Curable resin, curable resin composition, cured product and article

Abstract

Provided are a curable resin, a curable resin composition, a cured product, and an article which can exhibit good dielectric properties and excellent heat resistance. The curable resin has a structural unit represented by general formula (1) or general formula (2) and a terminal structural unit represented by general formula (3) or general formula (4). # imgabs0 #

Description

Technical Field

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

[0002] As a circuit board material for electronic devices, a prepreg obtained by impregnating glass cloth with a thermosetting resin and then heating and drying the impregnated glass cloth is widely used.

[0003] In recent years, the speed and frequency of signals have been increasing, and there has been a demand for a thermosetting resin composition that provides a cured product that maintains a sufficiently low dielectric constant and exhibits a sufficiently low dielectric loss tangent under these environments.

[0004] In addition, in order to cope with the multi-layering and thinning of substrates, a material having high heat resistance (glass transition temperature) is required.

[0005] On the other hand, for example, Patent Document 1 discloses a curable resin having a specific structural unit (1) and a specific terminal structure (2). Also, Patent Document 2 discloses a curable resin represented by a specific general formula (1).

[0006] [Prior art literature]

[0007] [Patent Document]

[0008] [Patent Document 1] International Publication No. 2021 / 251052

[0009] [Patent Document 2] Japanese Patent Application Publication No. 2022-102140 Summary of the invention

[0010] [Problems to be solved by the invention]

[0011] However, there is still room for improvement in the heat resistance of such curable resins.

[0012] Therefore, an object of the present invention is to provide a curable resin capable of exhibiting good dielectric properties and excellent heat resistance.

[0013] In addition, another object of the present invention is to provide a curable resin composition that can exhibit good dielectric properties and excellent heat resistance. Furthermore, another object of the present invention is to provide a cured product having good dielectric properties and excellent heat resistance. Furthermore, another object of the present invention is to provide an article including a cured product having good dielectric properties and excellent heat resistance.

[0014] [Technical means to solve the problem]

[0015] The curable resin of the present invention is a curable resin having:

[0016] A structural unit represented by the following general formula (1) or general formula (2), and

[0017] The terminal structural unit represented by the following general formula (3) or general formula (4),

[0018]

[0019] (In general formula (1),

[0020] R1 each independently represents a hydrogen atom or a methyl group;

[0021] Ar represents an arylene group having 6 to 18 carbon atoms;

[0022] In the general formula (3),

[0023] R2 each independently represents an alkyl group, an aryl group, an aralkyl group or a cycloalkyl group having 1 to 12 carbon atoms;

[0024] R3 represents a hydrogen atom or a methyl group;

[0025] x represents an integer of 1, 2, 3 or 4;

[0026] * represents the bonding position to the bond extending to the outside of the structural unit of the general formula (1) or the general formula (2);

[0027] In the general formula (4),

[0028] R2 each independently represents an alkyl group, an aryl group, an aralkyl group or a cycloalkyl group having 1 to 12 carbon atoms;

[0029] R3 represents a hydrogen atom or a methyl group;

[0030] y is an integer of 0, 1, 2, 3 or 4;

[0031] * represents the bonding position of the bond extending to the outside of the structural unit of the general formula (1) or the general formula (2). Thus, good dielectric properties and excellent heat resistance can be exhibited.

[0032] In one embodiment of the curable resin of 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 (3-2).

[0033]

[0034] In one embodiment of the curable resin of 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).

[0035]

[0036] In one embodiment of the curable resin of 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 (1-2).

[0037]

[0038] In one embodiment of the curable resin of the present invention, the weight average molecular weight is 500 to 5,000.

[0039] The curable resin composition of the present invention contains any one of the curable resins described above.

[0040] The cured product of the present invention is a cured product of the aforementioned curable resin composition.

[0041] The article of the present invention is an article comprising the aforementioned cured product, and the article is an article selected from the group consisting of prepreg, circuit substrate, semiconductor sealing material, semiconductor device, build-up film, build-up substrate, adhesive and resist material.

