Compound, method for producing same, curable resin composition and cured product thereof

Abstract

The present invention provides a compound having excellent low dielectric properties, a curable resin composition, and a cured product thereof. A compound according to the present invention is represented by formula (1). In formula (1), each of a plurality of R1 groups independently represents a hydrogen atom or a C1-5 hydrocarbon group. And each of the plurality of R2s independently represents a hydrocarbon group represented by formula (a). And X represents a structure represented by formulae (c) to (f). Each of the plurality of l independently represents an integer of 1 to 4. M existing in a plurality of fields independently represent integers from 0 to 3, and the average value mave of the m is 0 lt; and mave < = 3. N is a repetition number, and the average value nave of n is greater than or equal to 0.05 and less than or equal to 20; in formula (a), * represents a bonding position to the fluorene structure of formula (1). R3 represents a hydrogen atom or a C1-5 hydrocarbon group, and k represents an integer of 1-5; in the formulae (c) to (f), * represents a bonding position to the fluorene structure of formula (1). And each of the plurality of R4 groups independently represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. Each of the plurality of p independently represents an integer of 1 to 4, and each of the plurality of q independently represents an integer of 1 to 3.

Description

Technical Field

[0001] This invention relates to a compound having a specific structure, a curable resin composition, and the cured form thereof, suitable for use in electrical / electronic components such as semiconductor sealing materials, printed wiring boards, and laminated boards, as well as lightweight, high-strength materials such as carbon fiber reinforced plastics and glass fiber reinforced plastics, and for 3D printing applications. Background Technology

[0002] In recent years, laminates carrying electrical / electronic components have been required to have a wide range of characteristics and are becoming increasingly sophisticated due to the expanding applications of these components. While well-known semiconductor chips are mainly mounted on metal lead frames, high-performance 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 predicted to offer greater capacity and higher speeds. While 5G is progressing towards higher frequencies, reducing transmission losses is crucial for achieving high-speed communication using these frequencies, requiring substrate materials with even lower dielectric properties. Transmission losses on printed circuit boards originate from conductor losses and dielectric losses. As described in Non-Patent Document 1, dielectric loss α... D This is due to the specific dielectric constant ε of the dielectric material. r The dielectric constant tanδ is proportional to the square root of the dielectric constant, thus it can be said to effectively improve the dielectric tangent tanδ, which has a higher contribution to reducing transmission losses than the dielectric constant εr. Low-dielectric materials include thermoplastic materials such as PTFE (polytetrafluoroethylene) or LCP (liquid crystal polymer), but compared with thermosetting resins, they lack formability. Therefore, there is a strong desire to develop a thermosetting resin with excellent low-dielectric properties.

[0004] Against this backdrop, a polymer material with excellent low dielectric properties is being examined. For example, Patent Document 1 discloses a thermosetting resin composition comprising an imide compound having maleimide groups and a phenolic alkyl resin having aliphatic unsaturated bonds. However, on the other hand, phenolic hydroxyl groups that do not participate in the reaction remain during the curing reaction, so the electrical properties are not considered satisfactory. Furthermore, Patent Document 2 discloses an allyl ether modified biphenyl alkylphenol varnish resin with added phenolic hydroxyl groups to allyl groups. However, the allyl ether modified biphenyl alkylphenol varnish resin exhibits Claisen translocation at 190°C and produces phenolic hydroxyl groups that do not contribute to the curing reaction at 200°C, which is a typical molding temperature for substrates, thus failing to meet the electrical property requirements.

[0005] [Existing Technical Documents]

[0006] [Non-patent literature]

[0007] Non-Patent Document 1: “Reasons for Signal Loss in High-Speed ​​Signal Transmission on Printed Substrates”, 29th Spring Conference of the Electronic Packaging Society, Session 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. Summary of the Invention

[0011] [The problem the invention aims to solve]

[0012] The present invention was made in view of such circumstances, and aims to provide a compound having excellent low dielectric properties, a method for manufacturing the same, a curable resin composition and a cured product thereof.

[0013] [Methods for solving the problem]

[0014] That is, this invention relates to the following [1] to [7]. Furthermore, in this invention, "(numerical value 1) to (numerical value 2)" indicates that it includes upper and lower limits.

[0015] [1] A compound, as shown in the following formula (1).

[0016]

[0017] In the above formula (1), the multiple R1s independently represent hydrogen atoms or hydrocarbon groups with 1 to 5 carbon atoms, the multiple R2s independently represent hydrocarbon groups as shown in formula (a) below, X is a structure shown in any of formulas (c) to (f) below, the multiple ls independently represent integers from 1 to 4, the multiple ms independently represent integers from 0 to 3, and the average value of m is m ave 0 <m ave ≤3, where n is the number of repetitions, and n is the average value of n. ave For 0.05≤n ave ≤20;

[0018]

[0019] In the above formula (a), * indicates the bonding position of the fluorene structure in formula (1), R3 represents a hydrogen atom or a hydrocarbon group with 1 to 5 carbon atoms, and k represents an integer from 1 to 5.

[0020]

[0021] In equations (c) to (f) above, * represents the bonding position of the fluorene structure in equation (1), the multiple R4s independently represent hydrogen atoms or hydrocarbon groups with 1 to 5 carbon atoms, the multiple ps independently represent integers 1 to 4, and the multiple qs independently represent integers 1 to 3.

[0022] [2] A compound obtained by reacting the compound shown in formula (A) with the compound shown in formula (B).

[0023]

[0024] In the above formula (A), the multiple R2s that exist independently represent the hydrocarbon groups shown in formula (a) below, X is the structure shown in formulas (c) to (f) below, the multiple m that exist independently represent integers from 0 to 3, and the average value of m is m ave 0 <m ave ≤3, where n is the number of repetitions, and n is the average value of n. ave The value is 0.05≤nave≤20.

[0025]

[0026] In the above formula (a), * indicates the bonding position of the fluorene structure in formula (A), R3 represents a hydrogen atom or a hydrocarbon group with 1 to 5 carbon atoms, and k represents an integer from 1 to 5.

[0027]

[0028] In equations (c) to (f) above, * represents the bonding position of the fluorene structure in equation (A), the multiple R4s independently represent hydrogen atoms or hydrocarbon groups with 1 to 5 carbon atoms, the multiple ps independently represent integers 1 to 4, and the multiple qs independently represent integers 1 to 3.

[0029]

[0030] In the above formula (B), R1 represents a hydrogen atom or a hydrocarbon group with 1 to 5 carbon atoms, k represents an integer from 1 to 4, and Y represents a halogen atom.

[0031] [3] A curable resin composition comprising the compound described in [1] or [2] above.

[0032] [4] A hardener obtained by hardening the compound described in [1] or [2] above.

[0033] [5] A hardener obtained by hardening the hardening resin composition described in the preceding paragraph [3].

[0034] [6] A method for producing a compound, wherein the compound shown in formula (A) and the compound shown in formula (B) are reacted in an aprotic polar solvent in the presence of a basic catalyst to obtain the compound.

[0035]

[0036] In the above formula (A), the multiple R2s that exist independently represent the hydrocarbon groups shown in formula (a) below, X is the structure shown in formulas (c) to (f) below, the multiple m that exist independently represent integers from 0 to 3, and the average value of m is m ave 0 <m ave ≤3, where n is the number of repetitions, and n is the average value of n. ave For 0.05≤n ave ≤20.

[0037]

[0038] In the above formula (a), * indicates the bonding position of the fluorene structure in formula (A), R3 represents a hydrogen atom or a hydrocarbon group with 1 to 5 carbon atoms, and k represents an integer from 1 to 5.

[0039]

[0040] In equations (c) to (f) above, * represents the bonding position of the fluorene structure in equation (A), the multiple R4s independently represent hydrogen atoms or hydrocarbon groups with 1 to 5 carbon atoms, the multiple ps independently represent integers 1 to 4, and the multiple qs independently represent integers 1 to 3.

[0041]

[0042] In the above formula (B), R1 represents a hydrogen atom or a hydrocarbon group with 1 to 5 carbon atoms, k represents an integer from 1 to 4, and Y represents a halogen atom.

[0043] [7] A compound, as shown in the following formula (A),

[0044]

[0045] In the above formula (A), the multiple R2s that exist independently represent the hydrocarbon groups shown in formula (a) below, X is the structure shown in formulas (c) to (f) below, the multiple m that exist independently represent integers from 0 to 3, and the average value of m is m ave 0 <m ave ≤3, where n is the number of repetitions, and n is the average value of n. ave For 0.05≤n ave ≤20.

[0046]

[0047] In the above formula (a), * indicates the bonding position of the fluorene structure in formula (A), R3 represents a hydrogen atom or a hydrocarbon group with 1 to 5 carbon atoms, and k represents an integer from 1 to 5.

[0048]

[0049] In equations (c) to (f) above, * represents the bonding position of the fluorene structure in equation (A), the multiple R4s independently represent hydrogen atoms or hydrocarbon groups with 1 to 5 carbon atoms, the multiple ps independently represent integers 1 to 4, and the multiple qs independently represent integers 1 to 3.

[0050] [Invention Effects]

[0051] According to the present invention, a compound having excellent low dielectric properties and a curable resin composition can be provided. Attached Figure Description

[0052] Figure 1 The HP-LC diagram represents Example 1.

[0053] Figure 2 The GPC diagram represents Example 1.

[0054] Figure 3 Representing Example 1 1 H-NMR chart.

[0055] Figure 4 This represents the HP-LC chart for the comparative synthesis example 1.

[0056] Figure 5 Indicates the comparison of Example 1 1 H-NMR chart. Detailed Implementation

[0057] The embodiments of the present invention will be described in further detail below (hereinafter also referred to as "this embodiment").

[0058] The compound of this embodiment is shown in the following formula (1).

