Resin, electronic substrate material, coating liquid composition, film, sheet, electronic substrate, and resin production method

Abstract

This electronic substrate material contains a first resin. The first resin is at least one resin selected from the group consisting of polycarbonate, polyester, and polyester polycarbonate, and includes a structural unit represented by general formula (A1) and at least one structural unit selected from the group consisting of structural units represented by general formulae (B1), (C1), and (D1).

Description

Resin, electronic substrate material, coating composition, film, sheet, electronic substrate, and resin manufacturing method

[0001] The present invention relates to a resin, an electronic substrate material, a coating composition, a film, a sheet, an electronic substrate, and a method for producing a resin.

[0002] Next-generation high-speed communication technologies, known as 5G or 6G, boast features such as "high speed, large capacity," "multiple simultaneous connections," and "ultra-low latency." They are being introduced into various communication networks in fields such as electrical and electronic equipment, mobility (e.g., automobiles), and healthcare, bringing about economic and social transformation. The electronic circuit boards and semiconductor package substrates (hereinafter referred to as "electronic boards") used in these communication devices and other electronic devices also face various challenges in improving their performance. One major challenge is the increasing frequency used in communication due to the increase in information communication volume. As frequencies increase, materials used in conventional electronic boards experience increased transmission loss, which is the rate at which electrical signal energy is lost due to the conversion of unnecessary energy such as heat energy, resulting in energy loss and heat generation from the board. Transmission loss consists of two components: conductor loss and dielectric loss. Dielectric loss is proportional to the square root of the dielectric constant (Dk) and the dielectric loss tangent (Df) of the dielectric. Therefore, to reduce transmission loss in electronic boards and other devices using insulating materials, it is necessary to reduce the dielectric constant and dielectric loss tangent of the insulating material. Furthermore, in order to reduce conductor loss, there is a trend toward reducing the roughness of the interface between the substrate and the metal wiring. Therefore, insulating materials are required to have better adhesion to metal foils and metal plating. Electronic substrate materials are required to have not only reduced transmission loss but also various other properties. Examples include high heat resistance to withstand high-temperature solder reflow and low thermal expansion to prevent substrate warpage due to the difference in thermal expansion coefficient between the copper circuit and the insulating layer. Furthermore, when used as an insulating material for coating and molding onto a substrate, the properties required of the electronic substrate material include high solvent solubility, low solution viscosity, and filler dispersibility. Furthermore, the properties required of electronic substrate materials used to form thin films used in lamination molding of wiring layers include high solvent solubility, low viscosity, filler dispersibility, and minimal change in dielectric properties under the usage environment, such as temperature and humidity.As insulating materials, thermoplastic resins such as liquid crystal polymers, polyphenylene ethers, polyimides, and fluororesins, as well as thermosetting resins such as epoxy resins and maleimide resins, have been improved and developed for various applications in which electronic substrates are used. Among these resins, polycarbonate resins have been used as materials for molded products in various industrial fields due to their excellent mechanical properties, thermal properties, electrical properties, and transparency. However, for use in the above-mentioned high-frequency electronic substrates, general bisphenol A polycarbonates have poor solubility in organic solvents and solution stability, making them difficult to apply to the molding of insulating coating solutions for fine wiring or thin insulating films.

[0003] For example, Patent Document 1 describes a polycarbonate resin or a polyarylate resin having a predetermined molecular structure as a resin used in a photosensitive layer.

[0004] Furthermore, for example, Patent Document 2 describes that a copolycarbonate polymer derived from a bis(2-hydroxyaryl) type bisphenol and at least one other type of bisphenol has high solubility in non-halogenated solvents, and is excellent in solution stability, strength, and abrasion resistance, and is therefore suitable for use in fields requiring mechanical strength, such as binder resins for electrophotographic photoreceptors.

[0005] Furthermore, for example, Patent Document 3 describes a resin composition that is a mixture of two types of polycarbonate resins having specific molecular structures, and states that such a resin composition is suitable as a material for optical elements.

[0006] International Publication No. 2015 / 097903 JP 9-316186 JP 1-43559

[0007] Patent Documents 1, 2, and 3 do not describe or suggest the properties (e.g., dielectric properties and thermal properties) required for polycarbonate resins and polyarylate resins to be used as electronic substrate materials.

[0008] An object of the present invention is to provide a resin and an electronic substrate material that have dielectric properties that allow them to be used as electronic substrate materials and that have excellent solubility in non-halogenated solvents; to provide a coating composition, a film, a sheet, and an electronic substrate that contain the resin or electronic substrate material; and to provide a method for producing the resin.

[0009] As a result of extensive research, the present inventors have found that resins, copolymers, and electronic substrate materials having specific structural units have dielectric properties that allow them to be used as electronic substrate materials, and also have excellent solubility in non-halogenated solvents. That is, the gist of the present invention resides in the following [Configuration 1] to [Configuration 50].

[0010] [Configuration 1] An electronic board material comprising a first resin, the first resin being at least one resin selected from the group consisting of polycarbonate, polyester, and polyester polycarbonate, the first resin including a structural unit represented by the following general formula (A1) and at least one structural unit selected from the group consisting of structural units represented by the following general formulas (B1), (C1), and (D1):

[0011]

[0012]

[0013] (In the general formula (A1), R １ and R ２ are each independently a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, n represents 1, 2, 3, or 4, and a plurality of R １ are the same or different from each other, m represents 1, 2, 3 or 4, and a plurality of R ２ are the same or different from each other, R ３ and R ４are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 14 ring carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkoxy group having 3 to 20 ring carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 14 ring carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms, a substituted or unsubstituted aralkyloxy group having 7 to 20 carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 14 ring atoms, a halogen atom, a nitro group, an aldehyde group, a cyano group, or a carboxy group; p represents 0, 1, 2, or 3, and a plurality of R ３ are the same or different from each other, q represents 0, 1, 2 or 3, and a plurality of R ４are the same or different from each other, the sum of n and p is 1, 2, 3 or 4, the sum of m and q is 1, 2, 3 or 4, the structural unit represented by general formula (B1) is different from the carbonyl group in general formula (C1), in general formula (C1), Cx is a divalent group containing at least one group selected from the group consisting of a substituted or unsubstituted divalent aromatic hydrocarbon group, a substituted or unsubstituted divalent cyclic aliphatic hydrocarbon group, and a substituted or unsubstituted divalent chain aliphatic hydrocarbon group, in general formula (D1), Dx is a divalent group containing at least one group selected from the group consisting of a substituted or unsubstituted divalent aromatic hydrocarbon group, a substituted or unsubstituted divalent cyclic aliphatic hydrocarbon group, and a substituted or unsubstituted divalent chain aliphatic hydrocarbon group, the structural unit represented by general formula (A1) and the structural unit represented by general formula (D1) are different from each other, In the case of "substituted or unsubstituted", the substituents are bonded to each other to form a single ring, bonded to each other to form a fused ring, or not bonded to each other; * in the general formulas (A1), (B1), (C1), and (D1) represents a bond; when the first resin contains a plurality of structural units represented by the general formula (A1), the plurality of structural units represented by the general formula (A1) are the same as or different from each other; when the first resin contains a plurality of structural units represented by the general formula (C1), the plurality of structural units represented by the general formula (C1) are the same as or different from each other; and when the first resin contains a plurality of structural units represented by the general formula (D1), the plurality of structural units represented by the general formula (D1) are the same as or different from each other.

[0014] [Configuration 2] The electronic substrate material according to Configuration 1, wherein the first resin is a resin containing structural units represented by the general formulas (A1) and (B1).

[0015] [Configuration 3] The electronic substrate material according to Configuration 1, wherein the first resin is a resin containing structural units represented by the general formulas (A1), (B1), and (D1).

[0016] [Configuration 4] The electronic board material according to any one of Configurations 1 to 3, wherein the ratio a:d of the molar fraction a of the structural unit represented by General Formula (A1) to the molar fraction d of the structural unit represented by General Formula (D1) in the first resin is 5:95 to 100:0.

[0017] [Configuration 5] The electronic board material according to Configuration 3 or 4, wherein the ratio a:d of the molar fraction a of the structural unit represented by General Formula (A1) to the molar fraction d of the structural unit represented by General Formula (D1) in the first resin is 10:90 to 50:50.

[0018] [Configuration 6] The electronic substrate material according to any one of Configurations 1 to 5, wherein the structural unit represented by the general formula (A1) is represented by the following general formula (A10):

[0019]

[0020] (In the general formula (A10), R １ , R ２ , R ３ , R ４ , n, m, p, q, and * are each R in the general formula (A1). １ , R ２ , R ３ , R ４ , n, m, p, q and *.)

[0021] [Configuration 7] The electronic substrate material according to any one of Configurations 1 to 6, wherein n and m are 1.

[0022] [Configuration 8] The electronic substrate material according to any one of Configurations 1 to 7, wherein the structural unit represented by the general formula (A1) is represented by the following general formula (A11):

[0023]

[0024] (In the general formula (A11), R １ , R ２ , R ３ , R ４ , p, q, and * are each R in the general formula (A1). １ , R２ , R ３ , R ４ , p, q and *.)

[0025] [Configuration 9] The electronic substrate material according to any one of Configurations 1 to 8, wherein p and q are 1.

[0026] [Configuration 10] The electronic substrate material according to any one of Configurations 1 to 9, wherein the structural unit represented by the general formula (A1) is represented by the following general formula (A12):

[0027]

[0028] (In the general formula (A12), R １ , R ２ , R ３ , R ４ and * respectively represent R in the general formula (A1). １ , R ２ , R ３ , R ４ and * are synonymous.)

[0029] [Configuration 11] The electronic substrate material according to any one of Configurations 1 to 10, wherein the structural unit represented by the general formula (D1) is represented by the following general formula (D2):

[0030]

[0031] (In the general formula (D2), R １５１ ~R １５８are each independently selected from the group consisting of a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 18 carbon atoms, a substituted or unsubstituted cycloalkyl group having 6 to 20 ring carbon atoms, a substituted or unsubstituted cycloalkoxy group having 6 to 20 ring carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 14 ring carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 14 ring carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms, a substituted or unsubstituted aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxy group; １ is (i) a single bond, or (ii) a substituted or unsubstituted alkylene group having 1 to 28 carbon atoms, a substituted or unsubstituted alkylidene group having 2 to 28 carbon atoms, a substituted or unsubstituted cycloalkylene group having 5 to 15 ring carbon atoms, a substituted or unsubstituted cycloalkylidene group having 3 to 26 ring carbon atoms, a substituted or unsubstituted arylene group having 6 to 20 ring carbon atoms, -S-, -SO-, -SO ２ (iii) a divalent group formed by linking two or more groups selected from the group (ii), * represents a bond.

[0032] [Configuration 12] The electronic substrate material according to Configuration 11, wherein X １ is a substituted or unsubstituted cycloalkylidene group having 5 to 15 ring carbon atoms.

[0033] [Configuration 13] In the electronic substrate material according to Configuration 11 or Configuration 12, R １５１ ~R １５８ and each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, or a substituted or unsubstituted cycloalkyl group having 6 to 20 ring carbon atoms.

[0034] [Configuration 14] The electronic substrate material according to any one of Configurations 1 to 10, wherein the structural unit represented by the general formula (D1) is represented by the following general formula (D3):

[0035]

[0036] (In the general formula (D3), X ２ (i) is a single bond, or (ii) is a substituted or unsubstituted divalent organic group having 7 to 12 carbon atoms, and R １６１ ~R １６８ are each independently a hydrogen atom or a substituted or unsubstituted organic group having 1 to 10 carbon atoms, and * represents a bond.

[0037] [Configuration 15] The electronic board material according to any one of Configurations 1 to 14, wherein the first resin has a reduced viscosity of 0.80 dL / g or less, and the reduced viscosity of the first resin is the reduced viscosity at a temperature of 20°C of a solution containing the first resin as a solute and having a concentration of 0.5 g / dL in methylene chloride as a solvent.

[0038] [Configuration 16] The electronic board material according to any one of Configurations 1 to 15, wherein the first resin comprises a repeating unit represented by the following general formula (PC-AB1) in which a structural unit represented by the general formula (A1) and a structural unit represented by the general formula (B1) are bonded together, and wherein no chains between repeating units represented by the general formula (PC-AB1) exist in the first resin:

[0039]

[0040] (In the general formula (PC-AB1), R １ , R ２ , R ３ , R ４ , m, n, p, and q are each R in the general formula (A1). １ , R ２ , R ３ , R ４ , m, n, p, and q are synonymous with each other, and * represents a bond.

[0041] [Configuration 17] The electronic board material according to any one of Configurations 1 to 16, wherein the first resin is a polycarbonate resin.

[0042] [Configuration 18] The electronic board material according to any one of Configurations 1 to 17, wherein the content of the first resin in the electronic board material is 50 mass % or more.

[0043] [Configuration 19] The electronic board material according to any one of Configurations 1 to 18, wherein the first resin has a relative dielectric constant Dk of 2.70 or less.

[0044] [Configuration 20] The electronic board material according to any one of Configurations 1 to 19, wherein the dielectric loss tangent Df of the first resin is 0.00300 or less.

[0045] [Configuration 21] The electronic substrate material according to any one of Configurations 1 to 20, wherein the viscosity average molecular weight Mv of the first resin in the electronic substrate material is 1,000 or more and 30,000 or less.

[0046] [Configuration 22] A coating composition comprising the electronic substrate material according to any one of Configurations 1 to 21 and a non-halogenated solvent.

[0047] [Configuration 23] A film comprising the electronic substrate material according to any one of Configurations 1 to 21.

[0048] [Configuration 24] A sheet comprising the electronic substrate material according to any one of Configurations 1 to 21.

[0049] [Configuration 25] An electronic substrate comprising the electronic substrate material according to any one of Configurations 1 to 21.

[0050] [Configuration 26] At least one resin selected from the group consisting of polycarbonate, polyester, and polyester polycarbonate, the resin containing a structural unit represented by the following general formula (A1) and at least one structural unit selected from the group consisting of structural units represented by the following general formulas (B1), (C1), and (D1):

[0051]

[0052]

[0053] (In the general formula (A1), R １ and R ２ are each independently a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, n represents 1, 2, 3, or 4, and a plurality of R １ are the same or different from each other, m represents 1, 2, 3 or 4, and a plurality of R ２ are the same or different from each other, R ３ and R ４ are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 14 ring carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkoxy group having 3 to 20 ring carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 14 ring carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms, a substituted or unsubstituted aralkyloxy group having 7 to 20 carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 14 ring atoms, a halogen atom, a nitro group, an aldehyde group, a cyano group, or a carboxy group; p represents 0, 1, 2, or 3, and a plurality of R ３ are the same or different from each other, q represents 0, 1, 2 or 3, and a plurality of R ４are the same or different from each other, the sum of n and p is 1, 2, 3 or 4, the sum of m and q is 1, 2, 3 or 4, the structural unit represented by general formula (B1) is different from the carbonyl group in general formula (C1), in general formula (C1), Cx is a divalent group containing at least one group selected from the group consisting of a substituted or unsubstituted divalent aromatic hydrocarbon group, a substituted or unsubstituted divalent cyclic aliphatic hydrocarbon group, and a substituted or unsubstituted divalent chain aliphatic hydrocarbon group, in general formula (D1), Dx is a divalent group containing at least one group selected from the group consisting of a substituted or unsubstituted divalent aromatic hydrocarbon group, a substituted or unsubstituted divalent cyclic aliphatic hydrocarbon group, and a substituted or unsubstituted divalent chain aliphatic hydrocarbon group, the structural unit represented by general formula (A1) and the structural unit represented by general formula (D1) are different from each other, In the case of "substituted or unsubstituted", the substituents are bonded to each other to form a single ring, bonded to each other to form a fused ring, or not bonded to each other; * in the general formulas (A1), (B1), (C1), and (D1) represents a bond; when the resin contains a plurality of structural units represented by the general formula (A1), the plurality of structural units represented by the general formula (A1) are the same as or different from each other; when the resin contains a plurality of structural units represented by the general formula (C1), the plurality of structural units represented by the general formula (C1) are the same as or different from each other; and when the resin contains a plurality of structural units represented by the general formula (D1), the plurality of structural units represented by the general formula (D1) are the same as or different from each other.

[0054] [Configuration 27] The resin according to Configuration 26, wherein the resin contains structural units represented by the general formulas (A1) and (B1).

[0055] [Configuration 28] The resin according to Configuration 26, wherein the resin contains structural units represented by the general formulae (A1), (B1), and (D1).