[0042] [Effects of the Invention]

[0043] According to the present invention, a curable resin having good dielectric properties and excellent heat resistance can be provided. In addition, according to the present invention, a curable resin composition having good dielectric properties and excellent heat resistance can be provided. In addition, according to the present invention, a cured product having good dielectric properties and excellent heat resistance can be provided. In addition, according to the present invention, an article including a cured product having good dielectric properties and excellent heat resistance can be provided. DETAILED DESCRIPTION

[0044] Hereinafter, embodiments of the present invention will be described. These descriptions are for the purpose of illustrating the present invention and do not limit the present invention in any way.

[0045] In the present invention, two or more embodiments may be arbitrarily combined.

[0046] Unless otherwise specified, the materials, components, compounds, resins, structural units, terminal structural units, catalysts, and solvents described in the present specification may be used alone or in combination of two or more.

[0047] (hardening resin)

[0048] The curable resin of the present invention is a curable resin having:

[0049] A structural unit represented by the following general formula (1) or general formula (2), and

[0050] The terminal structural unit represented by the following general formula (3) or general formula (4),

[0051]

[0052] (In general formula (1),

[0053] R 1 each independently represents a hydrogen atom or a methyl group;

[0054] Ar represents an arylene group having 6 to 18 carbon atoms;

[0055] In the general formula (3),

[0056] R 2 Each independently represents an alkyl group, an aryl group, an aralkyl group or a cycloalkyl group having 1 to 12 carbon atoms;

[0057] R 3 represents a hydrogen atom or a methyl group;

[0058] x represents an integer of 1, 2, 3 or 4;

[0059] * represents the bonding position of the bond extending to the outside of the repeating unit of the general formula (1) or the general formula (2); in the general formula (4),

[0060] R 2 Each independently represents an alkyl group, an aryl group, an aralkyl group or a cycloalkyl group having 1 to 12 carbon atoms;

[0061] R 3 represents a hydrogen atom or a methyl group;

[0062] y is an integer of 0, 1, 2, 3 or 4;

[0063] * represents the bonding position to the bond extending to the outside of the repeating unit of the general formula (1) or (2).

[0064] The terminal structure of the curable resin of the present invention is one or more selected from the group consisting of general formula (3) and general formula (4), and the curable resin does not have a styryl structure at the terminal as in Patent Documents 1 and 2. The curable resin of the present invention has appropriate steric hindrance and can exhibit excellent heat resistance while having good dielectric properties.

[0065] In the 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.

[0066] As Ar, for example, the following divalent structures can be mentioned.

[0067]

[0068] In these structures, * represents a bonding point to the structure of the general formula (1).

[0069] Ar may be, for example, any of the structural formulas (4) in Japanese Patent No. 7320805.

[0070] In a preferred embodiment, Ar is one or more selected from the following structures.

[0071]

[0072] Examples of the structural unit of the general formula (1) include the following six units.

[0073]

[0074] In a preferred embodiment, the structural unit represented by the general formula (1) is one or more selected from the group consisting of the following general formula (1-1) and general formula (1-2).

[0075]

[0076] The number of the structural unit represented by the general formula (1) or (2) in the curable resin may be one, or two or more, for example, 2 to 20. In one embodiment, the number of the structural units represented by the general formula (1) or (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 number of structural units represented by general formula (1) or general formula (2) is independently less than 20, less than 15, less than 10, less than 5.0, less than 4.5, less than 4.0, less than 3.8, less than 3.5, less than 3.0, less than 2.5, less than 2.0, less than 1.9, less than 1.7 or less.

[0077] In the general formula (3), x is 1, 2, 3 or 4. In one embodiment, x is 1 or 2.

[0078] In one embodiment, R of the general formula (3) 2 In another embodiment, R of the general formula (3) 2 is methyl, and CH2=C(R 3 )The COO group is bonded to one or two adjacent carbon atoms of the carbon atoms to which the COO group is bonded.