[0059]

[0060] In the above formula (1), the plurality of R1s independently represent hydrogen atoms or hydrocarbon groups having 1 to 5 carbon atoms, preferably hydrogen atoms or hydrocarbon groups having 1 to 3 carbon atoms, and more preferably hydrogen atoms. If the number of carbon atoms is 5 or less, molecular vibrations are less likely to occur when exposed to high frequencies, thus resulting in excellent electrical properties. In addition, when R1 is a hydrogen atom, the deterioration of dielectric properties or water absorption properties caused by the formation of polar groups from the oxidation reaction of alkyl groups during high-temperature storage tests can be suppressed. The plurality of R2s independently represent hydrocarbon groups as shown in formula (a) below. X has the structure shown in formulas (c) to (f) below. The plurality of ls independently represent integers from 1 to 4, preferably 1. The plurality of ms independently represent integers from 0 to 3. The average value of m is m ave 0 <m ave ≤3, from the viewpoint of solvent solubility and heat resistance, with 0 <m ave ≤2.2 is preferred. ave It can be calculated from the loading ratio of raw materials or from NMR analysis results. n represents the number of replicates, and n represents the average value of n. ave For 0.05≤n ave ≤20. From the viewpoint of heat resistance and solvent solubility, the average value of n is n. ave A value of 0.05 to 15 is preferred, 0.1 to 12.5 is more preferred, and 0.1 to 10 is even more preferred. ave The molecular weight can be calculated from the filling ratio of the raw materials or from the NMR analysis results. That is, the compound of this embodiment belongs to the aggregate of compounds in Formula (1) where n is an integer greater than or equal to 0 (compounds with n=0, compounds with n=1, compounds with n=2, compounds with n=3, ...). As for the molecular weight of the compound shown in Formula (1) (the average molecular weight of the aggregate of the compound shown in Formula (1)), the analytical results using a differential refractive index detector in GPC (gel permeation chromatography) analysis show that a number average molecular weight of 200 to 5000 is preferred, more preferably 300 to 3000, and even more preferably 400 to 2000. When the number average molecular weight is less than 200, there is a concern that the heat resistance may be reduced due to the residue of the raw materials, or there is a concern that stickiness may occur during B-stage processing. When the number average molecular weight exceeds 5000, there is a concern that the viscosity of the compound may increase, which may impair the circuit embedding performance, or there is a concern that the solvent solubility may be reduced. Furthermore, regarding the weight-average molecular weight, 200 to 10,000 is preferred, 300 to 7,500 is more preferred, and 400 to 5,000 is even more preferred. When the weight-average molecular weight is less than 200, there is a concern about reduced heat resistance due to residual raw materials, or about stickiness during B-stage processing. When the weight-average molecular weight exceeds 10,000, there is a concern about impaired circuit embedding performance due to increased compound viscosity, or about reduced solvent solubility.

[0061]

[0062] In formula (a) above, * indicates the bonding position of the fluorene structure in formula (1). The multiple R3s each independently represent a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, preferably a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, and more preferably a hydrogen atom. If the number of carbon atoms is 5 or less, the electrical properties are excellent because molecular vibrations are less likely to occur when exposed to high frequencies. Furthermore, when R3 is a hydrogen atom, it can suppress the deterioration of dielectric or water absorption properties caused by the formation of polar groups derived from the oxidation reaction of alkyl groups during high-temperature storage tests. k represents an integer from 1 to 5, preferably 1.

[0063]

[0064] In formulas (c) to (f) above, * indicates the bonding position of the fluorene structure in formula (1). From the viewpoint of exhibiting low water absorption and low dielectric properties, the structure of any one of formulas (c) to (e) is preferred, the structure of any one of formulas (c) and (e) is more preferred, and the structure of formula (c) is particularly preferred. Each of the plurality of R4s independently represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, preferably a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, and more preferably a hydrogen atom. If the number of carbon atoms is 5 or less, molecular vibrations are less likely to occur when exposed to high frequencies, thus resulting in excellent electrical properties. In addition, when R4 is a hydrogen atom, the deterioration of dielectric properties or water absorption properties caused by the formation of polar groups from the oxidation reaction of alkyl groups during high-temperature storage tests can be suppressed. Each of the plurality of ps independently represents an integer from 1 to 4, preferably 1 to 3, more preferably 1 to 2, and most preferably 1. The multiple q values ​​each independently represent an integer from 1 to 3, with 1 to 2 being more preferred and 1 being the most preferred.

[0065] There is no particular limitation on the method of manufacturing the compound shown in formula (1), but it can be obtained by reacting the compound shown in formula (A) with the compound shown in formula (B).

[0066]

[0067] In the above formula (A), the values ​​of R2, X, m, and n, as well as the preferred ranges, are the same as in the aforementioned formula (1).

[0068]

[0069] In the above formula (B), the values ​​of R1 and k and the preferred ranges are the same as in the aforementioned formula (1). Y represents a halogen atom, and from the viewpoint of suppressing reactivity and waste generation, bromine or chlorine atoms are preferred, with chlorine atoms being more preferred.

[0070] When synthesizing the compound represented by formula (1), if the molar number of the compound represented by formula (A) is set as α and the molar number of the compound represented by formula (B) is set as β, it is more preferably β / α is 1.8 or more and 2.1 or less, more preferably 1.8 or more and 2.0 or less, and particularly preferably 1.8 or more and 1.95 or less. When β / α is less than 1.8, the compound represented by formula (A) remains unreacted, which not only raises concerns about reduced toughness of the hardened film but also about deterioration of dielectric properties. This is because the unreacted compound represented by formula (A) does not have a crosslinkable structure, and oxygen reacts with the methylene structure at position 9 of the compound represented by formula (A) to generate a ketone and increase polarity. When β / α is greater than 2.1, the halogen element in the compound shown in formula (B) that cannot be completely removed by purification may be removed during hardening (e.g., at a temperature above 175°C) or high temperature and high humidity tests (e.g., 85°C, 85% humidity or 120°C, 100% humidity, etc.), which may lead to corrosion of the copper wiring. The amount of residual halogen contained in the reactant containing the compound shown in formula (1) is preferably 1 to 10,000 ppm, more preferably 1 to 3,000 ppm, and even more preferably 1 to 2,000 ppm. Here, "residual halogen" comes from unreacted starting material compounds contained in the reactant containing the compound shown in formula (A) and the compound shown in formula (B) to obtain the compound shown in formula (1), and impurities contained in the starting material compounds.

[0071] The reaction between the compound shown in formula (A) and the compound shown in formula (B) is described in detail. The compound shown in formula (1) can be obtained by reacting the compound shown in formula (A) and the compound shown in formula (B) in an aprotic polar solvent in the presence of a basic catalyst. Examples of aprotic polar solvents include dimethyl sulfone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolinone, and N-methylpyrrolidone, and two or more of them may be used together. In addition, non-water-soluble solvents may be used together as needed. Examples of non-water-soluble solvents include aromatic solvents such as toluene and xylene, aliphatic solvents such as cyclohexane and n-hexane; ethers such as diethyl ether and diisopropyl ether; ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as methyl isobutyl ketone and cyclopentanone, but are not limited to these, and two or more may be used together. There is no particular limitation on the alkaline catalyst, but examples include sodium hydroxide, potassium hydroxide, and potassium carbonate. The order in which the compound shown in formula (A), the compound shown in formula (B), and the alkaline catalyst are added can be changed as needed, but a preferred method is to add the compound shown in formula (A), an aprotic polar solvent, and the alkaline catalyst, allowing the compound shown in formula (A) to be fully ionized, before adding the compound shown in formula (B). When the reaction is carried out without using an aprotic polar solvent, the reaction rate will be significantly reduced. When an aprotic polar solvent is not used, a phase-shifting catalyst is generally used for the reaction. In this case, the raw materials are dissolved in a non-aqueous solvent such as toluene, and the compound shown in formula (A) and the compound shown in formula (B) are reacted in the presence of an alkaline catalyst such as an aqueous solution of sodium hydroxide and a phase-shifting catalyst such as tetrabutylammonium bromide. In this case, it is difficult to completely remove interphase-moving catalysts such as tetrabutylammonium bromide, making it difficult to achieve low dielectric properties (low dielectric constant / low dielectric tangent). Furthermore, when using substrate materials containing the compounds of this embodiment for long-term damp heat reliability testing, the remaining interphase-moving catalysts can cause problems such as ion migration. Regarding the reaction temperature, 0 to 120°C is preferred, more preferably 0 to 100°C, and even more preferably 0 to 80°C. If the temperature exceeds the upper limit, there is a risk of self-polymerization and gelation of the compounds of this embodiment. If the lower limit is not reached, there is a risk of insufficient reaction. Regarding post-reaction treatment, neutralization can be performed using any acid compound. Alternatively, if an alcohol compound or water is added to the reaction solution as needed, crystals of the compound shown in formula (1) can be formed to recover the target substance. Alternatively, the obtained reaction solution or crystals can be redissolved in any solvent and an extraction step can be performed. The extraction step can be performed using aromatic hydrocarbon solvents such as toluene or xylene alone, or in combination with non-aromatic hydrocarbons such as cyclohexane or toluene.After extraction, the organic layer is washed with water until the wastewater becomes neutral, and the solvent is distilled off using a distillation apparatus to obtain the compound shown in formula (1).

[0072] The compound represented by the aforementioned formula (A) is derived from fluorene and the compound represented by the following formula (g), and the compounds represented by (i) to (l) below.

[0073]

[0074] In formula (g) above, the values ​​of R3 and k, and the preferred ranges, are the same as in formula (a) above. Z represents a hydroxyl group or a halogen atom. From the viewpoint of suppressing reactivity and waste generation, a hydroxyl group, a bromine atom, or a chlorine atom is preferred, and a hydroxyl group or a chlorine atom is more preferred.

[0075]

[0076] In formulas (i) to (l) above, the values ​​of R4, p, and q, and the preferred ranges, are the same as in formulas (c) to (f) above. Z represents a hydroxyl group or a halogen atom. From the viewpoint of suppressing reactivity and waste generation, a hydroxyl group, a bromine atom, or a chlorine atom is preferred, and a hydroxyl group or a chlorine atom is more preferred.

[0077] When fluorene reacts with the compound shown in formula (g) above, and with any one or more compounds selected from the compounds shown in formulas (i) to (l) above, the number of moles of the compound shown in formula (g) above relative to 1 mole of fluorene is preferably 0.01 to 10 moles, more preferably 0.1 to 7.5 moles, even more preferably 0.2 to 5 moles, and most preferably 0.3 to 2.5 moles. When the number of moles of the compound shown in formula (g) above reacting with fluorene is less than 0.01 moles, there is a concern that the storage stability after dissolving the compound shown in formula (1) in the solvent may deteriorate due to crystallization and prolonged storage. When the number of moles is greater than 10 moles, there is a concern that the heat resistance may decrease, or that the compound shown in formula (g) above may become excessive and remain in the reactants, thus impairing the low dielectric properties. Furthermore, relative to 1 mole of fluorene, the total number of moles of any one or more compounds selected from those shown in (i) to (l) is preferably 0.01 to 0.99 moles, more preferably 0.02 to 0.9 moles, and even more preferably 0.03 to 0.8 moles. When the total number of moles of the compounds shown in formulas (i) to (l) reacting with 1 mole of fluorene is less than 0.01 moles, there is a concern that the storage stability of the compound shown in formula (1) may deteriorate after prolonged storage, such as crystallization, after dissolving in the solvent. When the total number of moles is greater than 0.99 moles, there is a concern that the compound may become insoluble in the solvent during subsequent reaction steps, or that the compound shown in formulas (i) to (l) may become excessive and remain in the reactants containing the compound shown in formula (1), thereby impairing the low dielectric properties.

[0078] When fluorene reacts with the compound shown in formula (g) above, and with any one or more compounds selected from formulas (i) to (l), the acid catalyst may, as needed, be 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, silica, and alumina; and acidic ion exchange resins. These may be used alone or in combination of two or more. The amount of acid catalyst used is 0.1 to 40% by weight, preferably 0.1 to 20% by weight, relative to the total weight of the fluorene, the compound shown in formula (g) above, and any one or more compounds selected from formulas (i) to (l). If too much acid catalyst is used, the viscosity of the reaction solution will be too high, making stirring difficult; if too little is used, the reaction will proceed too slowly. The reaction can be carried out using organic solvents such as hexane, cyclohexane, octane, toluene, and xylene, or it can be carried out without solvents, depending on the needs.

