Curable resin, curable resin composition, cured product, and article

Abstract

To provide a curable resin capable of exhibiting favorable dielectric properties and excellent heat resistance.SOLUTION: The present invention provides a curable resin produced by the introduction of a (meth)acryloyloxy group into a phenol-aralkyl resin having an arylene group with 6 to 18 carbon atoms or a tricyclodecane ring.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a curable resin, a curable resin composition, a cured product, and an article. [Background technology]

[0002] Prepregs obtained by impregnating glass cloth with a thermosetting resin and drying it by heating are widely used as circuit board materials for electronic devices.

[0003] In recent years, signals have become faster and higher in frequency, and there is a demand for thermosetting resin compositions that give cured products that exhibit a sufficiently low dielectric tangent while maintaining a sufficiently low dielectric constant in these environments.

[0004] Furthermore, in order to accommodate the trend towards multi-layering or thinning of substrates, materials with high heat resistance (glass transition temperature) are required.

[0005] In response to this, for example, Patent Document 1 discloses a curable resin having a specific structural unit (1) and a specific terminal structure (2). Patent Document 2 discloses a curable resin represented by a specific general formula (1). [Prior art documents] [Patent documents]

[0006] [Patent Document 1] International Publication No. 2021 / 251052 [Patent Document 2] Patent Publication No. 2022-102140 Summary of the Invention [Problem to be solved by the invention]

[0007] However, there is still room for improvement in the heat resistance of such curable resins.

[0008] Therefore, an object of the present invention is to provide a curable resin capable of exhibiting good dielectric properties and excellent heat resistance.

[0009] Another object of the present invention is to provide a curable resin composition capable of exhibiting good dielectric properties and excellent heat resistance. Still another object of the present invention is to provide a cured product having good dielectric properties and excellent heat resistance. Still another object of the present invention is to provide an article including a cured product having good dielectric properties and excellent heat resistance. [Means for solving the problem]

[0010] The curable resin according to the present invention is A structural unit represented by the following general formula (1) or general formula (2), A terminal structural unit represented by the following general formula (3) or general formula (4), [ka] (In general formula (1), R 1 each independently represents a hydrogen atom or a methyl group; Ar represents an arylene group having 6 to 18 carbon atoms; In general formula (3), R 2 each independently represents an alkyl group, an aryl group, an aralkyl group, or a cycloalkyl group having 1 to 12 carbon atoms; R 3 represents a hydrogen atom or a methyl group; x represents an integer of 1, 2, 3, or 4; * represents the bonding position of the bond extending outside the structural unit of general formula (1) or (2); In general formula (4), R 2 each independently represents an alkyl group, an aryl group, an aralkyl group, or a cycloalkyl group having 1 to 12 carbon atoms; R 3 represents a hydrogen atom or a methyl group; y is an integer of 0, 1, 2, 3, or 4; * indicates the bonding position with a bond extending outside the structural unit of general formula (1) or (2). This makes it possible to exhibit good dielectric properties and excellent heat resistance.

[0011] In one embodiment of the curable resin according to the present invention, the terminal structural unit represented by the general formula (3) is a terminal structural unit represented by the following general formula (3-1) or general formula (3-2). [ka]

[0012] In one embodiment of the curable resin according to the present invention, the terminal structural unit represented by the general formula (4) is a terminal structural unit represented by the following general formula (4-1). [ka]

[0013] In one embodiment of the curable resin according to the present invention, the structural unit represented by the general formula (1) is a structural unit represented by the following general formula (1-1) or general formula (1-2). [ka]

[0014] In one embodiment of the curable resin according to the present invention, the weight average molecular weight is 500 to 5,000.

[0015] The curable resin composition according to the present invention contains any one of the curable resins described above.

[0016] The cured product according to the present invention is a cured product of the above-mentioned curable resin composition.

[0017] The article according to the present invention is an article comprising the above-mentioned cured product, and the article is an article selected from the group consisting of a prepreg, a circuit board, a semiconductor encapsulant, a semiconductor device, a build-up film, a build-up board, an adhesive, and a resist material. Effect of the Invention

[0018] According to the present invention, it is possible to provide a curable resin capable of exhibiting good dielectric properties and excellent heat resistance. Also, according to the present invention, it is possible to provide a curable resin composition capable of exhibiting good dielectric properties and excellent heat resistance. Also, according to the present invention, it is possible to provide a cured product having good dielectric properties and excellent heat resistance. Also, according to the present invention, it is possible to provide an article including a cured product having good dielectric properties and excellent heat resistance. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0019] Hereinafter, embodiments of the present invention will be described. These descriptions are intended to be illustrative of the present invention and are not intended to limit the present invention in any way.

