Resin compositions, curing agents, resin sheets, insulating layers, electrical and electronic components, printed wiring boards, and epoxy resin curing agents.

Abstract

The present invention relates to a resin composition comprising a phenol carbonate resin (A) and an epoxy resin (B), wherein the molar ratio (epoxy group / terminal hydroxyl group) of the epoxy resin (B) to the terminal hydroxyl group of the phenol carbonate resin (A) is 3.0 to 100,000.

Description

Technical Field

[0001] This invention relates to a resin composition comprising phenolic carbonate resin and epoxy resin. Furthermore, this invention relates to a cured form of the resin composition, a resin sheet and insulating layer obtained using the resin composition, electrical and electronic components and printed wiring boards having the insulating layer, and a curing agent for epoxy resin comprising phenolic carbonate resin. Prior Technology

[0002] In recent years, the miniaturization, weight reduction, and increased functionality of multilayer circuit boards used in electrical and electronic machinery have led to demands for improved processability, including multilayering, high density, thinning, and lightweighting, as well as reliability in harsh environments such as automotive applications. Furthermore, the increasing speed and frequency of signals in various electronic devices necessitates substrates with lower transmission losses. Therefore, the resin compositions used in these substrates require a technology that effectively and evenly improves various properties such as heat resistance, adhesion, water resistance, low dielectric constant, low dielectric loss factor, mechanical strength, film-forming properties, low linear expansion, and flame retardancy.

[0003] Resin compositions used in multilayer circuit boards are known to include epoxy resins. In such cases, since epoxy resins are usually used in combination with curing agents, it is important to select an appropriate curing system to achieve various required properties. Especially when epoxy resins are used as multilayer materials in multilayer circuit boards, it is necessary to achieve low dielectric constants and low dielectric loss factors. Reactive esters are a previously known representative curing agent. In the curing reaction between epoxy resins and reactive esters, crosslinking can occur without generating polar functional groups such as secondary hydroxyl groups.

[0004] On the other hand, Non-Patent Document 1 discloses a method for synthesizing polycarbonate, which involves reacting the epoxy groups of a 2-functional epoxy resin with the carbonate groups of diphenyl carbonate to synthesize polycarbonate. By using this method, a hardened product can be formed through reaction, similar to that of active esters, without generating polar functional groups such as secondary hydroxyl groups.

[0005] Patent Document 1 describes an example of synthesizing a carbonate resin using diphenyl carbonate, tricyclodecanediethanol, and bisphenol F, which can be used as an epoxy resin curing agent and yields a cured product with low dielectric constant and low dielectric loss factor. Furthermore, according to Patent Document 1, a laminate is obtained by preparing a resin varnish containing the carbonate resin and epoxy resin, impregnating the resin varnish into a fibrous substrate, and then curing it.

[0006] Furthermore, Patent Document 2 discloses a resin composition comprising epoxy resin, a hardener, polycarbonate resin, and inorganic filler. [Previous Technical Documents] [Patent Literature]

[0007] [Patent Document 1] Japanese Patent Application Publication No. 2019-89965 [Patent Document 2] Japanese Patent Application Publication No. 2019-35056 [Non-patent literature]

[0008] [Non-patent document 1] Takao Yashiro, Katsutomo Matsushima, Atsushi Kameyama, Tadatomi Nishikubo, Macromolecules, 2001, 34, 3205. Summary of the Invention

[0009] [The problem the invention aims to solve]

[0010] In recent years, the complexity and miniaturization of laminates for electrical and electronic circuits have continued to develop. With the long-term use of laminates for electrical and electronic circuits, the materials used, including resin compositions containing epoxy resin and hardeners, as well as the cured products containing such resin compositions, also need to have higher heat resistance than before in order to withstand continuous use under high temperature conditions.

[0011] When the curing agent is an active ester, the ester group 1 equivalent reacts with the epoxy group 1 equivalent. However, when the curing agent is a carbonate compound, the carbonate group 1 equivalent can react with the epoxy group 2 equivalent. Therefore, the crosslinking density becomes higher, and theoretically, a curing product with high Tg can be obtained.

[0012] The phenolic carbonate resin described in Patent Document 1 and the polycarbonate resin described in Patent Document 2 are polymers of monomers with hydroxyl groups at both ends, and the hydroxyl groups are relatively high. Therefore, by crosslinking phenolic carbonate resin or polycarbonate resin with epoxy resin, a cured product with a relatively low dielectric constant and dielectric loss factor can be obtained. However, since secondary hydroxyl groups are generated in the reaction between epoxy groups and hydroxyl groups, the dielectric constant and dielectric loss factor of the obtained cured product sometimes do not decrease further. Furthermore, the cured products obtained by the techniques described in these patent documents have high water absorption rates, resulting in problems with moisture resistance. In addition, the solvent solubility of the phenolic carbonate resin or polycarbonate resin used as the curing agent is not high enough, and the molding and processability of the epoxy resin composition is also insufficient.

[0013] The present invention aims to provide a resin composition comprising phenolic carbonate resin and epoxy resin, wherein the resin composition provides a cured product having a low dielectric constant, a low dielectric loss factor, and high heat resistance. Another object of the present invention is to provide a cured product of the resin composition, and electrical and electronic components and printed circuit boards using the resin composition. Yet another object of the present invention is to provide a curing agent for epoxy resin comprising phenolic carbonate resin. [Technical means to solve the problem]

[0014] To address the aforementioned problems, the inventors conducted intensive research and discovered that by formulating phenolic carbonate resin as a curing agent in a resin composition containing epoxy resin in a manner where the molar ratio (epoxy group / terminal hydroxyl group) of the epoxy resin to the terminal hydroxyl group of the phenolic carbonate resin is within a specific range, the aforementioned problems can be solved. Furthermore, the phenolic carbonate resin exhibits a viscosity-average molecular weight within a specific range and contains repeating units with a specific structure. In other words, the main points of this invention are as follows.

[0015] [1] A resin composition comprising phenolic carbonate resin (A) and epoxy resin (B), and The molar ratio (epoxy group / terminal hydroxyl group) of the epoxy resin (B) to the terminal hydroxyl group of the phenol carbonate resin (A) is 3.0 to 100,000. [2] The resin composition described in [1], wherein the phenolic carbonate resin (A) comprises repeating units represented by the following formula (1), [Chemistry 1] (In formula (1), A1 and A2 are independently represented by the bases in formula (2) or (3) below; X is a direct bond, a divalent hydrocarbon group with 1 to 15 carbon atoms that may have substituents, -O-, -S-, -SO-, -SO2-, -CO-, -OCO- or -COO-; n1 and n2 are independently integers from 1 to 50) [Chemistry 2] [Chemistry 3] (In formulas (2) and (3), R is independently an alkyl group with 1 to 12 carbon atoms, an aralkyl group with 7 to 12 carbon atoms, an alkoxy group with 1 to 12 carbon atoms, an aralkoxy group with 7 to 12 carbon atoms, an aryl group with 6 to 12 carbon atoms, an alkenyl group with 2 to 12 carbon atoms, an areneyl group with 8 to 12 carbon atoms, an alkynyl group with 2 to 12 carbon atoms, an arynyl group with 8 to 12 carbon atoms, a halogen atom, a hydroxyl group, a carboxyl group, a uryl group, an amino group, a cyano group, or a nitro group; p is an integer from 0 to 4; q is an integer from 0 to 6; * is the bond position). [3] The resin composition described in [1] or [2] has a viscosity average molecular weight (Mv) of 500 to 100,000. [4] The resin composition described in [2] further comprises a repeating unit represented by the following formula (4). [Chemistry 4] (In formula (4), A3 and A4 are independently the same as A1 in formula (1) above; Y is a direct bond, a divalent aromatic hydrocarbon group with 6 to 15 carbon atoms that may have substituents, or a divalent heteroaromatic hydrocarbon group with 6 to 15 carbon atoms that may have substituents; n3 and n4 are independently integers from 1 to 50). [5] The resin composition described in any one of [1] to [4], wherein the carbonate equivalent of the phenolic carbonate resin (A) is 100 to 10,000 g / eq. [6] The resin composition described in any one of [1] to [5] is wherein the weight ratio of the phenolic carbonate resin (A) to the epoxy resin (B) is 0.01 to 100. [7] The resin composition described in any one of [1] to [6] further comprises a curing accelerator (C), and the content of the curing accelerator (C) is 0.001 to 5 parts by weight relative to a total of 100 parts by weight of the phenolic carbonate resin (A) and the epoxy resin (B). [8] The resin composition described in [7] contains a curing accelerator (C) selected from one or more of the group consisting of phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, and metal-based curing accelerators. [9] A resin sheet having a resin composition layer formed from a resin composition as described in any one of [1] to [8].

[10] A hardener, which is formed by hardening a resin composition as described in any one of [1] to [8].

[11] An insulating layer formed by curing a resin composition as described in any one of [1] to [8].

[12] An electrical and electronic component having an insulating layer as described in

[11] .

[13] A printed wiring board having an insulating layer as described in

[11] .