[0079] For example, after reacting a mixture of fluorene, a compound represented by formula (g) above, and one or more compounds selected from those represented by formulas (i) to (l), and an organic solvent (or a solvent-free solvent), the reactants contain water, which is then removed from the system by azeotropic reaction or the like. The reaction is then carried out at 40 to 180°C, preferably 50 to 170°C, for 0.5 to 20 hours. After the reaction is terminated, the acidic catalyst can be neutralized with an alkaline aqueous solution, but neutralization may be omitted and the reaction can be carried out in a water washing step. The water washing step involves adding a non-water-soluble organic solvent to the oil layer and repeatedly washing until the wastewater becomes neutral.

[0080] Furthermore, the compound represented by formula (A) obtained in the above reaction can be continuously derived by adding a neutralizing agent such as a base, an aprotic polar solvent, a basic catalyst, and the compound represented by formula (B) after the reaction.

[0081] The softening point of the compound represented by formula (A) is preferably below 180°C, and more preferably below 150°C. When the softening point of the compound represented by formula (A) is below 180°C, the viscosity when derived into the compound represented by formula (1) becomes lower. Accordingly, it is easy to ensure flowability without compromising impregnation of fibrous materials such as glass cloth or carbon fiber, and the B-stage process such as prepreg physicochemical treatment becomes easier. When the viscosity is reduced by increasing the diluent, the resin containing the compound represented by formula (1) may not adhere sufficiently to fibrous materials during the impregnation step.

[0082] Resins containing compounds shown in the aforementioned formula (1) (aggregates of compounds in formula (1) where n is an integer greater than or equal to 0) can be cured individually by heating or the like, but can also be used to form curable resin compositions by adding various materials, thereby improving performance.

[0083] [Hardening Accelerator]

[0084] The curing properties of the curable resin composition of this embodiment can also be improved by adding a curing accelerator. The curing accelerator is preferably an anionic curing accelerator that promotes the curing reaction by generating anions through irradiation or heating with ultraviolet or visible light, or a cationic curing accelerator that promotes the curing reaction by generating cations through irradiation or heating with ultraviolet or visible light.

[0085] 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, benzyl dimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo(5,4,0)-undecene, with 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)-undecene being preferred. Other examples include phosphines such as triphenylphosphine, tetrabutylammonium salts, triisopropylmethylammonium salts, trimethyldecylammonium salts, cetyltrimethylammonium salts, and hexadecyltrimethylammonium hydroxide, but these are not limited to these. Furthermore, one type or multiple types can be used together.

[0086] Examples of cationic hardening accelerators include, but are not limited to, quaternary phosphonium salts such as triphenylbenzylphosphonium salt, triphenylethylphosphonium salt, and tetrabutylphosphonium salt (quaternary salts can be ionized by halogens, organic acid ions, hydroxide ions, etc., without specific designation, but organic acid ions and hydroxide ions are particularly preferred), tin octoate, zinc carboxylate (zinc 2-ethylhexanoate, zinc stearate, zinc docosate, zinc myristate), and zinc phosphate esters (zinc octyl phosphate, zinc stearyl phosphate), etc. Furthermore, one type or multiple types can be used in combination.

[0087] The amount of curing accelerator can be adjusted from 0.01 to 5.0 parts by weight relative to 100 parts by weight of the curing resin composition, as needed.

[0088] [Inorganic filler]

[0089] The curable resin composition of this embodiment may contain inorganic fillers. Examples of inorganic fillers include: fused silica, crystalline silica, porous silica, alumina, zircon, calcium silicate, calcium carbonate, quartz powder, silicon carbide, silicon nitride, boron nitride, zirconium oxide, aluminum nitride, graphite, forsterite, block talc, spinel, mullite, titanium dioxide, talc, clay, iron oxide asbestos, glass powder, and other powders, or inorganic fillers formed into spherical or fragmented shapes, but are not limited to these. Furthermore, one type or multiple types may be used.

[0090] When obtaining a curable resin composition for semiconductor sealing from inorganic filler, the amount 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 substrate materials such as interlayer insulating layer forming materials, copper foil laminates or prepregs, and RCC (Resin-Coated Copper), 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.

[0091] [Polymerization initiator]

[0092] The curable resin composition of this embodiment can also have its curability 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 with curability and moderate stability is preferred. A free radical polymerization initiator is a compound that generates free radicals and initiates a chain polymerization reaction through irradiation with ultraviolet or visible light or heating. Examples of usable free radical polymerization initiators include organic peroxides, azo compounds, and tetraphenylethylene glycol (benzopinacol), etc. Organic peroxides are preferred because they have less impact on curing temperature control, gas release inhibition, and the electrical properties of decomposition products.

[0093] 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 diisopropylphenyl peroxide and 1,3-bis-(tert-butylperoxyisopropyl)benzene; peroxy ketals such as tert-butylperoxybenzoate and 1,1-di-tert-butylperoxycyclohexane; α-isopropylphenyl peroxyneodecanate, tert-butylperoxyneodecanate, tert-butyl peroxyneodecanate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, and tert-pentylperoxy-2-ethylhexanoate. Alkyl peroxides such as esters, tert-butyl peroxide-2-ethylhexanoate, tert-pentyl peroxide-3,5,5-trimethylhexanoate, tert-butyl peroxide-3,5,5-trimethylhexanoate, and tert-pentyl peroxide benzoate; peroxide carbonates such as 2-ethylhexyl peroxydicarbonate, bis(4-tert-butylcyclohexyl) peroxydicarbonate, tert-butyl peroxyisopropyl carbonate, and 1,6-bis(tert-butylperoxycarbonyloxy)hexane; tert-butyl hydroperoxide, cumene hydroperoxide, tert-butyl peroxyoctanoate, and lauroyl peroxide, but not limited to these. Furthermore, one type or multiple types may be used. Among the above-mentioned organic peroxides, ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, alkyl peroxides, and peroxide carbonates are preferred, with dialkyl peroxides being more preferred.

[0094] Examples of the aforementioned azo compounds include, but are not limited to, azobisisobutyronitrile, 4,4'-azobis(4-cyanogacria), and 2,2'-azobis(2,4-dimethylpentanonitrile). Furthermore, one type may be used, or multiple types may be used in combination.

[0095] The amount of polymerization initiator added relative to 100 parts by weight of the curing resin composition is preferably 0.01 to 5 parts by weight, and particularly 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 may 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 may be impaired.

[0096] [Polymerization inhibitor]

[0097] The curable resin composition of this embodiment may contain a polymerization inhibitor. By containing a polymerization inhibitor, storage stability is improved, and the reaction initiation temperature can be controlled. Controlling the reaction initiation temperature makes it easier to ensure flowability, preserves the impregnation properties of glass cloth, etc., and facilitates B-stage processes such as prepreg conditioning. If the polymerization reaction is carried out during prepreg conditioning, undesirable situations may arise, such as difficulty in lamination during the lamination process.

[0098] The polymerization inhibitor may be added during the synthesis of the compound of this embodiment or after synthesis. The amount of polymerization inhibitor used is 0.008 to 1 part by weight relative to 100 parts by weight of the compound of this embodiment, preferably 0.01 to 0.5 parts by weight.

[0099] Examples of polymerization inhibitors include phenolic, sulfur-based, phosphorus-based, hindered amine-based, nitroso-based, and nitroxide-free radical-based inhibitors. Furthermore, one type of polymerization inhibitor may be used, or multiple types may be used in combination. Among these, phenolic, hindered amine-based, nitroso-based, and nitroxide-free radical-based inhibitors are preferred in this embodiment.

[0100] Examples of phenolic polymerization inhibitors include: 2,6-di-tert-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-tert-butyl-p-ethylphenol, stearyl-β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylaniline)-1,3,5-triazine, monophenols such as 2,4-bis[(octylthio)methyl]-o-cresol, and 2,2'-methylenebis(4-methyl-6- -tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 4,4'-butylenebis(3-methyl-6-tert-butylphenol), triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-cinnamoamide), 2,2'-thio-divinylbis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate] [5-Di-tert-butyl-4-hydroxyphenyl)propionate], 3,5-di-tert-butyl-4-hydroxyphenylmethyl phosphate-diethyl ester, 3,9-bis[1,1-dimethyl-2-{β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}ethyl]2,4,8,10-tetraoxospiro[5,5]undecane, bis(3,5-di-tert-butyl-4-hydroxyphenylmethyl sulfonate)calcium and other bisphenols, 1,1,3-trimethyl-2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-trimethyl-2-( 3,5-Di-tert-butyl-4-hydroxybenzene, tetra-[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane, bis[3,3'-bis-(4'-hydroxy-3'-tert-butylphenyl)butyrate]glycol, triazine-(3,5-di-tert-butyl-4-hydroxybenzene)-triisocyanate, 1,3,5-triazine-(3',5'-di-tert-butyl-4'-hydroxybenzene)-S-triazine-2,4,6-(1H,3H,5H)trione, tocopherol, and other high molecular weight phenols, but not limited to these.

[0101] Examples of sulfur-based polymerization inhibitors mentioned above include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearate-3,3'-thiodipropionate, etc., but are not limited to these.

[0102] Examples of phosphorus-based polymerization inhibitors include: triphenyl phosphite, diphenyl isodeyl phosphite, phenyl diisodecyl phosphite, triphenyl(nonylphenyl) phosphite, diisodecyl pentaerythritol phosphite, triphenyl(2,4-di-tert-butylphenyl) phosphite, cyclopentanetetrayl bis(octadecyl) phosphite, cyclopentanetetra bis(2,4-di-tert-butylphenyl) phosphite, cyclopentanetetra bis(2,4-di-tert-butyl-4-methylphenyl) phosphite, bis[2- Phosphites such as tert-butyl-6-methyl-4-{2-(octadecyloxycarbonyl)ethyl}phenyl]hydrophosphite, 9,10-dihydro-9-para-oxo-10-phosphaphenanthrene-10-oxide, 10-(3,5-di-tert-butyl-4-hydroxybenzyl)-9,10-dihydro-9-para-oxo-10-phosphaphenanthrene-10-oxide, and 10-deoxy-9,10-dihydro-9-para-oxo-10-phosphaphenanthrene-10-oxide, etc., but not limited to these.

[0103] Examples of hindered amine polymerization inhibitors mentioned above include: ADEKASTAB (registered trademark) LA-40MP, ADEKASTAB LA-40Si, ADEKASTAB LA-402AF, ADEKASTAB LA-87, ADEKASTAB LA-82, ADEKASTAB LA-81, ADEKASTAB LA-77Y, ADEKASTAB LA-77G, ADEKASTAB LA-72, ADEKASTAB LA-68, ADEKASTAB LA-63P, ADEKASTAB LA-57, and ADEKASTAB... LA-52 (all of the above are manufactured by ADEKA Corporation); Chimassorb (registered trademark) 2020FDL, Chimassorb944FDL, Chimassorb944LD, Tinuvin (registered trademark) 622SF, Tinuvin PA144, Tinuvin765, Tinuvin770DF, TinuvinXT55FB, Tinuvin111FDL, Tinuvin783FDL, Tinuvin791FB (all of the above are manufactured by BASF Corporation), etc., but not limited to these.

