, ω-undecanolactam, ω-dodecanolactam, etc.

[0181] [Polyimide resin]

[0182] Regarding polyimide resins, examples of reactions between the aforementioned diamines and the tetracarboxylic dianhydrides exemplified below can be cited, but are not limited to these. Furthermore, one or more of these can be used.

[0183] Tetracarboxylic dianhydride

[0184] 4,4'-(hexafluoroisopropylidene) phthalic anhydride, 5-(2,5-di-side-oxytetrahydro-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'-diaphthalic anhydride, 1,1-ethylidene-4,4'-diaphthalic anhydride, 2,2'-propylidene-4,4'-diaphthalic anhydride, 1,2-vinyl-4,4'-diaphthalic anhydride 1,3-Trimethylene-4,4'-Diphenic acid dianhydride, 1,4-Tetramethylene-4,4'-Diphenic acid dianhydride, 1,5-Pentamethylene-4,4'-Diphenic acid dianhydride, 4,4'-Oxydiphthalic acid dianhydride, Thio-4,4'-Diphenic acid dianhydride, Sulfonyl-4,4'-Diphenic acid dianhydride, 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, 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-phenanthrenetetracarboxylic acid dianhydride, vinyltetracarboxylic acid dianhydride, 1,2,3,4-butanetetracarboxylic acid dianhydride, 1, 2,3,4-Cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride, carbonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, methylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,2-vinyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,1-ethylidene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 2,2-propylidene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, oxy-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, thio-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, sulfonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, bicyclo[2,2,2]oct-7-en-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-disideoxytetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride, ethylene glycol-bis-(3,4-dicarboxylic acid anhydride phenyl) ether, 4,4'-biphenylbis(trimethylammonium phthalate anhydride), 9,9'-bis(3,4-dicarboxyphenyl)fluorene dianhydride, etc.

[0185] [cis-butenediamide compound]

[0186] The curable resin composition of this embodiment may also contain a maleic anhydride compound. A maleic anhydride compound is defined as a compound having one or more maleic anhydride groups within its molecule. Examples of cis-butene diimide compounds include: 4,4'-diphenylmethane bis-cis-butene diimide, polyphenylmethane cis-butene diimide, m-phenyl bis-cis-butene diimide, 2,2'-bis[4-(4-cis-butene diimide phenoxy)phenyl]propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bis-cis-butene diimide, 4-methyl-1,3-epylphenyl bis-cis-butene diimide, 4,4'-diphenyl ether bis-cis-butene diimide, 4,4'-diphenyl sulfone bis-cis-butene diimide, 1,3-bis(3-cis-butene diimide phenoxy)benzene, 1,3-bis(4-cis-butene diimide phenoxy)benzene, and XYLOCK-type cis-butene diimide. Butenyl diimide compounds (ANILIX-MI, manufactured by Anilix Chemicals), biphenyl aralkyl type maleic diimide compounds (solidified by removing the solvent from a resin solution containing maleic diimide compound (M2) as described in Example 4 of Japanese Patent Application Publication No. 2009-001783 under reduced pressure), diaminoisopropylphenylbenzene type maleic diimide (maleic diimide compounds described in International Publication No. 2020 / 054601), maleic diimide compounds having an indane structure as described in Japanese Patent No. 6629692 or International Publication No. 2020 / 217679; MATERIAL The cis-butenedimide compounds described in STAGE Vol. 18, No. 12 2019, “~Continued · Epoxy Resin CAS Registration Number ~ Hardener CAS Number Memorandum No. 31 bis(cis-butenedimide (1)” or MATERIAL STAGE Vol. 19, No. 2 2019, “~Continued · Epoxy Resin CAS Registration Number ~ Hardener CAS Number Memorandum No. 32 bis(cis-butenedimide (2)”, etc., are not limited to these. Furthermore, one or more of these compounds may be used.