[0056] [Structure 29] The resin according to any one of Structures 26 to 28, wherein the ratio a:d of the molar fraction a of the structural unit represented by General Formula (A1) to the molar fraction d of the structural unit represented by General Formula (D1) in the resin is 5:95 to 100:0.

[0057] [Structure 30] The resin according to Structure 28 or 29, wherein the ratio a:d of the molar fraction a of the structural unit represented by General Formula (A1) to the molar fraction d of the structural unit represented by General Formula (D1) in the resin is 10:90 to 50:50.

[0058] [Configuration 31] The resin according to any one of Configurations 26 to 30, wherein the structural unit represented by General Formula (A1) is represented by the following General Formula (A10):

[0059]

[0060] (In the general formula (A10), R １ , R ２ , R ３ , R ４ , n, m, p, q, and * are each R in the general formula (A1). １ , R ２ , R ３ , R ４ , n, m, p, q and *.)

[0061] [Configuration 32] The resin according to any one of Configurations 26 to 31, wherein n and m are 1.

[0062] [Configuration 33] The resin according to any one of Configurations 26 to 32, wherein the structural unit represented by General Formula (A1) is represented by the following General Formula (A11):

[0063]

[0064] (In the general formula (A11), R １ , R ２ , R ３ , R ４ , p, q, and * are each R in the general formula (A1). １ , R ２ , R ３ , R４ , p, q and *.)

[0065] [Configuration 34] The resin according to any one of Configurations 26 to 33, wherein p and q are 1.

[0066] [Configuration 35] The resin according to any one of Configurations 26 to 34, wherein the structural unit represented by General Formula (A1) is represented by the following General Formula (A12):

[0067]

[0068] (In the general formula (A12), R １ , R ２ , R ３ , R ４ and * respectively represent R in the general formula (A1). １ , R ２ , R ３ , R ４ and * are synonymous.)

[0069] [Configuration 36] The resin according to any one of Configurations 26 to 35, wherein the structural unit represented by General Formula (D1) is represented by the following General Formula (D2):

[0070]

[0071] (In the general formula (D2), R １５１ ~R １５８ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 18 carbon atoms, a substituted or unsubstituted cycloalkyl group having 6 to 20 ring carbon atoms, a substituted or unsubstituted cycloalkoxy group having 6 to 20 ring carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 14 ring carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 14 ring carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms, a substituted or unsubstituted aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxy group;１ is (i) a single bond, or (ii) a substituted or unsubstituted alkylene group having 1 to 28 carbon atoms, a substituted or unsubstituted alkylidene group having 2 to 28 carbon atoms, a substituted or unsubstituted cycloalkylene group having 5 to 15 ring carbon atoms, a substituted or unsubstituted cycloalkylidene group having 3 to 26 ring carbon atoms, a substituted or unsubstituted arylene group having 6 to 20 ring carbon atoms, -S-, -SO-, -SO ２ (iii) a divalent group formed by linking two or more groups selected from the group (ii), * represents a bond.

[0072] [Configuration 37] In the resin according to Configuration 36, X １ is a substituted or unsubstituted cycloalkylidene group having 5 to 15 ring carbon atoms.

[0073] [Configuration 38] In the resin according to Configuration 36 or 37, R １５１ ~R １５８ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, or a substituted or unsubstituted cycloalkyl group having 6 to 20 ring carbon atoms.

[0074] [Configuration 39] The resin according to any one of Configurations 26 to 35, wherein the structural unit represented by General Formula (D1) is represented by the following General Formula (D3):

[0075]

[0076] (In the general formula (D3), X ２ (i) is a single bond, or (ii) is a substituted or unsubstituted divalent organic group having 7 to 12 carbon atoms, and R １６１ ~R １６８ are each independently a hydrogen atom or a substituted or unsubstituted organic group having 1 to 10 carbon atoms, and * represents a bond.

[0077] [Configuration 40] The resin according to any one of Configurations 26 to 39, wherein the resin has a reduced viscosity of 0.80 dL / g or less, where the reduced viscosity is the reduced viscosity at 20°C of a solution containing the resin as a solute at a concentration of 0.5 g / dL in methylene chloride as a solvent.

[0078] [Configuration 41] The resin according to any one of Configurations 26 to 40, wherein the resin contains a repeating unit represented by the following general formula (PC-AB1) in which a structural unit represented by general formula (A1) and a structural unit represented by general formula (B1) are bonded together, and there is no chain between repeating units represented by general formula (PC-AB1) in the resin:

[0079]

[0080] (In the general formula (PC-AB1), R １ , R ２ , R ３ , R ４ , m, n, p, and q are each R in the general formula (A1). １ , R ２ , R ３ , R ４ , m, n, p, and q are synonymous with each other, and * represents a bond.

[0081] [Configuration 42] The resin according to any one of Configurations 26 to 38, wherein the resin is a polycarbonate resin.

[0082] [Configuration 43] The resin according to any one of Configurations 26 to 42, wherein the resin has a relative dielectric constant Dk of 2.70 or less.

[0083] [Configuration 44] The resin according to any one of Configurations 26 to 43, wherein the resin has a dielectric loss tangent Df of 0.00300 or less.

[0084] [Configuration 45] The resin according to any one of Configurations 26 to 44, wherein the viscosity average molecular weight Mv of the resin is 1,000 or more and 30,000 or less.

[0085] [Configuration 46] A coating composition comprising the resin according to any one of Configurations 26 to 45 and a non-halogenated solvent.

[0086] [Configuration 47] A film comprising the resin according to any one of Configurations 26 to 45.

[0087] [Configuration 48] A sheet comprising the resin according to any one of Configurations 26 to 45.

[0088] [Configuration 49] An electronic substrate comprising the resin according to any one of Configurations 26 to 45.

[0089] [Configuration 50] A method for producing the resin according to any one of Configurations 26 to 45, comprising a polymerization step of polymerizing the resin using a compound represented by the following general formula (MA1), wherein the polymerization step is carried out in the absence of the compound represented by the following general formula (MA1) and phosgene:

[0090]

[0091] (In the general formula (MA1), R １ , R ２ , R ３ , R ４ , m, n, p, and q are each R in the general formula (A1). １ , R ２ , R ３ , R ４ , m, n, p, and q.

[0092] According to one aspect of the present invention, it is possible to provide a resin and an electronic substrate material that have dielectric properties that allow them to be used as electronic substrate materials and that have excellent solubility in non-halogenated solvents. Also, according to another aspect of the present invention, it is possible to provide a coating composition, a film, a sheet, and an electronic substrate that contain the resin or the electronic substrate material, and to provide a method for producing the resin.

[0093] [First embodiment] [Resin] The resin according to this embodiment is at least one resin selected from the group consisting of polycarbonate, polyester, and polyester polycarbonate. Note that the resin according to this embodiment corresponds to the first resin in the electronic substrate material described below.

[0094] The resin according to this embodiment includes a structural unit represented by the following general formula (A1) and at least one structural unit selected from the group consisting of structural units represented by the following general formulas (B1), (C1), and (D1):

[0095]

[0096]

[0097] (In the general formula (A1), R １ and R ２ are each independently a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, n represents 1, 2, 3, or 4, and a plurality of R １ are the same or different from each other, m represents 1, 2, 3 or 4, and a plurality of R ２ are the same or different from each other, R ３ and R ４ are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 14 ring carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkoxy group having 3 to 20 ring carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 14 ring carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms, a substituted or unsubstituted aralkyloxy group having 7 to 20 carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 14 ring atoms, a halogen atom, a nitro group, an aldehyde group, a cyano group, or a carboxy group; p represents 0, 1, 2, or 3, and a plurality of R ３are the same or different from each other, q represents 0, 1, 2 or 3, and a plurality of R ４ are the same or different from each other, the sum of n and p is 1, 2, 3 or 4, the sum of m and q is 1, 2, 3 or 4, the structural unit represented by general formula (B1) is different from the carbonyl group in general formula (C1), in general formula (C1), Cx is a divalent group containing at least one group selected from the group consisting of a substituted or unsubstituted divalent aromatic hydrocarbon group, a substituted or unsubstituted divalent cyclic aliphatic hydrocarbon group, and a substituted or unsubstituted divalent chain aliphatic hydrocarbon group, in general formula (D1), Dx is a divalent group containing at least one group selected from the group consisting of a substituted or unsubstituted divalent aromatic hydrocarbon group, a substituted or unsubstituted divalent cyclic aliphatic hydrocarbon group, and a substituted or unsubstituted divalent chain aliphatic hydrocarbon group, the structural unit represented by general formula (A1) and the structural unit represented by general formula (D1) are different from each other, In the case of "substituted or unsubstituted", the substituents are bonded to each other to form a single ring, bonded to each other to form a fused ring, or not bonded to each other; * in the general formulas (A1), (B1), (C1), and (D1) represents a bond; when the resin contains a plurality of structural units represented by the general formula (A1), the plurality of structural units represented by the general formula (A1) are the same as or different from each other; when the resin contains a plurality of structural units represented by the general formula (C1), the plurality of structural units represented by the general formula (C1) are the same as or different from each other; and when the resin contains a plurality of structural units represented by the general formula (D1), the plurality of structural units represented by the general formula (D1) are the same as or different from each other.

[0098] The resin according to this embodiment contains the structural unit represented by the general formula (A1) above, and therefore has dielectric properties that allow it to be used as an electronic substrate material, and also has excellent solubility in non-halogen solvents.

[0099] In the resin according to this embodiment, the structural units represented by the general formula (A1) are not bonded to each other in succession, the structural units represented by the general formula (B1) are not bonded to each other in succession, the structural units represented by the general formula (C1) are not bonded to each other in succession, and the structural units represented by the general formula (D1) are not bonded to each other in succession.

[0100] One aspect of the resin according to this embodiment is a resin containing structural units represented by the general formulas (A1) and (B1).

[0101] One aspect of the resin according to this embodiment is a resin (polycarbonate resin or polyester polycarbonate resin) containing a repeating unit represented by the following general formula (PC-AB1) in which a structural unit represented by the general formula (A1) and a structural unit represented by the general formula (B1) are bonded together:

[0102]

[0103] (In the general formula (PC-AB1), R １ , R ２ , R ３ , R ４ , m, n, p, and q are each R in the general formula (A1). １ , R ２ , R ３ , R ４ , m, n, p, and q are synonymous with each other, and * represents a bond.

[0104] In one aspect of the resin according to this embodiment, the repeating units represented by the general formula (PC-AB1) may not be linked together in the resin.

[0105] In one aspect of the resin according to the present embodiment, the absence of a chain of repeating units represented by general formula (PC-AB1) means that the resin does not have a structure in which repeating units represented by general formula (PC-AB1) are directly bonded to each other, as shown in the following general formula (PC-AB12):

[0106]

[0107] (In the general formula (PC-AB12), R １ , R ２ , R ３, R ４ , m, n, p, and q are each R in the general formula (A1). １ , R ２ , R ３ , R ４ , m, n, p, and q are synonymous with each other, and * represents a bond.

[0108] Furthermore, one aspect of the resin according to this embodiment may be a resin (polycarbonate resin) containing only repeating units represented by general formula (PC-AB1) as repeating units. That is, in one aspect of the resin according to this embodiment, a chain of repeating units represented by general formula (PC-AB1) may be present in the resin.

[0109] One aspect of the resin according to this embodiment is a resin containing structural units represented by the general formulas (A1) and (C1).

[0110] One aspect of the resin according to this embodiment is a resin (polyester resin or polyester polycarbonate resin) containing a repeating unit represented by the following general formula (PE-AC1) in which a structural unit represented by the general formula (A1) and a structural unit represented by the general formula (C1) are bonded together:

[0111]

[0112] (In the general formula (PE-AC1), R １ , R ２ , R ３ , R ４ , m, n, p, and q are each R in the general formula (A1) or (C1). １ , R ２ , R ３ , R ４ , m, n, p, and q are defined the same as Cx in formula (C1), and * represents a bond.

[0113] In one aspect of the resin according to this embodiment, the structural unit represented by general formula (A1) is represented by the following general formula (A10).

[0114]

[0115] (In the general formula (A10), R １, R ２ , R ３ , R ４ , n, m, p, q, and * are each R in the general formula (A1). １ , R ２ , R ３ , R ４ , n, m, p, q and *.)

[0116] One aspect of the resin according to this embodiment is a resin (polycarbonate resin or polyester polycarbonate resin) containing a repeating unit represented by the following general formula (PC-AB101), in which a structural unit represented by the general formula (A10) and a structural unit represented by the general formula (B1) are bonded together:

[0117]

[0118] (In the general formula (PC-AB101), R １ , R ２ , R ３ , R ４ , m, n, p, and q are each R in the general formula (A1). １ , R ２ , R ３ , R ４ , m, n, p, and q are synonymous with each other, and * represents a bond.

[0119] One aspect of the resin according to this embodiment is a resin (polyester resin or polyester polycarbonate resin) containing a repeating unit represented by the following general formula (PE-AC101) in which a structural unit represented by the general formula (A10) and a structural unit represented by the general formula (C1) are bonded together:

[0120]

[0121] (In the general formula (PE-AC101), R １ , R ２ , R ３ , R ４ , m, n, p, and q are each R in the general formula (A1). １ , R ２ , R ３ , R ４, m, n, p, and q are defined the same as Cx in formula (C1), and * represents a bond.

[0122] In one aspect of the resin according to this embodiment, the structural unit represented by general formula (A1) is represented by the following general formula (A20).

[0123]

[0124] (In the general formula (A20), R １ , R ２ , R ３ , R ４ , n, m, p, q, and * are each R in the general formula (A1). １ , R ２ , R ３ , R ４ , n, m, p, q and *.)

[0125] In one aspect of the resin according to this embodiment, the structural unit represented by general formula (A1) is represented by the following general formula (A30).

[0126]

[0127] (In the general formula (A30), R １ , R ２ , R ３ , R ４ , n, m, p, q, and * are each R in the general formula (A1). １ , R ２ , R ３ , R ４ , n, m, p, q and *.)

[0128] In one aspect of the resin according to this embodiment, n and m are 1.

[0129] In one aspect of the resin according to this embodiment, the structural unit represented by general formula (A1) is represented by the following general formula (A11).

[0130]

[0131] (In the general formula (A11), R １ , R ２ , R ３ , R４ , p, q, and * are each R in the general formula (A1). １ , R ２ , R ３ , R ４ , p, q and *.)

[0132] One aspect of the resin according to this embodiment is a resin (polycarbonate resin or polyester polycarbonate resin) containing a repeating unit represented by the following general formula (PC-AB111), in which a structural unit represented by the general formula (A11) and a structural unit represented by the general formula (B1) are bonded together:

[0133]

[0134] (In the general formula (PC-AB111), R １ , R ２ , R ３ , R ４ , p and q are each R in the general formula (A1). １ , R ２ , R ３ , R ４ , p and q are synonymous, and * represents a bond.

[0135] One aspect of the resin according to this embodiment is a resin (polyester resin or polyester polycarbonate resin) containing a repeating unit represented by the following general formula (PE-AC111) in which a structural unit represented by the general formula (A11) and a structural unit represented by the general formula (C1) are bonded together:

[0136]

[0137] (In the general formula (PE-AC111), R １ , R ２ , R ３ , R ４ , p and q are each R in the general formula (A1). １ , R ２ , R ３ , R ４ , p, and q are defined the same as Cx in formula (C1), and * represents a bond.

[0138] In one aspect of the resin according to this embodiment, p and q are 1.

[0139] In one aspect of the resin according to this embodiment, the structural unit represented by general formula (A1) is represented by the following general formula (A12).

[0140]

[0141] (In the general formula (A12), R １ , R ２ , R ３ , R ４ and * respectively represent R in the general formula (A1). １ , R ２ , R ３ , R ４ and * are synonymous.)

[0142] One aspect of the resin according to this embodiment is a resin (polycarbonate resin or polyester polycarbonate resin) containing a repeating unit represented by the following general formula (PC-AB121) in which a structural unit represented by the general formula (A12) and a structural unit represented by the general formula (B1) are bonded together:

[0143]

[0144] (In the general formula (PC-AB121), R １ , R ２ , R ３ and R ４ are R in the general formula (A1), respectively. １ , R ２ , R ３ and R ４ and * represents a bond.)