[14] An epoxy resin curing agent comprising phenolic carbonate resin (A), and The above-mentioned phenolic carbonate resin (A) has a viscosity-average molecular weight (Mv) of 500 to 20,000 and a terminal aromatic hydrocarbon content of 95% by mass or more. [Effects of the Invention]

[0016] According to the present invention, a resin composition comprising phenolic carbonate resin and epoxy resin can be provided, which provides a cured material having a low dielectric constant, a low dielectric loss factor, and high heat resistance. Furthermore, the resin composition can be used to provide a cured material, electrical / electronic components, and printed wiring boards. Moreover, a curing agent for epoxy resin comprising phenolic carbonate resin can be provided. Implementation

[0017] The embodiments of the present invention will be described in detail below. However, the following description is only one example of the embodiments of the present invention. The present invention is not limited to the following description as long as it does not depart from its spirit. Furthermore, when the expression "~" is used in this specification, it is considered to be a representation that includes the numerical values ​​or physical property values ​​before and after it.

[0018] Furthermore, in the technical field of this invention, "epoxy resin" encompasses both polymers with repeating structures and epoxy compounds with monomolecular structures (i.e., non-polymeric compounds), both described as "epoxy resin" and sometimes sold. Also, mixtures of two or more epoxy resins are sometimes simply referred to as "epoxy resin." In this specification, "epoxy resin" means any one of polymers with repeating structures, epoxy compounds with monomolecular structures, and mixtures of two or more epoxy resins.

[0019] [Resin Composition] The resin composition of the first embodiment of the present invention comprises phenolic carbonate resin (A) and epoxy resin (B), characterized in that the molar ratio (epoxy group / terminal hydroxyl group) of the epoxy resin (B) to the terminal hydroxyl group of the phenolic carbonate resin (A) is 3.0 to 100,000.

[0020] The reason why the resin composition of this embodiment can provide a cured product with low dielectric constant, low dielectric loss factor and high heat resistance is not fully understood, but it is speculated to be caused by the following mechanism. That is, it is believed that because the molar ratio (epoxy group / terminal hydroxyl group) of the epoxy resin relative to the terminal hydroxyl group of the phenol carbonate resin is within a certain range in the resin composition of this embodiment, during thermosetting, as shown in process 1 below, the equivalent of carbonate group 1 of the phenol carbonate resin reacts with the equivalent of epoxy group 2 of the epoxy resin to form a high-density cross-linked structure without generating secondary hydroxyl groups. Furthermore, it is believed that because more of this cross-linked structure can be formed in the cured product, a cured product with low dielectric constant, low dielectric loss factor, and high heat resistance can be obtained.

[0021] [Chemistry 5] Process 1

[0022] <Phenolic carbonate resin (A)> In the resin composition of this embodiment, the molar ratio (epoxy group / terminal hydroxyl group) of the epoxy group of the epoxy resin (B) to the terminal hydroxyl group of the phenolic carbonate resin (A) is 3.0 to 100,000. Regarding the lower limit of this molar ratio, in terms of the reactivity of the epoxy group and the carbonate group, it is preferably 15 or more, more preferably 30 or more, further preferably 60 or more, further preferably 100 or more, particularly preferably 130 or more, particularly preferably 140 or more, and most preferably 150 or more. Furthermore, regarding the upper limit of this molar ratio, in terms of the heat resistance of the cured product, it is preferably 2,500 or less, more preferably 1,500 or less, and further preferably 1,000 or less.

[0023] The viscosity-average molecular weight (Mv) of the phenol carbonate resin (A) in the resin composition of this embodiment is preferably 500 to 100,000. The lower limit of Mv is more preferably 1,000 or more, further preferably 1,500 or more, and particularly preferably 2,000 or more. By setting the Mv of the phenol carbonate resin (A) to the above-mentioned lower limit or above, the glass transition temperature (Tg) of the cured resin composition increases, and the phenol carbonate resin (A) is less prone to side reactions during the curing reaction. On the other hand, the upper limit of the Mv of the phenol carbonate resin (A) is more preferably 50,000 or less, further preferably 20,000 or less, particularly preferably 10,000 or less, and most preferably 8,000 or less. By setting the Mv of the phenol carbonate resin (A) to the above-mentioned upper limit or below, the solvent solubility tends to increase.

[0024] Furthermore, the viscosity-average molecular weight (Mv) of phenol carbonate resin (A) is calculated based on the intrinsic viscosity and Schnell's viscosity formula (hereinafter). The intrinsic viscosity is obtained by dissolving phenol carbonate resin (A) in dichloromethane and measuring the intrinsic viscosity [η] (unit: dL / g) at 20°C using an Ubbelohde viscometer. [η] = 1.23 × 10⁻⁴ Mv 0.83

[0025] The structural units of the phenolic carbonate resin (A) are not particularly limited, but are preferably repeating units represented by the following formula (1).

[0026] [Chemistry 6]

[0027] In formula (1), A1 and A2 are independently represented by the bases in formula (2) or (3), X is a direct bond, a divalent hydrocarbon group with 1 to 15 carbon atoms that may have substituents, or a base represented by -O-, -S-, -SO-, -SO2-, -CO-, -OCO- or -COO-, and n1 and n2 are independently integers from 1 to 50.

[0028] [Chemistry 7]

[0029] [Chemistry 8]

[0030] From the perspective of improving solvent solubility, at least one of A1 and A2 in formula (1) should be a group represented by formula (2), and preferably both should be groups represented by formula (2). There is no particular limitation on the position of the bond between the benzene ring in formula (2) and the naphthalene ring in formula (3). In the case of formula (2), positions 1 and 2, 1 and 3, 1 and 4 can be used, but positions 1 and 4 are preferred in terms of improving Tg. In the case of formula (3), positions 1 and 2, 1 and 3, 1 and 4, 1 and 5, 1 and 6, 1 and 7, 1 and 8, 2 and 3, 2 and 6, 2 and 7 can be used, but positions 1 and 2, 1 and 4, 1 and 5, 2 and 6, 2 and 7 are preferred in terms of improving Tg.

[0031] In formula (1), X is a direct bond, and may have a divalent hydrocarbon group with 1 to 15 carbon atoms, such as -O-, -S-, -SO-, -SO 2-, -CO-, -OCO- or -COO-.

[0032] Examples of divalent hydrocarbon groups with 1 to 15 carbon atoms include: -CH2-, -CH(CH3)-, -C(CH3)2-, -CHPh-, -C(CH3)Ph-, and -CPh. 2-, 9,9-Endoyl, 1,1-Endocyclopropyl, 1,1-Endocyclobutyl, 1,1-Endocyclopentyl, 1,1-Endocyclohexyl, 3,3,5-Trimethyl-1,1-Endocyclohexyl, 1,1-Endocyclododecyl, 1,2-Endoethyl, 1,2-Endocyclopropyl, 1,2-Endocyclobutyl, 1,2-Endocyclopentyl, 1,2-Endocyclohexyl, 1,2-Endophenyl, 1,3-Endopropyl, 1,3-Endocyclobutyl, 1,3-Endocyclopentyl, 1,3-Endocyclohexyl, 1,3-Endophenyl, 1,4-Endobutyl, 1,4-Endocyclohexyl, 1,4-Endophenyl, etc. Furthermore, possible substituents include halogen atoms, hydroxyl groups, carboxyl groups, ternary groups, amino groups, cyano groups, nitro groups, etc., with fluorine atoms being preferred.

[0033] As for X, in terms of improving chemical resistance by reducing the rotational freedom of the aromatic rings in A1 and A2 adjacent to X, it is preferred to be a direct bond, -CH2-, -CH(CH3)-, -C(CH3)2-, -C(CF3)2-, -CHPh-, -C(CH3)Ph-, -CPh2-, 9,9-tendinyl, 1,1-tendinyl, 3,3,5-trimethyl-1,1-tendinyl, 1,1-tendinyl dodecyl, -O-, -S-, -SO2-, or -CO-, more preferably a direct bond, -CH2-, -C(CH3)2-, -C(CF3)2-, 9,9-tendinyl, 3,3,5-trimethyl-1,1-tendinyl, or 1,1-tendinyl dodecyl.

[0034] In formula (1), n1 and n2 are each an integer from 1 to 50, but in terms of improving solvent solubility and compatibility with other resins, it is preferred to be 1 to 30, and more preferably 1 to 10.

[0035] In formulas (2) and (3) above, the substituent R is independently an alkyl group having 1 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aralkoxy group having 7 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an areneyl group having 8 to 12 carbon atoms, an arynyl group having 2 to 12 carbon atoms, an arynyl group having 8 to 12 carbon atoms, a halogen atom, a hydroxyl group, a carboxyl group, a ternary group, an amino group, a cyano group, or a nitro group; p is an integer from 0 to 4; q is an integer from 0 to 6. Furthermore, alkyl, alkoxy, and alkenyl groups are not limited to straight-chain groups, and can also have branched structures or cyclic structures. Also, the position and number of double bonds in alkenyl groups and triple bonds in alkynyl groups are not particularly limited.

[0036] Examples of alkyl groups having 1 to 12 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, dibutyl, tributyl, n-pentyl, isopentyl, neopentyl, tripentyl, cyclopentyl, n-hexyl, isohexyl, cyclohexyl, n-heptyl, cycloheptyl, methylcyclohexyl, n-octyl, cyclooctyl, n-nonyl, 3,3,5-trimethylcyclohexyl, n-decyl, cyclodecyl, n-undecyl, n-dodecyl, and cyclododecyl.

[0037] Examples of aralkyl groups having 7 to 12 carbon atoms include benzyl, methylbenzyl, dimethylbenzyl, trimethylbenzyl, naphthylmethyl, phenethyl, and 2-phenylisopropyl.