[0079] Examples of the terminal structural unit of the general formula (3) include the following general formulas (3-1) and (3-2).

[0080]

[0081] In the general formula (3-1) and the general formula (3-2), R 3 represents a hydrogen atom or a methyl group.

[0082] Examples of the terminal structural unit of the general formula (3) include the following six units.

[0083]

[0084] In the formula, R 3 represents a hydrogen atom or a methyl group.

[0085] In the general formula (4), y is 0, 1, 2, 3 or 4. In one embodiment, y is 0.

[0086] Examples of the terminal structural unit of the general formula (4) include the following general formula (4-1).

[0087]

[0088] In the general formula (4-1), R 3 represents a hydrogen atom or a methyl group.

[0089] Examples of the terminal structural unit of the general formula (4) include the following seven units.

[0090]

[0091] In the formula, R 3 represents a hydrogen atom or a methyl group.

[0092] In one embodiment, the curable resin of the present invention has a structural unit of the general formula (1) and a terminal structural unit of the general formula (3). In another embodiment, the curable resin of the present invention has a structural unit of the general formula (1) and a terminal structural unit of the general formula (4). In another embodiment, the curable resin of the present invention has a structural unit of the general formula (1) and one or more terminal structural units selected from the group consisting of the general formula (3-1) and the general formula (3-2). In another embodiment, the curable resin of the present invention has a structural unit of the general formula (1) and a terminal structural unit of the general formula (4-1).

[0093] In one embodiment, the curable resin of the present invention has a structural unit of the general formula (2) and a terminal structural unit of the general formula (3). In another embodiment, the curable resin of the present invention has a structural unit of the general formula (2) and a terminal structural unit of the general formula (4). In another embodiment, the curable resin of the present invention has a structural unit of the general formula (2) and one or more terminal structural units selected from the group consisting of the general formula (3-1) and the general formula (3-2). In another embodiment, the curable resin of the present invention has a structural unit of the general formula (2) and a terminal structural unit of the general formula (4-1).

[0094] In one embodiment, the curable resin of the present invention is one or more selected from the group consisting of the following C1, C2, C3, and C4.

[0095]

[0096] Wherein, n is 1 to 20.

[0097] n in C1, C2, C3 and C4 is independently 1 to 20. In one embodiment, n in C1, C2, C3 and C4 is independently 2 to 20. In another embodiment, n in C1, C2, C3 and C4 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 yet another embodiment, n in C1, C2, C3 and C4 is 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.

[0098] 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.

[0099] ·Method for producing hardening resin

[0100] As a method for producing the curable resin of the present invention, for example, there is a method of reacting (meth)acrylic anhydride, (meth)acrylic acid halide or the like with a phenol resin to (meth)acrylate a hydroxyl group.

[0101] (Curing resin composition)

[0102] The curable resin composition of the present invention contains the curable resin of the present invention (hereinafter sometimes referred to as "curable resin I").

[0103] 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.

[0104] The curable resin composition may contain known components formulated in a curable resin composition 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, solvents, and the like.

[0105] ·Resins other than curable resin I

[0106] The resin other than the curable resin I is 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-containing polyolefin compounds, thermosetting polyimide resins, epoxy resins, phenol resins, active ester resins, benzoxazine resins, cyanate resins, and the like. In addition, examples of resins other than the curable resin I include vinyl-containing compounds such as styrene, ethylstyrene, and divinylbenzene, or unsaturated group-containing resins obtained by polymerizing these compounds with some unsaturated bonds remaining as raw materials, substances obtained by modifying the ends of hydroxy-terminated polyphenylene ethers with vinylbenzyl ethers using chloromethylstyrene or the like, (meth)acryloyl-containing compounds such as polyphenylene ether (meth)acrylates, 1,2-vinyl-containing polybutadiene, butadiene-styrene copolymers, and the like.

[0107] Examples of the components such as the hardener include those described in Patent Documents 1 and 2.