[0145] One aspect of the resin according to this embodiment is a resin (polyester resin or polyester polycarbonate resin) containing a repeating unit represented by the following general formula (PE-AC121) in which a structural unit represented by the general formula (A12) and a structural unit represented by the general formula (C1) are bonded together:

[0146]

[0147] (In the general formula (PE-AC121), R１ , R ２ , R ３ and R ４ are R in the general formula (A1), respectively. １ , R ２ , R ３ and R ４ Cx has the same meaning as Cx in general formula (C1), and * represents a bond.

[0148] [Copolymer] The resin according to this embodiment may be a copolymer. The copolymer according to this embodiment is at least one copolymer selected from the group consisting of polycarbonate copolymers, polyester copolymers, and polyester-polycarbonate copolymers. One aspect of the copolymer according to this embodiment includes a structural unit represented by the general formula (A1) and at least one structural unit selected from the group consisting of structural units represented by the general formulas (B1), (C1), and (D1). One aspect of the copolymer according to this embodiment includes a structural unit represented by the general formula (A1) and a structural unit represented by (B1), and at least one structural unit selected from the group consisting of structural units represented by the general formulas (C1) and (D1). One aspect of the copolymer according to this embodiment includes a structural unit represented by the general formula (A1) and a structural unit represented by (C1), and at least one structural unit selected from the group consisting of structural units represented by the general formulas (B1) and (C1). When the copolymer according to this embodiment includes a plurality of structural units represented by the general formula (A1), the plurality of structural units represented by the general formula (A1) may be the same or different. When the copolymer according to this embodiment contains a plurality of structural units represented by the general formula (C1), the structural units represented by the general formula (C1) may be the same or different from each other. When the copolymer according to this embodiment contains a plurality of structural units represented by the general formula (D1), the structural units represented by the general formula (D1) may be the same or different from each other.

[0149] In the copolymer according to this embodiment, the repeating units are not necessarily consecutive. One aspect of the copolymer according to this embodiment is a block copolymer, an alternating copolymer, or a random copolymer.

[0150] The resin and copolymer according to one aspect of this embodiment are resins and copolymers containing structural units represented by the general formulae (A1), (B1), and (D1), respectively.

[0151] In one aspect of the copolymer according to this embodiment, the structural unit represented by the general formula (A1) is a structural unit represented by the general formula (A10), (A11), (A12), (A20), or (A30).

[0152] One aspect of the resin and copolymer according to this embodiment is a resin (polycarbonate resin or polyester polycarbonate resin) and copolymer, respectively, that include a repeating unit represented by the general formula (PC-AB1), (PC-AB101), (PC-AB111), or (PC-AB121) and a repeating unit represented by the following general formula (PC-DB1):

[0153]

[0154] (In the general formula (PC-DB1), Dx has the same meaning as Dx in the general formula (D1), and * represents a bond.)

[0155] One aspect of the resin and copolymer according to this embodiment is a resin (polycarbonate resin) containing only repeating units represented by general formula (PC-AB1) and repeating units represented by general formula (PC-DB1).

[0156] In one aspect of this embodiment, with respect to the repeating units in the resin or copolymer according to this embodiment, the total molar fraction a+d of the molar fraction a of the repeating units represented by general formula (PC-AB1) and the molar fraction d of the repeating units represented by general formula (PC-DB1) is 50 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, or 99 mol% or more, and the total molar fraction a+d is 100 mol% or less.

[0157] In one aspect of the resin and copolymer according to this embodiment, the repeating unit represented by the general formula (PC-AB1) is the repeating unit represented by the general formula (PC-AB101), (PC-AB111), or (PC-AB121).

[0158] In one aspect of the resin and copolymer according to this embodiment, the ratio a:d of the molar fraction a of the structural unit represented by general formula (A1) to the molar fraction d of the structural unit represented by general formula (D1) in the resin according to this embodiment or in the copolymer according to this embodiment is 5:95 to 100:0.

[0159] In one aspect of the resin and copolymer according to this embodiment, the ratio a:d of the molar fraction a of the structural unit represented by general formula (A1) to the molar fraction d of the structural unit represented by general formula (D1) in the resin according to this embodiment or in the copolymer according to this embodiment is 10:90 to 50:50.

[0160] In one aspect of the resin and copolymer according to this embodiment, the ratio a:d of the molar fraction a of the structural unit represented by general formula (A1) to the molar fraction d of the structural unit represented by general formula (D1) in the resin according to this embodiment or in the copolymer according to this embodiment is 28:72 to 50:50, 30:70 to 50:50, or 30:70 to 40:55.

[0161] The molar fraction of each structural unit or repeating unit in the resin and copolymer according to this embodiment is calculated by nuclear magnetic resonance (NMR) measurement. １ H NMR measurement is carried out, and the value is calculated from the peak integral value derived from each structural unit or repeating unit.

[0162] In one aspect of the resin and copolymer according to this embodiment, Dx is a group represented by the following general formula (D10).

[0163]

[0164] (In the general formula (D10), R １５１ ~R １５８ , and X １ are R in the following general formula (D2): １５１ ~R １５８ , and X１ and * represents a bond.)

[0165] In one aspect of the resin and copolymer according to this embodiment, the structural unit represented by general formula (D1) is represented by the following general formula (D2).

[0166]

[0167] (In the general formula (D2), R １５１ ~R １５８ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 18 carbon atoms, a substituted or unsubstituted cycloalkyl group having 6 to 20 ring carbon atoms, a substituted or unsubstituted cycloalkoxy group having 6 to 20 ring carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 14 ring carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 14 ring carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms, a substituted or unsubstituted aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxy group; １ is (i) a single bond, or (ii) a substituted or unsubstituted alkylene group having 1 to 28 carbon atoms, a substituted or unsubstituted alkylidene group having 2 to 28 carbon atoms, a substituted or unsubstituted cycloalkylene group having 5 to 15 ring carbon atoms, a substituted or unsubstituted cycloalkylidene group having 3 to 26 ring carbon atoms, a substituted or unsubstituted arylene group having 6 to 20 ring carbon atoms, -S-, -SO-, -SO ２ (iii) a divalent group formed by linking two or more groups selected from the group (ii), * represents a bond.

[0168] In one aspect of the resin and copolymer according to this embodiment, the structural unit represented by general formula (B1) is different from the carbonyl groups in the structural units represented by general formulas (A1), (C1), and (D1).

[0169] In one aspect of the resin and copolymer according to this embodiment, the repeating unit represented by the general formula (PC-DB1) is represented by the following general formula (PC-DB2).

[0170]

[0171] (In the general formula (PC-DB2), R １５１ ~R １５８ and X １ are R in the general formula (D2), respectively. １５１ ~R １５８ and X １ and * represents a bond.)

[0172] In one aspect of the resin and copolymer according to this embodiment, X １ represents a substituted or unsubstituted cycloalkylidene group having 5 to 15 ring carbon atoms.

[0173] In one aspect of the resin and copolymer according to this embodiment, Dx is a group represented by the following general formula (D11).

[0174]

[0175] (In the general formula (D11), R １５１ ~R １５８ are R in the general formula (D2), respectively. １５１ ~R １５８ e is 1, 2, 3, 4, 5, 6, 7 or 8; f is 2e+6; and a plurality of R ５are each independently selected from the group consisting of a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 18 carbon atoms, a substituted or unsubstituted cycloalkyl group having 6 to 20 ring carbon atoms, a substituted or unsubstituted cycloalkoxy group having 6 to 20 ring carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 14 ring carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 14 ring carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms, a substituted or unsubstituted aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxy group; and * represents a bond.

[0176] In one aspect of the resin and copolymer according to this embodiment, when e in the group represented by general formula (D11) is 1, the group represented by general formula (D11) is represented by the following general formula (D111); when e is 2, the group represented by general formula (D11) is represented by the following general formula (D112); when e is 3, the group represented by general formula (D113) is represented by the following general formula (D113); and when e is 8, the group represented by general formula (D11) is represented by the following general formula (D118).

[0177]

[0178]

[0179] (In the general formulae (D111), (D112), (D113) and (D118), R １５１ ~R １５８ are R in the general formula (D2), respectively. １５１ ~R １５８ and plural R ５ each independently represents R in general formula (D11). ５ and * represents a bond.)

[0180] In one aspect of the resin and copolymer according to this embodiment, the repeating unit represented by the general formula (PC-DB1) is represented by the following general formula (PC-DB11).

[0181]

[0182] (In the general formula (PC-DB11), R １５１ ~R １５８ are R in the general formula (D2), respectively. １５１ ~R １５８ is synonymous with R ５ , e and f are R in the general formula (D11), ５ , e and f, and * represents a bond.

[0183] In one aspect of the resin and copolymer according to this embodiment, the repeating unit represented by general formula (PC-DB1) is at least one repeating unit selected from the group consisting of repeating units represented by the following general formulae (PC-DB111), (PC-DB112), (PC-DB113), and (PC-DB118):

[0184]

[0185]

[0186]

[0187]

[0188] (In the general formulae (PC-DB111), (PC-DB112), (PC-DB113) and (PC-DB118), R １５１ ~R １５８ are R in the general formula (D2), respectively. １５１ ~R １５８ is synonymous with R ５ are R in the general formula (D11), respectively. ５ and * represents a bond.)

[0189] In one aspect of the resin and copolymer according to this embodiment, R １５１ ~R １５８are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, or a substituted or unsubstituted cycloalkyl group having 6 to 20 ring carbon atoms.

[0190] In one aspect of the resin and copolymer according to this embodiment, a plurality of R ５ are each independently a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms.

[0191] In one aspect of the resin and copolymer according to this embodiment, the structural unit represented by general formula (D1) is represented by the following general formula (D3).

[0192]

[0193] (In the general formula (D3), X ２ (i) is a single bond, or (ii) is a substituted or unsubstituted divalent organic group having 7 to 12 carbon atoms, and R １６１ ~R １６８ are each independently a hydrogen atom or a substituted or unsubstituted organic group having 1 to 10 carbon atoms, and * represents a bond.

[0194] In the resin and copolymer according to this embodiment, the divalent organic group having 7 to 12 carbon atoms is, for example, an octylidene group, a cyclooctylidene group, a cyclododecylidene group, a 3,3,5-trimethylcyclohexylidene group, etc. In the resin and copolymer according to this embodiment, the organic group having 1 to 10 carbon atoms is, for example, a methyl group, a butyl group, a propyl group, an isopropyl group, a cyclohexyl group, a phenyl group, etc.

[0195] In one aspect of the resin and copolymer according to this embodiment, the repeating unit represented by the general formula (PC-DB1) is represented by the following general formula (PC-DB3).

[0196]

[0197] (In the general formula (PC-DB3), R １６１ ~R １６８ and X ２ are R in the general formula (D3), respectively. １６１ ~R１６８ and X ２ and * represents a bond.)

[0198] One aspect of the resin and copolymer according to this embodiment is a resin (polycarbonate resin or polyester polycarbonate resin) and copolymer that does not contain a repeating unit represented by the following general formula (PC-DB101).

[0199]

[0200] One embodiment of the resin and copolymer according to this embodiment is a resin (polycarbonate resin or polyester polycarbonate resin) and copolymer that does not contain a repeating unit represented by the following general formula (PC-DB102).

[0201]

[0202] (In the general formulae (PC-DB101) and (PC-DB102), * represents a bond.)

[0203] One aspect of the resin and copolymer according to this embodiment is a resin (polyester resin or polyester polycarbonate resin) and copolymer containing a repeating unit represented by the following general formula (PE-DC1).

[0204]

[0205] (In the general formula (PE-DC1), Dx has the same meaning as Dx in the general formula (D1), Cx has the same meaning as Cx in the general formula (C1), and * represents a bond.)

[0206] In one aspect of the resin and copolymer according to this embodiment, Cx is a group containing at least one selected from the group consisting of groups represented by the following general formulas (C10), (C11), (C12), and (C13):

[0207]

[0208] (In the general formula (C10), R ２１１ ~R ２１８are each independently selected from the group consisting of a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 18 carbon atoms, a substituted or unsubstituted cycloalkyl group having 6 to 20 ring carbon atoms, a substituted or unsubstituted cycloalkoxy group having 6 to 20 ring carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 14 ring carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 14 ring carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms, a substituted or unsubstituted aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxy group; ３ is (i) a single bond, or (ii) a substituted or unsubstituted alkylene group having 1 to 28 carbon atoms, a substituted or unsubstituted alkylidene group having 2 to 28 carbon atoms, a substituted or unsubstituted cycloalkylene group having 5 to 15 ring carbon atoms, a substituted or unsubstituted cycloalkylidene group having 3 to 26 ring carbon atoms, a substituted or unsubstituted arylene group having 6 to 20 ring carbon atoms, -S-, -SO-, -SO ２ (iii) a divalent group formed by linking two or more groups selected from the group (ii), * represents a bond.

[0209]

[0210] (In the general formulae (C11), (C12) and (C13), R ３１ ~R ３４are each independently selected from the group consisting of a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 18 carbon atoms, a substituted or unsubstituted cycloalkyl group having 6 to 20 ring carbon atoms, a substituted or unsubstituted cycloalkoxy group having 6 to 20 ring carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 14 ring carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 14 ring carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms, a substituted or unsubstituted aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxy group; p is 4, q is 2, 3, or 4, r is 2, 3, or 4, and q+r is 6; s is 1, 2, 3, 4, 5, 6, 7 or 8, t is 2s+6, and a plurality of R ３１ are the same or different from each other, and a plurality of R ３２ are the same or different from each other, and a plurality of R ３３ are the same or different from each other, and a plurality of R ３４ are the same or different, and * represents a bond.

[0211] In one aspect of the resin and copolymer according to this embodiment, when s in the group represented by general formula (C13) is 1, the group represented by general formula (C13) is represented by the following general formula (C131); when s is 2, the group represented by general formula (C13) is represented by the following general formula (C132); when s is 3, the group represented by general formula (C13) is represented by the following general formula (C133); and when s is 8, the group represented by general formula (C13) is represented by the following general formula (C138).

[0212]

[0213] (In the general formulae (C131), (C132), (C133) and (C138), R ３４ represents R in the general formula (C13). ３４ is synonymous with

[0214] The resin and copolymer according to this embodiment may contain structural units other than the above-described structural units, such as a terminal structure derived from a terminal capping agent described below and a structural unit containing a silicon atom.

[0215] The resin according to one aspect of the present embodiment is a polycarbonate resin. The copolymer according to one aspect of the present embodiment is a polycarbonate copolymer.

[0216] (Reduced Viscosity) In one aspect of the resin and copolymer according to this embodiment, the reduced viscosity of the resin or copolymer is 0.80 dL / g or less. However, in this embodiment, the reduced viscosity of the resin or copolymer is the reduced viscosity of a solution of methylene chloride as a solvent and the resin or copolymer as a solute at a concentration of 0.5 g / dL at a temperature of 20°C. In one aspect of the resin and copolymer according to this embodiment, the reduced viscosity of the resin or copolymer is 0.75 dL / g or less, or 0.70 dL / g or less. In one aspect of the resin and copolymer according to this embodiment, the reduced viscosity of the resin or copolymer is 0.30 dL / g or more, or 0.35 dL / g or more.

[0217] (Dielectric Properties) There are various methods for evaluating dielectric properties. One commonly used method is the cavity resonator perturbation method (hereinafter referred to as the cavity resonance method), which uses an electric field along the sample to evaluate dielectric properties. However, the electric field at both ends of the sample is deflected outside the sample. Because no known quantitative explanation for this imperfection has been established, it is common to calculate the dielectric constant assuming that the electric field passes through the entire sample. Therefore, even though the electric field is not applied at both ends of the sample, the dielectric constant is measured as low because the dielectric properties are calculated assuming that the electric field is applied throughout the sample. On the other hand, the split cylinder resonator perturbation method (hereinafter referred to as the split cylinder method), which uses a circular electric field along the sample surface, does not produce errors due to the deflection of the electric field at both ends of the sample, which occurs in the cavity resonance method. Therefore, the split cylinder method outputs dielectric properties closer to the true value than the cavity resonance method.

[0218] The dielectric constant Dk of the resin and copolymer according to one aspect of this embodiment is preferably 2.80 or less, more preferably 2.75 or less, more preferably 2.70 or less, even more preferably 2.65 or less, even more preferably 2.60 or less, and even more preferably 2.50 or less. In this specification, the dielectric constant Dk of the resin and copolymer is a value measured at room temperature (23°C) and a frequency of 10 GHz using a split cylinder resonator.