[0187] [Cyanate ester resin]

[0188] Regarding cyanate ester resins, these are cyanate ester compounds obtained by reacting phenolic resins with cyanide halides. Specific examples include: dicyanophenyl, tricyanophenyl, dicyanonaphthalene, dicyanobiphenyl, 2,2'-bis(4-cyanophenyl)propane, bis(4-cyanophenyl)methane, bis(3,5-dimethyl-4-cyanophenyl)methane, 2,2'-bis(3,5-dimethyl-4-cyanophenyl)propane, 2,2'-bis(4-cyanophenyl)ethane, 2,2'-bis(4-cyanophenyl)hexafluoropropane, bis(4-cyanophenyl)sulfone, bis(4-cyanophenyl) sulfide, phenolic varnish cyanate, and compounds that convert 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.

[0189] Furthermore, the cyanate ester compound described in the synthesis method of Japanese Patent Application Publication No. 2005-264154 is particularly suitable as a cyanate ester compound because of its low hygroscopicity, flame retardancy, and excellent dielectric properties.

[0190] In the case of cyanate ester resins, if the cyanate ester groups are trimerized to form a sym-triazine ring as required, catalysts such as zinc naphthenate, cobalt naphthenate, copper naphthenate, lead naphthenate, zinc octanoate, tin octanoate, lead acetylacetone, and dibutyltin maleate may also be included.

[0191] In 100 parts by weight of the cyanate ester resin and the curing resin composition, the catalyst is preferably used in amounts of 0.0001 to 0.10 parts by weight, and more preferably in amounts of 0.00015 to 0.0015 parts by weight.

[0192] Polybutadiene and its modified derivatives

[0193] Polybutadiene and its modified derivatives refer to polybutadiene or compounds with structures derived from polybutadiene within the molecule. These polybutadiene-derived structures can also be converted from some or all unsaturated bonds to single bonds through hydrogenation.

[0194] Examples of polybutadiene and its modified derivatives 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 RICON-100, RICON-181, RICON-184 (all manufactured by CRAY VALLEY), and 1,2-SBS (manufactured by Nippon Soda), while examples of polybutadiene include B-1000, B-2000, and B-3000 (all manufactured by Nippon Soda). Regarding the molecular weight of polybutadiene and styrene-butadiene rubber, based on weight-average molecular weight, it is preferably 500 to 10,000, more preferably 750 to 7,500, and even more preferably 1,000 to 5,000. If it is below the lower limit of the above range, the volatile content is too high, making it difficult to adjust the solid content when making prepregs. In addition, if it is above the upper limit of the above range, the compatibility with other curing resins will deteriorate. Generally speaking, if it is a compound containing heteroatoms such as bis(cis-butenedimide) or poly(cis-butenedimide), its polarity makes it difficult to guarantee its compatibility with "low-polarity compounds such as compounds mainly composed of hydrocarbons or compounds composed only of hydrocarbons". On the other hand, the compound shown in the above formula (1) has excellent compatibility with "materials with low polarity and low dielectric properties or compounds composed only of hydrocarbons" because its skeleton is not designed to actively introduce heteroatoms such as oxygen or nitrogen.

[0195] Polystyrene and its modified forms

[0196] The term "polystyrene and its modified forms" refers to polystyrene or compounds that have a structure derived from polystyrene within their molecules.