[0108] ·Method for preparing curable resin composition

[0109] The method for preparing the curable resin composition is not particularly limited, and the curable resin composition can be obtained by mixing the curable resin I and any optional components.

[0110] ·Application of curable resin composition

[0111] Examples of uses of the curable resin composition include printed wiring board materials, resin compositions for flexible wiring boards, interlayer insulating materials for build-up boards, insulating materials for circuit boards such as build-up adhesive films, resin casting materials, adhesives, semiconductor sealing materials, semiconductor devices, prepregs, conductive pastes, build-up films, build-up boards, fiber-reinforced composite materials, and molded products obtained by curing the composite materials. In addition, examples of uses described in Patent Documents 1 and 2 include the following.

[0112] (hardened material)

[0113] The cured product of the present invention is a cured product of the curable resin composition. The cured product of the present invention can be obtained by curing the curable resin composition by the method described in Patent Documents 1 and 2, for example.

[0114] As a method for obtaining a cured product, for example, the curable resin composition may be cured by heat curing. The temperature during heat curing is, for example, 100° C. to 300° C. The heating time is, for example, 1 hour to 24 hours.

[0115] The uses of the cured product are the same as those of the curable resin composition.

[0116] (thing)

[0117] The article of the present invention is an article comprising the hardened article, wherein:

[0118] The article is an article selected from the group consisting of prepreg, circuit substrate, semiconductor sealing material, semiconductor device, build-up film, build-up substrate, adhesive and resist material.

[0119] [Example]

[0120] Hereinafter, the present invention will be described in further detail with reference to Examples. However, these Examples are provided for the purpose of illustrating the present invention and do not limit the present invention in any way.

[0121] The materials used in the examples are as follows.

[0122] Dicyclopentadiene: manufactured by ZEON Corporation of Japan, product name "CP dimer".

[0123] Phenol aralkyl resin: manufactured by Air Water Performance Chemical Co., Ltd., product name “HE100C-15”, hydroxyl equivalent: 181 g / equivalent, softening point: 74° C., used in Comparative Example 2.

[0124] Dicyclopentadiene-phenol resin: manufactured by JFE Chemical Co., Ltd., product name “J-DPP-115”, hydroxyl equivalent: 180 g / equivalent, softening point: 111° C., used in Comparative Example 3.

[0125] Maleimide resin: Maleimide compound A-1 described in Synthesis Example 1 of Japanese Patent No. 6797356 was used.

[0126] The apparatus used in the examples are as follows.

[0127] Solid viscoelasticity measuring device: manufactured by Rheometric Instruments, product name “RSAII” Network analyzer: manufactured by Keysight Technology, product name “N5247A”.

[0128] Evaluation of Gel Permeation Chromatography (GPC)

[0129] As a sample, a substance (50 μl) obtained by filtering a tetrahydrofuran solution of 1.0% by mass in terms of solid content of the resin obtained in the following synthesis example using a microfilter was used, and in addition, a GPC measurement was performed in the same manner as the GPC measurement described in the embodiment of Japanese Patent Laid-Open No. 2023-127139 to obtain a GPC graph. Based on the number average molecular weight (Mn) of the GPC graph, the average number of repeating units n was calculated.

[0130] Synthesis Example 1 of Intermediate Phenol Compound

[0131] In a flask including a stirrer, a Dean-Stark apparatus, a cooling tube and a nitrogen-sealed inlet, 250.0 parts by mass of 2,6-dimethylphenol, 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 nitrogen. While stirring the mixture, 286.5 parts by mass of a 20% aqueous sodium hydroxide solution was added at room temperature. 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 volatile components were distilled off while the temperature was raised to 160°C and maintained for 3 hours. After the reaction was completed, the mixture was diluted with toluene while cooling. The solution was neutralized with a 49% sodium hydroxide aqueous solution until the pH became neutral. The solution was washed with water to remove the catalyst residue. Then, the volatile components were removed from the solution by distillation to obtain 2,6-dimethylphenol-biphenyl aralkyl resin A1 as an intermediate phenol compound. The hydroxyl equivalent of resin A1 was 252 g / equivalent and the softening point was 87°C.