[0219] Furthermore, the dielectric loss tangent Df of the resin and copolymer according to one aspect of this embodiment is preferably 0.02000 or less, preferably 0.00700 or less, preferably 0.00500 or less, preferably 0.00350 or less, more preferably 0.00300 or less, even more preferably 0.00250 or less, even more preferably 0.00200 or less, and even more preferably 0.00140 or less. In this specification, the dielectric loss tangent Df of the resin and copolymer is a value measured at room temperature (23°C) and a frequency of 10 GHz using a split cylinder resonator. When the relative permittivity Dk and dielectric loss tangent Df of the resin and copolymer according to this embodiment are below the upper limit of the above range, the loss of electrical signals in the electronic board can be reduced when the resin and copolymer according to this embodiment are used as an electronic board material.

[0220] (Viscosity Average Molecular Weight) From the viewpoint of solution viscosity, the viscosity average molecular weight Mv of the resin and copolymer according to one aspect of this embodiment is preferably 500 or more and 100,000 or less, more preferably 1,000 or more and 80,000 or less, even more preferably 1,000 or more and 70,000 or less, and even more preferably 1,000 or more and 30,000 or less. In this specification, the viscosity average molecular weight Mv is calculated by dissolving the resin or copolymer in methylene chloride as a solvent to prepare a solution, measuring the intrinsic viscosity [η] of this solution at 20°C using an Ubbelohde viscometer, and then calculating it using the following Schnell formula: [η] = 1.23 × 10 －５ Mv ０．８３

[0221] (Thermal Expansion Coefficient) Since the resin and copolymer according to this embodiment preferably have a low thermal expansion coefficient, the thermal expansion coefficient of the resin and copolymer according to one aspect of this embodiment at temperatures from 40° C. to 100° C. is preferably 150 [ppm / K] or less, more preferably 120 [ppm / K] or less, more preferably 115 [ppm / K] or less, even more preferably 100 [ppm / K] or less, even more preferably 90 [ppm / K] or less, and even more preferably 80 [ppm / K] or less. The thermal expansion coefficient can be measured by the method described in the Examples section.

[0222] (Glass Transition Temperature (Tg)) The resin and copolymer according to this embodiment preferably have a glass transition temperature (Tg) of 80° C. or higher, more preferably 100° C. or higher, even more preferably 120° C. or higher, even more preferably 150° C. or higher, and even more preferably 170° C. or higher. The glass transition temperature can be measured by the method described in the Examples section.

[0223] (Explanation of Substituents, etc.) In the resin and copolymer according to this embodiment, examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0224] In the resins and copolymers according to this embodiment, examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, butyl, sec-butyl, tert-butyl, various pentyl groups, and various hexyl groups. In this specification, when the term "various" is added to the name of a substituent, this term includes linear and branched groups, and the same applies hereinafter. In the resins and copolymers according to this embodiment, examples of the substituted alkyl group include trifluoromethyl. In the resins and copolymers according to this embodiment, the number of carbon atoms in the alkyl group is preferably, for example, 1 to 28, 1 to 20, 1 to 18, 1 to 10, or 1 to 5.

[0225] In this specification, a numerical range expressed using "AA to BB" means a range that includes the number AA written before "AA to BB" as the lower limit and the number BB written after "AA to BB" as the upper limit.

[0226] In the resin and copolymer according to this embodiment, examples of the alkylene group include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, and a hexamethylene group. In the resin and copolymer according to this embodiment, the number of carbon atoms in the alkylene group is preferably, for example, 1 to 28, 1 to 20, 1 to 18, 1 to 10, or 1 to 5.

[0227] In the resin and copolymer according to this embodiment, examples of the alkylidene group include an ethylidene group and an isopropylidene group. In the resin and copolymer according to this embodiment, the alkylidene group preferably has 2 to 28, 2 to 20, 2 to 18, 2 to 10, or 2 to 5 carbon atoms.

[0228] In the resin and copolymer according to this embodiment, examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, various pentyloxy groups, various hexyloxy groups, etc. In the resin and copolymer according to this embodiment, the number of carbon atoms in the alkoxy group is, for example, 1 to 20, 1 to 18, 1 to 10, or 1 to 5.

[0229] In the resin and copolymer according to this embodiment, examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, an adamantyl group, and a norbornyl group. In the resin and copolymer according to this embodiment, the number of ring carbon atoms of the cycloalkyl group is preferably, for example, 3 to 26, 3 to 20, or 6 to 20.

[0230] In the resin and copolymer according to this embodiment, examples of the cycloalkylene group include a cyclopentanediyl group, a cyclohexanediyl group, and a cyclooctanediyl group. In the resin and copolymer according to this embodiment, the number of ring carbon atoms of the cycloalkylene group is, for example, preferably 5 to 15, or 5 to 10.

[0231] In the resin and copolymer according to this embodiment, examples of the cycloalkylidene group include a cyclohexylidene group, a 3,5,5-trimethylcyclohexylidene group, and a 2-adamantylidene group. In the resin and copolymer according to this embodiment, the number of ring carbon atoms of the cycloalkylidene group is preferably, for example, 3 to 26, 5 to 15, or 5 to 10.

[0232] In the resin and copolymer according to this embodiment, the cycloalkoxy group may be, for example, a group in which the cycloalkyl group moiety is the cycloalkyl group described above, i.e., a group in which Arx is the cycloalkyl group described above. In the resin and copolymer according to this embodiment, the cycloalkoxy group preferably has 3 to 20 ring carbon atoms, or 6 to 20 ring carbon atoms.

[0233] In the resin and copolymer according to this embodiment, examples of the alkenyl group include ethenyl (vinyl), 1-propenyl, 2-propenyl (allyl), butenyl, pentenyl, and hexenyl groups. In the resin and copolymer according to this embodiment, the alkenyl group preferably has, for example, 2 to 10 carbon atoms, or 2 to 6 carbon atoms.

[0234] In the resin and copolymer according to this embodiment, examples of the alkynyl group include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 1-butynyl group, and a 3-hexynyl group. In the resin and copolymer according to this embodiment, the number of carbon atoms in the alkynyl group is preferably, for example, 2 to 10, or 2 to 6.

[0235] In the resin and copolymer according to this embodiment, examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, an anthryl group, and a phenanthryl group. In the resin and copolymer according to this embodiment, examples of the substituted aryl group include a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 4-ethylphenyl group, a dichlorophenyl group, and a methylnaphthyl group. In the resin and copolymer according to this embodiment, the number of ring carbon atoms of the aryl group is preferably, for example, 6 to 20, 6 to 14, or 6 to 10.

[0236] In the resin and copolymer according to this embodiment, examples of the arylene group include a phenylene group, a naphthylene group, an anthracenediyl group, a biphenylene group, and a terphenyldiyl group. In one aspect of the resin and copolymer according to this embodiment, the number of ring carbon atoms of the arylene group is preferably, for example, 6 to 20, 6 to 14, or 6 to 10.

[0237] In the resin and copolymer according to this embodiment, examples of the aryloxy group include a phenoxy group and a naphthyloxy group. In the resin and copolymer according to this embodiment, examples of the substituted aryloxy group include a tolyloxy group. In the resin and copolymer according to this embodiment, the number of ring carbon atoms of the aryloxy group is preferably, for example, 6 to 14, or 6 to 10.

[0238] In the resin and copolymer according to this embodiment, examples of the aralkyl group include a phenylmethyl group and a phenylethyl group. In the resin and copolymer according to this embodiment, the number of carbon atoms in the aralkyl group is preferably, for example, 7 to 20, or 7 to 15.

[0239] In the resin and copolymer according to this embodiment, the aralkyloxy group may be, for example, an aralkyl group moiety, i.e., an aralkyl group in the group represented by -O-Ary, where Ary is the aralkyl group. In the resin and copolymer according to this embodiment, the number of carbon atoms in the aralkyloxy group is preferably, for example, 7 to 20 or 7 to 15.

[0240] In the resin and copolymer according to this embodiment, the heteroaryl group contains at least one heteroatom as a ring-forming atom. For example, the heteroaryl group may contain one, two, or three heteroatoms as ring-forming atoms. The heteroatoms contained in the heteroaryl group as ring-forming atoms are one or more atoms selected from the group consisting of nitrogen, oxygen, sulfur, silicon, phosphorus, and boron atoms. When the heteroaryl group contains multiple heteroatoms as ring-forming atoms, the multiple heteroatoms may be the same or different. In the resin and copolymer according to this embodiment, examples of the heteroaryl group include pyrrolyl, imidazolyl, furyl, thienyl, pyridinyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, indolyl, benzofuranyl, benzothienyl, quinolyl, isoquinolyl, phenanthrolinyl, and acridinyl groups. In the resin and copolymer according to this embodiment, the heteroaryl group preferably has 5 to 20, 5 to 14, or 5 to 10 ring atoms.

[0241] In the resin and copolymer according to this embodiment, examples of the monovalent aromatic hydrocarbon group include the aryl group. In the resin and copolymer according to this embodiment, examples of the divalent aromatic hydrocarbon group include a divalent group derived by removing one hydrogen atom from the aryl ring of the aryl group.

[0242] In the resins and copolymers according to this embodiment, examples of the monovalent alicyclic hydrocarbon group include saturated or unsaturated alicyclic groups. The alicyclic group has, for example, 3 to 20 carbon atoms, preferably 3 to 12 carbon atoms, and more preferably 4 to 8 carbon atoms. Specific examples of saturated or unsaturated alicyclic groups include cycloalkyl groups, which are saturated alicyclic groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, and norbornyl, and cycloalkenyl groups, which are unsaturated alicyclic groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, and cycloheptenyl. Note that unsaturated alicyclic groups do not contain aromatic groups. In the resins and copolymers according to this embodiment, examples of the divalent alicyclic hydrocarbon group include divalent groups derived by removing one hydrogen atom from the ring of the saturated or unsaturated alicyclic group.

[0243] In the resin and copolymer according to this embodiment, examples of the monovalent chain aliphatic hydrocarbon group include the alkyl groups described above.

[0244] In the resin and copolymer according to this embodiment, the divalent chain aliphatic hydrocarbon group is, for example, a divalent group derived by removing one hydrogen atom from the alkyl chain of the alkyl group.

[0245] In the resin and copolymer according to this embodiment, the chain aliphatic hydrocarbon group includes a straight-chain aliphatic hydrocarbon group and a branched-chain aliphatic hydrocarbon group.

[0246] In this specification, when referring to "substituted or unsubstituted," the substituents may bond to each other to form a monocycle, a fused ring, or not bond to each other. Here, when referring to "substituted or unsubstituted," the substituents may bond to each other to form a monocycle or a fused ring, and this also includes cases where the substituents bond to each other to form a multi-membered ring. This multi-membered ring is preferably a two-membered ring (bicyclo), a three-membered ring (tricyclo), or a four-membered ring (tetracyclo). For example, when referring to a "substituted or unsubstituted" group (a cycloalkyl group, a cycloalkylene group, a cycloalkylidene group) derived from a cycloalkane, examples of when the substituents bond to each other to form a multi-membered ring include monovalent or divalent groups derived from a bicycloalkane, a tricycloalkane, and a tetracycloalkane.

[0247] In this specification, the substituents in the "substituted" part of "substituted or unsubstituted" are preferably at least one substituent selected from the group consisting of an alkyl group, a cycloalkyl group, an alkoxy group, an aryl group, an aryloxy group, and a halogen atom, each independently. Specific examples of these substituents include the same groups as the specific examples described above. Furthermore, in this specification, "unsubstituted" in the "substituted or unsubstituted" part means that the group is not substituted with the substituent and is bonded to a hydrogen atom.

[0248] In the present specification, in specific examples of compounds, D may represent a deuterium atom, Me may represent a methyl group, Ph may represent a phenyl group, and tBu may represent a tert-butyl group.

[0249] In this specification, the preferred provisions can be adopted arbitrarily, and it can be said that a combination of preferred provisions is more preferred.

[0250] [Method for Producing Resin and Copolymer] (Dihydric Phenol Compound) The resin and copolymer according to this embodiment can be suitably produced using a dihydric phenol compound (ma) represented by the following general formula (MA1). The structural unit represented by the general formula (A1) is derived from the dihydric phenol compound (ma). Therefore, this embodiment also provides the use of the dihydric phenol compound (ma) represented by the following general formula (MA1) for producing the resin and copolymer according to this embodiment.

[0251]

[0252] (In the general formula (MA1), R １ , R ２ , R ３ , R ４ , m, n, p, and q are each R in the general formula (A1). １ , R ２ , R ３ , R ４ , m, n, p, and q.

[0253] The resin and copolymer production methods according to this embodiment (resin production method and copolymer production method) preferably include a polymerization step of polymerizing the resin or copolymer using the compound represented by general formula (MA1). In the resin and copolymer production methods according to this embodiment, the polymerization step is preferably carried out in the absence of the compound represented by general formula (MA1) and phosgene.

[0254] In one aspect of the method for producing a resin and the method for producing a copolymer according to this embodiment, the dihydric phenol compound (ma) represented by the general formula (MA1) is at least one selected from the group consisting of dihydric phenol compounds represented by the following general formulas (MA10), (MA20), and (MA30):

[0255]

[0256]

[0257]

[0258] (In the general formulae (MA10), (MA20) and (MA30), R １ , R ２ , R ３ , R ４ , n, m, p, and q are each R in the general formula (A1). １ , R ２ , R ３ , R ４ , n, m, p, and q.

[0259] In one aspect of the resin production method and copolymer production method according to this embodiment, the dihydric phenol compound (ma) represented by the general formula (MA1) is represented by the following general formula (MA11).

[0260]

[0261] (In the general formula (MA11), R １ , R ２ , R ３ , R ４ , p and q are each R in the general formula (A1). １ , R ２ , R ３ , R ４ , p and q are synonymous.)

[0262] In one aspect of the resin production method and copolymer production method according to this embodiment, the dihydric phenol compound (ma) represented by the general formula (MA1) is represented by the following general formula (MA12).

[0263]

[0264] (In the general formula (MA12), R １ , R ２ , R ３ and R ４ are R in the general formula (A1), respectively. １ , R ２ , R ３ and R ４ is synonymous with

[0265] [Methods for producing polycarbonate resins and polycarbonate copolymers] Resins and copolymers containing the structural unit represented by general formula (A1) as a polycarbonate-based repeating unit (repeating unit represented by general formula (PC-AB1)) can be produced by a known method for producing a polycarbonate resin, for example, using a dihydric phenol compound (ma) represented by general formula (MA1) as the dihydric phenol compound. Examples of methods for producing polycarbonate resins and polycarbonate copolymers include the following production methods (P1-1), (P1-2), and (P1-3).

[0266] <Production Method (P1-1)> The production method (P1-1) is an interfacial polymerization method (phosgene method) in which a dihydric phenol compound and phosgene are reacted in the presence of an organic solvent inert to the reaction and an aqueous alkaline solution, and then a polymerization catalyst such as a tertiary amine or a quaternary ammonium salt is added to carry out polymerization.

[0267] <Production Method (P1-2)> Production method (P1-2) is a melt polymerization method (transesterification method) in which a dihydric phenol compound and a carbonic acid diester are subjected to a transesterification reaction in a molten state without using a solvent by adding a basic catalyst.

[0268] <Production Method (P1-3)> Production method (P1-3) is a pyridine method in which a dihydric phenol compound is dissolved in pyridine or a mixed solution of pyridine and an inert solvent, and phosgene is introduced to directly produce the compound.

[0269] In the above reaction, at least one additive selected from the group consisting of a molecular weight regulator (terminal terminator) and a branching agent may be used as needed.

[0270] The following production method (P1-4) is preferred as a production method for the polycarbonate resin and polycarbonate copolymer according to this embodiment. <Production Method (P1-4)> Production method (P1-4) is a production method for an aromatic polycarbonate resin, which includes a step of interfacially polycondensing a dihydric phenol compound and a polycarbonate oligomer in the presence of a water-insoluble organic solvent and an aqueous alkaline compound solution, wherein the dihydric phenol compound includes a dihydric phenol compound (ma) represented by general formula (MA1).

[0271] Specifically, in the case of the interfacial polymerization method of the above-mentioned production methods (P1-1) or (P1-4), the polycarbonate resin and polycarbonate copolymer according to this embodiment can be produced by dissolving a pre-produced polycarbonate oligomer described below in a water-insoluble organic solvent (e.g., methylene chloride), adding an alkaline compound aqueous solution of a dihydric phenol compound (e.g., sodium hydroxide aqueous solution), and using a tertiary amine (e.g., triethylamine) or a quaternary ammonium salt (e.g., trimethylbenzylammonium chloride) as a polymerization catalyst, and optionally in the presence of a terminal terminator (a monohydric phenol such as p-tert-butylphenol). Furthermore, in the case of the above-mentioned interfacial polymerization method, the polycarbonate resin and polycarbonate copolymer according to this embodiment can be produced by copolymerizing a dihydric phenol with phosgene, a carbonate ester, or a chloroformate.