[0104] Examples of nitrosyl-based polymerization inhibitors include, but are not limited to, p-nitrosophenol, N-nitrosodiphenylamine, and ammonium salts of N-nitrosophenylhydroxylamine (Cupferron). Among these, ammonium salts of N-nitrosophenylhydroxylamine (Cupferron) are preferred.

[0105] Examples of nitrogen oxide free radical polymerization inhibitors mentioned above include: di-tert-butylnitrooxyhydroxide, 2,2,6,6-tetramethylpiperidine-1-oxide, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxide, 4-sideoxy-2,2,6,6-tetramethylpiperidine-1-oxide, 4-amino-2,2,6,6-tetramethylpiperidine-1-oxide, 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxide, 4-acetoxy-2,2,6,6-tetramethylpiperidine-1-oxide, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-1-oxide, etc., but are not limited to these.

[0106] [Flame retardant]

[0107] The curable resin composition of this embodiment may use a flame retardant. Examples of flame retardants include halogen-based flame retardants, inorganic flame retardants (antimony compounds, metal hydroxides, nitrogen compounds, boron compounds, etc.), and phosphorus-based flame retardants, but from the viewpoint of achieving halogen-free flame resistance, phosphorus-based flame retardants are preferred.

[0108] The aforementioned phosphorus-based flame retardants can be reactive or additive. Specific examples include: trimethyl phosphate, triethyl phosphate, tricresyl phosphate, tridimethyl phosphate, cresol diphenyl phosphate, cresol-2,6-didimethyl phosphate, 1,3-phenylenebis(didimethyl phosphate), 1,4-phenylenebis(didimethyl phosphate), 4,4'-biphenyl(didimethyl phosphate), and other phosphate esters; phosphine derivatives such as 9,10-dihydro-9-phenanthroline-10-oxide and 10(2,5-dihydroxyphenyl)-10H-9-phenanthroline-10-oxide; and phosphorus-containing epoxy compounds obtained by reacting epoxy resin with the active hydrogen of the aforementioned phosphine derivatives, as well as red phosphorus, but these are not limited to these. Furthermore, one type or multiple types can be used. Among the above-described substances, phosphate esters, phosphine compounds, or phosphorus-containing epoxy compounds are preferred, with 1,3-phenylenebis(dithiomethyl phosphate), 1,4-phenylenebis(dithiomethyl phosphate), 4,4'-biphenyl(dithiomethyl phosphate), or phosphorus-containing epoxy compounds being particularly preferred.

[0109] The flame retardant content is preferably in the range of 0.1 to 0.6 parts by weight relative to 100 parts by weight of the curing resin composition. If it is less than 0.1 parts by weight, there is a concern that the flame retardancy may be insufficient; if it is more than 0.6 parts by weight, there is a concern that it may adversely affect the hygroscopicity and dielectric properties of the cured material.

[0110] [Light stabilizer]

[0111] The curable resin composition of this embodiment may use a light stabilizer. Hindered amine light stabilizers (HALS) are suitable. Examples of HALS reactions include: dibutylamine / 1,3,5-tris(2,2,6,6-tetramethyl-4-piperidinyl-1,6-hexamethylenediamine and N-(2,2,6,6-tetramethyl-4-piperidinyl)butylamine, dimethyl-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidinyl succinate, and poly[{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-tris(2,4-diyl){(2,2,6,6-tetramethyl-4-piperidinyl)imino}hexamethylene{(2,2,6,6-tetramethyl-4-piperidinyl)imino}]. Bis(1,2,2,6,6-pentamethyl-4-piperidinyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butyl malonate, 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-butylmalonic acid bis(1,2,2,6,6-pentamethyl-4-piperidinyl), etc., but not limited to these. Furthermore, one type may be used, or multiple types may be used in combination.

[0112] The preferred content of light stabilizer is 0.001 to 0.1 parts by weight relative to 100 parts by weight of the curing resin composition. If the content is less than 0.001 parts by weight, there is a concern that the light stabilizing effect may be insufficient; if the content 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.

[0113] [Adhesive Resin]

[0114] The curable resin composition of this embodiment may use an adhesive resin. Examples of adhesive resins include, but are not limited to, butyral resins, acetal resins, acrylic resins, epoxy-nylon resins, NBR-phenol resins, epoxy-NBR resins, and polysiloxane resins. Furthermore, one type may be used, or multiple types may be used in combination.

[0115] The amount of adhesive resin used is preferably within the range that does not impair the flame retardancy and heat resistance of the cured material. It is preferably 0.05 to 50 parts by weight relative to 100 parts by weight of the curing resin composition, and more preferably 0.05 to 20 parts by weight as needed.

[0116] [additive]

[0117] Additives may also be used in the curable resin composition of this embodiment. Examples of additives include: modified acrylonitrile copolymers, surface treatment agents for fillers such as polyethylene, fluoropolymers, polysiloxane gels, polysiloxane oils, silane coupling agents, release agents, carbon black, phthalocyanine blue, phthalocyanine green, and other colorants.

[0118] 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, relative to 100 parts by weight of the curing resin composition.

[0119] The curable resin composition of this embodiment can also use epoxy resin, reactive ester compound, phenolic resin, polyphenylene ether compound, amine resin, compound having vinyl unsaturated bonds, isocyanate resin, polyamide resin, maleimide compound, cyanate ester resin, polyimide resin, polybutadiene and its modified forms, polystyrene and its modified forms, polyethylene and its modified forms, etc. One type of these can be used, or multiple types can be used in combination. Among these compounds, those containing polyphenylene ether compound, compound having vinyl unsaturated bonds, cyanate ester resin, polybutadiene and its modified forms, and polystyrene and its modified forms are more preferred in terms of the balance of heat resistance, adhesion, and dielectric properties. By containing these compounds, the brittleness of the cured product and the adhesion to metal can be improved, and cracking of the package during solder reflow or reliability tests such as thermal cycling can be suppressed. Unless otherwise specified, the total amount of the above compounds used is preferably 10 parts by weight or less, more preferably 5 parts by weight or less, and particularly preferably 3 parts by weight or less, relative to the compound of this embodiment. Furthermore, a preferred lower limit is 0.1 parts by mass or more, more preferably 0.25 parts by mass or more, and even more preferably 0.5 parts by mass or more. By being within the above range, the low dielectric properties of the compound of this embodiment can be utilized, while also enhancing the effects of each added compound. These components may include the components exemplified below.

[0120] [Epoxy Resin]

[0121] The following examples illustrate preferred epoxy resins, but are not limited to these. Furthermore, the epoxy resin may be in liquid or solid form, and one type may be used, or multiple types may be used in combination.

[0122] 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, epoxy propyl ester type epoxy resin, epoxy propylamine type epoxy resin, phenolic varnish type epoxy resin, alicyclic epoxy resin with ester skeleton, cyclohexane type epoxy resin, cyclohexanediol type epoxy resin, epoxy propylamine 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), “HP-4032”, “HP-4032D”, “HP-4032SS” (all manufactured by DIC Corporation, naphthalene type epoxy resin), “jER (registered trademark) 828US”, “jER828EL”, “jER825”, “jER828EL” (all manufactured by Mitsubishi). CHEMICAL (manufactured by CHEMICAL Corporation, bisphenol A type epoxy resin), "jER807", "jER1750" (all manufactured by Mitsubishi CHEMICAL Corporation, bisphenol F type epoxy resin), "jER152" (manufactured by Mitsubishi CHEMICAL Corporation, phenolic varnish type epoxy resin), "jER630", "jER630LSD" (all manufactured by Mitsubishi CHEMICAL Corporation, epoxypropylamine type epoxy resin), "ZX1059" (manufactured by Nippon Steel & Sumitomo Metal Chemicals Co., Ltd., a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin), "EX-721" (NAGASE The following epoxy resins are available: CHEMTEX (epoxypropyl ester type), CELOXIDE 2021P (DAICEL alicyclic epoxy resin with an ester backbone), PB-3600 (DAICEL butadiene structure epoxy resin), ZX1658, and ZX1658GS (all Nippon Steel & Sumitomo Chemicals liquid 1,4-epoxypropylcyclohexane type epoxy resins). These can be used individually or in combination of two or more.

[0123] Solid epoxy resins may include, for example: xylenol-type epoxy resin, naphthalene-type epoxy resin, naphthalene-type tetrafunctional epoxy resin, cresol-phenolic varnish-type epoxy resin, dicyclopentadiene-type epoxy resin, succinate-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, and tetraphenylethane-type epoxy resin. Naphthol-type epoxy resin, bisphenol AF-type epoxy resin, naphthalene-type epoxy resin, and biphenyl-type epoxy resin are preferred examples.Specific examples include: "HP4032H" (manufactured by DIC, naphthalene-type epoxy resin), "HP-4700", "HP-4710" (all manufactured by DIC, naphthalene-type tetrafunctional epoxy resin), "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", "HP-7200HH", "H" P-7200H (all of the above are dicyclopentadiene type epoxy resins manufactured by DIC Corporation), EXA-7311, EXA-7311-G3, EXA-7311-G4, EXA-7311-G4S, HP-6000 (all of the above are naphthyl ether type epoxy resins manufactured by DIC Corporation), EPPN-502H (manufactured by Nippon Kayaku Co., Ltd., phenolic epoxy resin), NC-7000L, NC-7300 (all of the above are naphthyl ether type epoxy resins manufactured by Nippon Kayaku Co., Ltd., naphthyl- Epoxy resins of various types include: "Cresol-phenolic varnish type", "NC-3000H", "NC-3000", "NC-3000L", "NC-3100" (all manufactured by Nippon Kayaku Co., Ltd., biphenyl arylane type epoxy resins), "XD-1000-2L", "XD-1000-L", "XD-1000-H", "XD-1000-H" (all manufactured by Nippon Kayaku Co., Ltd., dicyclopentadiene type epoxy resins), and "ESN475V" (manufactured by Nippon Steel & Sumitomo Metal Chemicals Co., Ltd., naphthol type epoxy resin). “ESN485” (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., naphthol phenolic resin 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) These include epoxy resins manufactured by CHEMICAL (fluorene-based), "YL-7760" (bisphenol AF type epoxy resin manufactured by Mitsubishi CHEMICAL), "YL-7800" (fluorene type epoxy resin manufactured by Mitsubishi CHEMICAL), "jER1010" (solid bisphenol A type epoxy resin manufactured by Mitsubishi CHEMICAL), and "jER1031S" (tetraphenylethane type epoxy resin manufactured by Mitsubishi CHEMICAL). These can be used individually or in combination of two or more.