[0020] In the present invention, two or more embodiments can be combined in any manner.

[0021] Unless otherwise specified, the materials, components, compounds, resins, structural units, terminal structural units, catalysts and solvents described in this specification may be used alone or in combination of two or more.

[0022] (curable resin) The curable resin according to the present invention is A structural unit represented by the following general formula (1) or general formula (2), A terminal structural unit represented by the following general formula (3) or general formula (4), [ka] (In general formula (1), R 1 each independently represents a hydrogen atom or a methyl group; Ar represents an arylene group having 6 to 18 carbon atoms; In general formula (3), R 2each independently represents an alkyl group, an aryl group, an aralkyl group, or a cycloalkyl group having 1 to 12 carbon atoms; R 3 represents a hydrogen atom or a methyl group; x represents an integer of 1, 2, 3, or 4; * indicates the bonding position with a bond extending outside the repeating unit of general formula (1) or (2); In general formula (4), R 2 each independently represents an alkyl group, an aryl group, an aralkyl group, or a cycloalkyl group having 1 to 12 carbon atoms; R 3 represents a hydrogen atom or a methyl group; y is an integer of 0, 1, 2, 3, or 4; * indicates the bonding position with the bond extending outside the repeating unit of general formula (1) or (2). It is a curable resin having the following structure.

[0023] The curable resin of the present invention has an end structure of at least one selected from the group consisting of general formula (3) and general formula (4), and does not have a styryl structure at the end of the curable resin as in Patent Documents 1 and 2. The curable resin of the present invention has a moderate steric hindrance, and therefore can exhibit excellent heat resistance while having good dielectric properties.

[0024] In general formula (1), R 1 each independently represents a hydrogen atom or a methyl group, and Ar represents an arylene group having 6 to 18 carbon atoms.

[0025] Examples of Ar include the following divalent structures: [ka] In these structures, * represents the point of attachment to the structure of general formula (1).

[0026] In addition, Ar may be, for example, any of the structural formula (4) in Japanese Patent No. 7320805.

[0027] In a preferred embodiment, Ar is one or more selected from the following structures: [ka]

[0028] Examples of the structural unit of general formula (1) include the following six units. [ka] In a preferred embodiment, the structural unit represented by general formula (1) is at least one type selected from the group consisting of the following general formulae (1-1) and (1-2). [ka]

[0029] The number of structural units represented by general formula (1) or general formula (2) in the curable resin may be 1 or 2 or more, for example, 2 to 20. In one embodiment, the number of structural units represented by general formula (1) or general formula (2) is independently 1.0 or more, 1.5 or more, 1.7 or more, 1.9 or more, 2.0 or more, 2.5 or more, 3.0 or more, 3.5 or more, 3.8 or more, 4.0 or more, 4.5 or more, 5.0 or more, 10 or more, or 15 or more. In another embodiment, the structural units represented by general formula (1) or general formula (2) are each independently 20 or less, 15 or less, 10 or less, 5.0 or less, 4.5 or less, 4.0 or less, 3.8 or less, 3.5 or less, 3.0 or less, 2.5 or less, 2.0 or less, 1.9 or less, 1.7 or less, or 1.5 or less.

[0030] In general formula (3), x is 1, 2, 3 or 4. In one embodiment, x is 1 or 2.

[0031] In one embodiment, R in general formula (3) 2 In another embodiment, R in general formula (3) is a methyl group. 2 is a methyl group, and CH2=C(R3 ) bonded to the carbon atom adjacent to one or both of the carbons bonded to the COO group.

[0032] Examples of the terminal structural unit of general formula (3) include the following general formulae (3-1) and (3-2). [ka] In the general formulas (3-1) and (3-2), R 3 represents a hydrogen atom or a methyl group.

[0033] Examples of the terminal structural unit of general formula (3) include the following six units. [ka] In the formula, R 3 represents a hydrogen atom or a methyl group.

[0034] In general formula (4), y is 0, 1, 2, 3 or 4. In one embodiment, y is 0.