[0272] Polycarbonate oligomers can be produced by reacting a dihydric phenol compound with a carbonate precursor (e.g., phosgene, triphosgene, etc.) in an organic solvent such as methylene chloride, chlorobenzene, chloroform, etc. When producing a polycarbonate oligomer using the transesterification method, it can also be produced by reacting a dihydric phenol compound with a carbonate precursor such as diphenyl carbonate.

[0273] In the method for producing a polycarbonate resin and a polycarbonate-based copolymer according to this embodiment, the dihydric phenol includes a dihydric phenol compound (ma) represented by the general formula (MA1) from which the structural unit represented by the general formula (A1) is derived. In one aspect of the method for producing a polycarbonate resin and a polycarbonate-based copolymer according to this embodiment, the dihydric phenol further includes a dihydric phenol compound (md) represented by the following general formula (MD1) from which the structural unit represented by the general formula (D1) is derived. The dihydric phenol compound (md) is a compound different from the dihydric phenol compound (ma).

[0274]

[0275] (In the general formula (MD1), Dx has the same meaning as Dx in the general formula (D1).)

[0276] In one aspect of the method for producing a polycarbonate resin and a polycarbonate-based copolymer according to this embodiment, Dx is a group represented by general formula (D11).

[0277] In one aspect of the method for producing a polycarbonate resin and a polycarbonate-based copolymer according to this embodiment, Dx is a group represented by general formula (D111), (D112), (D113), or (D118).

[0278] In one aspect of the method for producing the polycarbonate resin and polycarbonate copolymer according to this embodiment, it is preferable to use, as the dihydric phenol compound (md), at least one selected from the group consisting of dihydric phenol compounds represented by the following general formulas (MD111), (MD112), (MD113), and (MD118).

[0279]

[0280]

[0281] (In the general formulae (MD111), (MD112), (MD113) and (MD118), R １５１ ~R １５８ are R in the general formula (D2), respectively. １５１ ~R１５８ and plural R ５ each independently represents R in general formula (D11). ５ is synonymous with

[0282] Examples of the dihydric phenol compound (md) include bis(hydroxyphenyl)alkane dihydric phenols, bis(hydroxyphenyl)cycloalkane dihydric phenols, dihydroxybiphenyl compounds, dihydroxybenzene compounds, dihydroxynaphthalene compounds, bis(4-hydroxyphenyl)oxide, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxy-3-methylphenyl)sulfide, bis(4-hydroxyphenyl)ether, bis(3-fluoro-4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxy-3-methylphenyl)sulfone, bis(4-hydroxyphenyl)sulfoxide, and 4,4'-dihydroxybenzophenone.

[0283] Examples of bis(hydroxyphenyl)alkane dihydric phenols include bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3-methylphenyl)methane, 1,1-bis(4-hydroxyphenyl)-1,1-diphenylmethane, 1,1-bis(2-tert-butyl-4-hydroxy-5-methylphenyl)-1-phenylmethane, 1,1-bis(4-hydroxyphenyl)-1-phenylmethane, bis(3-chloro-4-hydroxyphenyl)methane, bis(3,5-dibromo-4-hydroxyphenyl)methane, 1 , 1-bis(4-hydroxyphenyl)ethane, 1,2-bis(4-hydroxyphenyl)ethane, 2-(4-hydroxy-3-methylphenyl)-2-(4-hydroxyphenyl)-1-phenylethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,1-bis(2-tert-butyl-4-hydroxy-3-methylphenyl)ethane, 1-phenyl-1,1-bis(3-fluoro-4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane [bisphenol A (BPA)], 2,2- Bis(4-hydroxy-3,5-dimethylphenyl)propane, 1,1-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 1,1-bis(4-hydroxy-3-phenylphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-2-methylphenyl)propane, 1,1-bis(2-tert-butyl-4-hydroxy-5-methylphenyl)propane, 2,2-bis(3-chloro-4-hydroxyphenyl)propane, 2,2-bis(3-fluoro-4-hydroxyphenyl)propane 2,2-bis(3-bromo-4-hydroxyphenyl)propane, 2,2-bis(3,5-difluoro-4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, 2,2-bis(3-bromo-4-hydroxy-5-chlorophenyl)propane, 2,2-bis(3-hydroxyphenyl)hexafluoropropane, 2,2-bis(3-phenyl-4-hydroxyphenyl)propane, 1,Examples of such hydroxyphenyl esters include 1-bis(2-butyl-4-hydroxy-5-methylphenyl)butane, 1,1-bis(2-tert-butyl-4-hydroxy-5-methylphenyl)butane, 1,1-bis(2-tert-butyl-4-hydroxy-5-methylphenyl)isobutane, 1,1-bis(2-tert-amyl-4-hydroxy-5-methylphenyl)butane, 2,2-bis(4-hydroxy-3-methylphenyl)butane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)butane, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, 4,4-bis(4-hydroxyphenyl)heptane, and 1,1-bis(2-tert-butyl-4-hydroxy-5-methylphenyl)heptane.

[0284] Examples of bis(hydroxyphenyl)cycloalkane dihydric phenols include 1,1-bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-hydroxy-3,5-dimethylphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(3-cyclohexyl-4-hydroxyphenyl)cyclohexane, 1,1-bis(3-phenyl-4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxy-3-phenylphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)cyclododecane, 1,1-bis(4-hydroxy-3-methylphenyl)cyclododecane, and 1,1-bis(4-hydroxy-3,5-dimethylphenyl)cyclododecane.

[0285] Examples of dihydroxybiphenyl compounds include 4,4'-dihydroxybiphenyl, 3,3'-difluoro-4,4'-dihydroxybiphenyl, 4,4'-dihydroxy-3,3'-dimethylbiphenyl, 4,4'-dihydroxy-2,2'-dimethylbiphenyl, 4,4'-dihydroxy-2,2',5,5'-dimethylbiphenyl, and 4,4'-dihydroxy-3,3'-dicyclohexylbiphenyl.

[0286] Examples of dihydroxybenzene compounds include hydroquinone, resorcinol, and catechol.

[0287] Examples of dihydroxynaphthalene compounds include 2,6-dihydroxynaphthalene and 1,4-dihydroxynaphthalene. These dihydric phenol compounds (md) may be used alone or in combination of two or more.

[0288] In one aspect of the method for producing the polycarbonate resin and copolymer according to the present embodiment, the dihydric phenol compound (md) alone can be used as the dihydric phenol compound for producing the polycarbonate oligomer. In this case, in the interfacial polycondensation reaction step, the dihydric phenol compound (ma) and the dihydric phenol compound (md) may be used in combination, or the dihydric phenol compound (ma) alone may be used.

[0289] In order to adjust the molecular weight of the polycarbonate resin and copolymer according to this embodiment, a terminal terminator (molecular weight regulator) can be used. Examples of terminal terminators include monohydric phenols such as phenol, p-cresol, p-tert-butylphenol, p-tert-octylphenol, p-cumylphenol, p-nonylphenol, m-pentadecylphenol, and p-tert-amylphenol. These monohydric phenols may be used alone or in combination of two or more.

[0290] [Method for producing polyester resin and polyester copolymer] Resins and copolymers containing the structural unit represented by the general formula (A1) as a polyester-based repeating unit (structural unit represented by the general formula (PE-AC1)) can be produced by a known method for producing polyester resins, for example, using a dihydric phenol compound (ma) represented by the general formula (MA1) as the dihydric phenol compound. Examples of methods for producing polyester resins include a method of condensation polymerization of a bisphenol for constituting a bisphenol-derived repeating unit and a dicarboxylic acid for constituting a dicarboxylic acid-derived repeating unit. Examples of condensation polymerization methods include solution polymerization, melt polymerization, and interfacial polymerization.

[0291] In one aspect of the method for producing the polyester resin and copolymer according to this embodiment, at least one dihydric phenol compound (ma) selected from the group consisting of dihydric phenol compounds (ma) represented by the general formulas (MA1), (MA10), (MA11), (MA12), (MA20), and (MA30) can be used as a bisphenol for constituting the bisphenol-derived repeating units. Furthermore, in one aspect of the method for producing the polyester resin and copolymer according to this embodiment, in addition to the dihydric phenol compound (ma), a dihydric phenol compound (md) represented by the general formula (MD1) can also be used as a bisphenol for constituting the bisphenol-derived repeating units.

[0292] In one aspect of the method for producing the polyester resin and copolymer according to this embodiment, a dicarboxylic acid compound (mc) represented by the following general formula (MC1) can be used as the dicarboxylic acid for constituting the dicarboxylic acid-derived repeating unit.

[0293]

[0294] (In the general formula (MC1), Cx has the same meaning as Cx in the general formula (C1).)

[0295] In one aspect of the method for producing the polyester resin and copolymer according to this embodiment, Cx is a group represented by general formula (C10), (C11), (C12), or (C13).

[0296] In one aspect of the method for producing the polyester resin and copolymer according to the present embodiment, it is preferable to use, as the dicarboxylic acid compound (mc), at least one selected from the group consisting of dicarboxylic acid compounds represented by the following general formulas (MC10), (MC11), (MC12), and (MC13).

[0297]

[0298]

[0299] (In the general formula (MC10), R ２１１ ~R ２１８ and X ３ are R in the general formula (C10), respectively. ２１１ ~R ２１８ and X ３ In the general formula (MC11), R ３１ and p are each R in the general formula (C11). ３１ and p, and in formula (MC12), R ３２ , R ３３ , q and r are each R in the general formula (C12). ３２ , R ３３ , q and r are the same as those defined above, and in general formula (MC13), R ３４ , t and s are each R in the general formula (C13). ３４ , t and s are synonymous.)

[0300] In one aspect of the method for producing the polyester resin and copolymer according to this embodiment, the bisphenol may be derivatized to an aromatic diacetate before use. In one aspect of the method for producing the polyester resin and copolymer according to this embodiment, the dicarboxylic acid compound (mc) may be derivatized before use. Examples of derivatives of the dicarboxylic acid compound (mc) include dicarboxylic acid dichloride, dicarboxylic acid dimethyl ester, dicarboxylic acid diethyl ester, and dicarboxylic acid anhydride. Dicarboxylic acid dichloride is a compound in which two "-C(=O)-OH" groups in a dicarboxylic acid are replaced with "-C(=O)-Cl" groups. For example, the dichloride of the dicarboxylic acid compound (ma) represented by the general formula (MC1) is represented by the following general formula (MC1-CL):

[0301]

[0302] (In the general formula (MC1-CL), Cx has the same meaning as Cx in the general formula (C1).)

[0303] In one aspect of the method for producing the polyester resin and copolymer according to the present embodiment, a terminal terminator may be added during the condensation polymerization reaction of the bisphenol and the dicarboxylic acid. Examples of the terminal terminator include p-tert-butylphenol, 2,6-dimethylphenol, and 1H,1H-perfluoro-1-heptanol.

[0304] In one aspect of the method for producing the polyester resin and copolymer according to the present embodiment, a base and / or a catalyst may be added during the condensation polymerization reaction of the bisphenol and the dicarboxylic acid. Examples of the base include sodium hydroxide. Examples of the catalyst include benzyltributylammonium chloride, ammonium chloride, ammonium bromide, quaternary ammonium salts, triethylamine, and trimethylamine.

[0305] [Method for producing polyester polycarbonate resin and polyester polycarbonate copolymer] A resin and copolymer containing a polyester repeating unit as well as the structural unit represented by the general formula (A1) as a polycarbonate repeating unit (structural unit represented by the general formula (PC-AB1)) can be produced by a known method for producing a polyester polycarbonate resin, for example, using a dihydric phenol compound (ma) represented by the general formula (MA1) as the dihydric phenol compound.

[0306] Furthermore, resins and copolymers containing the structural unit represented by the general formula (A1) as a polyester-based repeating unit (structural unit represented by the general formula (PE-AC1)) and also containing a polycarbonate-based repeating unit can be produced, for example, by a known method for producing a polyester polycarbonate resin using a dihydric phenol-based compound (ma) represented by the general formula (MA1) as a dihydric phenol-based compound.

[0307] The polyester polycarbonate resin and copolymer according to one aspect of this embodiment can be produced using a dihydric phenol compound (ma) represented by the general formula (MA1) and a dicarboxylic acid compound (mc) represented by the general formula (MC1). One example of a method for producing the polyester polycarbonate resin and copolymer is a method of condensation polymerization of a bisphenol for forming a bisphenol-derived repeating unit, a dicarboxylic acid for forming a dicarboxylic acid-derived repeating unit, and a compound for forming a carbonate-derived repeating unit. The polyester polycarbonate resin and copolymer according to one aspect of this embodiment can be produced in the presence of at least one additive selected from the group consisting of an acid binder, a catalyst, a molecular weight modifier such as a terminal capping agent or a branching agent, and a solvent, as needed. Examples of methods for producing the polyester polycarbonate resin and copolymer according to this embodiment include a melt polymerization method in which bisphenol, dicarboxylic acid, and diphenyl carbonate are subjected to a transesterification reaction in the presence of a non-solvent and a basic catalyst, and an interfacial polymerization method in which bisphenol, dicarboxylic acid, and phosgene are reacted in the presence of an organic solvent inert to the reaction and an aqueous basic solution, and then a polymerization catalyst such as a tertiary amine or a quaternary ammonium salt is added to carry out polymerization. In particular, a method similar to production method (P1-4), in which bisphenol, dicarboxylic acid chloride, and a polycarbonate oligomer are subjected to interfacial polycondensation in the presence of a water-insoluble organic solvent and an aqueous basic compound solution, is preferred because it is simple, does not cause side reactions, and allows for easy molecular weight control.

[0308] In one aspect of the method for producing the polyester polycarbonate resin and copolymer according to the present embodiment, in addition to the dihydric phenol compound (ma), a dihydric phenol compound (md) represented by the general formula (MD1) can also be used as the dihydric phenol compound. These dihydric phenol compounds may be used alone or in combination of two or more.

[0309] In one aspect of the method for producing the polyester polycarbonate resin and copolymer according to this embodiment, a derivative of the dicarboxylic acid compound (mc) can be used instead of the dicarboxylic acid compound (mc) represented by the general formulas (MC1), (MC10), (MC11), (MC12), and (MC13). As the derivative of the dicarboxylic acid compound (mc), for example, a dicarboxylic acid halide such as dicarboxylic acid dichloride, and the derivative of the dicarboxylic acid compound (mc) exemplified in the description of the method for producing the polyester resin and copolymer described above can also be used.

[0310] One specific example of a reaction type suitable for producing the polyester polycarbonate resin and copolymer according to this embodiment is a two-stage polymerization in which the following steps (P3-1) and (P3-2) are carried out.

[0311] <Step (P3-1)> The first step (P3-1) is a step of synthesizing a polycarbonate oligomer using a part of the dihydric phenol compound (ma) and a carbonate ester-forming compound.

[0312] <Step (P3-2)> The second step, step (P3-2), is a step of mixing the polycarbonate oligomer synthesized in step (P3-1) with a reaction system consisting of the remainder of the dihydric phenol compound (ma) and the dicarboxylic acid compound (mc) or a derivative thereof to carry out a polycondensation reaction.

[0313] In one aspect of the method for producing the polyester polycarbonate resin and copolymer according to the present embodiment, the synthesis of the polycarbonate oligomer in the first step (P3-1) can be carried out by the following synthesis methods (P3-1a) and (P3-1b).

[0314] <Synthesis Method (P3-1a)> Synthesis Method (P3-1a) is a method of carrying out a polycondensation reaction in the presence of a suitable acid binder using a carbonyl dihalide, a haloformate, a carbonate ester compound, or the like as a carbonate ester-forming compound. Examples of the carbonyl dihalide include phosgene, and examples of the haloformates include chloroformate compounds.

[0315] The polycondensation reaction using a carbonyl dihalide, haloformates, a carbonate ester compound, or the like as a carbonate ester-forming compound in the presence of an acid binder is usually carried out in a solvent. The proportion of the carbonate ester-forming compound used may be appropriately adjusted taking into account the stoichiometric ratio (equivalents) of the reaction. When a gaseous carbonate ester-forming compound such as phosgene is used, it is preferable to blow it into the reaction system.