[0197] Examples of polystyrene and its modified derivatives include: polystyrene, styrene-2-isopropenyl-2-oxazoline copolymers (EPOCROS RPS-1005, RP-61, both manufactured by Nippon Catalyst Co., Ltd.); SEP (styrene-ethylene-propylene copolymer: SEPTON (registered trademark) 1020, manufactured by KURARAY Co., Ltd.); SEPS (styrene-ethylene-propylene-styrene copolymers: SEPTON2002, SEPTON2004F, SEPTON2005, SEPTON2006, SEPTON2063, SEPTON2104, all manufactured by KURARAY Co., Ltd.); SEEPS (styrene-ethylene / ethylene-propylene-styrene block copolymers: SEPTON4003, SEPTON4044, SEPTON4055, SEPTON4077, SEPTON4099). All are manufactured by KURARAY; SEBS (styrene-ethylene-butene-styrene block copolymers: SEPTON 8004, SEPTON 8006, SEPTON 8007L, all manufactured by KURARAY); SEEPS-OH (styrene-ethylene / ethylene-propylene-styrene block copolymers with hydroxyl groups at the end: SEPTON HG252, manufactured by KURARAY); SIS (styrene-isoprene-styrene block copolymers: SEPTON 5125, SEPTON 5127, all manufactured by KURARAY); hydrogenated SIS (hydrogenated styrene-isoprene-styrene block copolymers: HYBRAR (registered trademark) 7125F, HYBRAR... 7311F (all manufactured by KURARAY); SIBS (styrene-isobutylene-styrene block copolymer: SIBSTAR (registered trademark) 073T, SIBSTAR 102T, SIBSTAR 103T, all manufactured by Kaneka); SEPTON V9827 (manufactured by KURARAY), etc., but not limited to these. Furthermore, one or more of these can be used. Regarding polystyrene and its modified products, those without unsaturated bonds exhibit higher heat resistance and are less prone to oxidative degradation, thus being preferred. In addition, there are no particular restrictions on the weight average molecular weight of polystyrene and its modified products if it is above 10,000. However, if it is too large, not only will the compatibility with polyphenylene ether compounds deteriorate, but the compatibility with "low molecular weight components with a weight average molecular weight of about 50 to 1,000 and oligomer components with a weight average molecular weight of about 1,000 to 5,000" will also deteriorate, making it difficult to guarantee the stability of mixing and solvents. Therefore, a weight average molecular weight of about 10,000 to 300,000 is preferred.

[0198] Polyethylene and its modified forms

[0199] Polyethylene and its modified derivatives refer to polyethylene or compounds having a structure derived from polyethylene within their molecules. Examples of polyethylene and its modified derivatives include: ethylene-propylene copolymers, ethylene-styrene copolymers, ethylene-propylene-ethylene norbornene copolymers (Mitsui Chemicals EBT: K-8370EM, K-9330M, etc.); ethylene-propylene-vinyl norbornene copolymers (Mitsui Chemicals VNB-EPT: PX-006M, PX-008M, PX-009M, etc.); ethylene-vinyl alcohol copolymers, ethylene-vinyl acetate copolymers, etc., 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 crosslinkable 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 it is too large, not only will the compatibility with polyphenylene ether compounds deteriorate, but the compatibility with "low molecular weight components with a weight average molecular weight of about 50 to 1,000 and oligomer components with a weight average molecular weight of about 1,000 to 5,000" will also deteriorate, making it difficult to guarantee the stability of mixing and solvents. Therefore, a weight average molecular weight of about 10,000 to 300,000 is preferred.

[0200] Regarding the curable resin composition of this embodiment, it can be obtained by mixing the above-mentioned components in a predetermined ratio, pre-curing at 130 to 180°C for 30 to 500 seconds, and further post-curing at 150 to 200°C for 2 to 15 hours, thereby obtaining a cured product through a sufficient curing reaction. 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.

[0201] There are no particular limitations on the method for preparing the curable resin composition of this embodiment. The components may simply be mixed uniformly, or prepolymerization may be performed. In the case of prepolymerization, for example, the compound shown in formula (1) or the polymer containing the structural unit shown in formula (2) may be prepolymerized by heating 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, maleic anhydride compounds, cyanate compounds, polybutadiene and its modified forms, polystyrene and its modified forms, inorganic fillers, and other additives". Regarding the mixing or prepolymerization of the components, in the absence of a solvent, mixing is performed by using, for example, an extruder, kneader, or roller, to soften the components above their softening point while kneading. In the presence of a solvent, homogenization is performed by using a reaction vessel equipped with a stirring device, or by adding solvent after measuring each component.