[0035] An example of the terminal structural unit of general formula (4) is the following general formula (4-1). [ka] In general formula (4-1), R 3 represents a hydrogen atom or a methyl group.

[0036] Examples of the terminal structural unit of general formula (4) include the following seven units. [ka] In the formula, R 3 represents a hydrogen atom or a methyl group.

[0037] In one embodiment, the curable resin of the present invention has a structural unit of general formula (1) and a terminal structural unit of general formula (3). In another embodiment, the curable resin of the present invention has a structural unit of general formula (1) and a terminal structural unit of general formula (4). In another embodiment, the curable resin of the present invention has a structural unit of general formula (1) and one or more terminal structural units selected from the group consisting of general formulas (3-1) and (3-2). In another embodiment, the curable resin of the present invention has a structural unit of general formula (1) and a terminal structural unit of general formula (4-1).

[0038] In one embodiment, the curable resin of the present invention has a structural unit of general formula (2) and a terminal structural unit of general formula (3). In another embodiment, the curable resin of the present invention has a structural unit of general formula (2) and a terminal structural unit of general formula (4). In another embodiment, the curable resin of the present invention has a structural unit of general formula (2) and one or more terminal structural units selected from the group consisting of general formulas (3-1) and (3-2). In another embodiment, the curable resin of the present invention has a structural unit of general formula (2) and a terminal structural unit of general formula (4-1).

[0039] In one embodiment, the curable resin of the present invention is one or more selected from the group consisting of C1, C2, C3 and C4 below. [ka] In the formula, n is 1 to 20.

[0040] n in C1, C2, C3 and C4 is each independently 1 to 20. In one embodiment, n in C1, C2, C3 and C4 is each independently 2 to 20. In another embodiment, n in C1, C2, C3 and C4 is each independently 1.0 or more, 1.5 or more, 1.7 or more, 1.9 or more, 2.0 or more, 2.5 or more, 3.0 or more, 3.5 or more, 3.8 or more, 4.0 or more, 4.5 or more, 5.0 or more, 10 or more or 15 or more. In yet another embodiment, n in C1, C2, C3 and C4 is each independently 20 or less, 15 or less, 10 or less, 5.0 or less, 4.5 or less, 4.0 or less, 3.8 or less, 3.5 or less, 3.0 or less, 2.5 or less, 2.0 or less, 1.9 or less, 1.7 or less or 1.5 or less.

[0041] The weight average molecular weight (Mw) of the curable resin of the present invention is, for example, 400 to 10,000. In one embodiment, the Mw of the curable resin is 500 to 5,000.

[0042] - Manufacturing method of hardening resin The method for producing the curable resin of the present invention may, for example, be a method in which a phenolic resin is reacted with (meth)acrylic anhydride or (meth)acrylic acid halide to convert the hydroxyl group to (meth)acryloyl.

[0043] (Curable resin composition) The curable resin composition of the present invention contains the curable resin of the present invention (hereinafter sometimes referred to as "curable resin I").

[0044] The amount of the curable resin I in the curable resin composition is not particularly limited and can be appropriately adjusted. The amount of the curable resin I in the curable resin composition is, for example, 5 to 95 parts by mass relative to 100 parts by mass of the resin component of the curable resin composition. In one embodiment, the amount of the curable resin I in the curable resin composition is 5 parts by mass or more, 10 parts by mass or more, 20 parts by mass or more, 30 parts by mass or more, 40 parts by mass or more, 50 parts by mass or more, 60 parts by mass or more, 70 parts by mass or more, 80 parts by mass or more, or 90 parts by mass or more relative to 100 parts by mass of the resin component of the curable resin composition. In another embodiment, the amount of the curable resin I in the curable resin composition is 95 parts by mass or less, 90 parts by mass or less, 80 parts by mass or less, 70 parts by mass or less, 60 parts by mass or less, 50 parts by mass or less, 40 parts by mass or less, 30 parts by mass or less, 20 parts by mass or less, or 10 parts by mass or less relative to 100 parts by mass of the resin component of the curable resin composition.

[0045] The curable resin composition may contain known components that are blended into curable resin compositions, in addition to the curable resin I. Examples of such components include resins other than the curable resin I, curing agents, curing accelerators, flame retardants, fillers, silane coupling agents, release agents, pigments, emulsifiers, and solvents.