[0316] Examples of the acid binder used in the synthesis method (P3-1a) include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, and mixtures thereof. The proportion of the acid binder used may also be determined appropriately taking into account the stoichiometric ratio (equivalents) of the reaction. Specifically, it is preferable to use 2 equivalents or a slight excess of the acid binder per mole of the dihydric phenol compound (ma) used.

[0317] The solvent used in synthesis method (P3-1a) may be a solvent used in the production of known polycarbonates, either singly or as a mixture of solvents. Examples of the solvent include hydrocarbon solvents (e.g., xylene, etc.) and halogenated hydrocarbon solvents (e.g., methylene chloride, chlorobenzene, etc.). In synthesis method (P3-1a), the interfacial polycondensation reaction may be carried out using two mutually immiscible solvents.

[0318] In the synthesis method (P3-1a), a small amount of an antioxidant may be added, if desired. Examples of antioxidants include sodium sulfite and hydrosulfite. The reaction in the synthesis method (P3-1a) is usually carried out at a temperature in the range of 0 to 50°C, preferably 10 to 30°C. The reaction pressure can be reduced, normal pressure, or increased pressure, but is usually preferably carried out at normal pressure or the pressure of the reaction system. The reaction time depends on the reaction temperature and other factors, but is usually about 10 to 60 minutes, preferably about 15 to 30 minutes.

[0319] <Synthesis Method (P3-1b)> The synthesis method (P3-1b) is a method in which a transesterification reaction is carried out using a bisaryl carbonate as a carbonate ester-forming compound.

[0320] When a polycarbonate oligomer is synthesized by transesterification using a bisarylcarbonate as the carbonate ester-forming compound, suitable reaction methods include melt polycondensation and solid-phase polycondensation. Examples of bisarylcarbonate include di-p-tolylcarbonate, phenyl-p-tolylcarbonate, di-p-chlorophenylcarbonate, and dinaphthylcarbonate. When melt polycondensation is used in synthesis method (P3-1b), the dihydric phenol compound (ma) and the bisarylcarbonate are mixed and reacted in a molten state at a high temperature under reduced pressure. The reaction is typically carried out at a temperature in the range of 150 to 350°C, preferably 200 to 300°C. When solid-phase polycondensation is performed in synthesis method (P3-1b), the dihydric phenol compound (ma) and bisaryl carbonate are mixed and heated in the solid state to a temperature below the melting point of the resulting polycarbonate oligomer to carry out polycondensation. The reaction time depends on the reaction temperature and the degree of vacuum, but is usually about 30 minutes to 2 hours. The reaction is preferably carried out in an inert gas atmosphere such as nitrogen or argon, and the reaction may be carried out by adding the above-mentioned antioxidant, etc., as desired.

[0321] Next, we will explain the step (P3-2) relating to the second stage in one embodiment of the method for producing the polyester polycarbonate resin and copolymer according to this embodiment. In the step (P3-2) relating to the second stage, the ratio of the two components used in preparing the reaction system consisting of the remainder of the dihydric phenol compound (ma) and the dicarboxylic acid compound (mc) or a derivative thereof can be appropriately selected taking into account the stoichiometric ratio of the polycondensation reaction, and is not particularly limited. However, it is generally appropriate to use about 1 mole of the dicarboxylic acid compound (mc) or a derivative thereof per mole of the dihydric phenol compound (ma). The reaction system consisting of the remainder of the dihydric phenol compound (ma) and the dicarboxylic acid compound (mc) or a derivative thereof is usually prepared by dissolving the remainder of the dihydric phenol compound (ma) in an aqueous solution of the alkali metal hydroxide or alkali metal carbonate, mixing this with the dicarboxylic acid compound (mc) or a derivative thereof dissolved in the water-immiscible organic solvent, and stirring. In this reaction system, a condensation reaction between the remainder of the dihydric phenol compound (ma) and the dicarboxylic acid compound (mc) or a derivative thereof proceeds, producing a polyester oligomer.

[0322] Next, in the second-stage reaction of step (P3-2), the polycarbonate oligomer synthesized in step (P3-1), preferably a solution of the polycarbonate oligomer in methylene chloride or the like, is mixed with the system in which the polyester oligomer is produced, and a polycondensation reaction is carried out. The reaction temperature for this polycondensation reaction is typically in the range of about 0 to 50°C, preferably about 5 to 20°C. A reaction time of about 5 minutes to 3 hours, preferably about 10 minutes to 1.5 hours, is generally sufficient. The reaction pressure is not particularly limited, but is typically suitably carried out under normal pressure or slightly elevated pressure. When carrying out this polycondensation reaction, at least one additive component selected from the group consisting of a suitable molecular weight modifier, catalyst, solvent, etc., can be added to the reaction system as needed. In this manner, the polyester polycarbonate resin and copolymer according to this embodiment can be obtained.

[0323] As another example of the two-stage polymerization method for the polyester polycarbonate resin and copolymer according to the present embodiment, a polycarbonate oligomer may be synthesized in the first stage in the same manner as in the step (P3-1) described above, and then the following step (P3-3) may be carried out in the second stage.

[0324] <Step (P3-3)> Step (P3-3) is a step of adding a solution of the dicarboxylic acid compound (mc) or a derivative thereof dissolved in the aqueous solution of the alkali metal hydroxide or the aqueous solution of the alkali metal carbonate to a solution of the polycarbonate oligomer synthesized in the step (P3-1) in a water-insoluble organic solvent, and carrying out a reaction in the presence of at least one of a terminal terminator and a catalyst.

[0325] Further, as yet another example of the two-stage polymerization method for the polyester polycarbonate resin and copolymer according to this embodiment, there can be mentioned two-stage polymerization in which the following steps (P3-4) and (P3-5) are carried out.

[0326] <Step (P3-4)> The first step, step (P3-4), is a step of synthesizing a polyester oligomer from a part of the dihydric phenol compound (ma) and a dicarboxylic acid compound (mc) or a derivative thereof in the same manner as in step (P3-2).

[0327] <Step (P3-5)> The second step, step (P3-5), is a step in which a solution in which the remainder of the dihydric phenol compound (ma) is dissolved in an aqueous solution of the alkali metal hydroxide or the alkali metal carbonate is added to a solution in which the polyester oligomer synthesized in step (P3-4) is dissolved in an organic solvent, and a reaction is carried out in the presence of the carbonate ester-forming compound and at least one of a terminal terminator and a catalyst.

[0328] As a method for producing the polyester polycarbonate resin and copolymer according to this embodiment, a synthesis method may be selected depending on the structure and composition of the desired polyester polycarbonate.

[0329] In the method for producing the polyester polycarbonate resin and copolymer according to this embodiment, examples of the catalyst that can be used include tertiary amines such as triethylamine, and quaternary ammonium salts.

[0330] Examples of the branching agent that can be used in the method for producing the resin and copolymer according to this embodiment include phloroglucin, pyrogallol, 1,1,1-tris(4-hydroxyphenyl)methane, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,1,1-tris(4-hydroxyphenyl)propane, 1,1,1-tris(3-methyl-4-hydroxyphenyl)ethane, 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)-2-heptene, 4,6-dimethyl-2,4, 6-tris(4-hydroxyphenyl)heptane, 2,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)-3-heptene, 1,3,5-tris(2-hydroxyphenyl)benzene, 1,3,5-tris(4-hydroxyphenyl)benzene, tris(4-hydroxyphenyl)-phenylmethane, 2,2-bis[4,4-bis(4-hydroxyphenyl)cyclohexyl]propane, 2,4-bis(4-hydroxyphenylisopropyl)phenol, 2,6-bis(2-hydroxy- 5-methylbenzyl)-4-methylphenol, 2-(4-hydroxyphenyl)-2-(2,4-dihydroxyphenyl)propane, α,α',α"-tris(4-hydroxyphenyl)-1,3,5-triisopropylbenzene, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, hexakis[4-(4-hydroxyphenylisopropyl)phenyl]-o-terephthalic acid ester, tetrakis(4-hydroxyphenyl)methane, tetrakis[4-(4-hydroxyphenylisopropyl)phenyl]-o-terephthalic acid ester [phenylisopropyl)phenoxy]methane, 1,4-bis[(4',4"-dihydroxytriphenyl)methyl]benzene, 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric acid chloride, 3,3-bis(3-methyl-4-hydroxyphenyl)-2-oxo-2,3-dihydroindole, 3,3-bis(4-hydroxyaryl)oxindole [=isatin bisphenol], 5-chloroisatin, 5,7-dichloroisatin, 5-bromoisatin, and phloroglyside.

[0331] Examples of the end terminator that can be used in the method for producing the resin and copolymer according to this embodiment include phenol, α-naphthol, β-naphthol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, p-ethylphenol, p-propylphenol, p-butylphenol, p-pentylphenol, p-hexylphenol, p-heptylphenol, p-octylphenol, p-nonylphenol, p-decylphenol, p-undecylphenol, p-dodecylphenol, p-isopropylphenol, p-tert-butylphenol, 2,6-dimethyl-p-tert-butylphenol, 2-tert-amyl-4-methylphenol, 3-methyl-6-tert-butylphenol, 2-methyl ... Examples of the end-stopping agent include 4,6-di-tert-butylphenol, 2,4-di-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, 4-tert-octylphenol, 4-tert-amylphenol, 2,4,6-tri-tert-butylphenol, p-phenylphenol, 2,6-di-tert-butyl-4-phenylphenol, 2,6-di-sec-butyl-4-methylphenol, o-anisole, m-anisole, p-anisole, o-chlorophenol, m-chlorophenol, p-chlorophenol, o-bromophenol, m-bromophenol, p-bromophenol, p-ethoxyphenol, o-aminophenol, m-aminophenol, p-aminophenol, p-cyanophenol, p-nitrophenol, 3-methyl-6-isopropylphenol, and 2-methyl-5-isopropylphenol. Preferred end-stopping agents are p-tert-butylphenol and p-phenylphenol. In this embodiment, by using p-tert-butylphenol as a terminal terminator, a resin and copolymer having a terminal group represented by the following general formula (T1) can be produced.

[0332]

[0333] (In the general formula (T1), * indicates a bond to the repeating unit located at the end of the resin or copolymer.)

[0334] The reduced viscosity of the resin and copolymer according to this embodiment can be adjusted to a predetermined range by various methods, such as selecting the reaction conditions and adjusting the amounts of the end-capping agent and branching agent used. Furthermore, the obtained polyester polycarbonate resin and copolymer can be subjected to at least one of physical and chemical treatments to obtain a resin and copolymer with a predetermined reduced viscosity. Examples of physical treatments include mixing and fractionation. Examples of chemical treatments include polymer reaction, crosslinking, and partial decomposition.

[0335] Second Embodiment Electronic Substrate One aspect of the electronic substrate according to this embodiment contains the resin or copolymer according to the first embodiment.

[0336] One aspect of the electronic substrate according to this embodiment contains the electronic substrate material according to this embodiment.

[0337] Electronic substrates can be broadly divided into semiconductor substrates and electronic circuit boards. (1) Semiconductor Substrates Semiconductor substrates are substrates for forming wiring layers that handle the input and output of electrical signals to and from chips such as logic ICs, memories, and sensors. This wiring layer is a connection layer used to connect identical or different types of chips in parallel or when stacked. Examples of chip types include FC-CSP (flip chip chip scale package), FC-BGA (flip chip ball grid array), and FO-WLP (fan-out package). (2) Electronic Circuit Boards Electronic circuit boards are substrates on which wiring layers are formed to connect multiple electronic components such as semiconductors and capacitors. Types of electronic circuit boards include multilayer boards (rigid and flexible) with stacked wiring.

[0338] [Electronic Substrate Material] The electronic substrate material according to this embodiment is used in the form of a coating composition (varnish), film, or sheet to form the electronic substrate according to this embodiment. That is, this coating composition (varnish), film, and sheet include the electronic substrate material according to this embodiment. The electronic substrate material according to this embodiment is excellent in low dielectric properties, low thermal expansion coefficient, and high heat resistance. The electronic substrate material according to this embodiment can provide a composition for a coating liquid that has high solvent solubility and low solution viscosity characteristics for coating molding.

[0339] The electronic substrate material according to this embodiment contains a first resin.

[0340] <First Resin> In one aspect of the electronic board material according to the present embodiment, the first resin is at least one resin selected from the group consisting of polycarbonate, polyester, and polyester polycarbonate. In the electronic board material according to the present embodiment, the first resin is the resin or copolymer according to the first embodiment.

[0341] <Inorganic Filler> The electronic substrate material according to this embodiment may further contain an inorganic component. In one aspect of the electronic substrate material according to this embodiment, the inorganic component preferably contains at least one component selected from the group consisting of an inorganic filler, glass fiber, and glass cloth. In this embodiment, the inorganic filler is preferably at least one filler selected from the group consisting of silica, boron nitride, aluminum nitride, silicon nitride, silicon carbide, zinc oxide, titanium oxide, aluminum oxide, magnesium oxide, aluminum hydroxide, and magnesium hydroxide. The silica used as the inorganic filler is preferably at least one silica selected from the group consisting of spherical silica, pulverized silica, hollow silica, and fumed silica.

[0342] <Thermoplastic Resin (Third Resin)> The electronic substrate material according to this embodiment may further contain a thermoplastic resin (this thermoplastic resin may be referred to as a third resin). The third resin is a thermoplastic resin different from the first resin. As the third resin, for example, a known thermoplastic resin may be used.

[0343] In one aspect of the electronic board material according to the present embodiment, the content of the first resin in the electronic board material is 50 mass % or more.

[0344] [Coating composition] The electronic substrate material according to this embodiment may be contained in a coating composition. The coating composition according to this embodiment contains the electronic substrate material, and the electronic substrate material is specifically the resin or copolymer according to the first embodiment. The coating composition according to this embodiment may be called a varnish. The coating composition according to this embodiment contains the electronic substrate material and an organic solvent. During the molding step of molding an electronic substrate using the coating composition, the solvent in the coating composition is removed by heating.

[0345] The organic solvent for the coating liquid composition can be appropriately selected taking into consideration the solubility of materials such as the resin or copolymer according to the first embodiment, the drying speed after molding, the effect of the solvent remaining on the molded product, and hazards (fire or health hazards).

[0346] Examples of organic solvents used in the coating composition according to this embodiment include cyclic ethers (such as tetrahydrofuran (THF), dioxane, and dioxolane), cyclic ketones (such as cyclohexanone, cyclopentanone, and cycloheptanone), aromatic hydrocarbons (such as toluene, xylene, and chlorobenzene), ketones (such as methyl ethyl ketone (MEK) and methyl isobutyl ketone (MIBK)), halogenated hydrocarbons (such as dichloromethane and chloroform), esters (such as ethyl acetate, isopropyl acetate, isobutyl acetate, and butyl acetate), ethers (such as ethylene glycol dimethyl ether and ethylene glycol monoethyl ether), amides (such as N,N-dimethylformamide (DMF) and dimethylacetamide (DMAc)), and aprotic polar solvents (such as dimethyl sulfoxide (DMSO)).

[0347] In the coating liquid composition of the present embodiment, in consideration of the environment and safety, the organic solvent is preferably an organic solvent other than halogenated hydrocarbons, i.e., a non-halogenated solvent, and more preferably at least one solvent selected from the group consisting of toluene, cyclohexanone, methyl ethyl ketone, tetrahydrofuran, dioxolane, and cyclopentanone.

[0348] One aspect of the coating liquid composition according to this embodiment contains an electronic substrate material and a non-halogen-based solvent.

[0349] One aspect of the coating liquid composition according to this embodiment contains the resin or copolymer according to the first embodiment and a non-halogen-based solvent.

[0350] The concentration of the resin or copolymer according to the first embodiment in the coating composition according to this embodiment may be any concentration that provides an appropriate viscosity for the intended use of the coating composition, and is preferably 0.1% by mass or more and 40% by mass or less. The concentration of the resin or copolymer according to the first embodiment in the coating composition according to this embodiment is more preferably 1% by mass or more, and even more preferably 5% by mass or more. The concentration of the resin or copolymer according to the first embodiment in the coating composition according to this embodiment is more preferably 35% by mass or less, and even more preferably 30% by mass or less. When the concentration of the resin or copolymer according to the first embodiment in the coating composition according to this embodiment is 40% by mass or less, the viscosity does not become too high and the coatability is good. When the concentration of the resin or copolymer according to the first embodiment in the coating composition according to this embodiment is 0.1% by mass or more, the viscosity can be maintained at an appropriate level, and a homogeneous film can be obtained. Furthermore, when the concentration is 0.1% by mass or more, the drying time after application of the coating composition can be shortened and a film of the desired thickness can be easily formed.