[0202] Regarding the method of uniform mixing, the resin composition is formed by kneading at a temperature ranging from 50 to 100°C using devices such as kneaders, rollers, or planetary mixers. The resulting resin composition can be pulverized and formed into cylindrical ingots using molding machines such as ingot beaters, or it can be made into granular powder or powdered molded articles. Alternatively, these compositions can be melt-formed onto a surface support into sheets with a thickness of 0.05 mm to 10 mm to produce curable resin composition molded articles. The obtained molded articles become non-sticky molded articles at 0 to 20°C, and their fluidity and curability hardly decrease even after storage at -25 to 0°C for more than one week.

[0203] The obtained molded body can be formed into a hardened material using a transfer molding machine or a compression molding machine.

[0204] In the curable resin composition of this embodiment, an organic solvent may also be added to form a varnish-like composition (hereinafter also referred to as "varnish"). 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 form a varnish, which is then impregnated in a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, or paper. After heating and drying, a prepreg is obtained, and then hot-pressed to produce a cured product of the curable resin composition of this embodiment. Regarding the solvent, in the mixture of the curable resin composition and the solvent in this embodiment, it is used in an amount of 10 to 70% by weight (preferably 15 to 70% by weight). Alternatively, if it is a liquid composition, a cured product containing carbon fibers can be obtained directly by, for example, RTM.

[0205] 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. Such a film-type resin composition is obtained by applying the curable resin composition of this embodiment as a varnish onto a release film, removing the solvent under heat, and then performing B-stage processing to obtain a sheet-like adhesive. This sheet-like adhesive can be used as an "interlayer insulating layer for multilayer substrates, etc."

[0206] The curable resin composition of this embodiment can also be melted by heating to reduce viscosity, and a prepreg can be obtained by impregnating it with reinforcing fibers such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, and alumina fiber. 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; as well as inorganic fibers other than glass, organic fibers such as poly(p-phenylene terephthalamide) (KEVLAR (registered trademark), manufactured by DuPont), fully aromatic polyamide, polyester, poly(p-phenylene benzoxazole), polyimide, and carbon fiber, but are not limited to these. The shape of the substrate is not particularly limited, and examples include woven fabric, nonwoven fabric, roving, and chopped strand mat. In addition, the weaving methods of the woven fabric are known to include plain weave, basket weave, and twill weave, and appropriate selection can be made from these known materials according to the intended use and performance. Additionally, glass fabrics that have undergone fiber opening treatment or surface treatment with silane coupling agents are suitable. The thickness of the substrate is not particularly limited, but is preferably around 0.01 to 0.4 mm. Alternatively, a prepreg can be obtained by impregnating the aforementioned varnish into reinforcing fibers and then heating and drying it.

[0207] Alternatively, the aforementioned prepregs can also be used to manufacture laminates. For laminates, having one or more prepregs is sufficient and is not particularly limited; other layers are also permissible. Regarding the manufacturing method of the laminate, generally known methods are suitable and are not particularly limited. For example, when forming a laminate covered with metal foil, a multi-stage press, a multi-stage vacuum press, a continuous forming machine, or an autoclave forming machine can be used to stack the aforementioned prepregs and perform heating and pressure forming to obtain the laminate. In this case, the heating temperature is not particularly limited, but 65 to 300°C is preferred, and 120 to 270°C is more preferred. Regarding the pressure applied, while there is no particular limitation, if the pressure is too high, it will be difficult to adjust the solid content of the resin in the laminate, resulting in unstable quality. Conversely, if the pressure is too low, air bubbles may appear or the adhesion between the layers may deteriorate. Therefore, 2.0 to 5.0 MPa is preferred, and 2.5 to 4.0 MPa is more preferred. The laminate of this embodiment has a layer made of metal foil, so it is suitable for use as a laminate covered with metal foil as described later.