[0038] Examples of alkoxy groups having 1 to 12 carbon atoms include: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, dibutoxy, tributoxy, n-pentoxy, isopentoxy, neopentoxy, tripentoxy, cyclopentoxy, n-hexyloxy, isohexyloxy, cyclohexyloxy, n-heptoxy, cycloheptoxy, methylcyclohexyloxy, n-octoxy, cyclooctoxy, n-nonoxy, 3,3,5-trimethylcyclohexyloxy, n-decyloxy, cyclodecyloxy, n-undecyloxy, n-dodecyloxy, cyclododecyloxy, etc.

[0039] Examples of arylalkoxy groups with 7 to 12 carbon atoms include benzyloxy, methylbenzyloxy, dimethylbenzyloxy, trimethylbenzyloxy, naphthylmethoxy, phenylethoxy, and 2-phenylisopropoxy.

[0040] Examples of aryl groups with 6 to 12 carbon atoms include: phenyl, o-tolyl, m-tolyl, p-tolyl, ethylphenyl, xylyl, n-propylphenyl, isopropylphenyl, etc. It includes hydroxyl, ethynylphenyl, naphthyl, vinylnaphthyl, etc.

[0041] Examples of alkenyl groups with 2 to 12 carbon atoms include vinyl, 1-propenyl, 2-propenyl, 1-methylvinyl, 1-butenyl, 2-butenyl, 3-butenyl, 1,3-butadienyl, cyclohexenyl, cyclohexadienyl, cinnamyl, naphthylvinyl, etc.

[0042] Examples of aryl groups with 8 to 12 carbon atoms include styryl, cinnamyl, and naphthylvinyl groups.

[0043] Examples of alkynyl groups with 2 to 12 carbon atoms include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, and 3-butynyl.

[0044] Examples of aryynyl groups with 8 to 12 carbon atoms include phenylethynyl and naphthylethynyl.

[0045] From the viewpoint that substituent R has the tendency to improve molecular filling properties and thus heat resistance, it is preferred to be an alkyl group with 1 to 12 carbons, more preferably an alkyl group with 1 to 6 carbons, and even more preferably a methyl group.

[0046] p represents an integer from 0 to 4. From the perspective of balancing the improvement of solvent solubility and the increase of glass transition temperature (Tg) of the cured material, 0 to 2 is preferred. When p is 1 or 2, there is a tendency for the dielectric loss factor to decrease, so it is particularly favorable.

[0047] q represents an integer from 0 to 6. From the perspective of balancing the improvement of solvent solubility and the increase of glass transition temperature (Tg) of the cured product, 0 to 2 is preferred. When q is 1 or 2, there is a tendency for the dielectric loss factor to decrease, so it is particularly favorable.

[0048] The substitution position of R on the aromatic ring in Equations (2) and (3) is not particularly limited. If it is a base represented by the following formula, there is a tendency for the dielectric loss factor to decrease, which is particularly desirable.

[0049] [Chemistry 9]

[0050] When the phenol carbonate resin (A) contains the repeating unit represented by the above formula (1), the proportion of the repeating unit represented by formula (1) is not particularly limited. Among all the structural units constituting the phenol carbonate resin (A), it is preferably 80 mol% or more, more preferably 90 mol% or more, more preferably 95 mol% or more, and especially preferably 100 mol%. The phenol carbonate resin (A) may be a repeating unit comprising a single structure, or it may be a copolymer comprising repeating units of a structure represented by formula (1) or a plurality of different structures. When the phenol carbonate resin (A) is a copolymer, the phenol carbonate resin (A) is preferably a repeating unit comprising the repeating unit represented by formula (1) and a repeating unit represented by formula (4) having a structure different from the repeating unit represented by formula (1).

[0051] [Chemistry 10]

[0052] In formula (4), A3 and A4 are independently the same as A1 above; Y is a direct bond, a divalent aromatic hydrocarbon group with 6 to 15 carbon atoms that may have substituents, or a divalent heteroaromatic hydrocarbon group with 6 to 15 carbon atoms that may have substituents; n3 and n4 are independently integers from 1 to 50 (except for combinations of A3, A4, n3 and n4 that are completely identical to combinations of A1, A2, n1 and n2 in formula (1)).

[0053] Examples of divalent aromatic hydrocarbon groups with 6 to 15 carbon atoms that may have substituents, or divalent heteroaromatic hydrocarbon groups with 6 to 15 carbon atoms that may have substituents, include: pentenyl, pentenyl-naphthyl, pentenyl-anthrayl, 2,7-pentenyl, 9,9-pentenyl, pentenylpyridyl, pentenylthiophenyl, pentenylfuranyl, etc. Among these, 9,9-pentenyl is preferred in terms of its tendency to increase Tg and decrease dielectric loss factor.

[0054] n3 and n4 are each an integer from 1 to 50, but in terms of improving solvent solubility and compatibility with other resins, it is more preferably 1 to 30, and even more preferably 1 to 10.

[0055] The carbonate equivalent of the phenol carbonate resin (A) is not particularly limited, but is preferably 100 g / eq or more, more preferably 110 g / eq or more, further preferably 120 g / eq or more, and preferably 10,000 g / eq or less, more preferably 5,000 g / eq or less, further preferably 1,000 g / eq or less, and particularly preferably 500 g / eq or less. By setting the carbonate equivalent of the phenol carbonate resin (A) to the lower limit or above mentioned above, there is a tendency for reduced curing shrinkage, and also a tendency for improved impact resistance and weather resistance of the cured resin composition. Furthermore, by setting the carbonate equivalent of the phenol carbonate resin (A) to the upper limit mentioned above, there is a tendency for increased crosslinking density and increased Tg of the cured resin composition.

[0056] The amount of terminal hydroxyl groups in the phenol carbonate resin (A) is not particularly limited, but is preferably 10 ppm or more, more preferably 50 ppm or more, and even more preferably 100 ppm or more, and preferably 5,000 ppm or less, more preferably 1,000 ppm or less, and even more preferably 300 ppm or less. By ensuring that the amount of terminal hydroxyl groups in the phenol carbonate resin (A) is above the aforementioned lower limit, a sufficient curing speed can be obtained; by ensuring that it is below the aforementioned upper limit, the dielectric constant and dielectric loss factor of the cured product can be reduced. The amount of terminal hydroxyl groups in the phenol carbonate resin (A) can be determined by the colorimetric quantitative method used in the examples below.

[0057] The glass transition temperature (Tg) of phenol carbonate resin (A) is not particularly limited, but it is preferably above 70°C, more preferably above 100°C, and even more preferably above 120°C. It is typically below 250°C, but can also be below 200°C or below 180°C. There is a tendency that the higher the glass transition temperature of phenol carbonate resin (A), the higher the Tg of the cured product.

[0058] Phenolic carbonate resin (A) may also be commercially available. Furthermore, it may be manufactured using previously known polymerization methods.

[0059] The polymerization method can be either solution polymerization using phosgene or melt polymerization involving the reaction of diester with hydroxyl compounds. Preferably, in the presence of a polymerization catalyst, a melt polymerization method is used to react a dihydroxy compound having the structure represented by formula (1) above, and other dihydroxy compounds used as needed, such as a dihydroxy compound having the structure represented by formula (4), with a diester.

[0060] As a diester used in melt polymerization, one type of diester can be used alone, or two or more types can be used in any combination and ratio. Examples of diesters include aromatic carbonates and aliphatic carbonates. Examples of aromatic carbonates include diphenyl carbonate; substituted diphenyl carbonates such as dimethyl carbonate and dimethyl carbonate. Examples of aliphatic carbonates include dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. Among these, aromatic carbonates are preferred, diphenyl carbonates or substituted diphenyl carbonates are more preferred, and diphenyl carbonates are especially preferred.

[0061] In the above melt polymerization method, the diester is preferably used in a molar ratio of 0.90 to 1.10 relative to all the dihydroxy compounds represented by formula (1) used in the reaction, and more preferably in a molar ratio of 0.96 to 1.04. If the molar ratio of the diester used in the melt polymerization process is too small, the terminal hydroxyl groups of the manufactured polycarbonate resin will increase, the thermal stability of the polymer will deteriorate, and it will be difficult to obtain the desired high molecular weight polymer. On the other hand, if the molar ratio of the diester used is too large, the transesterification reaction rate will decrease under the same polymerization conditions, making it difficult to manufacture the desired viscosity-average molecular weight phenolic carbonate resin (A). Furthermore, there is a tendency for an increase in the amount of diester remaining in the manufactured phenolic carbonate resin (A), which may lead to an odor during molding or in the molded product.

[0062] As described above, in the method for manufacturing the phenol carbonate resin (A) used in this embodiment, it is preferable to use an aromatic carbonate such as diphenyl carbonate as the diester. In this case, the manufactured phenol carbonate resin (A) has an aromatic hydrocarbon terminal group (hereinafter, sometimes referred to as "aromatic hydrocarbon terminal") as exemplified by the terminal group (hereinafter, sometimes referred to as "phenyl terminal") represented by the following formula (5). The ratio (T1 / T2) of the number of aromatic hydrocarbon terminals (T1) of the phenol carbonate resin (A) to the total number of terminals (T2) is preferably 0.20 or more, more preferably 0.25 or more, and more preferably 0.30 or more, and is generally 1.00 or less. If the ratio (T1 / T2) of the number of aromatic hydrocarbon terminal groups (T1) to the total number of terminal groups (T2) is too small, there is a risk of increased coloring under conditions such as higher polymerization reaction temperature or injection molding temperature.