[0046] Resins other than hardening resin I Resins other than the curable resin I are not particularly limited, and known resins can be used. Examples of resins other than the curable resin I include bismaleimides, allyl ether compounds, allylamine compounds, triallyl cyanurate, alkenylphenol compounds, vinyl group-containing polyolefin compounds, thermosetting polyimide resins, epoxy resins, phenolic resins, active ester resins, benzoxazine resins, cyanate resins, etc. Examples of resins other than the curable resin I include vinyl group-containing compounds such as styrene, ethylstyrene, and divinylbenzene, or unsaturated group-containing resins obtained by polymerizing these compounds as raw materials while leaving some unsaturated bonds, polyphenylene ethers whose ends are terminated with hydroxyl groups modified with vinylbenzyl ether using chloromethylstyrene, etc., (meth)acryloyl group-containing compounds such as polyphenylene ether (meth)acrylate, 1,2-vinyl group-containing polybutadiene, and 1,2-vinyl group-containing resins such as butadiene-styrene copolymers.

[0047] Examples of the components such as the curing agent described above include the components described in Patent Documents 1 and 2.

[0048] Method for preparing a curable resin composition The method for preparing the curable resin composition is not particularly limited, and the composition can be obtained by mixing the curable resin I with any optional components.

[0049] ·Applications of curable resin compositions Applications of the curable resin composition include, for example, printed wiring board materials, resin compositions for flexible wiring boards, interlayer insulating materials for build-up boards, insulating materials for circuit boards such as adhesive films for build-up, resin casting materials, adhesives, semiconductor encapsulation materials, semiconductor devices, prepregs, conductive pastes, build-up films, build-up boards, fiber-reinforced composite materials, molded articles obtained by curing the composite materials, etc. Applications also include, for example, those described in Patent Documents 1 and 2.

[0050] (cured product) The cured product of the present invention is a cured product of the above-mentioned curable resin composition. The cured product of the present invention can be obtained by curing the curable resin composition by the method described in, for example, Patent Document 1 and Patent Document 2.

[0051] A method for obtaining a cured product may be, for example, to heat-cure the curable resin composition. The temperature for heat-cure is, for example, 100 to 300° C. The heating time is, for example, 1 to 24 hours.

[0052] The uses of the cured product are similar to those of the curable resin composition described above.

[0053] (Goods) The article of the present invention is an article comprising the above-mentioned cured product, The article is an article selected from the group consisting of a prepreg, a circuit board, a semiconductor encapsulant, a semiconductor device, a build-up film, a build-up board, an adhesive, and a resist material. EXAMPLES

[0054] The present invention will be described in more detail below by way of examples. However, these examples are intended to illustrate the present invention and are not intended to limit the present invention in any way.

[0055] The materials used in the examples are as follows: Dicyclopentadiene: Zeon Corporation, product name "CP Dimer" Phenol aralkyl resin: Air Water Performance Chemicals, product name "HE100C-15", hydroxyl equivalent 181 g / equivalent, softening point 74°C, used in Comparative Example 2 Dicyclopentadiene-phenol resin: manufactured by JFE Chemical Corporation, product name "J-DPP-115", hydroxyl equivalent 180 g / equivalent, softening point 111°C, used in Comparative Example 3 Maleimide resin: The maleimide compound A-1 described in Synthesis Example 1 of Japanese Patent No. 6797356 was used.

[0056] The devices used in the examples are as follows: Solid viscoelasticity measuring device: Rheometrics, product name "RSAII" Network analyzer: Keysight Technologies, product name "N5247A"

[0057] Evaluation of GPC measurements As a sample, a 1.0 mass% tetrahydrofuran solution (50 μl) of the resin obtained in the following synthesis example was filtered through a microfilter, and a GPC chart was obtained in the same manner as in the GPC measurement described in the examples of JP-A-2023-127139. The average repeating unit number n was calculated based on the number average molecular weight (Mn) of the GPC chart.