[0208] The prepreg is cut into the desired shape and laminated with copper foil as needed. While applying pressure to the laminate using a pressure forming method, a hot press forming method, a sheet winding forming method, etc., the curable resin composition is heated and cured, thereby obtaining an electronic laminate (printed wiring board) and a carbon fiber reinforced material.

[0209] The curable resin composition of this embodiment can also be made into a resin sheet. Regarding the method of obtaining a resin sheet from the curable resin composition of this embodiment, an example is a method of forming a resin composition layer on a support film (support body) by coating the curable resin composition onto the support film and then drying it. When using the curable resin composition of this embodiment for a resin sheet, the key point is that "the film softens under the lamination temperature conditions (70°C to 140°C) of the vacuum laminating method, and simultaneously with the lamination with the circuit board, it exhibits the fluidity (resin flow) to fill the via holes or through holes present in the circuit board." To achieve such characteristics, it is preferable to incorporate the aforementioned components. Furthermore, in order to prevent localized differences in characteristic values ​​due to phase separation or the like in the obtained resin sheet and circuit board (copper-clad laminate, etc.), and to ensure that certain properties are exhibited in any location, uniform appearance is required.

[0210] Here, the diameter of the through hole in the circuit board is 0.1 to 0.5 mm, and the depth is 0.1 to 1.2 mm, preferably filled with resin within this range. Furthermore, when laminating both sides of the circuit board, it is preferable to fill approximately half of the through hole.

[0211] Regarding the specific method for manufacturing the aforementioned resin sheet, one example is: after preparing a resin composition by mixing an organic solvent and varnishing it, coating the surface of a support film (Y) with the aforementioned varnished resin composition, and further heating or blowing hot air to dry the organic solvent to form a resin composition layer (X).

[0212] Regarding the organic solvent used here, it is preferable to use, for example: ketones such as acetone, methyl ethyl ketone, and cyclohexanone; acetates such as ethyl acetate, butyl acetate, celexate acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; and dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. Furthermore, it is preferable to use the organic solvent in a manner that makes the non-volatile components account for 30 to 60% by mass of the total.

[0213] Furthermore, the thickness of the aforementioned 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. Since the thickness of the conductor layer of the circuit board ranges from 5 to 70 μm, a thickness of 10 to 100 μm is more preferably desired for the aforementioned resin composition layer (X). Additionally, the aforementioned resin composition layer (X) of this embodiment can also be protected by a protective film, as described later. This protective film prevents dust from adhering to the surface of the resin composition layer (X) or causing scratches.

[0214] Examples of the aforementioned support and protective films include: polyolefins such as polyethylene, polypropylene, and polyvinyl chloride; polyesters such as polyethylene terephthalate (PET) and polyethylene terephthalate (PET); polycarbonate, polyimide, and release paper, or metal foils such as copper foil and aluminum foil. Furthermore, the support and protective films can undergo matte treatment, corona treatment, and release treatment. The thickness of the support film is not particularly limited, but is preferably in the range of 10 to 150 μm, and more preferably 25 to 50 μm. The thickness of the protective film is preferably set to 1 to 40 μm.

[0215] Regarding the aforementioned support film (Y), it is peeled off after the aforementioned resin composition layer (X) is pressed onto the circuit board, or after the aforementioned resin composition layer (X) is heat-cured to form an insulating layer. Peeling off the support film (Y) after the resin composition layer (X) constituting the resin sheet has been heat-cured prevents the adhesion of dust or other contaminants during the curing process. In the case of peeling off the support film (Y) after the aforementioned resin composition layer (X) has cured, a demolding treatment is performed on the support film (Y) beforehand.