[0124] [Active ester compounds]

[0125] An active ester compound is a compound whose structure contains at least one ester bond, with aliphatic chains, aliphatic rings, or aromatic rings bonded to both sides of the ester bond. Examples of active ester compounds include phenolic esters, thiophenolic esters, N-hydroxyamine esters, and esters of heterocyclic hydroxyl compounds, which are compounds having two or more highly reactive ester groups in one molecule. These compounds can be obtained through a condensation reaction of a carboxylic acid compound, an acyl chloride, or a thiocarboxylic acid compound, and a hydroxyl compound or a thiol compound. In particular, from the viewpoint of improving heat resistance, it is preferable to obtain the compound from a carboxylic acid compound or an acyl chloride and a hydroxyl compound; regarding the hydroxyl compound, a phenolic compound or a naphthol compound is preferred. An active ester compound can be used alone or in combination of two or more.

[0126] Examples of the aforementioned carboxylic acid compounds include: benzoic acid, acetic acid, succinic acid, maleic acid, erythric acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.

[0127] Examples of acyl chlorides mentioned above include: acetyl chloride, acryloyl chloride, methacryloyl chloride, malonyl chloride, succinyl dichloride, diacetyl chloride, glutaryl dichloride, octanoyl dichloride, sebacyl dichloride, adipyl dichloride, dodecyl dichloride, azelaic dichloride, 2,5-furan dichloride, phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, trimelliticoyl chloride, bis(4-chlorocarbonylphenyl) ether, 4,4'-diphenyldicarbonyl chloride, 4,4'-azobisbenzoyl dichloride, etc.

[0128] 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, benzotriol, dicyclopentadiene-type diphenol compounds, phenolic varnishes, and phenolic resins described later. Here, "dicyclopentadiene-type diphenol compounds" refers to diphenol compounds obtained by the condensation of two phenol molecules into one molecule of dicyclopentadiene.

[0129] 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 examples 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 phenylene-dicyclopentadiene-phenylene.

[0130] Regarding commercially available active ester compounds, examples include those containing a dicyclopentadiene-type diphenol structure such as: "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "HPC-8000H-65TM", "EXB-8000L-65TM31", and "EXB-8150-65T" (manufactured by DIC); and active ester compounds containing a naphthalene structure such as: "EXB9416". -70BK (manufactured by DIC); active ester compounds containing acetylated compounds of phenolic varnishes include: "DC808" (manufactured by Mitsubishi Chemical); active ester compounds containing benzoyl compounds of phenolic varnishes include: "YLH1026", "YLH1030", "YLH1048" (manufactured by Mitsubishi Chemical); active ester curing agents containing phosphorus atoms include: "EXB-9050L-62M" manufactured by DIC, etc.

[0131] The preferred ratio (α / β) of the active ester compound and epoxy resin formulation is 0.5 to 1.5, more preferably 0.8 to 1.2, and even more preferably 0.90 to 1.10. Exceeding these ranges may result in excess epoxy groups or active ester groups remaining in the system, potentially leading to deterioration of properties during high-temperature storage tests (150°C, 1000 hours, etc.) or long-term reliability tests under high-temperature and high-humidity conditions (temperature: 85°C, humidity: 85%, etc.).

[0132] [Phenolic resin]

[0133] Phenolic resins are 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 biphenyl compounds, reactants of phenols with substituted phenyl compounds, and reactants of bisphenols with aldehydes. Furthermore, one type of these can be used, or multiple types can be used in combination.

[0134] The following are specific examples of the above-mentioned raw materials, but are not limited to these.

[0135] <Phenolic compounds>

[0136] Phenols, alkyl-substituted phenols, aromatic-substituted phenols, hydroquinone, resorcinol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.

[0137] Aldehydes

[0138] Formaldehyde, acetaldehyde, alkyl aldehydes, benzaldehyde, alkyl-substituted benzaldehydes, hydroxybenzenealdehydes, naphthalaldehyde, glutaraldehyde, benzoxaldehyde, crotonaldehyde, cinnamaldehyde, furfural, etc.

[0139] <Diene Compounds>

[0140] Dicyclopentadiene, terpenes, vinylcyclohexene, nordiene, vinyl nordiene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.

[0141] Ketones

[0142] Acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenyl, benzophenone, fluorenone, etc.

[0143] <Substituted biphenyls>

[0144] 4,4'-bis(chloromethyl)-1,1'-biphenyl, 4,4'-bis(methoxymethyl)-1,1'-biphenyl, 4,4'-bis(hydroxymethyl)-1,1'-biphenyl, etc.

[0145] <Substituted phenyl>

[0146] 1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene, 1,4-bis(hydroxymethyl)benzene, etc.

[0147] [Polyphenylene ether compounds]

[0148] From the viewpoint of heat resistance and electrical properties, polyphenylene ether compounds with vinyl unsaturated bonds are preferred, and those with acrylic, methacrylic, or styrene structures are even more preferred. Commercially available examples include SA-9000 (manufactured by SABIC, a polyphenylene ether compound with methacrylic groups) and OPE-2St 1200 (manufactured by Mitsubishi Gas Chemical, a polyphenylene ether compound with a styrene structure), etc.

[0149] The number average molecular weight (Mn) of the polyphenylene ether compound is preferably between 500 and 5000, more preferably between 2000 and 5000, and even more preferably between 2000 and 4000. If the number average molecular weight is less than 500, the heat resistance of the cured product tends to be insufficient. Furthermore, if the number average molecular weight is greater than 5000, the melt viscosity becomes higher, resulting in insufficient flowability and a tendency for poor molding. Additionally, reactivity decreases, and the curing reaction requires a longer time, leading to an increase in unreacted material not absorbed by the curing system, a decrease in the glass transition temperature of the cured product, and a reduction in its heat resistance.

[0150] If the number average molecular weight of a polyphenylene ether compound is between 500 and 5000, it can directly maintain excellent dielectric properties and exhibit excellent heat resistance and formability. Furthermore, the number average molecular weight can be specifically determined using methods such as gel permeation chromatography.

[0151] Polyphenylene ether compounds can be obtained through polymerization or through a redistribution reaction of high molecular weight polyphenylene ether compounds with a number average molecular weight of approximately 10,000 to 30,000. Alternatively, these compounds can be used as raw materials to impart free radical polymerization properties through reaction with compounds containing vinyl unsaturated bonds, such as methacryloyl chloride, acryloyl chloride, and chloromethylstyrene. Polyphenylene ether compounds obtained through redistribution reactions are obtained, for example, by heating and redistributing high molecular weight polyphenylene ether compounds in a solvent such as toluene in the presence of a phenolic compound and a free radical initiator. Polyphenylene ether compounds obtained through redistribution reactions thus possess hydroxyl groups derived from phenolic compounds at both ends of the molecular chain, which contributes to hardening. This is preferable because it maintains higher heat resistance and, after modification with compounds containing vinyl unsaturated bonds, allows for the introduction of functional groups at both ends of the molecular chain. Furthermore, polyphenylene ether compounds obtained through polymerization reactions are preferred due to their excellent flowability.

[0152] The molecular weight of polyphenylene ether compounds can be adjusted by adjusting polymerization conditions when the polyphenylene ether compound is obtained through polymerization. Similarly, the molecular weight of polyphenylene ether compounds obtained through redistribution reactions can be adjusted by adjusting the conditions of the redistribution reaction. More specifically, adjusting the amount of phenolic compound used in the redistribution reaction is conceivable. That is, the more phenolic compound used, the lower the molecular weight of the resulting polyphenylene ether compound. In this case, for high molecular weight polyphenylene ether compounds subjected to redistribution reactions, poly(2,6-dimethyl-1,4-phenylene ether) can be used. Furthermore, there are no particular limitations on the phenolic compound used in the aforementioned redistribution reaction, but it is preferable to use polyfunctional phenolic compounds with two or more phenolic hydroxyl groups in their molecules, such as bisphenol A, phenolic varnish, and cresol varnish. These can be used alone or in combination of two or more.

[0153] The content of the polyphenylene ether compound is not particularly limited, but it is more preferably 5 to 1000 parts by weight relative to 100 parts by weight of the curing resin composition, and more preferably 10 to 750 parts by weight. If the content of the polyphenylene ether compound is within the above range, not only are the heat resistance and other properties excellent, but a cured product that can fully utilize the excellent dielectric properties of the polyphenylene ether compound can also be obtained, which is more preferred in this respect.

[0154] [Amine resin]

[0155] Amine resins are compounds with 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 by the reaction of aniline with xylene chloride. The invention relates to aniline resins, reactants of aniline with substituted biphenyl compounds (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 phenyl compounds (such as 1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene and 1,4-bis(hydroxymethyl)benzene, 4,4'-(1,3-phenylenediisopropylidene)bisaniline, reactants of aniline with diisopropylidene, and dimer diamines, but is not limited to these. Furthermore, one type of these may be used, or multiple types may be used in combination.

[0156] [Compounds containing vinyl unsaturated bonds]

[0157] A compound containing ethylene unsaturated bonds is a compound that has one or more ethylene unsaturated bonds in its molecule that can be polymerized by heat or light, regardless of whether a polymerization initiator is used or not.

[0158] Compounds containing vinyl unsaturated bonds can be listed as, but are not limited to, the reactants of the aforementioned phenolic resins with halogen compounds containing vinyl unsaturated bonds (chloromethylstyrene, acryloyl 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 halogen compounds (1,4-bis(chloromethyl)benzene, 4,4'-bis(chloromethyl)biphenyl, 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-dibromobenzophenone, cyanochlorophenone, etc.); reactants of epoxy resins or alcohols with (meth)acrylic acids (acrylic acid, methacrylic acid, etc.); and acid-modified derivatives of these compounds. Furthermore, one type or multiple types may be used.

[0159] [Isocyanate resin]

[0160] Isocyanate resins are compounds having two or more isocyanate groups within their molecules. Examples of isocyanate resins include, but are not limited to, aromatic diisocyanates such as p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, and naphthalene diisocyanate; aliphatic or alicyclic diisocyanates such as isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, northocyanide diisocyanate, and lysine diisocyanate; biuret forms of one or more isocyanate monomers; polyisocyanates such as isocyanates formed by trimerizing the above diisocyanate compounds; and polyisocyanates obtained by urethane reaction of the above isocyanate compounds with polyol compounds, etc. In addition, these can be used in one type or in combination with multiple types.

[0161] [Polyamide resin]

[0162] Examples of polyamide resins include: reactants of diamines, diisocyanates, oxazolines, and dicarboxylic acids; reactants of diamines and acyl chlorides; and ring-opening polymers of lactam compounds. Furthermore, one type of these may be used, or multiple types may be used in combination.

[0163] Specific examples of the above-mentioned raw materials are shown below, but are not limited to these.