[0058] Synthesis example 1 of intermediate phenol compound In a flask equipped with a stirrer, a Dean-Stark apparatus, a condenser, and a nitrogen inlet, 250.0 parts by mass of 2,6-xylenol, 171.4 parts by mass of 4,4'-bis(chloromethyl)biphenyl (BCMB), 421.4 parts by mass of toluene, and 0.6 parts by mass of tetrabutylammonium bromide (TBAB) were added while blowing in nitrogen gas. 286.5 parts by mass of 20% aqueous sodium hydroxide solution was added at room temperature while stirring the mixture. The solution was heated to 80°C and the reaction was continued for 9 hours. Stirring was stopped and the lower layer was removed. 4.2 parts by mass of p-toluenesulfonic acid monohydrate was added to the organic layer, and the temperature was raised to 160°C while distilling off the volatile matter and maintained for 3 hours. After the reaction was completed, the mixture was diluted with toluene while cooling. The solution was neutralized using a 49% aqueous sodium hydroxide solution until the pH was neutral. The solution was washed with water to remove catalyst residues. Next, the volatile matter was removed from the solution by distillation to obtain 2,6-xylenol-biphenyl aralkyl resin A1, which is an intermediate phenol compound. The hydroxyl equivalent of resin A1 was 252 g / equivalent, and the softening point was 87°C.

[0059] Synthesis example 2 of intermediate phenol compound In a flask equipped with a stirrer, a Dean-Stark apparatus, a condenser, and a nitrogen inlet, 250.0 parts by mass of o-cresol, 397.1 parts by mass of 4,4'-bis(methoxymethyl)biphenyl (BMMB), and 6.5 parts by mass of p-toluenesulfonic acid monohydrate were added while blowing in nitrogen gas. Stirring of the mixture was started, and the temperature was raised to 150°C while distilling off volatiles, and maintained for 3 hours. 150.0 parts by mass of 2,6-xylenol was added to the mixture, and the internal temperature was maintained at 180°C for 9 hours. After the reaction was completed, the mixture was diluted with toluene while cooling. The solution was neutralized using a 49% aqueous sodium hydroxide solution until the pH was neutral. The solution was washed with water to remove catalyst residues. Next, the volatiles were distilled off from the solution by heating and reducing the pressure, to obtain an intermediate phenolic compound, o-cresol-biphenyl aralkyl resin A2. Resin A2 had a hydroxyl equivalent of 278 g / equivalent and a softening point of 115°C.

[0060] Synthesis example 3 of intermediate phenolic compound In a flask equipped with a stirrer, a cooling tube, and a nitrogen injection port, 360 parts by mass of 1-naphthol, 586 parts by mass of toluene, and 263 parts by mass of p-xylylene dichloride were added while blowing in nitrogen gas, and the mixture was heated to 80°C. 245 parts by mass of 49% aqueous sodium hydroxide solution were added dropwise to the mixture over 1 hour. Then, the solution was heated to 90°C and maintained for 11 hours. The solution was neutralized using 85% phosphoric acid until the pH was neutral. Stirring was stopped, and the lower layer was removed. 15 parts by mass of p-toluenesulfonic acid was added to the organic layer, and the mixture was heated to 180°C over 2 hours while distilling off the volatile matter. Then, the solution was neutralized using a 49% aqueous sodium hydroxide solution until the pH was neutral. Then, the pressure was reduced while maintaining the internal temperature, and the volatile matter was distilled off. The obtained resin was taken out to obtain naphthol aralkyl resin A3, which is an intermediate phenol compound. Resin A3 had a hydroxyl equivalent of 220 g / equivalent and a softening point of 78°C.

[0061] Synthesis example 4 of intermediate phenolic compounds In a flask equipped with a stirrer, a Dean-Stark apparatus, a condenser, and a nitrogen inlet, 324.4 parts by mass of o-cresol and 5.2 parts by mass of boron trifluoride diethyl ether complex were added while blowing in nitrogen gas. The mixture was heated to 80°C while stirring. Next, 198.3 parts by mass of dicyclopentadiene was added dropwise to the mixture over 2 hours while heating to 110°C. After the dropwise addition was completed, the mixture was reacted for 3 hours while maintaining the temperature. The reaction was further continued for 2 hours at 130°C and for 4 hours at 150°C. After the reaction was completed, the mixture was diluted with toluene while cooling. The solution was neutralized using an aqueous sodium carbonate solution until the pH was neutral. The solution was washed with water to remove the catalyst residue. Next, the volatile matter was distilled off from the solution by heating and reducing the pressure to obtain o-cresol-dicyclopentadiene resin A4. The hydroxyl equivalent of resin A4 was 207g / equivalent, and the softening point was 114°C.