[0216] Furthermore, the resin sheet obtained as described above can be used to manufacture multilayer printed circuit boards. For example, when the aforementioned resin composition layer (X) is protected by a protective film, after peeling off the protective film from the resin composition layer (X), the resin composition layer (X) is pressed onto one or both sides of the circuit board in direct contact with the circuit board using, for example, a vacuum pressing method. The pressing method can be batch-type or continuous-type using rollers. Additionally, depending on the need, the resin sheet and the circuit board can optionally be heated (preheated) before pressing. Regarding the pressing conditions, it is preferable to set the pressing temperature (pressing temperature) to 70 to 140°C, and it is preferable to set the pressing pressure to 1 to 11 kgf / cm². 2 (9.8×10 4 Up to 107.9×10 4 N / m 2 Furthermore, it is preferable to perform the pressing by reducing the air pressure to below 20 mmHg (26.7 hPa).

[0217] Alternatively, the curable resin composition of this embodiment can be used to manufacture semiconductor devices. Examples of semiconductor devices include: DIP (Dual Inline Package), QFP (Quad Flat Package), BGA (Ball Grid Array), CSP (Chip Size Package), SOP (Small Outline Package), TSOP (Thin Small Outline Package), and TQFP (Thin Quad Flat Package).

[0218] 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. The cured product of the curable resin composition described in this embodiment exhibits excellent heat resistance and dielectric properties, making it suitable for use in electrical / electronic components such as semiconductor component packaging materials, liquid crystal display component packaging materials, organic EL component packaging materials, and laminated boards (printed wiring boards, BGA substrates, multilayer substrates, etc.), as well as lightweight, high-strength structural composite materials such as carbon fiber reinforced plastics and glass fiber reinforced plastics, and in 3D printing.

[0219] [Example]

[0220] Secondly, the present invention will be described in more detail with reference to embodiments. Hereinafter, unless otherwise stated, parts refer to parts by weight. Furthermore, the present invention is not limited to these embodiments.

[0221] The following describes the various analysis methods used in the embodiments.

[0222] • GPC (Gel Permeation Chromatography) Analysis

[0223] The apparatus, including the online degassing unit (DGU-20A), liquid delivery unit (LC-20AD), automatic sampler (SIL-20A), photodiode array detector (SPD-M40), column oven (CTO-20A), and system controller (CBM-20A), is manufactured by Shimadzu Corporation.

[0224] Tubing strings: SHODEX GPC KF-601 (2 strings), KF-602, KF-602.5, KF-603

[0225] Flow rate: 1.5 ml / min.

[0226] Column temperature: 40℃

[0227] Solvent used: THF (tetrahydrofuran)

[0228] Detector: Differential refractive index detector (RID-20A), manufactured by Shimadzu Corporation, for iodine value determination.

[0229] Weigh 0.096 g of the compound to be determined and dissolve it in 4 ml of dichloromethane. Add 10 ml of Widmanstätten reagent and let it stand in the dark for 30 minutes. Measure 8 ml of potassium iodide solution (100 g / L) and 40 ml of water and add them to the sample. Titrate using a 0.1 mol / L sodium thiosulfate aqueous solution, with starch solution as an indicator. Regarding the starch reagent, the endpoint is set at the point where the color disappears.

[0230] [Synthesis example 1]

[0231] A thermometer, cooling tube, and stirrer were installed in a flask, and the cooling tube was connected to an alkali trap and a vacuum pump. 370.1 parts of 2-bromoethylbenzene (manufactured by Tokyo Chemical Industry Co., Ltd.), 175.1 parts of α,α'-dichloro-p-xylene (manufactured by Tokyo Chemical Industry Co., Ltd.), and 27.3 parts of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were packed into the flask. The reaction was carried out at 130°C for 6 hours while the generated hydrogen chloride was captured using the alkali trap. 100 parts of toluene and 600 parts of cyclohexane were added and extracted. The organic layer was washed 5 times with 100 parts of water. Under heating and reduced pressure, the solvent and excess 2-bromoethylbenzene were distilled off to obtain 380 parts (Mn: 938, Mw: 1290) of a compound (BEB-1) having the 2-bromoethylbenzene structure shown in formula (7) in liquid resin form. The GPC diagram of the obtained compound is shown in [the diagram is missing from the original text]. Figure 1 The average value n of repeating cells calculated from the area % of the GPC plot is 2.2.