[0132] Synthesis Example 2 of Intermediate Phenol Compound

[0133] In a flask including a stirrer, a Dean-Stark apparatus, a cooling tube and a nitrogen-sealed 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 nitrogen. Stirring of the mixture was started, while distilling off the volatile components, the temperature was raised to 150°C and maintained for 3 hours. 150.0 parts by mass of 2,6-dimethylphenol was added to the mixture, and the internal temperature was maintained at 180°C and maintained for 9 hours. After the reaction was completed, the mixture was cooled while being diluted with toluene. The solution was neutralized with a 49% aqueous sodium hydroxide solution until the pH became neutral. The solution was washed with water to remove the catalyst residue. Subsequently, the volatile components were distilled off from the solution by heating and reducing pressure to obtain o-cresol-biphenyl aralkyl resin A2 as an intermediate phenol compound. The hydroxyl equivalent of resin A2 is 278 g / equivalent, and the softening point is 115°C.

[0134] Synthesis Example 3 of Intermediate Phenol Compound

[0135] Into a flask including a stirrer, a cooling tube and a nitrogen-sealed inlet, nitrogen was blown in while adding 360 parts by mass of 1-naphthol, 586 parts by mass of toluene and 263 parts by mass of terephthaloyl chloride, and heated to 80°C. 245 parts by mass of a 49% aqueous sodium hydroxide solution were added dropwise to the mixture over a period of 1 hour. Then, the solution was heated to 90°C and maintained for 11 hours. The solution was neutralized with 85% phosphoric acid until the pH became 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 volatile components were distilled out while heating to 180°C for 2 hours. Then, the solution was neutralized with a 49% aqueous sodium hydroxide solution until the pH became neutral. Then, the internal temperature was maintained while the pressure was reduced to distill out the volatile components. The resulting resin was taken out to obtain naphthol aralkyl resin A3 as an intermediate phenol compound. The hydroxyl equivalent of resin A3 is 220 g / equivalent, and the softening point is 78°C.

[0136] ·Synthesis Example 4 of Intermediate Phenol Compound

[0137] In a flask including a stirrer, a Dean-Stark apparatus, a cooling tube and a nitrogen-sealed inlet, nitrogen was blown in while adding 324.4 parts by mass of o-cresol and 5.2 parts by mass of a boron trifluoride diethyl ether complex. The mixture was stirred while being heated to 80°C. Then, 198.3 parts by mass of dicyclopentadiene was added dropwise to the mixture over a period of 2 hours while being heated to 110°C. After the addition was completed, the reaction was continued for 3 hours while maintaining the temperature. The reaction was then continued at 130°C for 2 hours and at 150°C for 4 hours. After the reaction was completed, the mixture was cooled while being diluted with toluene. The solution was neutralized with an aqueous sodium carbonate solution until the pH became neutral. The solution was washed with water to remove the catalyst residue. Then, the volatile components were distilled off from the solution by heating and reducing pressure to obtain o-cresol-dicyclopentadiene resin A4. The hydroxyl equivalent of resin A4 is 207 g / equivalent, and the softening point is 114°C.

[0138] Comparative Synthesis Example 1

[0139] The synthesis was carried out according to Example 1 described in Patent Document 1. The obtained resin was diluted with toluene and neutralized with an aqueous sodium carbonate solution until the pH became neutral. The solution was washed with water to remove the catalyst residue. Then, the volatile components 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.