[0351] The electronic substrate material according to this embodiment may be applied in solution, i.e., as a coating composition, directly onto a core material made of polyimide, epoxy resin, or the like. In this case, an inorganic filler such as silica may be dispersed in the coating composition. Suitable solvents for dispersing the inorganic filler in the coating composition include, for example, toluene, cyclohexanone, and MEK.

[0352] [Film] One aspect of the film according to this embodiment contains the resin or copolymer according to the first embodiment.

[0353] One aspect of the film according to this embodiment contains the electronic substrate material according to this embodiment.

[0354] The film according to this embodiment can be produced by thermoforming (e.g., melt extrusion molding) or solution casting the electronic substrate material according to this embodiment. When a thin film (e.g., a thickness of several μm to several tens of μm) is desired, solution casting is preferred. Furthermore, for purposes such as reducing thermal expansion, the electronic substrate material may be impregnated into glass cloth during film formation, or an electronic substrate material in a state where an inorganic filler such as silica is dispersed may be formed into a film. Furthermore, for purposes such as improving dielectric properties and adjusting the modulus of elasticity, the composition may be used when forming a film from an electronic substrate material containing a known thermoplastic resin as a third resin. Furthermore, when the electronic substrate material according to this embodiment has crosslinked moieties, or when an electronic substrate material having crosslinked moieties is used to form a film by solution casting, it is possible to control the degree of crosslinking by adding a curing material to the electronic substrate material and adjusting the heating temperature, thereby changing the modulus of elasticity of the film.

[0355] [Sheet] One aspect of the sheet according to this embodiment contains the resin or copolymer according to the first embodiment.

[0356] One aspect of the sheet according to this embodiment contains the electronic substrate material according to this embodiment.

[0357] When the electronic substrate material according to this embodiment is used as a sheet, the substrate or the like can be impregnated with the coating liquid composition (varnish) to form the sheet.

[0358] Next, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples and various modifications and applications are possible within the scope of the present invention.

[0359] [Production Examples: Preparation of Oligomers] <Production Example 1: Synthesis of 1,1-bis-(4-hydroxyphenyl)cyclohexane Oligomer> 60.1 g (224 mmol) of 1,1-bis-(4-hydroxyphenyl)cyclohexane was suspended in 1,080 mL of methylene chloride, and 66.0 g (667 mmol) of phosgene was added thereto. A solution prepared by dissolving 44.0 g (435 mmol) of triethylamine in 120 mL of methylene chloride was added dropwise to this solution at a temperature between 5°C and 15°C. After stirring for 30 minutes, the methylene chloride was distilled off until the predetermined concentration was reached. The remaining liquid was washed with 210 mL of pure water, 1.2 g of concentrated hydrochloric acid, and 450 mg of hydrosulfite. Subsequently, washing was repeated five times with 210 mL of pure water to obtain a methylene chloride solution of 1,1-bis-(4-hydroxyphenyl)cyclohexane oligomer having chloroformate groups at the molecular terminals. The resulting solution had a chloroformate concentration of 1.10 mol / L, a solid concentration of 0.222 kg / L, and an average number of monomers of 1.04. Hereinafter, the resulting oligomer (bischloroformate) according to Production Example 1 will be referred to as Z-CF.

[0360] <Production Example 2: Synthesis of 1,1-bis-(4-hydroxy-3-methylphenyl)cyclohexane oligomer> The oligomer (bischloroformate) according to Production Example 2 was produced in the same manner as in Production Example 1, except that 66.4 g (224 mmol) of 1,1-bis-(4-hydroxy-3-methylphenyl)cyclohexane was used instead of 1,1-bis-(4-hydroxyphenyl)cyclohexane. The chloroformate concentration of the resulting solution was 1.07 mol / L, the solid concentration was 0.232 kg / L, and the average number of monomers was 1.07. Hereinafter, the obtained oligomer according to Production Example 2 will be referred to as CZ-CF.

[0361] <Production Example 3: Synthesis of 1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane oligomer> The oligomer (bischloroformate) according to Production Example 3 was produced in the same manner as in Production Example 1, except that 69.5 g (224 mmol) of 1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane was used instead of 1,1-bis-(4-hydroxyphenyl)cyclohexane. The chloroformate concentration of the resulting solution was 1.07 mol / L, the solid concentration was 0.229 kg / L, and the average number of monomers was 1.03. Hereinafter, the obtained oligomer according to Production Example 3 will be referred to as TMC-CF.

[0362] <Production Example 4: Synthesis of 1,1-bis-(4-hydroxy-3-methylphenyl)-3,3,5-trimethylcyclohexane oligomer> The oligomer (bischloroformate) according to Production Example 4 was produced in the same manner as in Production Example 1, except that 75.8 g (224 mmol) of 1,1-bis-(4-hydroxy-3-methylphenyl)-3,3,5-trimethylcyclohexane was used instead of 1,1-bis-(4-hydroxyphenyl)cyclohexane. The chloroformate concentration of the resulting solution was 0.92 mol / L, the solid concentration was 0.223 kg / L, and the average number of monomers was 1.06. Hereinafter, the obtained oligomer according to Production Example 4 will be referred to as OCTMC-CF.

[0363] <Production Example 5: Synthesis of 1,1-bis-(4-hydroxy-3-methylphenyl)-cyclododecane oligomer> The oligomer (bischloroformate) according to Production Example 5 was produced in the same manner as in Production Example 1, except that 85.2 g (224 mmol) of 1,1-bis-(4-hydroxy-3-methylphenyl)-cyclododecane was used instead of 1,1-bis-(4-hydroxyphenyl)cyclohexane. The chloroformate concentration of the resulting solution was 0.84 mol / L, the solid concentration was 0.218 kg / L, and the average number of monomers was 1.04. Hereinafter, the obtained oligomer according to Production Example 5 will be referred to as OCCDE-CF.

[0364] Synthesis Example 1 (Production of PC Polymer) 225 mL of Z-CF from Production Example 1, 339 mL of methylene chloride, 38.9 g of 2,2'-methylenebis(6-cyclohexyl-p-cresol), and 0.235 g of p-tert-butylphenol were added to a reaction vessel equipped with a mechanical stirrer, a stirring blade, and a baffle, and the mixture was stirred to ensure thorough mixing, thereby obtaining a methylene chloride solution (M1). 2,2'-methylenebis(6-cyclohexyl-p-cresol) may be referred to as MBCC hereinafter, and p-tert-butylphenol may be referred to as PTBP hereinafter. In addition, 864 mL of 2.0 N aqueous sodium hydroxide solution (23.3 g of sodium hydroxide) was cooled to below room temperature, and then 0.23 g of sodium hydrosulfite and 0.33 g of benzyltripropylammonium chloride were added and completely dissolved to prepare an aqueous sodium hydroxide solution (SH1). The entire amount of the aqueous sodium hydroxide solution (SH1) was added to this methylene chloride solution (M1), and while stirring, an aqueous triethylamine solution (7% by volume, 2.52 mL) was added, and stirring was continued for 1 hour. The reaction mixture obtained after stirring was diluted with 0.72 L of methylene chloride and 0.04 L of water and washed (first wash). After this first wash, the lower layer was separated and further washed once with 0.23 L of water, once with 0.23 L of 0.03 N hydrochloric acid, and three times with 0.23 L of water (second wash). After this second washing, the resulting methylene chloride solution was added dropwise to methanol under stirring, and the resulting reprecipitate was filtered and dried to obtain a PC polymer (PC-1) having the following structure.

[0365] (Identification of PC polymer) The PC polymer (PC-1) thus obtained was dissolved in methylene chloride to prepare a solution with a concentration of 0.5 g / dL. The reduced viscosity [ηsp / C] at 20°C was measured and found to be 0.69 dL / g. The structure and composition of the obtained PC polymer (PC-1) were as follows: １ Analysis by H-NMR spectrum confirmed that the polymer was a PC polymer consisting of repeating units of the following formula (PC-1).

[0366]

[0367] In the PC polymer (PC-1) according to Synthesis Example 1, the repeating unit [Z] derived from the oligomer Z-CF according to Production Example 1 contained a structural unit represented by the general formula (B1) and a structural unit represented by the general formula (D1), and the repeating unit [MBCC] derived from the raw material monomer MBCC contained a structural unit represented by the general formula (A1) and a structural unit represented by the general formula (B1). With regard to the compositional ratio of the repeating units in the PC polymer (PC-1), the molar fraction d of the repeating unit [Z] was 60 mol %, and the molar fraction a of the repeating unit [MBCC] was 40 mol %.

[0368] Synthesis Example 2 (Production of PC Polymer) A PC polymer (PC-2) having the following structure was obtained in the same manner as in Synthesis Example 1, except that oligomer CZ-CF obtained in Production Example 2 was used instead of oligomer Z-CF.

[0369] (Identification of PC polymer) The PC polymer (PC-2) thus obtained was dissolved in methylene chloride to prepare a solution with a concentration of 0.5 g / dL. The reduced viscosity [ηsp / C] at 20°C was measured and found to be 0.64 dL / g. The structure and composition of the obtained PC polymer (PC-2) were as follows: １ Analysis by H-NMR spectrum confirmed that the polymer was a PC polymer having the repeating unit and composition shown in the following formula (PC-2).

[0370]

[0371] In the PC polymer (PC-2), the repeating unit [CZ] derived from the oligomer CZ-CF of Production Example 2 contained a structural unit represented by the general formula (B1) and a structural unit represented by the general formula (D1), and the repeating unit [MBCC] derived from the raw material monomer MBCC contained a structural unit represented by the general formula (A1) and a structural unit represented by the general formula (B1). With regard to the compositional ratio of the repeating units in the PC polymer (PC-2), the molar fraction d of the repeating unit [CZ] was 60 mol %, and the molar fraction a of the repeating unit [MBCC] was 40 mol %.

[0372] Synthesis Example 3 (Production of PC Polymer) A PC polymer (PC-3) having the following structure was obtained in the same manner as in Synthesis Example 1, except that the oligomer TMC-CF obtained in Production Example 3 was used instead of the oligomer Z-CF.

[0373] (Identification of PC polymer) The PC polymer (PC-3) thus obtained was dissolved in methylene chloride to prepare a solution with a concentration of 0.5 g / dL. The reduced viscosity [ηsp / C] at 20°C was measured and found to be 0.42 dL / g. The structure and composition of the obtained PC polymer (PC-3) were as follows: １ Analysis by H-NMR spectrum confirmed that the polymer was a PC polymer having the repeating unit and composition shown in the following formula (PC-3).

[0374]

[0375] In the PC polymer (PC-3), the repeating unit [TMC] derived from the oligomer TMC-CF of Production Example 3 contained a structural unit represented by the general formula (B1) and a structural unit represented by the general formula (D1), and the repeating unit [MBCC] derived from the raw material monomer MBCC contained a structural unit represented by the general formula (A1) and a structural unit represented by the general formula (B1). With regard to the compositional ratio of the repeating units in the PC polymer (PC-3), the molar fraction d of the repeating unit [TMC] was 60 mol %, and the molar fraction a of the repeating unit [MBCC] was 40 mol %.

[0376] Synthesis Example 4 (Production of PC Polymer) A PC polymer (PC-4) having the following structure was obtained in the same manner as in Synthesis Example 1, except that the oligomer OCTMC-CF obtained in Production Example 4 was used instead of the oligomer Z-CF.

[0377] (Identification of PC polymer) The PC polymer (PC-4) thus obtained was dissolved in methylene chloride to prepare a solution with a concentration of 0.5 g / dL, and the reduced viscosity [ηsp / C] at 20°C was measured and found to be 0.68 dL / g. The structure and composition of the obtained PC polymer (PC-4) were as follows: １ Analysis by H-NMR spectrum confirmed that the polymer was a PC polymer having the repeating unit and composition shown in the following formula (PC-4).

[0378]

[0379] In the PC polymer (PC-4), the repeating unit [OCTMC] derived from the oligomer OCTMC-CF of Production Example 4 contained a structural unit represented by the general formula (B1) and a structural unit represented by the general formula (D1), and the repeating unit [MBCC] derived from the raw material monomer MBCC contained a structural unit represented by the general formula (A1) and a structural unit represented by the general formula (B1). With regard to the compositional ratio of the repeating units in the PC polymer (PC-4), the molar fraction d of the repeating unit [OCTMC] was 60 mol %, and the molar fraction a of the repeating unit [MBCC] was 40 mol %.

[0380] Synthesis Example 5 (Production of PC Polymer) A PC polymer (PC-5) having the following structure was obtained in the same manner as in Synthesis Example 1, except that the oligomer OCCDE-CF obtained in Production Example 5 was used instead of the oligomer Z-CF.

[0381] (Identification of PC polymer) The PC polymer (PC-5) thus obtained was dissolved in methylene chloride to prepare a solution with a concentration of 0.5 g / dL, and the reduced viscosity [ηsp / C] at 20°C was measured to be 0.63 dL / g. The structure and composition of the obtained PC polymer (PC-5) were １ Analysis by H-NMR spectrum confirmed that the polymer was a PC polymer having the repeating unit and composition shown in the following formula (PC-5).

[0382]

[0383] In the PC polymer (PC-5), the repeating unit [OCCDE] derived from the oligomer OCCDE-CF of Production Example 5 contained a structural unit represented by the general formula (B1) and a structural unit represented by the general formula (D1), and the repeating unit [MBCC] derived from the raw material monomer MBCC contained a structural unit represented by the general formula (A1) and a structural unit represented by the general formula (B1). With regard to the compositional ratio of the repeating units in the PC polymer (PC-5), the molar fraction d of the repeating unit [OCCDE] was 60 mol %, and the molar fraction a of the repeating unit [MBCC] was 40 mol %.

[0384] <Preparation of Coating Composition Containing Polycarbonate Resin, and Fabrication of Resin Film> [Example 1] A PC polymer (PC-1) (1.1 g) was weighed into a sample tube with a screw cap and dissolved in 6 g of tetrahydrofuran to obtain a coating composition. The obtained coating composition was cast onto a glass plate using an applicator with a gap of 500 μm to form a film of the coating composition. After air-drying for 1 hour, the film of the coating composition was dried under reduced pressure in a vacuum dryer at a temperature of 50°C for 8 hours, and then at 110°C for 8 hours to remove the solvent, thereby obtaining a resin film of Example 1 having a thickness of 50 to 100 μm.

[0385] Example 2 A resin film according to Example 2 was obtained in the same manner as in Example 1, except that the PC polymer (PC-2) was used instead of the PC polymer (PC-1).

[0386] Example 3 A resin film according to Example 3 was obtained in the same manner as in Example 1, except that the PC polymer (PC-3) was used instead of the PC polymer (PC-1).

[0387] Example 4 A resin film according to Example 4 was obtained in the same manner as in Example 1, except that the PC polymer (PC-4) was used instead of the PC polymer (PC-1).

[0388] Example 5 A resin film according to Example 5 was obtained in the same manner as in Example 1, except that the PC polymer (PC-5) was used instead of the PC polymer (PC-1).

[0389] Comparative Example 1 A resin film according to Comparative Example 1 was obtained in the same manner as in Example 1, except that a polycarbonate resin (Z-PC) made from 1,1-bis-(4-hydroxyphenyl)cyclohexane was used instead of the PC polymer (PC-1). The polycarbonate resin (Z-PC) had the following repeating units and a reduced viscosity [ηsp / C] at 20°C of 0.91 dL / g.

[0390]

[0391] Comparative Example 2 A resin film according to Comparative Example 2 was obtained in the same manner as in Example 1, except that a polycarbonate resin (CZ-PC) made from 1,1-bis-(4-hydroxy-3-methylphenyl)cyclohexane was used instead of the PC polymer (PC-1). The polycarbonate resin (CZ-PC) had the following repeating units and a reduced viscosity [ηsp / C] at 20°C of 0.75 dL / g.

[0392]

[0393] Comparative Example 3 A resin film according to Comparative Example 3 was obtained in the same manner as in Example 1, except that a polycarbonate resin (TMC-PC) made from 1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane was used instead of the PC polymer (PC-1). The polycarbonate resin (TMC-PC) had the following repeating units and a reduced viscosity [ηsp / C] at 20°C of 0.42 dL / g.