[0232]

[0233] [Synthesis example 2]

[0234] In a flask equipped with a thermometer, cooling pipe, and stirrer, 300 parts of BEB-1 obtained from Synthesis Example 1, 245 parts of toluene, 735 parts of dimethyl sulfoxide, 0.15 parts of 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxy free radical, and 146.4 parts of 50 wt% sodium hydroxide aqueous solution were added, and the reaction was continued at 40°C for 6 hours. After adding 100 parts of water to wash the organic layer, the organic layer was returned to the reaction vessel. 735 parts of dimethyl sulfoxide and 9.8 parts of 50 wt% sodium hydroxide aqueous solution were added, and the reaction was carried out again at 40°C for 1 hour. Then, 300 parts of toluene were added, and the organic layer was repeatedly washed with 100 parts of water until the water was neutral. The mixture was concentrated under reduced pressure using an evaporator to obtain 180 parts of compound (O-1) having two or more styrene structures in the molecule, as shown in formula (8). The GPC diagram of the obtained compound is shown in [the diagram is missing in the original text]. Figure 2 The average value n of the repeating units, calculated from the area % of the GPC plot, is 2.2 (the molecular weights of the resin components are Mn: 797, Mw: 1187). Additionally, the iodine value is 150.

[0235]

[0236] [Synthesis example 3]

[0237] In a flask equipped with a thermometer, cooling pipe, and stirrer, 507 parts of divinylbenzene, 304 parts of ethylvinylbenzene, 915 parts of styrene, and 1532 parts of n-propyl acetate were added, and the mixture was heated to 70°C. Further, 41 parts of boron trifluoride diethyl ether complex were added, and the reaction was continued at 70°C for 4 hours. A saturated sodium bicarbonate aqueous solution was added, and after the reaction was stopped, the organic layer was washed three times with 100 parts of pure water. The washed organic layer was concentrated under reduced pressure using an evaporator to obtain a polymer having the structural units shown in formula (2), formula (3-a), and formula (3-c). The obtained polymer had a number-average molecular weight Mn of 4170 and a weight-average molecular weight Mw of 37468. Additionally, the iodine value was 80.

[0238]

[0239] [Examples 1 & 2, Comparative Examples 1 & 2]

[0240] Using the compounds obtained in Synthesis Example 2, the polymer obtained in Synthesis Example 3, and OPE-2St 2200 (terminated styrene polyphenylene ether compound, Mn: 2110, manufactured by Mitsubishi Gas Chemical Co., Ltd.) and SEPTON2104 (styrene-ethylene / propylene-styrene rubber, manufactured by KURARAY Co., Ltd.) as shown in Table 1, a toluene solution with a solid content of 40% by weight was prepared. This solution was then coated onto a mirror-finish copper foil (T4X: manufactured by Fukuda Metal Copper Foil Co., Ltd.) using an applicator with a coating thickness of 200 μm. The solution was then cured in an inert oven at 200°C for 2 hours. The cured product was obtained by removing the copper foil. During the experiment, test pieces were cut to the desired size using a laser cutter as needed.

[0241] <Glass transition temperature (Tg)>

[0242] Dynamic Mechanical Analysis (DMA)

[0243] Using a viscoelasticity measuring apparatus (DMAQ800, TA Instruments), with a tensile probe, a heating rate of 2°C / min, a measuring temperature range of 25°C to 350°C, and a measuring frequency of 10Hz, the temperature at which the tanδ value reaches its maximum was defined as the glass transition temperature (Tg). The sample size was set to 5 mm wide × 40 mm long and 0.06 mm thick for the test.

[0244] <Modulus of elasticity>

[0245] Tensile tests were conducted using a benchtop precision universal testing machine (autograph AGS-X500N, manufactured by Shimadzu Corporation) with a clamping distance of 50 mm, a tensile speed of 0.5 mm / min, and sample dimensions of 5 mm wide × 75 mm long and 0.06 mm thick. The modulus of elasticity when the load reaches 10 N to 13 N was set as the tensile modulus of elasticity.