[0062] Comparative synthesis example 1 The synthesis was carried out according to Example 1 described in Patent Document 1. The obtained resin was diluted with toluene and neutralized using an aqueous sodium carbonate solution until the pH was neutral. The solution was washed with water to remove the catalyst residue. Next, volatile matters were distilled off from the solution by heating and reducing pressure to obtain a styrene-modified phenol aralkyl resin. The hydroxyl equivalent of the resin was 295 g / equivalent, and the softening point was 73°C.

[0063] Example 1: Synthesis of curable resin C1 252 parts by mass of resin A1, 504 parts by mass of toluene, and 6.7 parts by mass of 4-dimethylaminopyridine were added to a flask equipped with a stirrer, a Dean-Stark apparatus, a cooling tube, and a nitrogen inlet. The mixture was heated to 60°C while stirring to dissolve. 141.7 parts by mass of triethylamine and 203.5 parts by mass of methacrylic anhydride were added to the solution, and the reaction was allowed to proceed for 12 hours. After the reaction was completed, the solution was washed with water to remove the catalyst residue and the by-product methacrylic acid. Next, the volatile content of the solution was adjusted by heating and reducing the pressure to obtain a toluene solution of 2,6-xylenol-biphenyl aralkyl methacrylate resin C1. The number of repeating units n was 1.7.

[0064] Example 2: Synthesis of curable resin C2 The same procedure as in Example 1 was carried out except that 252 parts by mass of resin A1 in Example 1 was replaced with 278 parts by mass of resin A2, to obtain a toluene solution of o-cresol-biphenyl aralkyl methacrylate resin C2. The repeating unit number n was 3.8.

[0065] Example 3: Synthesis of curable resin C3 The same procedure as in Example 1 was carried out except that 252 parts by mass of resin A1 in Example 1 was replaced with 220 parts by mass of resin A3, to obtain a toluene solution of naphthol aralkyl methacrylate resin C3. The repeating unit number n was 1.5.

[0066] Example 4: Synthesis of curable resin C4 The same procedure as in Example 1 was carried out except that 252 parts by mass of resin A1 in Example 1 was replaced with 207 parts by mass of o-cresol-dicyclopentadiene resin A4, to obtain a toluene solution of o-cresol-dicyclopentadiene type methacrylate resin C4. The repeating unit number n was 1.9.

[0067] Comparative Example 1: Synthesis of Comparative Resin 1 The same procedure as in Example 1 was carried out except that 252 parts by mass of Resin A1 in Example 1 was replaced with 295 parts by mass of the styrene-modified phenol aralkyl resin in Comparative Synthesis Example 1, to obtain a toluene solution of a styrene-modified phenol aralkyl methacrylate resin as Comparative Resin 1. The number of repeating units n was 1.7.

[0068] Comparative Example 2: Synthesis of Comparative Resin 2 The same procedure as in Example 1 was carried out except that 252 parts by mass of resin A1 in Example 1 was replaced with 181 parts by mass of a phenol aralkyl resin, to obtain a toluene solution of a phenol aralkyl methacrylate resin as comparative resin 2. The number of repeating units n was 2.6.

[0069] Comparative Example 3: Synthesis of Comparative Resin 3 The same procedure as in Example 1 was carried out except that 252 parts by mass of Resin A1 in Example 1 was replaced with 180 parts by mass of dicyclopentadiene-phenol resin, to obtain a toluene solution of dicyclopentadiene-phenol type methacrylate resin as Comparative Resin 3. The number of repeating units n was 1.6.

[0070] Preparation of curable resin composition A curable resin composition was prepared according to the following formulation. Resin C1 obtained in Example 1: 37 parts by mass Maleimide resin: 63 parts by weight Dicumyl peroxide: 0.5 parts by mass

[0071] Curable resin compositions were prepared in the same manner as in Example 1, except that Resin C1 in Example 1 was replaced with the resins obtained in Examples 2 to 4 or Comparative Examples 1 to 3.

[0072] - Preparation of hardened material The curable resin composition was heated at 220° C. for 2 hours to be thermally cured to produce a cured product (molded product). The plate thickness of the molded cured product was 1.8 mm.

[0073] The heat resistance and dielectric properties of the obtained cured products were evaluated by the following methods.