[0164] Diamine

[0165] 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, dimer Diamine, cyclohexanediamine, bis-(4-aminocyclohexyl)methane, bis(3-methyl-4-aminocyclohexyl)methane, xylenediamine, northioninediamine, isophoronediamine, diaminomethyltricyclodecane, phenylenediamine, diethyltoluenediamine, naphthyldiamine, diaminodiphenylmethane, bis(4-amino-3,5-dimethylphenyl)methane, bis(4-amino-3,5-diethylphenyl)methane, 4,4'-methylenebis-o-toluidine, 4,4'-Methylenebis-o-ethylaniline, 4,4'-Methylenebis-2-ethyl-6-methylaniline, 4,4'-Methylenebis-2,6-diisopropylaniline, 4,4-ethylenediphenylamine, diaminodiphenyl sulfone, diaminodiphenyl ether, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 4,4-bis(4-aminophenoxy)biphenyl, 2,2-bis[4-(4-aminophenoxy) [4-(4-aminophenoxy)phenyl]propane, bis[4-(4-aminophenoxy)phenyl]sulfone, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-(1,3-phenylenediisopropylidene)bisaniline, 4,4'-(1,4-phenylenediisopropylidene)bisaniline, 9,9-bis(4-aminophenyl)fluorene, 2,7-diaminofluorene, aminobenzylmethylamine, diaminobenzophenone, etc.

[0166] Diisocyanate

[0167] 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'-diisocyanoxy, etc.

[0168] Dicarboxylic Acid

[0169] Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, octanoic acid, azelaic acid, sebacic acid, undecanoic acid, dodecanoic acid, terephthalic acid, isophthalic acid, 5-hydroxyisophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfonate isophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, cyclohexanedicarboxylic acid, biphenyldicarboxylic acid, naphthalenedicarboxylic acid, benzophenonedicarboxylic acid, furandicarboxylic acid, 4,4'-dicarboxylic acid diphenyl ether, 4,4'-dicarboxylic acid diphenyl sulfide, etc.

[0170] Acyl chloride>

[0171] Acetyl chloride, acryloyl chloride, methacryloyl chloride, malonyl chloride, succinyl dichloride, diacetyl oxide, glutaryl dichloride, octanoyl dichloride, sebacyl dichloride, adipyl dichloride, dodecyl dichloride, azelaic chloride, 2,5-furan dicarbonyl dichloride, phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, trimelliticoyl chloride, bis(4-chlorocarbonylphenyl) ether, 4,4'-diphenyldicarboxylate chloride, 4,4'-azodibenzoyl dichloride, etc.

[0172] <lactam>

[0173] ε-caprolactam, ω-undecanolactam, ω-laurolactam, etc.

[0174] [Polyimide resin]

[0175] Examples of polyimide resins include, but are not limited to, the reaction products of the aforementioned diamines with the tetracarboxylic dianhydrides exemplified below. Furthermore, one type may be used, or multiple types may be used in combination.

[0176] Tetracarboxylic dianhydride

[0177] 4,4'-(hexafluoroisopropylidene) phthalic anhydride, 5-(2,5-dioxytetrahydro-3-furanyl)-3-methyl-cyclohexene-1,2-dicarboxylic anhydride, pyromellitic dianhydride, 1,2,3,4-benzenetetracarboxylic anhydride, 3,3',4,4'-benzophenonetetracarboxylic anhydride, 2,2',3,3'-benzophenonetetracarboxylic anhydride, 3,3',4,4'-biphenyltetracarboxylic anhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic anhydride, 2,2',3,3'-biphenyltetracarboxylic anhydride, methylene-4,4'-phthalic anhydride, 1,1-ethylidene-4,4'-phthalic anhydride, 2,2'-propylidene-4,4'-phthalic anhydride, 1,2-vinyl-4, 4'-Diphenyl dianhydride, 1,3-trimethylene-4,4'-diphenyl dianhydride, 1,4-tetramethylene-4,4'-diphenyl dianhydride, 1,5-pentamethylene-4,4'-diphenyl dianhydride, 4,4'-oxophthalic dianhydride, sulfonyl-4,4'-diphenyl dianhydride, sulfonyl-4,4'-diphenyl 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 [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, vinyl Tetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, 3,3',4,4'-bicyclohexyltetracarboxylic 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, oxygen-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, thio-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, sulfonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, rel-[1S,5R,6R]-3-oxobicyclo[3,2,1]octane-2, 4-Diketone-6-spiro-3'-(tetrahydrofuran-2',5'-diketone), 4-(2,5-dioxytetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, ethylene glycol-bis-(3,4-dicarboxylic anhydride phenyl) ether, 4,4'-biphenylbis(trimethacrylate monoester anhydride), 9,9'-bis(3,4-dicarboxyphenyl)fluorene dihydride, etc.

[0178] [Maleimide compounds]

[0179] The curable resin composition of this embodiment may contain a maleimide compound. A maleimide compound is a compound having one or more maleimide groups within its molecule. Examples of maleimide compounds include: 4,4'-diphenylmethane bismaleimide, polyphenylmethane maleimide, m-phenylene bismaleimide, 2,2'-bis[4-(4-maleimidephenoxy)phenyl]propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 4,4'-diphenyl ether bismaleimide, 4,4'-diphenyl sulfone bismaleimide, 1,3-bis(3-maleimidephenoxy)benzene, 1,3-bis(4-maleimidephenoxy)benzene, and XYLOC type maleimide compounds (ANILIX). Maleimide (manufactured by Mitsui Chemicals FINE Co., Ltd.), biphenyl aralkyl maleimide compounds (resin solutions containing maleimide compound (M2) described in Example 4 of Japanese Patent Application Publication No. 2009-001783 are solidified by distilling off the solvent under reduced pressure), diaminoisopropylphenylbenzene maleimide (maleimide compounds described in International Publication No. 2020 / 054601), maleimide compounds with an indene structure described in Japanese Patent Application No. 6629692 or International Publication No. 2020 / 217679, MATERIAL STAGE Vol. 18, No. 122019 『Continued / Epoxy Resin CAS Number Stories to Hardener CAS Number Memorandum No. 31 Bismaleimide (1)』 or MATERIAL STAGE Vol. 19, The maleimide compounds described in No. 22019 "Continued / Epoxy Resin CAS Number Story to Hardener CAS Number Memorandum No. 32 Bismaleimide (2)" are not limited to these. In addition, one type of these may be used, or multiple types may be used together.

[0180] [Cyanate ester resin]

[0181] Cyanate ester resins are cyanate ester compounds obtained by reacting phenolic resins with cyanide halides. Specific examples include: benzene dicyanate, benzene tricyanate, naphthalene dicyanate, biphenyl dicyanate, 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 cyanates obtained by converting the hydroxyl groups of phenol / dicyclopentadiene cocondensates to cyanate groups, etc., but are not limited to these. Furthermore, one type or multiple types can be used.

[0182] Furthermore, the cyanate ester compound synthesized by the method disclosed in Japanese Patent Application Publication No. 2005-264154 is particularly preferred as a cyanate ester compound due to its excellent low hygroscopicity, flame retardancy, and dielectric properties.

[0183] Cyanate ester resins may contain catalysts such as zinc naphthenate, cobalt naphthenate, copper naphthenate, lead naphthenate, zinc octanoate, tin octanoate, lead acetylacetone, and dibutyltin maleate, depending on the desired cyanate ester group trimerization to form a sym-tricyclohexane ring.

[0184] The catalyst is used in amounts of 0.0001 to 0.10 parts by weight relative to 100 parts by weight of the cyanate resin and the curing resin composition, more preferably 0.00015 to 0.0015 parts by weight.

[0185] Polybutadiene and its modified forms

[0186] Polybutadiene and its modified forms are compounds that have polybutadiene or polybutadiene-derived structures within their molecules. Polybutadiene-derived structures can be hydrogenated to convert some or all of the unsaturated bonds into single bonds.

[0187] Examples of polybutadiene and its modified forms include, but are not limited to, polybutadiene, hydroxyl-terminated polybutadiene, terminal (meth)acrylated polybutadiene, carboxylic acid-terminated polybutadiene, amine-terminated polybutadiene, and styrene-butadiene rubber. Furthermore, one type or multiple types may be used. From the viewpoint of dielectric properties, polybutadiene or styrene-butadiene rubber is preferred. Examples of styrene-butadiene rubber (SBR) include, for example, RICON-100, RICON-181, RICON-184 (all manufactured by CRAY VALLEY), and 1,2-SBS (manufactured by Nippon Soda); examples of polybutadiene include, for example, B-1000, B-2000, and B-3000 (all manufactured by Nippon Soda). The molecular weight of polybutadiene and styrene-butadiene rubber is preferably 500 to 10,000 by weight average, more preferably 750 to 7,500, and even more preferably 1,000 to 5,000. Below the lower limit of the above range, the volatility is high, making it difficult to adjust the solid content during prepreg preparation; above the upper limit of the above range, the compatibility with other curing resins deteriorates. Generally, compounds containing heteroatoms such as oxygen or nitrogen, such as bismaleimide or polymaleimide, are difficult to ensure compatibility with low-polarity compounds such as compounds mainly composed of hydrocarbons or compounds composed only of hydrocarbons due to their polarity. On the other hand, the compounds of this embodiment are designed with a framework containing heteroatoms such as oxygen or nitrogen, which is not actively incorporated into the compound itself, and exhibit excellent compatibility with materials having low polarity and low dielectric properties, or compounds composed only of hydrocarbons.

[0188] Polystyrene and its modified forms

[0189] Polystyrene and its modified forms are compounds that have polystyrene in their molecules or that are derived from polystyrene.

[0190] Examples of polystyrene and its modified forms include: polystyrene, styrene / 2-isopropenyl-2-oxazoline copolymer (EPOCROS RPS-1005, RP-61, both manufactured by Nippon Catalyst Co., Ltd.), and SEP (styrene-ethylene / propylene copolymer: SEPTON (registered trademark) 1020). (Made by KURARAY), SEPS (styrene-ethylene / propylene-styrene copolymers: SEPTON2002, SEPTON2004F, SEPTON2005, SEPTON2006, SEPTON2063, SEPTON2104, all manufactured by KURARAY), SEEPS (styrene-ethylene / ethylene / propylene-styrene block copolymers: SEPTON4003, SEPTON4044, SEPTON4055, SEPTON4077, SEPTON4099, all manufactured by KURARAY), SEBS (styrene-ethylene / butene-styrene block copolymers: SEPTON8004, SEPTON8006, SEPTON8007L, all manufactured by KURARAY), SEEPS-OH (a compound with hydroxyl groups at the end of a styrene-ethylene / ethylene / propylene-styrene block copolymer: SEPTONHG252). Polystyrene (manufactured by KURARAY), SIS (styrene-isoprene-styrene block copolymers: SEPTON 5125, SEPTON 5127, both manufactured by KURARAY), hydrogenated SIS (hydrogenated styrene-isoprene-styrene block copolymers: HYBRAR (registered trademark) 7125F, HYBRAR 7311F, both manufactured by KURARAY), SIBS (styrene-isobutylene-styrene block copolymers: SIBSTAR (registered trademark) 073T, SIBSTAR 102T, SIBSTAR 103T (each manufactured by KANEKA), SEPTON V9827 (manufactured by KURARAY)), etc., but not limited to these. Furthermore, one type or multiple types can be used. Polystyrene and its modified forms have higher heat resistance and are less prone to oxidative degradation; therefore, those without unsaturated bonds are preferred. In addition, there are no particular restrictions on the weight average molecular weight of polystyrene and its modified products as long as it is above 10,000. However, if it is too large, the compatibility with low molecular weight components with a weight average molecular weight of about 50 to 1,000 and oligomer components with a weight average molecular weight of about 1,000 to 5,000 will become poor, making it difficult to ensure mixing and solvent stability. Therefore, a weight average of about 10,000 to 300,000 is preferred.