[0140] Example 1: Synthesis of curable resin C1

[0141] In a flask including a stirrer, a Dean-Stark apparatus, a cooling tube and a nitrogen-sealed inlet, 252 parts by mass of resin A1, 504 parts by mass of toluene and 6.7 parts by mass of 4-dimethylaminopyridine were added. The mixture was heated to 60°C while being stirred 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 mixture was reacted for 12 hours in the above state. After the reaction was completed, the solution was washed with water to remove the catalyst residue and methacrylic acid as a by-product. Then, the volatile components of the solution were adjusted by heating and reducing pressure to obtain a toluene solution of 2,6-dimethylphenol-biphenyl aralkyl type methacrylate resin C1. The number of repeating units n was 1.7.

[0142] Example 2: Synthesis of curable resin C2

[0143] A toluene solution of o-cresol-biphenyl aralkyl type methacrylate resin C2 was obtained by the same operation as in Example 1 except that 252 parts by mass of resin A1 in Example 1 was replaced by 278 parts by mass of resin A2. The number of repeating units n was 3.8.

[0144] Example 3: Synthesis of curable resin C3

[0145] A toluene solution of naphthol aralkyl type methacrylate resin C3 was obtained by the same operation as in Example 1 except that 252 parts by mass of resin A1 in Example 1 was replaced by 220 parts by mass of resin A3. The number of repeating units n was 1.5.

[0146] Example 4: Synthesis of curable resin C4

[0147] A toluene solution of o-cresol-dicyclopentadiene type methacrylate resin C4 was obtained by the same operation as in Example 1 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. The number of repeating units n was 1.9.

[0148] Comparative Example 1: Synthesis of Comparative Resin 1

[0149] A toluene solution of a styrene-modified phenol aralkyl type methacrylate resin as Comparative Resin 1 was obtained in the same manner as in Example 1 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 of Comparative Synthesis Example 1. The number of repeating units n was 1.7.

[0150] Comparative Example 2: Synthesis of Comparative Resin 2

[0151] The same operation as in Example 1 was carried out except that 252 parts by mass of the resin A1 in Example 1 was replaced with 181 parts by mass of the phenol aralkyl resin to obtain a toluene solution of a phenol aralkyl type methacrylate resin as a comparative resin 2. The number of repeating units n was 2.6.

[0152] Comparative Example 3: Synthesis of Comparative Resin 3

[0153] The same operation as in Example 1 was carried out except that 252 parts by mass of the resin A1 in Example 1 was replaced with 180 parts by mass of the dicyclopentadiene-phenol resin to obtain a toluene solution of a dicyclopentadiene phenol type methacrylate resin as Comparative Resin 3. The number of repeating units n was 1.6.

[0154] Preparation of curable resin composition

[0155] A curable resin composition was prepared according to the following formulation.

[0156] Resin C1 obtained in Example 1: 37 parts by mass

[0157] Maleimide resin: 63 parts by mass

[0158] Dicumyl peroxide: 0.5 parts by mass

[0159] Except that the resin C1 of Example 1 was replaced with the resin obtained in Examples 2 to 4 or Comparative Examples 1 to 3, a curable resin composition was prepared in the same manner.

[0160] ·Production of hardened materials

[0161] The curable resin composition was heated at 220° C. for 2 hours to be thermally cured to produce a cured product (molded product). The thickness of the cured product after molding was 1.8 mm.

[0162] The heat resistance and dielectric properties of the obtained cured products were evaluated by the following methods.

[0163] Evaluation of heat resistance

[0164] The cured product was cut into a size of 5 mm in width and 54 mm in length to serve as a test piece. The test piece was evaluated using a solid viscoelasticity measuring device under the measurement conditions of a rectangular tension method, a frequency of 1 Hz, and a heating rate of 3°C / min, and the temperature at which the elastic modulus changed to the maximum (tanδ change rate was the maximum) was taken as the glass transition temperature.

[0165] Evaluation of dielectric properties

[0166] Regarding the dielectric properties in the in-plane direction of the hardened material, the dielectric constant (Dk) and dielectric loss tangent (dissipation factor (Df)) were measured at a frequency of 1 GHz using a network analyzer by the Split Post Dielectric Resonator method. The dielectric loss tangent is preferably 0.0050 or less, more preferably 0.0030 or less, and further preferably 0.0025 or less. The dielectric constant is preferably 2.70 or less, and more preferably 2.50 or less.