[0063] [Chemistry 11]

[0064] There are no particular limitations on the method of adjusting the ratio (T1 / T2) of the number of aromatic hydrocarbon ends (T1) to the total number of ends (T2) of the phenol carbonate resin to the range mentioned above. For example, the method of adjusting the ratio of the diester to the total amount of dihydroxy compounds used in the reaction to a range that can obtain the desired high molecular weight product; removing the residual monomers from the reaction system by degassing in the later stage of the polymerization reaction; or increasing the stirring efficiency of the reactor in the later stage of the polymerization reaction to increase the reaction rate.

[0065] The ratio (T1 / T2) of the number of aromatic hydrocarbon terminus groups (T1) to the total number of terminus groups (T2) in phenol carbonate resin can be calculated by using an NMR (Nuclear Magnetic Resonance) spectrometer with deuterium chloroform containing TMS (tetramethylsilane) as the determination solvent and by measuring the 1H-NMR (1Hydrogen-Nuclear Magnetic-Resonance) spectrum.

[0066] Alkali metal compounds and / or alkaline earth metal compounds are used as polymerization catalysts (ester exchange catalysts) in melt polymerization. Alkaline compounds such as basic boron compounds, basic phosphorus compounds, basic ammonium compounds, and amine compounds may also be used in conjunction with alkali metal compounds and / or alkaline earth metal compounds as adjuncts, but it is particularly preferred to use only alkali metal compounds and / or alkaline earth metal compounds.

[0067] Examples of alkali metal compounds that can be used as polymerization catalysts include: sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium bicarbonate, potassium bicarbonate, lithium bicarbonate, cesium bicarbonate, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, sodium acetate, potassium acetate, lithium acetate, cesium acetate, sodium stearate, potassium stearate, lithium stearate, cesium stearate, sodium borohydride, potassium borohydride, lithium borohydride, and cesium borohydride. Sodium boron phenylide, potassium boron phenylide, lithium boron phenylide, cesium boron phenylide, sodium benzoate, potassium benzoate, lithium benzoate, cesium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, dicesium hydrogen phosphate, disodium phenyl phosphate, dipotassium phenyl phosphate, dilithium phenyl phosphate, dicesium phenyl phosphate; alcohols and phenols of sodium, potassium, lithium, and cesium; disodium salts, dipotassium salts, dilithium salts, and dicesium salts of bisphenol A, etc.

[0068] Examples of alkaline earth metal compounds include: calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium bicarbonate, barium bicarbonate, magnesium bicarbonate, strontium bicarbonate, calcium carbonate, barium carbonate, magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, and strontium stearate. These alkali metal compounds and / or alkaline earth metal compounds can be used alone, or in any combination and ratio, in two or more compounds.

[0069] Specific examples of basic boron compounds used in conjunction with alkali metal compounds and / or alkaline earth metal compounds include sodium, potassium, lithium, calcium, barium, magnesium, and strontium salts of tetramethylboron, tetraethylboron, tetrapropylboron, tetrabutylboron, trimethylethylboron, trimethylbenzylboron, trimethylphenylboron, triethylmethylboron, triethylbenzylboron, triethylphenylboron, tributylbenzylboron, tributylphenylboron, tetraphenylboron, benzyltriphenylboron, methyltriphenylboron, and butyltriphenylboron.

[0070] Examples of basic phosphorus compounds include: triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tributylphosphine, quaternary phosphorus salts, etc.

[0071] Examples of basic ammonium compounds include: tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide, butyltriphenylammonium hydroxide, etc.

[0072] Examples of amine compounds include: 4-aminopyridine, 2-aminopyridine, N,N-dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine, 2-dimethylaminoimidazolium, 2-methoxyimidazolium, imidazolium, 2-mercaptoimidazolium, 2-methylimidazolium, aminoquinoline, etc.

[0073] Alkaline compounds such as basic boron compounds, basic phosphorus compounds, basic ammonium compounds, and amine compounds can be used alone, or in any combination and ratio of two or more.

[0074] Regarding the amount of polymerization catalyst used, when using alkali metal compounds and / or alkaline earth metal compounds, the amount, in metal equivalents, is typically in the range of 0.1 to 100 μmol, preferably in the range of 0.5 to 50 μmol, and even more preferably in the range of 1 to 25 μmol, relative to 1 mol of all dihydroxy compounds used in the reaction. If the amount of polymerization catalyst used is too small, there is a tendency to fail to obtain the polymerization activity required to produce polycarbonate resin of the desired molecular weight. On the other hand, if the amount of polymerization catalyst used is too large, there is a tendency for the obtained phenolic carbonate resin to have a poor color, produce by-products, and result in decreased flowability or increased colloid production, thereby making it difficult to produce phenolic carbonate resin of the target quality.

[0075] When manufacturing the phenolic carbonate resin used in this embodiment, the dihydroxy compound having the structure represented by the above structural formula (1) can be supplied in solid form, or it can be supplied in a molten state by heating, or it can be supplied in aqueous solution form.

[0076] In this embodiment, in the presence of a polymerization catalyst, the method of reacting a dihydroxy compound having the structure represented by formula (1), an alicyclic dihydroxy compound, and other dihydroxy compounds used as needed with a diester carbonate is generally carried out in multiple steps of two or more stages. Specifically, the first stage reaction is carried out at a temperature of 140~220℃, preferably 150~200℃, for 0.1~10 hours, preferably 0.5~3 hours. In the second stage and thereafter, the pressure of the reaction system is gradually reduced from the pressure of the first stage, while the reaction temperature is increased. At the same time, the aromatic monohydroxy compounds such as phenols produced are removed from the reaction system, and finally, the polycondensation reaction is carried out at a pressure below 200 Pa and a temperature range of 210~280℃. During the decompression process in polycondensation, it is crucial to control the balance between temperature and pressure within the reaction system. In particular, if either temperature or pressure changes rapidly and excessively, unreacted monomers may distill off, causing a change in the molar ratio of the diester to the dihydroxy compound, thereby resulting in a decrease in the degree of polymerization. The reaction can be carried out in any of the following forms: batch, continuous, or a combination of batch and continuous.

[0077] [Epoxy Resin (B)] Epoxy resin (B) is not particularly limited, but examples include: bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol C type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, triphenol type epoxy resin, naphthol phenolic varnish type epoxy resin, phenolic phenolic varnish type epoxy resin, tert-butylcatechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene... Epoxy resins include: glycidylamine type epoxy resins, glycidyl ester type epoxy resins, cresol phenolic varnish type epoxy resins, biphenyl type epoxy resins, linear aliphatic epoxy resins, epoxy resins with butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, spirocyclic epoxy resins, cyclohexane type epoxy resins, cyclohexane-diethanol type epoxy resins, naphthyl ether type epoxy resins, trimethylolpropionic acid type epoxy resins, and tetraphenylethane type epoxy resins. Among these, epoxy resin (B) is preferably an aromatic epoxy resin, and more preferably an aromatic epoxy resin that is liquid at 20°C. Epoxy resins can be used alone or in any combination and ratio, with two or more types used together.

[0078] The weight ratio of phenolic carbonate resin (A) to epoxy resin (B) is not particularly limited, but is generally 0.01 or more, preferably 0.1 or more, and from the viewpoint of reactivity, more preferably 0.2 or more, and even more preferably 0.4 or more. Furthermore, this weight ratio is preferably 100 or less, and from the viewpoint of storage stability, more preferably 20 or less, even more preferably 10 or less, and particularly preferably 5 or less.

[0079] [Hardening Accelerator (C)] The resin composition of this embodiment may also include a curing accelerator (C). There are no particular limitations on the curing accelerator (C), but examples include: phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and metal-based curing accelerators. Among these, the curing accelerator (C) is preferably a phosphorus-based curing accelerator, an amine-based curing accelerator, an imidazole-based curing accelerator, or a metal-based curing accelerator, and more preferably an amine-based curing accelerator. The curing accelerator (C) can be used alone, or two or more can be combined in any combination and ratio.

[0080] Examples of phosphorus-based curing accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphine tetraphenylborate, tetraphenylphosphine n-butylphosphine tetraphenylborate, tetrabutylphosphine decanoate, (4-methylphenyl)triphenylphosphine thiocyanate, tetraphenylphosphine thiocyanate, butyltriphenylphosphine thiocyanate, etc., with triphenylphosphine and tetrabutylphosphine decanoate being preferred.

[0081] Examples of amine-based hardening accelerators include: trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine (DMAP), benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, etc., with 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)-undecene being more preferred, and 4-dimethylaminopyridine being even more preferred.