[0191] Polyethylene and its modified forms

[0192] Polyethylene and its modified forms are compounds that have a polyethylene structure or a structure derived from polyethylene within their molecules. Examples of polyethylene and its modified forms include: ethylene-propylene copolymers, ethylene-styrene copolymers, ethylene-propylene-ethylenenorphine copolymers (Mitsui Chemicals EBT: K-8370EM, K-9330M, etc.), ethylene-propylene-vinylnorphine 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-ethylenenorphine copolymers and ethylene-propylene-vinylnorphine copolymers containing a crosslinkable structure are preferred. Furthermore, one type or multiple types can be used. There are no particular restrictions on the weight average molecular weight of polyethylene and its modified products as long as it is above 10,000. However, if it is too large, the compatibility with low molecular weight components with a weight average molecular weight of about 50 to 1,000 and oligomer components with a weight average molecular weight of about 1,000 to 5,000 will become poor, making it difficult to ensure mixing and solvent stability. Therefore, a weight average molecular weight of about 10,000 to 300,000 is preferred.

[0193] The curable resin composition of this embodiment can be obtained by preparing the above-mentioned components in a predetermined ratio, and then curing it by pre-curing at 130 to 180°C for 30 to 500 seconds, followed by post-curing at 150 to 200°C for 2 to 15 hours to allow for a sufficient curing reaction, thereby obtaining the cured product of this embodiment. Alternatively, the components of the curable resin composition can be uniformly dispersed or dissolved in a solvent, and then cured after removing the solvent.

[0194] The method for preparing the curable resin composition of this embodiment is not particularly limited, but as long as the components are mixed uniformly, or prepolymerization can be performed. For example, for a mixture containing the compounds of this embodiment, prepolymerization can be performed 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 can be performed by adding amine compounds, compounds having ethylene unsaturated bonds, maleimide compounds, cyanate ester compounds, compounds of polybutadiene and its modifications, polystyrene and its modifications, inorganic fillers, and other additives. The mixing or prepolymerization of the components can be performed in the absence of a solvent using, for example, an extruder, kneader, rollers, etc., or in the presence of a solvent using a reaction vessel equipped with a stirring device, etc.

[0195] Regarding the method of uniform mixing, the resin composition is formed by kneading using devices such as kneaders, rollers, or planetary mixers at temperatures ranging from 50 to 100°C. The resulting resin composition is then pulverized and shaped into cylindrical ingots, granular powders, or powdered molded bodies using a molding machine such as an ingot beater. Alternatively, these compositions can be melted on a surface support and shaped into sheets with a thickness of 0.05 mm to 10 mm, or they can be formed into curable resin composition molded bodies. The resulting molded bodies become non-sticky at temperatures between 0 and 20°C, and even after storage at -25 to 0°C for more than one week, their fluidity and curability show almost no reduction.

[0196] The resulting molded body can be molded into a hardened material using a transfer molding machine or a compression molding machine.

[0197] The curable resin composition of this embodiment can also be modified by adding an organic solvent to form a varnish-like composition (hereinafter, simply referred to as varnish). The curable resin composition of this embodiment is dissolved as needed in solvents such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone to form a varnish. A prepreg obtained by impregnating a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, or paper with heat and drying is then hot-pressed to form a cured product of the curable resin composition of this embodiment. In this case, the solvent used in the mixture of the curable resin composition of this embodiment and the solvent is 10 to 70% by weight, preferably 15 to 70% by weight. Alternatively, if it is a liquid composition, a cured product containing carbon fibers in an RTM manner can be directly obtained, for example.

[0198] Alternatively, the curable resin composition of this embodiment can also be used as a modifier for the film-type composition. Specifically, it can be used to improve flexibility, etc., in the B-stage. In this film-type resin composition, the curable resin composition of this embodiment is applied as a varnish to a release film, and after the solvent is removed by heating, a sheet-like adhesive is obtained by performing the B-stage. This sheet-like adhesive can be used as an interlayer insulating layer in multilayer substrates, etc.

[0199] The curable resin composition of this embodiment can also be obtained by heating and melting to achieve a low viscosity, and then impregnating it with reinforcing fibers such as glass fibers, carbon fibers, polyester fibers, polyamide fibers, and alumina fibers to obtain a prepreg. Specific examples include glass fibers such as E-glass cloth, D-glass cloth, S-glass cloth, Q-glass cloth, spherical glass cloth, NE-glass cloth, and T-glass cloth. In addition, inorganic fibers other than glass or organic fibers such as poly(p-phenylene terephthalamide) (Kevlar (registered trademark), manufactured by DuPont), fully aromatic polyamide, polyester, poly(p-phenylenebenzoxazole), polyimide, and carbon fiber can be used, but are not particularly limited to these. The shape of the substrate is not particularly limited, but examples include woven fabric, nonwoven fabric, roving, and chopped strand mat. In addition, the weaving methods of woven fabrics include plain weave, twill weave, and satin weave, etc. From these publicly known weaving methods, the appropriate method can be selected according to the intended use or performance. Alternatively, woven 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, the prepreg can be obtained by impregnating the aforementioned varnish into the reinforcing fibers and then heating and drying it.

[0200] Alternatively, the aforementioned prepregs can be used to manufacture laminates. The laminate is not particularly limited as long as it contains one or more prepregs, and may also have any other layers. Regarding the manufacturing method of the laminate, generally known methods are suitable and there are no particular limitations. For example, in forming metal foil laminates, multi-stage extruders, multi-stage vacuum extruders, continuous forming machines, autoclave forming machines, etc., can be used, and the aforementioned prepregs can be stacked together and subjected to 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. Furthermore, the pressure applied is not particularly limited, but if the pressure is too high, it is difficult to adjust the resin solids content of the laminate, and the quality is unstable. Conversely, if the pressure is too low, air bubbles or poor adhesion between layers will occur. 2.0 to 5.0 MPa is preferred, and 2.5 to 4.0 MPa is more preferred. The laminate of this embodiment, by having a layer made of metal foil, is suitable for use as a metal foil laminate as described later.

[0201] By cutting the prepreg into the desired shape and stacking it with copper foil or the like as needed, pressure is applied to the stack by extrusion molding, autoclave molding, or sheet winding, while the curable resin composition is heated and cured. In this way, electro-electronic laminates (printed wiring boards) or carbon fiber reinforced materials can be obtained.

[0202] The curable resin composition of this embodiment can also be formed into a resin sheet. A method for obtaining a resin sheet from the curable resin composition of this embodiment can be exemplified by, for example, coating a curable resin composition onto a support film (support body), drying it, and thus forming a resin composition layer on the support film. When the curable resin composition of this embodiment is used in a resin sheet, the film is softened at the lamination temperature conditions (70°C to 140°C) in a vacuum lamination process. Simultaneously with the lamination of the circuit board, it is important to exhibit good flowability (resin flow) in the resin filling within the holes or through-holes of the circuit board. To achieve this characteristic, it is preferable to formulate the aforementioned components accordingly. Furthermore, in the obtained resin sheet or circuit board (copper foil laminate, etc.), phenomena such as locally different characteristic values ​​due to phase separation do not occur, and certain properties are exhibited in any location; therefore, uniform appearance is required.

[0203] 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 within which resin can be filled. Furthermore, when both sides of the circuit board are laminated, it is desirable to fill approximately half of the through-hole.

[0204] A specific method for manufacturing the aforementioned resin sheet can be described as follows: after preparing a varnished resin composition by mixing an organic solvent, the aforementioned varnished resin composition is coated on the surface of a support film (Y), and the organic solvent is dried by heating or blowing hot air to form a resin composition layer (X).

[0205] The organic solvents used herein are preferably ketones such as acetone, methyl ethyl ketone, and cyclohexanone; acetates such as ethyl acetate, butyl acetate, cellolytic acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitols such as cellolytic agents 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 at a proportion of 30 to 60% by mass of the non-volatile components as a whole.

[0206] 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, the thickness of the aforementioned resin composition layer (X) is preferably 10 to 100 μm. Additionally, in this embodiment, the aforementioned resin composition layer (X) can be protected by a protective film, as described later. By protecting it with a protective film, the adhesion or damage of dust or other contaminants to the surface of the resin composition layer (X) can be prevented.

[0207] Examples of the aforementioned support film and protective film include: polyethylene, polypropylene, polyvinyl chloride and other polyolefins; polyethylene terephthalate (PET), polyethylene naphthalate and other polyesters; polycarbonate; polyimide; and release paper or metal foils such as copper foil and aluminum foil. In addition to matte finishing and corona treatment, the support film and protective film may also undergo release treatment. The thickness of the support film is not particularly limited, but is 10 to 150 μm, preferably in the range of 25 to 50 μm. The thickness of the protective film is preferably set to 1 to 40 μm.

[0208] The aforementioned support film (Y) is peeled off after the aforementioned resin composition layer (X) is laminated 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 the like during the curing process. When peeling off the support film (Y) after the aforementioned resin composition layer (X) has been cured, a release treatment is applied to the support film (Y) beforehand.

[0209] Furthermore, multilayer printed circuit boards can be manufactured from the resin sheet obtained as described above. For example, when the aforementioned resin composition layer (X) is protected with a protective film, after peeling off the protective film from the aforementioned resin composition layer (X), the aforementioned resin composition layer (X) is directly contacted to the circuit board on one or both sides of the circuit board, for example, by vacuum lamination. The lamination method can be batch lamination or continuous lamination by roller lamination. In addition, if necessary, the resin sheet and the circuit board can be heated (preheated) before lamination. The lamination conditions are preferably a pressing temperature (lamination temperature) of 70 to 140°C, and preferably a pressing pressure of 1 to 11 kgf / cm2 (9.8 × 10⁻⁶ kgf / cm²). 4 Up to 107.9×10 4 N / m 2 It is preferred that the lamination is carried out under reduced pressure of air pressure below 20 mmHg (26.7 hPa).

[0210] Furthermore, 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), TQFP (Thin Quad Flat Package), etc.

[0211] The curable resin composition and its cured product of the present 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, coatings, etc. The cured product of the curable resin composition described in the present embodiment can be suitably used for electrical / electronic parts such as sealing materials for semiconductor elements, sealing materials for liquid crystal display elements, sealing materials for organic EL elements, laminated boards (printed wiring boards, substrates for BGA (Ball Grid Array), build-up substrates, etc.), composite materials for lightweight and high-strength structural materials such as carbon fiber reinforced plastics and glass fiber reinforced plastics, 3D printing, etc., because it exhibits excellent heat resistance and dielectric properties.

[0212] Examples

[0213] Next, the present invention will be described more specifically by way of examples. Hereinafter, parts are by mass unless otherwise specified. In addition, the present invention is not limited to these examples.

[0214] The following describes various analysis methods used in the examples.