[0167] [Table 1]

[0168] Table 1. Cured resin composition

[0169] Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Hardening resin C1 C2 C3 C4 Comparison Resin 1 Comparison Resin 2 Comparison Resin 3 Tg(℃) 225 241 227 241 213 237 240 Dk(1GHz) 2.61 2.61 2.66 2.58 2.64 2.64 2.63 Df(1GHz) 0.0019 0.0016 0.0021 0.0023 0.0029 0.0044 0.0048

[0170] ·Production of glass cloth laminate

[0171] The prepared curable resin composition was adjusted to a nonvolatile content of 60% with methyl ethyl ketone (MEK), and dissolved using a rotary mixer. A glass cloth laminate was prepared under the following conditions.

[0172] (Laminate plate manufacturing conditions)

[0173] Base material: Glass cloth "#2116" (210mm×280mm) manufactured by Nittobo Co., Ltd.

[0174] Copper foil: JTC foil manufactured by JX Metals Co., Ltd. (18 μm)

[0175] Number of plies: 6

[0176] Prepreg conditions: 140°C

[0177] Hardening conditions: 220℃, 40kg / cm 2 Next 2.0 hours

[0178] Thickness after forming: 0.8mm

[0179] Evaluation of dielectric properties

[0180] The dielectric properties of the obtained laminate were evaluated in the same manner as for the cured product.

[0181] Determination of peel strength

[0182] The obtained laminate was cut into a size of 10 mm in width and 200 mm in length according to Japanese Industrial Standards (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.

[0183] Determination of interlayer delamination

[0184] The interlayer adhesion of the test piece was measured in accordance with JIS-K6854-1. The results are shown in Table 2.

[0185] [Table 2]

[0186] Table 2. Laminated Boards

[0187] Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Hardening resin C1 C2 C3 C4 Comparison Resin 1 Comparison Resin 2 Comparison Resin 3 Tg(℃) 246 260 250 263 228 264 271 <![CDATA[Peeling strength (kN / m 2 )]]> 0.9 1 0.9 0.9 0.9 0.9 0.9 <![CDATA[Interlayer stripping (kN / m 2 )]]> 0.7 0.6 0.6 0.7 0.6 0.6 0.6 Dk(1GHz) 4.1 3.7 4.1 3.8 - 3.7 3.8 Df(1GHz) 0.0041 0.0037 0.0038 0.0035 - 0.0048 0.0051

[0188] [Industrial Applicability]

[0189] According to the present invention, a curable resin having good dielectric properties and excellent heat resistance can be provided. In addition, according to the present invention, a curable resin composition having good dielectric properties and excellent heat resistance can be provided. In addition, according to the present invention, a cured product having good dielectric properties and excellent heat resistance can be provided. In addition, according to the present invention, an article including a cured product having good dielectric properties and excellent heat resistance can be provided.

Claims

1. A curable resin, characterized in that: have: A structural unit represented by the following general formula (1) or general formula (2), and The terminal structural unit represented by the following general formula (3) or general formula (4), In the 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 the 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 to the outside of the structural unit of the general formula (1) or the general formula (2); in the 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 to the bond extending to the outside of the structural unit of the general formula (1) or (2).

2. The curable resin according to claim 1, characterized in that 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), 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), 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), 5. The curable resin according to claim 1, wherein The curable resin has a weight average molecular weight of 500 to 5,000.

6. A curable resin composition, characterized in that Contains the hardening resin as claimed in claim 1.

7. A hardened product, characterized in that: The cured product is a cured product of the curable resin composition according to claim 6.

8. An article, characterized in that The hardened material according to claim 7, wherein: The article is an article selected from the group consisting of prepreg, circuit substrate, semiconductor sealing material, semiconductor device, build-up film, build-up substrate, adhesive and resist material.

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