[0082] Examples of imidazole-based hardening accelerators include: 2-methylimidazolium, 2-undecylimidazolium, 2-heptadecylimidazolium, 1,2-dimethylimidazolium, 2-ethyl-4-methylimidazolium, 1,2-dimethylimidazolium, 2-ethyl-4-methylimidazolium, 2-phenylimidazolium, 2-phenyl-4-methylimidazolium, 1-benzyl-2-methylimidazolium, 1-benzyl-2-phenylimidazolium, 1-cyanoethyl-2-methylimidazolium, 1-cyanoethyl-2-undecylimidazolium, 1-cyanoethyl-2-ethyl-4-methylimidazolium, 1-cyanoethyl-2-phenylimidazolium, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-symmetric triazine, 2,4-diamino- 6-[2'-Undecylimidazolyl-(1')]-ethyl-symmetric trichloroisocyanuric acid adduct, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-symmetric trichloroisocyanuric acid adduct, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-symmetric trichloroisocyanuric acid adduct, 2-phenylimidazolyl isocyanuric acid adduct, 2-phenyl-4,5-dichloroisocyanuric acid adduct The imidazole compounds, such as hydroxymethylimidazolium, 2-phenyl-4-methyl-5-hydroxymethylimidazolium, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, as well as adducts of imidazole compounds with epoxy resins, are preferred, with 2-ethyl-4-methylimidazolium and 1-benzyl-2-phenylimidazolium being the most preferred.

[0083] Examples of guanidine-based hardening promoters include: dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanidine, 1-ethylbiguanidine, 1-n-butylbiguanidine, 1-n-octadecylbiguanidine, 1,1-dimethylbiguanidine, 1,1-diethylbiguanidine, 1-cyclohexylbiguanidine, 1-allylbiguanidine, 1-phenylbiguanidine, 1-(o-tolyl)biguanidine, etc., with dicyandiamide and 1,5,7-triazabicyclo[4.4.0]dec-5-ene being preferred.

[0084] Examples of organometallic hardening accelerators include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include: cobalt(II) acetoacetone, cobalt(III) acetoacetone, copper(II) acetoacetone, zinc(II) acetoacetone, iron(III) acetoacetone, nickel(II) acetoacetone, and manganese(II) acetoacetone. Examples of organometallic salts include: zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

[0085] The content of the curing accelerator (C) is not particularly limited, but it is preferably 0.001 parts by weight or more relative to the total 100 parts by weight of the above-mentioned phenolic carbonate resin (A) and epoxy resin (B). From the viewpoint of reactivity, it is more preferably 0.01 parts by weight or more, and even more preferably 0.1 parts by weight or more. It is also preferably 5 parts by weight or less, and from the viewpoint of the storage stability of the resin composition, it is more preferably 3 parts by weight or less, and even more preferably 1 part by weight or less.

[0086] [hardener] The resin composition of this embodiment may also include curing agents other than phenol carbonate resin (A) (hereinafter referred to as "other curing agents") without impairing the effects of the present invention. Other curing agents are not particularly limited, and examples include: phenolic curing agents, naphthol curing agents, amide curing agents, reactive ester curing agents, benzo[a]pyrene curing agents, cyanate ester curing agents, carbodiimide curing agents, and phenol carbonate resins other than phenol carbonate resin (A). Among these, reactive ester curing agents, phenolic curing agents, benzo[a]pyrene curing agents, cyanate ester curing agents, and carbodiimide curing agents are preferred, and reactive ester curing agents, phenolic curing agents, and carbodiimide curing agents are even more preferred. Other curing agents may be used alone or in any combination and ratio of two or more.

[0087] [solvent] Regarding the resin composition of this embodiment, during the film formation process, a solvent can be added for dilution to appropriately adjust the viscosity of the resin composition. In the resin composition of this embodiment, the solvent is used to ensure the operability and workability of the resin composition during molding, and its amount is not particularly limited. Furthermore, in this specification, the term "solvent" and the aforementioned term "solvent medium" are used to distinguish them according to their usage, but the same type can be used independently, or different types can be used.

[0088] Solvents that may be included in the resin composition of this embodiment include, for example, ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, and cyclohexanone; esters such as ethyl acetate; glycol ethers such as ethylene glycol monomethyl ether; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; alcohols such as methanol and ethanol; alkanes such as hexane and cyclohexane; and aromatics such as toluene and xylene. Only one of the solvents listed above may be used, or two or more may be used in any combination and ratio.

[0089] [Other ingredients] The resin composition of this embodiment may also contain components other than those listed above (sometimes referred to as "other components" in this invention) to further improve the functionality of the resin composition. Examples of such other components include: thermosetting resins or photocurable resins other than epoxy resins, curing accelerators (excluding those included in "curing agents"), ultraviolet inhibitors, antioxidants, coupling agents, plasticizers, fluxes, flame retardants, colorants, dispersants, emulsifiers, low-elasticity agents, diluents, defoamers, ion scavengers, inorganic fillers, organic fillers, etc.

[0090] [Curing of resin composition] The method for curing the resin composition of this embodiment to form a cured product varies depending on the formulation components or amounts in the resin composition, but typically, heating at 80-280°C for 60-360 minutes is exemplified. This heating is preferably a two-stage process: a first heating at 80-160°C for 10-90 minutes and a second heating at 120-200°C for 60-150 minutes. Furthermore, it is preferable to perform a third heating at 150-280°C for 60-120 minutes in a formulation system where the glass transition temperature (Tg) exceeds the temperature of the second heating. From the viewpoint of reducing poor curing or solvent residue, this second and third heating method is preferred.

[0091] [Uses of the Resin Composition] The resin composition of this embodiment can form a cured material with low dielectric constant, low dielectric loss factor, and high heat resistance. Therefore, the resin composition of this embodiment is suitable for use as an insulating layer for electrical and electronic components, printed wiring boards, etc.; and as a semiconductor sealing material.

[0092] [Resin Sheets] The second embodiment of the present invention is a resin sheet having a resin composition layer formed from the resin composition of the first embodiment of the present invention. The resin sheet of this embodiment can form an insulating layer containing a hardened resin composition by curing the resin composition layer. Therefore, the resin sheet of this embodiment is suitable for use as an insulating layer for forming electronic components, printed wiring boards, etc.

[0093] The thickness of the resin composition layer is not particularly limited, but is usually less than 50 μm. From the perspective of thinning printed wiring boards, it is preferably less than 25 μm, more preferably less than 15 μm, and even more preferably less than 13 μm, especially preferably less than 10 μm, and most preferably less than 8 μm. Also, it is usually more than 1.0 μm, but can also be more than 1.5 μm or more or more than 2.0 μm.

[0094] The resin sheet of this embodiment can be a sheet containing only a resin composition layer, or a sheet on which a resin composition layer is formed. When the resin sheet of this embodiment is used to form an insulating layer for electronic components, printed circuit boards, etc., the support can be removed from the insulating layer by peeling after the insulating layer is formed, and it can also be used as part of electronic components, printed circuit boards, etc.

[0095] Examples of suitable support materials include plastic film, metal foil, and release paper, with plastic film or metal foil being preferred. Materials constituting plastic films include, for example: polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); polycarbonate; acrylic resins such as polymethyl methacrylate (PMMA); cyclic polyolefins; triacetin cellulose (TAC); polyether sulfides; polyether ketones; polyimides, etc., with polyethylene terephthalate or polyethylene naphthalate being preferred. Examples of metal foils include copper foil, aluminum foil, copper alloy foil, and aluminum alloy foil, with copper foil being the most preferred.

[0096] The surface where the support adheres to the resin composition layer can be treated with matte finish, corona treatment, or antistatic treatment. Furthermore, a release layer can be formed on the surface where the support adheres to the resin composition layer. As the release agent, a suitable selection can be made from known release agents, such as alkyd resins, polyolefin resins, polyurethane resins, and silicone resins.

[0097] The thickness of the support is not particularly limited, but is preferably 5~75 μm, more preferably 10~60 μm. Furthermore, when a release layer is provided in the support, it is preferable that the overall thickness of the support including the release layer is within the above-mentioned range.

[0098] The resin sheet of this embodiment may also include other layers as needed. Examples of other layers include, for instance, a protective film. The protective film is typically disposed on the side of the resin composition layer that is not in contact with the support. The thickness of the protective film is not particularly limited, but may be, for example, 1 to 40 μm.

[0099] There are no particular limitations on the manufacturing method of resin sheets. For example, the following method can be used: a resin varnish made by dissolving a resin composition in an organic solvent is applied to a support and dried using a die coating machine to form a resin composition layer.

[0100] Examples of organic solvents include: ketones such as acetone, methyl ethyl ketone (MEK), and cyclohexanone; esters such as ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; and amide solvents such as dimethylformamide (DMF) and N-methylpyrrolidone (NMP). A single organic solvent can be used, or two or more solvents can be used in any combination and ratio.

[0101] Drying can be carried out using known methods such as heating or hot air blowing. There are no particular limitations on drying conditions; drying is generally carried out when the content of organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. In the case of using, for example, a resin varnish containing 30-60% by mass of organic solvent, the resin composition layer can be formed by drying at 50-150°C for 3-10 minutes, but this varies depending on the boiling point of the organic solvent in the resin varnish.

[0102] [Epoxy Resin Hardener] The epoxy resin curing agent of the third embodiment of the present invention comprises phenolic carbonate resin (A). The epoxy resin curing agent of this embodiment can be used to cure the epoxy resin (B) of the first embodiment of the present invention, and can also be used to cure various epoxy resins other than epoxy resin (B). By using the epoxy resin curing agent of this embodiment, epoxy resin cured products with low dielectric constant, low dielectric loss factor, and high heat resistance can be obtained. Furthermore, the epoxy resin curing agent of this embodiment may also contain other components within the scope of not impairing the effect of the present invention, such as curing accelerators, solvents, etc., which are any components of the resin composition of the first embodiment of the present invention.