[0215] <GPC (Gel Permeation Chromatography) Analysis>

[0216] Apparatus: On-line degassing unit (DGU-20A), liquid delivery unit (LC-20AD), automatic sampler (SIL-20A), photodiode array detector (SPD-M40), column oven (CTO-20A), system controller (CBM-20A), all of which are manufactured by Shimadzu Corporation

[0217] Columns: SHODEX GPC KF-601 (2 pieces), KF-602, KF-602.5, KF-603

[0218] Flow rate: 1.5 ml / min.

[0219] Column temperature: 40 °C

[0220] Solvent used: THF (tetrahydrofuran)

[0221] Detector: Differential refractive index detector (RID-20A, manufactured by Shimadzu Corporation)

[0222] <High Performance Liquid Chromatography (HP-LC)>

[0223] HP-LC: Liquid delivery unit (LC-20AB), on-line degasser (DGU-20A3), automatic sampler (SIL-20A), column oven (CTO-20A), system controller (CBM-20A), absorbance detector (SPD-M20A) (all of which are manufactured by Shimadzu)

[0224] Column: ODS-2 (manufactured by GL Science)

[0225] Connecting solution: Tetrahydrofuran: Water = 3:1 (no gradient)

[0226] Flow rate: 0.5 ml / min.

[0227] Column temperature: 40℃

[0228] Detection: PDA (Photodiode Array Detector)

[0229] [Example 1]

[0230] Nitrogen gas was applied to a flask equipped with a thermometer, cooling tube, stirrer, and Dean Stark tube. 16.6 parts fluorene, 3.5 parts 1,4-benzenedimethanol, 21.6 parts benzyl alcohol, and 2.1 parts methanesulfonic acid were added. The temperature was raised to 130°C, and the generated water was drained from the system using the Dean Stark tube. The reaction was allowed to proceed for 5 hours. After cooling to 70°C, 1.0 part sodium hydroxide was added and stirred for 5 minutes. Then, 100 parts dimethyl sulfoxide and 12 parts sodium hydroxide were added, and the mixture was stirred at 60°C for 30 minutes. Afterward, the internal temperature was maintained below 65°C, and 29.0 parts of CMS-14 (manufactured by AGC SEIMI CHEMICAL, a mixture of 4-chloromethylstyrene and 3-chloromethylstyrene, 4-chloromethylstyrene:3-chloromethylstyrene = 95:5 (molar ratio), purity 96.87% by weight) were added dropwise over 2 hours. The reaction was continued at 65°C for 3 hours. Add 200 parts toluene and wash the organic layer five times with 100 parts water. Concentrate the obtained organic layer to obtain 42.6 parts of compound (F1) as shown in formula (f-1). The HP-LC diagram of the obtained compound (F1) is shown in [image / image / description]. Figure 1 In the middle, the GPC chart is represented in Figure 2 In addition, the obtained compounds 1 H-NMR chart (dichloroform) is shown in Figure 3 In the middle. GPC analysis yielded a number-average molecular weight (Mn) of 806 and a weight-average molecular weight (Mw) of 2276 for F1. 1 The H-NMR spectrum shows signals originating from the terminal hydrogen of the vinyl group (two hydrogens relative to one vinyl group) at 4.95–5.65 ppm, signals originating from the 1,4-benzylenedimethanol-modified structure at 3.05–3.45 ppm, and signals originating from the benzyl alcohol-modified structure at 3.75–4.25 ppm. With the integral value of the peak originating from the terminal hydrogen of the vinyl group taken as 4.00, the integral value of the peak originating from the methylene hydrogen of the benzyl alcohol-modified benzyl group is 4.05. The average value of m in the following equation (f-1) calculated here (mave The integral value of n is 2.02. Additionally, the integral value of the peak derived from the methylene hydrogen in the 1,4-benzenedimethanol-modified structure is 3.40. The average value of n in the following equation (f-1) calculated here is... ave The value is 0.85.

[0231]

[0232] [Comparative Synthesis Example 1]

[0233] While purging the flask with nitrogen, a thermometer, cooling pipe, and stirrer, 133 parts of methyl isobutyl ketone (hereinafter also referred to as MIBK), 33.3 parts of fluorene, 1.9 parts of tetrabutylammonium bromide, 0.49 parts of hydroquinone, and 64 parts of 50 wt% sodium hydroxide aqueous solution were added, and the internal temperature was raised to 60°C. After this, 71.2 parts of CMS-P (manufactured by AGC SEIMI CHEMICAL, a mixture of 4-chloromethylstyrene and 3-chloromethylstyrene, 4-chloromethylstyrene:3-chloromethylstyrene = 1:1 (molar ratio), purity 95.59% by weight) were added dropwise over 1 hour, and the reaction was carried out at 60°C for 9 hours. Neutralization was performed with 41.6 parts of 35 wt% hydrochloric acid aqueous solution, and the organic layer was washed three times with 100 parts of water. Recrystallization with toluene and methanol yielded 35.6 parts of compound (F2) as shown in formula (f-2). The HP-LC diagram of the obtained compound (F2) is shown in [the figure]. Figure 4 In the middle, 1 H-NMR data (dichloroform) are expressed as follows: Figure 5 middle.

[0234]

[0235] [Example 2, Comparative Examples 1 and 2]

[0236] The compounds (F1, F2) obtained in Example 1 and Comparative Synthesis 1, as well as OPE-2St (manufactured by Mitsubishi Gas Chemical Co., Ltd., a polyphenylene ether compound), were used in the amounts shown in Table 1. They were vacuum extruded while being sandwiched between mirror-finished copper foil (T4X: manufactured by Fukuda Metal Copper Foil Co., Ltd.), and then cured at 220°C for 2 hours. At this time, a 150mm x 150mm diameter spacer was cut out in the center of a 250μm thick buffer paper. For evaluation, the test pieces were cut to the desired size using a laser cutter as needed, and the evaluation was then performed.

[0237] <Dielectric conductivity test / Dielectric tangent test>

[0238] A 10 GHz void resonator manufactured by AET Corporation was used for testing at 25°C using the void resonator perturbation method. The specimen size was 1.7 mm wide × 100 mm long, with a thickness of 0.1 mm. The evaluation results are shown in Table 1.

[0239] [Table 1]

[0240]

[0241] The results in Table 1 confirm that the compounds of the present invention have a lower dielectric tangent than Comparative Examples 1 and 2, and exhibit excellent low dielectric properties.

[0242] [Industry availability]

[0243] The compounds of this invention are suitable for use in electrical / electronic components such as semiconductor sealing materials, printed wiring boards, and multilayer laminates.

[0244] This application claims priority based on Japanese Patent Application No. 2023-156530 filed on September 21, 2023.

Claims

1. A compound, as shown in the following formula (1); In the above formula (1), the multiple R1s independently represent hydrogen atoms or hydrocarbon groups with 1 to 5 carbon atoms, the multiple R2s independently represent hydrocarbon groups as shown in formula (a) below, X is the structure shown in formulas (c) to (f) below, the multiple ls independently represent integers from 1 to 4, the multiple ms independently represent integers from 0 to 3, and the average value of m is m ave 0 <m ave ≤3, where n is the number of repetitions, and the average value of n is 0.05≤n. ave ≤20; In the above formula (a), * indicates the bonding position of the fluorene structure in formula (1), R3 represents a hydrogen atom or a hydrocarbon group with 1 to 5 carbon atoms, and k represents an integer from 1 to 5. In equations (c) to (f) above, * represents the bonding position of the fluorene structure in equation (1), the multiple R4s independently represent hydrogen atoms or hydrocarbon groups with 1 to 5 carbon atoms, the multiple ps independently represent integers 1 to 4, and the multiple qs independently represent integers 1 to 3.

2. A compound obtained by reacting a compound represented by formula (A) with a compound represented by formula (B); In the above formula (A), the multiple R2s that exist independently represent the hydrocarbon groups shown in formula (a) below, X is the structure shown in formulas (c) to (f) below, the multiple m that exist independently represent integers from 0 to 3, and the average value of m is m ave 0 <m ave ≤3, where n is the number of repetitions, and n is the average value of n. ave For 0.05≤n ave ≤20; In the above formula (a), * indicates the bonding position of the fluorene structure in formula (A), R3 represents a hydrogen atom or a hydrocarbon group with 1 to 5 carbon atoms, and k represents an integer from 1 to 5. In equations (c) to (f) above, * indicates the bonding position of the fluorene structure in equation (A), the multiple R4s independently represent hydrogen atoms or hydrocarbon groups with 1 to 5 carbon atoms, the multiple ps independently represent integers 1 to 4, and the multiple qs independently represent integers 1 to 3. In the above formula (B), R1 represents a hydrogen atom or a hydrocarbon group with 1 to 5 carbon atoms, k represents an integer from 1 to 4, and Y represents a halogen atom.

3. A curable resin composition comprising the compound described in claim 1 or 2.

4. A hardener obtained by hardening the compound described in claim 1 or 2.

5. A hardener obtained by hardening the hardening resin composition of claim 3.

6. A method for producing a compound, comprising reacting a compound represented by formula (A) and a compound represented by formula (B) in an aprotic polar solvent in the presence of a basic catalyst to obtain the compound; In the above formula (A), the multiple R2s that exist independently represent the hydrocarbon groups shown in formula (a) below, X is the structure shown in formulas (c) to (f) below, the multiple m that exist independently represent integers from 0 to 3, and the average value of m is m ave 0 <m ave ≤3, where n is the number of repetitions, and n is the average value of n. ave For 0.05≤n ave ≤20; In the above formula (a), * indicates the bonding position of the fluorene structure in formula (A), R3 represents a hydrogen atom or a hydrocarbon group with 1 to 5 carbon atoms, and k represents an integer from 1 to 5. In equations (c) to (f) above, * represents the bonding position of the fluorene structure in equation (1), the multiple R4s independently represent hydrogen atoms or hydrocarbon groups with 1 to 5 carbon atoms, the multiple ps independently represent integers 1 to 4, and the multiple qs independently represent integers 1 to 3. In the above formula (B), R1 represents a hydrogen atom or a hydrocarbon group with 1 to 5 carbon atoms, k represents an integer from 1 to 4, and Y represents a halogen atom.

7. A compound, as shown in the following formula (A); In the above formula (A), the multiple R2s that exist independently represent the hydrocarbon groups shown in formula (a) below, X is the structure shown in formulas (c) to (f) below, the multiple m that exist independently represent integers from 0 to 3, and the average value of m is m ave 0 <m ave ≤3, where n is the number of repetitions, and n is the average value of n. ave For 0.05≤n ave ≤20; In the above formula (a), * indicates the bonding position of the fluorene structure in formula (A), R3 represents a hydrogen atom or a hydrocarbon group with 1 to 5 carbon atoms, and k represents an integer from 1 to 5. In equations (c) to (f) above, * represents the bonding position of the fluorene structure in equation (A), the multiple R4s independently represent hydrogen atoms or hydrocarbon groups with 1 to 5 carbon atoms, the multiple ps independently represent integers 1 to 4, and the multiple qs independently represent integers 1 to 3.

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