[0074] Heat resistance evaluation The cured product was cut into a size of 5 mm in width and 54 mm in length to prepare a test piece. The test piece was evaluated using a solid viscoelasticity measuring device under the following measurement conditions: rectangular tension method, frequency 1 Hz, and heating rate 3°C / min. The temperature at which the elastic modulus change was maximum (the rate of change in tan δ was the largest) was determined as the glass transition temperature.

[0075] Dielectric property evaluation The dielectric properties of the cured product in the in-plane direction were measured by a network analyzer using a split post dielectric resonator method at a frequency of 1 GHz, with the dielectric constant (Dk) and dielectric loss tangent (Df). The dielectric loss tangent is preferably 0.0050 or less, more preferably 0.0030 or less, and even more preferably 0.0025 or less. The dielectric constant is preferably 2.70 or less, and more preferably 2.50 or less.

[0076] [Table 1]

[0077] -Making glass cloth laminates The prepared curable resin composition was adjusted to a non-volatile content of 60% with methyl ethyl ketone (MEK) and dissolved using a planetary centrifugal mixer. A glass cloth laminate was produced under the following conditions. (Conditions for making laminates) Base material: Glass cloth "#2116" (210 x 280 mm) manufactured by Nittobo Copper foil: JX Metals Co., Ltd., "JTC foil" (18μm) Number of plies: 6 Prepreg conditions: 140℃ Curing conditions: 220℃, 40kg / cm 2 2.0 hours Plate thickness after molding: 0.8mm

[0078] Dielectric property evaluation The dielectric properties of the resulting laminate were evaluated in the same manner as for the cured product, and the results are shown in Table 2.

[0079] Peel strength measurement The obtained laminate was cut into a size of 10 mm in width and 200 mm in length according to JIS-K6854-1 to prepare a test piece. The peel strength of the copper foil was measured for the test piece. The results are shown in Table 2.

[0080] Delamination Measurement The interlayer adhesion of the test pieces was measured in accordance with JIS-K6854-1, and the results are shown in Table 2. [Table 2] [Industrial Applicability]

[0081] According to the present invention, it is possible to provide a curable resin capable of exhibiting good dielectric properties and excellent heat resistance. Also, according to the present invention, it is possible to provide a curable resin composition capable of exhibiting good dielectric properties and excellent heat resistance. Also, according to the present invention, it is possible to provide a cured product having good dielectric properties and excellent heat resistance. Also, according to the present invention, it is possible to provide an article including a cured product having good dielectric properties and excellent heat resistance.

Claims

1. A structural unit represented by the following general formula (1) or general formula (2), A curable resin having a terminal structural unit represented by the following general formula (3) or general formula (4): 【Chemistry 1】 (In general formula (1), R １ each independently represents a hydrogen atom or a methyl group; Ar represents an arylene group having 6 to 18 carbon atoms; In general formula (3), R ２ each independently represents an alkyl group, an aryl group, an aralkyl group, or a cycloalkyl group having 1 to 12 carbon atoms; R ３ represents a hydrogen atom or a methyl group; x represents an integer of 1, 2, 3 or 4; * represents the bonding position of the bond extending outside the structural unit of general formula (1) or (2); In general formula (4), R ２ each independently represents an alkyl group, an aryl group, an aralkyl group, or a cycloalkyl group having 1 to 12 carbon atoms; R ３ represents a hydrogen atom or a methyl group; y is an integer of 0, 1, 2, 3 or 4; * represents the bonding position with a bond extending outside the structural unit of general formula (1) or (2).

2. The curable resin according to claim 1, wherein the terminal structural unit represented by the general formula (3) is a terminal structural unit represented by the following general formula (3-1) or general formula (3-2): 【Chemistry 2】

3. The curable resin according to claim 1, wherein the terminal structural unit represented by the general formula (4) is a terminal structural unit represented by the following general formula (4-1): 【Chemistry 3】

4. The curable resin according to claim 1, wherein the structural unit represented by the general formula (1) is a structural unit represented by the following general formula (1-1) or general formula (1-2): 【Chemistry 4】

5. The curable resin according to claim 1, having a weight average molecular weight of 500 to 5,000.

6. A curable resin composition comprising the curable resin according to claim 1.

7. A cured product of the curable resin composition according to claim 6.

8. An article comprising the cured product according to claim 7, The article is selected from the group consisting of a prepreg, a circuit board, a semiconductor encapsulant, a semiconductor device, a build-up film, a build-up board, an adhesive, and a resist material.

Images