[0103] <Phenolic carbonate resin (A)> The phenol carbonate resin (A)' is a modified version of the phenol carbonate resin (A) of the first embodiment of the present invention, with its viscosity-average molecular weight (Mv) and the amount of terminal aromatic hydrocarbon groups varying to a specific range. That is, elements other than the range of Mv and the range of terminal aromatic hydrocarbon groups in the phenol carbonate resin (A)' (e.g., the method for measuring Mv, structural units, carbonate equivalent, amount of terminal hydroxyl groups, glass transition temperature, and manufacturing method, etc.) are also included, and are the same as those in the phenol carbonate resin (A). Therefore, regarding elements other than the range of Mv and the range of terminal aromatic hydrocarbon groups in the phenol carbonate resin (A)', the description in that section is referenced.

[0104] The viscosity-average molecular weight (Mv) of the phenol carbonate resin (A)' is 500 to 20,000. The lower limit of Mv is preferably 1,000 or more, more preferably 1,500 or more, and even more preferably 2,000 or more. By setting the Mv of the phenol carbonate resin (A)' to the above-mentioned lower limit, the glass transition temperature (Tg) of the cured resin composition increases, and the phenol carbonate resin (A)' is less prone to side reactions during the curing reaction. On the other hand, the upper limit of the Mv of the phenol carbonate resin (A)' is preferably 10,000 or less, more preferably 8,000 or less. By setting the Mv of the phenol carbonate resin (A)' to the above-mentioned upper limit, the solvent solubility tends to increase.

[0105] The lower limit of the amount of terminal aromatic hydrocarbon groups in phenol carbonate resin (A)', i.e., the amount of aromatic hydrocarbon groups at the end of the molecular chain, is not particularly limited, but is 95.0% by mass, preferably 96.0% by mass or more, more preferably 97.0% by mass or more, further preferably 98.0% by mass or more, particularly preferably 99.0% by mass or more, and most preferably 99.5% by mass or more. By setting the amount of terminal aromatic hydrocarbon groups in phenol carbonate resin (A)' to the above-mentioned lower limit or above, there is a tendency for the dielectric loss factor of the cured resin composition to decrease. The upper limit of the amount of terminal aromatic hydrocarbon groups in phenol carbonate resin (A)' is not particularly limited, and is usually 100% by mass or less.

[0106] The amount of terminal aromatic hydrocarbon groups in phenol carbonate resin (A)' is calculated by subtracting the amount of terminal hydroxyl groups from the total amount of terminal groups in phenol carbonate resin (A)'. [Example]

[0107] The present invention will now be described in more detail based on embodiments, but the present invention is not limited to any of the following embodiments. Furthermore, the values ​​of various manufacturing conditions or evaluation results in the following embodiments have the meaning of preferred values ​​as upper or lower limits in the implementation of the present invention, and the preferred range may also be the range defined by the combination of the above-mentioned upper or lower limit values ​​and the values ​​of the following embodiments or the values ​​of the embodiments.

[0108] [Methods for evaluating physical properties and characteristics] In the following embodiments, the evaluation of physical properties and characteristics is performed by the methods described in 1) to 8) below.

[0109] 1) Viscosity average molecular weight (Mv) of phenolic carbonate resin The viscosity-average molecular weight (Mv) of phenol carbonate resin was calculated using dichloromethane as the solvent and the intrinsic viscosity (limiting viscosity) [η] (unit dL / g) at 20°C was obtained using an Ubbelohde viscometer (manufactured by Moritomo Rika Co., Ltd.), and then calculated according to Schnell's viscosity formula (the following formula). [η] = 1.23 × 10⁻⁴ Mv 0.83

[0110] 2) The amount of terminal hydroxyl groups in phenolic carbonate resin The amount of terminal hydroxyl groups in the phenol carbonate resin was determined by a colorimetric method using titanium tetrachloride / acetic acid. Specifically, it was determined by the method described below. This allows for the determination of the amount of terminal hydroxyl groups obtained using the colorimetric method of titanium tetrachloride / acetic acid described in the examples.

[0111] (a) Preparation of 5 v / v% acetic acid solution Add 50 mL of acetic acid to a 1,000 mL volumetric flask, bring the volume to a final volume using dichloromethane, and mix to prepare a 5 v / v% acetic acid solution.

[0112] (b) Preparation of titanium tetrachloride solution Add 90 mL of dichloromethane to a 300 mL flask using a graduated cylinder, then add 10 mL of 5 v / v% acetic acid solution using the graduated cylinder. Place a stir bar in the flask and stir with a magnetic stirrer while slowly adding 2.5 mL of titanium tetrachloride solution and 2.0 mL of methanol using a 5 mL measuring pipette to prepare titanium tetrachloride solution.

[0113] (c) Preparation of calibration curve samples A dichloromethane solution was prepared by ensuring the terminal hydroxyl content of the dihydroxy compound in the raw material reached 10 ppm by weight. 0, 3, and 5 mL of the solution were added sequentially to a 25 mL volumetric flask. Then, 5 mL of 5 v / v% acetic acid was added sequentially, followed by 10 mL of titanium tetrachloride solution. The solutions were then brought to a final volume with dichloromethane and thoroughly mixed.

[0114] (d) Creation of calibration curves The absorbance of the prepared calibration samples was measured at a detection wavelength of 546 nm. The obtained absorbance was plotted against the concentration of the calibration curve sample. The reciprocal of the slope was used as a factor.

[0115] (e) Sample preparation and absorbance measurement 0.2 g of the polycarbonate resin composition was dissolved in 5 mL of dichloromethane in a 25 mL volumetric flask. Then, 5 mL of 5 v / v% acetic acid solution and 10 mL of titanium tetrachloride solution were added, and the mixture was brought to volume with dichloromethane and thoroughly mixed. The absorbance of the solution prepared in this manner was measured at a detection wavelength of 546 nm.

[0116] (f) Calculation of the amount of terminal hydroxyl groups The amount of terminal hydroxyl groups in the polycarbonate resin composition is calculated by dividing the product of the measured absorbance and the factor by the concentration of the sample. Furthermore, in a polycarbonate resin composition containing multiple structures of raw material dihydroxy compounds, samples were prepared by mixing corresponding raw material dihydroxy compounds at at least three concentration levels according to the copolymerization ratio. After plotting a calibration curve based on the data from these three or more points, the amount of terminal hydroxyl groups was measured. The detection wavelength was set to 546 nm.

[0117] 3) Amount of terminal aromatic hydrocarbon groups in phenolic carbonate resins As shown in the following formula, the amount of terminal aromatic hydrocarbon groups in phenol carbonate resin is calculated by subtracting the amount of terminal hydroxyl groups measured by the above method from the total amount of terminal groups in phenol carbonate resin. The amount of terminal aromatic hydrocarbon groups (mass%) of phenol carbonate resin = 100 - {the amount of terminal hydroxyl groups (mass%) of phenol carbonate resin}

[0118] 4) Weight average molecular weight (Mw) and number average molecular weight (Mn) of epoxy resin. Calibration curves were prepared using the "HLC-8320GPC apparatus" manufactured by Tosoh Corporation, under the following test conditions, using TSK Standard Polystyrene F-128 (Mw: 1,090,000, Mn: 1,030,000), F-10 (Mw: 106,000, Mn: 103,000), F-4 (Mw: 43,000, Mn: 42,700), F-2 (Mw: 17,200, Mn: 16,900), A-5000 (Mw: 6,400, Mn: 6,100), A-2500 (Mw: 2,800, Mn: 2,700), and A-300 (Mw: 453, Mn: 387) as standard polystyrene. The weight-average molecular weight (Mw) and number-average molecular weight (Mn) were determined using polystyrene conversion values.

[0119] Tube Column: "TSKGEL SuperHM-H+H5000+H4000+H3000+H2000" manufactured by Tosoh Co., Ltd. Eluent: Tetrahydrofuran Flow rate: 0.5 mL / min Detection: UV (ultraviolet) (wavelength 254 nm) Temperature: 40℃ Sample concentration: 0.1% by weight Injection volume: 10 μL

[0120] 5) Epoxy equivalent The determination was carried out according to JIS K 7236, and the converted value of solid content was recorded.

[0121] 6) The molar ratio of epoxy groups in epoxy resin to terminal hydroxyl groups in phenolic carbonate resin (epoxy group / terminal hydroxyl group) Calculate it according to the following formula. Epoxy group / terminal hydroxyl group = (weight of epoxy resin / epoxy equivalent) / (weight of phenolic carbonate resin × amount of terminal hydroxyl groups of phenolic carbonate resin / 17.0)

[0122] 7) Heat resistance of the hardened material: glass transition temperature (Tg) For the epoxy resin cured films (thickness: approximately 50 μm) obtained in Examples 1-7, the glass transition temperature was measured using a DSC7020 manufactured by SII Nano Technology Co., Ltd., with the temperature increased from 30°C to 250°C at a rate of 10°C / min. Furthermore, the glass transition temperature referred to here is based on the "midpoint glass transition temperature: Tmg" described in JIS K 7121 "Method for determination of transition temperature of plastics".