[0246] <Coefficient of linear expansion>

[0247] Thermomechanical Analysis (TMA)

[0248] Thermomechanical analysis was performed using a TMAQ400 instrument (TA Instruments), employing a tensile probe, with a heating rate of 2°C / min, a measurement temperature range of 25°C to 330°C, and a load of 0.05 N. The sample dimensions were set to 4 mm wide × 35 mm long and 0.06 mm thick. The measurement method involved heating from 25°C to 270°C, then cooling back to 25°C, and then heating again to 330°C. The coefficient of linear expansion from 60°C to 90°C was designated as α1, and the coefficient of linear expansion from 225°C to 240°C was designated as α2.

[0249] <Dielectric Tangent Test>

[0250] A 10GHz cavity resonator manufactured by AET Corporation was used for testing at 25°C using the cavity resonator perturbation method. The sample size was set to 2.5mm wide × 50mm long and 0.06mm thick for the test.

[0251] [Table 1]

[0252]

[0253]

[0254] The results in Table 1 show that Comparative Example 1 has the problem of high dielectric tangent, while Comparative Example 2 has the problem of low mechanical strength (elastic modulus) and high coefficient of linear expansion. On the other hand, it was confirmed that Examples 1 and 2 have excellent properties (high Tg, high elastic modulus, low coefficient of linear expansion, and low dielectric tangent).

[0255] This application asserts priority based on Japanese Patent Application No. 2023-050699, filed on March 28, 2023.

[0256] [Industry availability]

[0257] The curable resin composition of the present invention is suitable for electrical / electronic components such as semiconductor packaging materials, printed wiring boards, and additive laminates.

Claims

1. A curable resin composition comprising: a compound of formula (1) below, and a polymer comprising structural units of formula (2) below, In equation (1), multiple Rs exist independently, representing hydrogen atoms, hydrocarbon groups with 1 to 10 carbon atoms, or alkyl halides with 1 to 10 carbon atoms; p and r are integers from 0 to 4, q is an integer from 0 to 3, n is the average of the number of repetitions, and 1 ≤ n ≤ 20.

2. The curable resin composition according to claim 1, wherein, The polymer comprising the structural unit shown in formula (2) further comprises: the structural unit shown in formula (3) below. In formula (3), R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

3. The curable resin composition according to claim 1, further comprising: a polyphenylene ether compound having unsaturated double bonds; and / or a hydrogenated block copolymer composed of block units of a polymer made of styrene monomers and block units of a polymer made of conjugated diene compounds.

4. The curable resin composition according to claim 3, wherein, The aforementioned polyphenylene ether compounds with unsaturated double bonds are as shown in formula (4) or formula (5) below. In equation (4), n is the average number of repetitions, and 1 <n<10; In equation (5), n is the average number of repetitions, and 1 <n<10。 5. The curable resin composition according to claim 3, wherein, The hydride of the aforementioned block copolymer is a compound represented by the following formula (6): In equation (6), l, m, and n are the average values ​​of the number of repetitions, representing rational numbers from 1 to 10000 respectively; the order of the repetition units enclosed by l, m, and n is not limited, and the bonding pattern can be any of interleaved, segmented, or random.

6. The curable resin composition according to claim 1, further comprising: one or more selected from maleic anhydride compounds, compounds having ethylene unsaturated bonds, cyanate ester resins, polybutadiene and its modified forms, polystyrene and its modified forms, and polyethylene and its modified forms.

7. A prepreg comprising holding the curable resin composition of any one of claims 1 to 6 in a sheet-like fibrous substrate.

8. A cured material obtained by curing the curable resin composition according to any one of claims 1 to 6.

9. A hardened material obtained by hardening the prepreg described in claim 7.

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