[0123] 8) Dielectric properties The epoxy resin cured films obtained in Examples 1-7 were cut into test pieces with a width of 2 mm and a length of 80 mm. For these test pieces, the specific dielectric constant (εr) and dielectric loss factor (tanδ) were measured using a network analyzer and the resonant cavity perturbation method at a measurement frequency of 1 GHz and 10 GHz and a measurement temperature of 23°C.

[0124] [Components of the resin composition] The various components used in the resin compositions of the following examples are described below.

[0125] [Low molecular weight epoxy resin] (B-1): "jER 828US" (Bisphenol A type epoxy resin, epoxy equivalent 185 g / equivalent) manufactured by Mitsubishi Chemical Co., Ltd.

[0126] [High molecular weight epoxy resin] (B-2): Manufactured by Mitsubishi Chemical Co., Ltd., trade name "YL7891T30", Mn: 10,000, Mw: 30,000, epoxy equivalent: 6,000 g / equivalent, 30 wt% toluene solution of high molecular weight epoxy resin.

[0127] [Phenolic carbonate resin (A)] (A-1): 2,2-bis(4-hydroxyphenyl)propane-type phenolic carbonate resin (n=7) (A-2): 2,2-bis(4-hydroxy-3-methylphenyl)propane-type phenolic carbonate resin (n=5) (A-3): 9,9-bis(4-hydroxy-3-methylphenyl) phenolic carbonate resin (n=4) (A-4): A copolymer of 9,9-bis(4-hydroxy-3-methylphenyl)propane and 2,2-bis(4-hydroxy-3-methylphenyl)propane phenolic carbonate resin (n=9) (A-5): A copolymer of 1,1-bi-2-naphthol and 4,4-(3,3,5-trimethyl-1,1-cyclohexanediyl)bisphenol A phenolic carbonate resin (n=2) (A-6): A copolymer of 1,1-bi-2-naphthol and 4,4-(3,3,5-trimethyl-1,1-cyclohexanediyl)bisphenol A phenolic carbonate resin (n=2) (A-7): 2,2-bis(4-hydroxyphenyl)propane-type phenolic carbonate resin (n=7) The above (A-1) to (A-7) are synthesized in the following synthetic examples 1 to 7, and have the following repeating units.

[0128] [Chemistry 12]

[0129] [Hardening Accelerator] (C-1): N,N'-Dimethylaminopyridine (DMAP), 5 wt% toluene solution

[0130] [Leveling agent] S-651: Fluorine-based surfactant (nonionic) manufactured by AGC Seimi Chemical Co., Ltd.

[0131] Synthesis of phenolic carbonate resin (A) [Synthesis Example 1: Synthesis of Phenolic Carbonate Resin (A-1)] A raw material mixture was prepared by adding 116.71 g (approximately 0.5112 mol) of 2,2-bis(4-hydroxyphenyl)propane (BPA), 137.99 g (approximately 0.6442 mol) of diphenyl carbonate (DPC), and a 0.04% by mass aqueous solution of cesium carbonate as a catalyst to a 150 mL glass reactor equipped with a reactor stirrer, reactor heating device, and reactor pressure adjustment device.

[0132] Next, the pressure inside the glass reactor was reduced to approximately 100 Pa (0.75 Torr), and then restored to atmospheric pressure using nitrogen. This process was repeated three times to replace the reactor's interior with nitrogen. After nitrogen replacement, the external temperature of the reactor was set to 220°C, allowing the internal temperature to rise slowly and dissolve the raw material mixture. Then, the stirrer was rotated at 100 rpm. Subsequently, while distilling away the phenols generated as a byproduct of the oligomerization reaction of the dihydroxy compound and DPC occurring inside the reactor, the pressure inside the reactor was reduced from 101.3 kPa (760 Torr) to 13.3 kPa (100 Torr) using an absolute pressure gauge over a period of 40 minutes.

[0133] Next, while maintaining the pressure inside the reactor at 13.3 kPa, the phenol was further removed by distillation, and an 80-minute transesterification reaction was carried out. Afterward, the pressure inside the reactor was reduced from 13.3 kPa (100 Torr) to 399 Pa (3 Torr) over 40 minutes to remove the distilled phenol. Then, the pressure inside the reactor was reduced to 70 Pa (approximately 0.5 Torr) to carry out a polycondensation reaction. The polycondensation reaction was terminated when the reactor agitator reached a predetermined stirring power.

[0134] Subsequently, the pressure inside the reactor was restored to 101.3 kPa using nitrogen gas. Then, the phenol carbonate resin (A-1) was extracted from the reactor into an aluminum container, and the cured (A-1) was crushed. The Mv, terminal hydroxyl content, terminal aromatic hydrocarbon content, carbonate equivalent, and Tg of the phenol carbonate resin (A-1) are shown in Table 1.

[0135] [Synthesis Example 2: Synthesis of Phenolic Carbonate Resin (A-2)] A raw material mixture was prepared by adding 116.71 g (approximately 0.4553 mol) of 2,2-bis(4-hydroxy-3-methylphenyl)propane (BPC), 146.30 g (approximately 0.6829 mol) of diphenyl carbonate (DPC), and a 0.4% by mass aqueous solution of cesium carbonate as a catalyst to a 150 mL glass reactor equipped with a reactor stirrer, reactor heating device, and reactor pressure adjustment device.

[0136] Next, the pressure inside the glass reactor was reduced to approximately 100 Pa (0.75 Torr), and then restored to atmospheric pressure using nitrogen. This process was repeated three times to replace the reactor's interior with nitrogen. After nitrogen replacement, the external temperature of the reactor was set to 220°C, allowing the internal temperature to rise slowly and dissolve the raw material mixture. Then, the stirrer was rotated at 100 rpm. Subsequently, while distilling away the phenols generated as a byproduct of the oligomerization reaction of the dihydroxy compound and DPC occurring inside the reactor, the pressure inside the reactor was reduced from 101.3 kPa (760 Torr) to 13.3 kPa (100 Torr) using an absolute pressure gauge over a period of 40 minutes.

[0137] Next, while maintaining the pressure inside the reactor at 13.3 kPa to further remove phenol by distillation, an 80-minute transesterification reaction was carried out. Afterward, the external temperature of the reactor was raised to 260°C, and the pressure inside the reactor was reduced from 13.3 kPa (100 Torr) to 399 Pa (3 Torr) over 40 minutes to remove the distilled phenol. Then, the absolute pressure inside the reactor was reduced to 70 Pa (approximately 0.5 Torr) to carry out a polycondensation reaction. The polycondensation reaction was terminated when the reactor agitator reached a predetermined stirring power.

[0138] Subsequently, the pressure inside the reactor was restored to 101.3 kPa using nitrogen gas. Then, the phenol carbonate resin (A-2) was extracted from the reactor into an aluminum container, and the cured (A-2) was crushed. The Mv, terminal hydroxyl content, terminal aromatic hydrocarbon content, carbonate equivalent, and Tg of the phenol carbonate resin (A-2) are shown in Table 1.

[0139] [Synthesis Example 3: Synthesis of Phenolic Carbonate Resin (A-3)] A raw material mixture was prepared by adding 116.71 g (approximately 0.3083 mol) of 9,9-bis(4-hydroxy-3-methylphenyl)fentanyl (BCF), 99.08 g (approximately 0.4625 mol) of DPC, and a 4% by mass aqueous solution of cesium carbonate as a catalyst to a 150 mL glass reactor equipped with a reactor stirrer, reactor heating device, and reactor pressure adjustment device. Otherwise, the method described in Synthesis Example 2 was followed.

[0140] The Mv, terminal hydroxyl content, terminal aromatic hydrocarbon content, carbonate equivalent, and Tg of the obtained phenol carbonate resin (A-3) are shown in Table 1.

[0141] [Synthesis Example 4: Synthesis of Phenolic Carbonate Resin (A-4)] A raw material mixture was prepared by adding 80.41 g (approximately 0.2124 mol) of 9,9-bis(4-hydroxy-3-methylphenyl)propane (BCF), 36.30 g (approximately 0.1416 mol) of 2,2-bis(4-hydroxy-3-methylphenyl)propane (BPC), 113.77 g (approximately 0.5311 mol) of DPC, and a 4% by mass aqueous solution of cesium carbonate as a catalyst to a 150 mL glass reactor equipped with a reactor stirrer, reactor heating device, and reactor pressure adjustment device. Otherwise, the method described in Example 2 was followed.

[0142] The Mv, terminal hydroxyl content, terminal aromatic hydrocarbon content, carbonate equivalent, and Tg of the obtained phenol carbonate resin (A-4) are shown in Table 1.

[0143] [Synthesis Example 5: Synthesis of Phenolic Carbonate Resin (A-5)] A raw material mixture was prepared by adding 60.71 g (approximately 0.196 mol) of 4,4'-(3,3,5-trimethylcyclohexylene)bisphenol (BP-TMC), 56.00 g (approximately 0.196 mol) of 1,1'-bi-2-naphthol (BN), 108.93 g (approximately 0.5085 mol) of DPC, and a 4% by mass aqueous solution of cesium carbonate as a catalyst to a 150 mL glass reactor equipped with a reactor stirrer, reactor heating device, and reactor pressure adjustment device.

[0144] The Mv, terminal hydroxyl content, terminal aromatic hydrocarbon content, carbonate equivalent, and Tg of the obtained phenol carbonate resin (A-5) are shown in Table 1.

[0145] [Synthesis Example 6: Synthesis of Phenolic Carbonate Resin (A-6)] A raw material mixture was prepared by adding 60.71 g (approximately 0.196 mol) of 4,4'-(3,3,5-trimethylcyclohexylene)bisphenol (BP-TMC), 56.00 g (approximately 0.196 mol) of 1,1'-bi-2-naphthol (BN), 108.93 g (approximately 0.5085 mol) of DPC, and a 4% by mass aqueous solution of cesium carbonate as a catalyst to a 150 mL glass reactor equipped with a reactor stirrer, reactor heating device, and reactor pressure adjustment device.

[0146] The Mv, terminal hydroxyl content, terminal aromatic hydrocarbon content, carbonate equivalent, and Tg of the obtained phenol carbonate resin (A-6) are shown in Table 1.

[0147] [Synthesis Example 7: Synthesis of Phenolic Carbonate Resin (A-7)] A raw material mixture was prepared by adding 116.71 g (approximately 0.5112 mol) of 2,2-bis(4-hydroxyphenyl)propane (BPA), 102.95 g (approximately 0.4806 mol) of diphenyl carbonate (DPC), and a 0.04% by mass aqueous solution of cesium carbonate as a catalyst to a 150 mL glass reactor equipped with a reactor stirrer, reactor heating device, and reactor pressure adjustment device.

[0148] Next, the pressure inside the glass reactor was reduced to approximately 100 Pa (0.75 Torr), and then restored to atmospheric pressure using nitrogen. This process was repeated three times to replace the reactor's interior with nitrogen. After nitrogen replacement, the external temperature of the reactor was set to 220°C, allowing the internal temperature to rise slowly and dissolve the raw material mixture. Then, the stirrer was rotated at 100 rpm. Subsequently, while distilling away the phenols generated as a byproduct of the oligomerization reaction of the dihydroxy compound and DPC occurring inside the reactor, the pressure inside the reactor was reduced from 101.3 kPa (760 Torr) to 13.3 kPa (100 Torr) using an absolute pressure gauge over a period of 40 minutes.

[0149] Next, while maintaining the pressure inside the reactor at 13.3 kPa to further remove phenol by distillation, an 80-minute transesterification reaction was carried out. Afterward, the external temperature of the reactor was raised to 280°C, and the pressure inside the reactor was reduced from 13.3 kPa (100 Torr) to 399 Pa (3 Torr) over 40 minutes to remove the distilled phenol. Then, the absolute pressure inside the reactor was reduced to 70 Pa (approximately 0.5 Torr) to carry out a polycondensation reaction. The polycondensation reaction was terminated when the reactor agitator reached a predetermined stirring power.

[0150] Subsequently, the pressure inside the reactor was restored to 101.3 kPa using nitrogen gas, and the phenol carbonate resin (A-7) was extracted from the reactor into an aluminum container, and the cured (A-7) was crushed.

[0151] The Mv, terminal hydroxyl content, terminal aromatic hydrocarbon content, carbonate equivalent, and Tg of the obtained phenol carbonate resin (A-7) are shown in Table 1.

[0152] [Table 1] Table 1 Phenolic carbonate resin (A-1) (A-2) (A-3) (A-4) (A-5) (A-6) (A-7) Mv — 3,490 2,930 2,040 3,960 2670 2880 5100 Terminal hydroxyl amount (ppm) 158 55 108 200 670 511 9018 Terminal aromatic hydrocarbon content (quality%) 99.984 99.995 99.989 99.980 99.933 99.949 99.098 carbonate equivalent (g / eq) 127 141 133 178 162 162 127 Tg (°C) 82 73 133 150 169 173 82

[0153] [Manufacturing and Evaluation of Resin Compositions / Curings] <Examples 1-7> A resin composition was obtained by mixing epoxy resin (B-1), cyclohexanone solution of phenolic carbonate resin (A-1) to (A-7) (20 wt% in Examples 1 and 7, 30 wt% in Examples 2 to 6), curing accelerator (C-1), high molecular weight epoxy resin (B-2) serving as a film-forming agent, and leveling agent, as shown in Table 2. The obtained resin composition solution was coated onto a spacer (silicone-treated polyethylene terephthalate film) using a coating apparatus, dried at 160°C for 1.5 hours, and then dried at 200°C for 1.5 hours to obtain a cured epoxy resin film. The heat resistance and dielectric properties of the obtained film were evaluated according to the above method. The results are shown in Table 2.

[0154] As can be seen from the results in Table 2, the cured products obtained by using the resin compositions of Examples 1 to 7 have a good balance between heat resistance and dielectric properties.

[0155] [Table 2] Table 2 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Raw material composition of the resin composition (parts by weight) Low molecular weight epoxy resin (B-1) 53.91 51.6 43.46 46.34 48.30 48.30 53.90 High molecular weight epoxy resin (B-2) 9.11 9.08 9.08 9.08 9.08 9.08 9.08 hardener (Phenolic carbonate resin) (A-1) 36.98 - - - - - - (A-2) - 9.32 - - - - - (A-3) - - 47.46 - - - - (A-4) - - - 44.58 - - - (A-5) - - - - 42.31 - - (A-6) - - - - - 42.31 - (A-7) - - - - - - 37.02 hardening accelerator (C-1) 0.49 0.52 0.52 0.50 0.50 0.50 0.74 Leveling agent S-651 0.49 0.52 0.52 0.51 0.48 0.48 0.50 solvent Cyclohexanone, Toluene 178.76 122.5 141.42 134.75 129.39 129.39 229.8 The molar ratio (epoxy group / terminal hydroxyl group) of epoxy resin to the terminal hydroxyl group of phenolic carbonate resin. 852 2204 784 480 157 205 14.8 Hardening properties Tg (°C) 134 127 164 163 165 168 130 -1 GHz - 2.9 3.1 3.1 2.8 2.7 3.2 2.8 -10 GHz - 2.7 2.4 2.9 2.6 2.1 2.3 2.8 tanδ-1 GHz - 0.018 0.013 0.013 0.009 0.015 0.017 0.019 tanδ-10 GHz - 0.017 0.012 0.012 0.009 0.013 0.014 0.019

Claims

1. A resin composition comprising a phenolic carbonate resin (A) and an epoxy resin (B), wherein the molar ratio (epoxy group / terminal hydroxyl group) of the epoxy resin (B) to the terminal hydroxyl group of the phenolic carbonate resin (A) is 3.0 to 100,000, and the amount of terminal hydroxyl group of the phenolic carbonate resin (A) is 5,000 ppm or less.

2. The resin composition of claim 1, wherein the phenol carbonate resin (A) comprises a repeating unit represented by the following formula (1), [Chemical 1] (in formula (1), A1 and A2 are each independently represented by the following formula (2) or (3); X is a direct bond, a divalent hydrocarbon group having 1 to 15 carbon atoms that may have substituents, -O-, -S-, -SO-, -SO2-, -CO-, -OCO- or -COO-; n1 and n2 are each independently an integer from 1 to 50) [Chemical 2] [Chemical 3] (In formulas (2) and (3), R is independently an alkyl group having 1 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aralkoxy group having 7 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an areneyl group having 8 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an arynyl group having 8 to 12 carbon atoms, a halogen atom, a hydroxyl group, a carboxyl group, a uryl group, an amino group, a cyano group, or a nitro group; p is an integer from 0 to 4; q is an integer from 0 to 6; * is the bond position).

3. The resin composition of claim 1, wherein the viscosity average molecular weight (Mv) of the phenolic carbonate resin (A) is 500 to 100,000.

4. The resin composition of claim 2, wherein the phenol carbonate resin (A) further comprises a repeating unit represented by the following formula (4), [Chemical 4] (in formula (4), A3 and A4 are independently equivalent to A1 in the above formula (1); Y is a direct bond, a divalent aromatic hydrocarbon group having 6 to 15 carbon atoms that may have substituents, or a divalent heteroaromatic hydrocarbon group having 6 to 15 carbon atoms that may have substituents; n3 and n4 are independently integers from 1 to 50).

5. The resin composition of claim 1 or 2, wherein the carbonate equivalent of the phenolic carbonate resin (A) is 100 to 10,000 g / eq.

6. The resin composition of claim 1 or 2, wherein the weight ratio of the phenolic carbonate resin (A) to the epoxy resin (B) is 0.01 to 100.

7. The resin composition of claim 1 or 2 further comprises a curing accelerator (C), wherein the content of the curing accelerator (C) is 0.001 to 5 parts by weight relative to the total 100 parts by weight of the phenolic carbonate resin (A) and the epoxy resin (B).

8. The resin composition of claim 7, wherein the curing accelerator (C) is one or more selected from the group consisting of phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, and metal-based curing accelerators.

9. A resin sheet having a resin composition layer formed from the resin composition of claim 1 or 2.

10. A hardener formed by hardening a resin composition as claimed in claim 1 or 2.

11. An insulating layer formed by curing a resin composition as claimed in claim 1 or 2.

12. An electrical or electronic component having an insulating layer as claimed in claim 11.

13. A printed wiring board having an insulating layer as claimed in claim 11.

14. A curing agent for epoxy resin, comprising a phenol carbonate resin (A)', wherein the phenol carbonate resin (A)' has a viscosity-average molecular weight (Mv) of 500 to 20,000 and a terminal aromatic hydrocarbon content of 95% by mass or more.

Images