[0394]

[0395] Comparative Example 4 A resin film according to Comparative Example 4 was obtained in the same manner as in Example 1, except that a polycarbonate resin (OCTMC-PC) made from 1,1-bis-(4-hydroxy-3-methylphenyl)-3,3,5-trimethylcyclohexane was used instead of the PC polymer (PC-1). The polycarbonate resin (OCTMC-PC) had the following repeating units and a reduced viscosity [ηsp / C] at 20°C of 0.47 dL / g.

[0396]

[0397] Comparative Example 5 A resin film according to Comparative Example 5 was obtained in the same manner as in Example 1, except that a polycarbonate resin (OCCDE-PC) made from 1,1-bis-(4-hydroxy-3-methylphenyl)-cyclododecane was used instead of the PC polymer (PC-1). The polycarbonate resin (OCCDE-PC) had the following repeating units and a reduced viscosity [ηsp / C] at 20°C of 0.70 dL / g.

[0398]

[0399] [Evaluation of Physical Properties of Polycarbonate Resin] The physical properties of the polycarbonate resin (PC polymer) were evaluated by the following methods.

[0400] <Reduced Viscosity: [ηsp / C]> A polycarbonate resin was dissolved in methylene chloride as a solvent to prepare a solution with a concentration of 0.5 g / dL, and the reduced viscosity [ηsp / C] of this solution was measured using an Ubbelohde viscometer. The reduced viscosity [ηsp / C] of this methylene chloride solution was measured using the Ubbelohde viscometer at a temperature of 20±0.01°C. The flow time of the solvent alone was 72.4 seconds.

[0401] <Viscosity Average Molecular Weight: Mv> The viscosity average molecular weight (Mv) was calculated by dissolving a polycarbonate resin in methylene chloride as a solvent to prepare a polymer solution, measuring the intrinsic viscosity [η] of this solution at 20°C using an Ubbelohde viscometer, and then calculating the viscosity average molecular weight (Mv) using the following Schnell equation: [η] = 1.23 × 10 －５ Mv ０．８３ The intrinsic viscosity [η] was measured using a viscosity measuring device (manufactured by Rigo Co., Ltd., product name: RIGO AUTO VISCOMETER / VRM-052USPC). The polymer solution used for the measurement was prepared by adding 40 mL of methylene chloride to 200 mg of polycarbonate resin and dissolving it.

[0402] <Evaluation of Relative Dielectric Constant and Dielectric Loss Tangent> A square film measuring 60 mm in length and 60 mm in width was cut out from the resin film, and after 24 hours of conditioning under conditions of room temperature of 22±1°C and humidity of 33±5%, the relative dielectric constant (Dk) and dielectric loss tangent (Df) were measured at a frequency of 10 GHz using a split cylinder resonator (manufactured by EMlabs) and a network analyzer (manufactured by Keysight Technologies, Inc.). The obtained results are shown in Table 1.

[0403] <Evaluation of Solubility in Non-Halogenated Solvents (Toluene, Methyl Ethyl Ketone, Cyclohexanone)> 0.5 g (20% by mass) or 0.105 g (5% by mass) of resin film and 2.0 g of toluene, methyl ethyl ketone (MEK), or cyclohexanone were placed in a sample tube and stirred at room temperature to prepare a solution. After 24 hours, the appearance of the solution was visually confirmed. The results are shown in Table 1. A: No insoluble matter in the 20% by mass solution, transparent. B: White turbidity was visually observed in the 20% by mass solution, and no insoluble matter in the 5% by mass solution, transparent. C: Insoluble matter was present in both the 20% by mass and 5% by mass solutions.

[0404] <Evaluation of Glass Transition Temperature and Thermal Expansion Coefficient> A strip of film 40 mm long and 4 mm wide was cut out from the resin film and measured using a TMA (manufactured by Hitachi High-Tech Science, product name: TMA7100). The results are shown in Table 1. Measurement mode: Tensile Temperature conditions: -30°C to 320°C Heating rate: 5°C / min Data processing method: The coefficient of thermal expansion (CTE) was calculated from 40°C to 100°C, and the temperature at the inflection point was used as the glass transition temperature (Tg).

[0405]

[0406] The polycarbonate resins according to Examples 1 to 5, which contain a structural unit represented by general formula (A1) in their repeating units, were well soluble in non-halogenated solvents such as methyl ethyl ketone, cyclohexanone, and toluene at specific concentrations, demonstrating good solubility in multiple types of non-halogenated solvents. On the other hand, the polycarbonate resin according to Comparative Example 1 was insoluble in methyl ethyl ketone, and the polycarbonate resins according to Comparative Examples 3 and 5 exhibited poorer solubility in cyclohexanone than those of Examples 1 to 5. The polycarbonate resin according to Comparative Example 4 exhibited poorer dielectric properties than that of Example 4. The polycarbonate resin according to Comparative Example 2 exhibited poorer thermal properties than that of Example 2. Furthermore, the polycarbonate resins according to Examples 1 to 5 possessed dielectric properties suitable for use as electronic substrate materials. Therefore, resins according to one aspect of the present invention are suitable for solution molding using non-halogenated solvents without impairing the dielectric and thermal properties of the resins.

Claims

1. An electronic board material comprising a first resin, the first resin being at least one resin selected from the group consisting of polycarbonate, polyester, and polyester polycarbonate, the first resin including a structural unit represented by the following general formula (A1) and at least one structural unit selected from the group consisting of structural units represented by the following general formulas (B1), (C1), and (D1): (In the above general formula (A1), R １ and R ２ each independently represents a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms; n represents 1, 2, 3, or 4; １ are the same or different from each other, m represents 1, 2, 3 or 4, and a plurality of R ２ are the same or different from each other, R ３ and R ４ each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 14 ring carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkoxy group having 3 to 20 ring carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 14 ring carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms, a substituted or unsubstituted aralkyloxy group having 7 to 20 carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 14 ring atoms, a halogen atom, a nitro group, an aldehyde group, a cyano group, or a carboxy group; p represents 0, 1, 2, or 3, and ３ are the same or different from each other, q represents 0, 1, 2 or 3, and a plurality of R ４ are the same or different from each other, the sum of n and p is 1, 2, 3 or 4, the sum of m and q is 1, 2, 3 or 4, the structural unit represented by general formula (B1) is different from the carbonyl group in general formula (C1), in general formula (C1), Cx is a divalent group containing at least any group selected from the group consisting of a substituted or unsubstituted divalent aromatic hydrocarbon group, a substituted or unsubstituted divalent cyclic aliphatic hydrocarbon group, and a substituted or unsubstituted divalent chain aliphatic hydrocarbon group, in general formula (D1), Dx is a divalent group containing at least any group selected from the group consisting of a substituted or unsubstituted divalent aromatic hydrocarbon group, a substituted or unsubstituted divalent cyclic aliphatic hydrocarbon group, and a substituted or unsubstituted divalent chain aliphatic hydrocarbon group, the structural unit represented by general formula (A1) and the structural unit represented by general formula (D1) are different from each other, In the case of "substituted or unsubstituted", the substituents are bonded to each other to form a single ring, bonded to each other to form a condensed ring, or are not bonded to each other; * in the general formulas (A1), (B1), (C1), and (D1) represents a bond; when the first resin contains a plurality of structural units represented by the general formula (A1), the plurality of structural units represented by the general formula (A1) are the same or different from each other; when the first resin contains a plurality of structural units represented by the general formula (C1), the plurality of structural units represented by the general formula (C1) are the same or different from each other; when the first resin contains a plurality of structural units represented by the general formula (D1), the plurality of structural units represented by the general formula (D1) are the same or different from each other.

2. The electronic circuit board material according to claim 1, wherein the first resin is a resin containing structural units represented by the general formulas (A1) and (B1).

3. The electronic board material according to claim 1, wherein the first resin is a resin containing structural units represented by the general formulae (A1), (B1) and (D1).

4. An electronic board material according to any one of claims 1 to 3, wherein the ratio a:d of the molar fraction a of the structural unit represented by general formula (A1) to the molar fraction d of the structural unit represented by general formula (D1) in the first resin is 5:95 to 100:

0.

5. The electronic board material according to claim 3 or 4, wherein the ratio a:d of the molar fraction a of the structural unit represented by general formula (A1) to the molar fraction d of the structural unit represented by general formula (D1) in the first resin is 10:90 to 50:

50.

6. An electronic board material according to any one of claims 1 to 5, wherein the structural unit represented by the general formula (A1) is represented by the following general formula (A10): (In the general formula (A10), R １ , R ２ , R ３ , R ４ , n, m, p, q and * each represent R in the general formula (A1). １ , R ２ , R ３ , R ４ , n, m, p, q and * are synonymous.) 7. The electronic substrate material according to any one of claims 1 to 6, wherein n and m are 1.

8. An electronic board material according to any one of claims 1 to 7, wherein the structural unit represented by the general formula (A1) is represented by the following general formula (A11): (In the general formula (A11), R １ , R ２ , R ３ , R ４ , p, q and * each represent R in the general formula (A1). １ , R ２ , R ３ , R ４ , p, q and * are synonymous.) 9. The electronic substrate material according to any one of claims 1 to 8, wherein p and q are 1.

10. The electronic board material according to any one of claims 1 to 9, wherein the structural unit represented by the general formula (A1) is represented by the following general formula (A12): (In the general formula (A12), R １ , R ２ , R ３ , R ４ and * respectively represent R in the general formula (A1). １ , R ２ , R ３ , R ４ and * are synonymous.) 11. The electronic board material according to any one of claims 1 to 10, wherein the structural unit represented by the general formula (D1) is represented by the following general formula (D2): (In the above general formula (D2), R １５１ ~R １５８ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 18 carbon atoms, a substituted or unsubstituted cycloalkyl group having 6 to 20 ring carbon atoms, a substituted or unsubstituted cycloalkoxy group having 6 to 20 ring carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 14 ring carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 14 ring carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms, a substituted or unsubstituted aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxy group; １ is (i) a single bond, or (ii) a substituted or unsubstituted alkylene group having 1 to 28 carbon atoms, a substituted or unsubstituted alkylidene group having 2 to 28 carbon atoms, a substituted or unsubstituted cycloalkylene group having 5 to 15 ring carbon atoms, a substituted or unsubstituted cycloalkylidene group having 3 to 26 ring carbon atoms, a substituted or unsubstituted arylene group having 6 to 20 ring carbon atoms, -S-, -SO-, -SO ２ (iii) a divalent group formed by linking two or more groups selected from the group (ii), * represents a bond.

12. The electronic substrate material according to claim 11, １ is a substituted or unsubstituted cycloalkylidene group having 5 to 15 ring carbon atoms.

13. The electronic substrate material according to claim 11 or 12, １５１ ~R １５８ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, or a substituted or unsubstituted cycloalkyl group having 6 to 20 ring carbon atoms.

14. The electronic board material according to any one of claims 1 to 10, wherein the structural unit represented by the general formula (D1) is represented by the following general formula (D3): (In the above general formula (D3), X ２ (i) is a single bond, or (ii) is a substituted or unsubstituted divalent organic group having 7 to 12 carbon atoms, R １６１ ~R １６８ are each independently a hydrogen atom or a substituted or unsubstituted organic group having 1 to 10 carbon atoms, and * represents a bond.

15. An electronic board material according to any one of claims 1 to 14, wherein the first resin has a reduced viscosity of 0.80 dL / g or less, and the reduced viscosity of the first resin is a reduced viscosity at a temperature of 20°C of a solution having a concentration of 0.5 g / dL and containing the first resin as a solute in methylene chloride as a solvent.

16. An electronic board material according to any one of claims 1 to 15, wherein the first resin contains a repeating unit represented by the following general formula (PC-AB1) in which a structural unit represented by the general formula (A1) and a structural unit represented by the general formula (B1) are bonded together, and in the first resin, there is no chain between the repeating units represented by the general formula (PC-AB1). (In the above general formula (PC-AB1), R １ , R ２ , R ３ , R ４ , m, n, p and q are each R in the general formula (A1). １ , R ２ , R ３ , R ４ , m, n, p and q are synonymous, and * represents a bond.

17. The electronic circuit board material according to any one of claims 1 to 16, wherein the first resin is a polycarbonate resin.

18. The electronic board material according to any one of claims 1 to 17, wherein the content of the first resin in the electronic board material is 50 mass % or more.

19. The electronic circuit board material according to any one of claims 1 to 18, wherein the first resin has a relative dielectric constant Dk of 2.70 or less.

20. An electronic board material according to any one of claims 1 to 19, wherein the dielectric tangent Df of the first resin is 0.00300 or less.

21. The electronic board material according to any one of claims 1 to 20, wherein the first resin in the electronic board material has a viscosity average molecular weight Mv of 1,000 or more and 30,000 or less.

22. A coating composition comprising the electronic substrate material according to any one of claims 1 to 21 and a non-halogen-based solvent.

23. A film comprising the electronic substrate material of any one of claims 1 to 21.

24. A sheet comprising an electronic substrate material according to any one of claims 1 to 21.

25. An electronic substrate comprising the electronic substrate material according to any one of claims 1 to 21.

26. At least one resin selected from the group consisting of polycarbonate, polyester, and polyester polycarbonate, the resin containing a structural unit represented by the following general formula (A1) and at least one structural unit selected from the group consisting of structural units represented by the following general formulas (B1), (C1), and (D1): (In the above general formula (A1), R １ and R ２ each independently represents a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms; n represents 1, 2, 3, or 4; １ are the same or different from each other, m represents 1, 2, 3 or 4, and a plurality of R ２ are the same or different from each other, R ３ and R ４ each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 14 ring carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkoxy group having 3 to 20 ring carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 14 ring carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms, a substituted or unsubstituted aralkyloxy group having 7 to 20 carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 14 ring atoms, a halogen atom, a nitro group, an aldehyde group, a cyano group, or a carboxy group; p represents 0, 1, 2, or 3, and ３ are the same or different from each other, q represents 0, 1, 2 or 3, and a plurality of R ４ are the same or different from each other, the sum of n and p is 1, 2, 3 or 4, the sum of m and q is 1, 2, 3 or 4, the structural unit represented by general formula (B1) is different from the carbonyl group in general formula (C1), in general formula (C1), Cx is a divalent group containing at least any group selected from the group consisting of a substituted or unsubstituted divalent aromatic hydrocarbon group, a substituted or unsubstituted divalent cyclic aliphatic hydrocarbon group, and a substituted or unsubstituted divalent chain aliphatic hydrocarbon group, in general formula (D1), Dx is a divalent group containing at least any group selected from the group consisting of a substituted or unsubstituted divalent aromatic hydrocarbon group, a substituted or unsubstituted divalent cyclic aliphatic hydrocarbon group, and a substituted or unsubstituted divalent chain aliphatic hydrocarbon group, the structural unit represented by general formula (A1) and the structural unit represented by general formula (D1) are different from each other, In the case of "substituted or unsubstituted", the substituents are bonded to each other to form a single ring, bonded to each other to form a condensed ring, or are not bonded to each other; * in the general formulas (A1), (B1), (C1), and (D1) represents a bond; when the resin contains a plurality of structural units represented by the general formula (A1), the plurality of structural units represented by the general formula (A1) are the same or different from each other; when the resin contains a plurality of structural units represented by the general formula (C1), the plurality of structural units represented by the general formula (C1) are the same or different from each other; when the resin contains a plurality of structural units represented by the general formula (D1), the plurality of structural units represented by the general formula (D1) are the same or different from each other.

27. The resin according to claim 26, which is a resin containing structural units represented by the general formulas (A1) and (B1).

28. The resin according to claim 26, which is a resin containing structural units represented by the general formulas (A1), (B1) and (D1).

29. The resin according to any one of claims 26 to 28, wherein the ratio of the molar fraction a of the structural unit represented by general formula (A1) to the molar fraction d of the structural unit represented by general formula (D1) in the resin, a:d, is 5:95 to 100:

0.

30. The resin according to claim 28 or 29, wherein the ratio a:d of the molar fraction a of the structural unit represented by general formula (A1) to the molar fraction d of the structural unit represented by general formula (D1) in the resin is 10:90 to 50:

50.

31. The resin according to any one of claims 26 to 30, wherein the structural unit represented by the general formula (A1) is represented by the following general formula (A10): (In the general formula (A10), R １ , R ２ , R ３ , R ４ , n, m, p, q and * each represent R in the general formula (A1). １ , R ２ , R ３ , R ４ , n, m, p, q and * are synonymous.) 32. The resin according to any one of claims 26 to 31, wherein n and m are 1.

33. The resin according to any one of claims 26 to 32, wherein the structural unit represented by the general formula (A1) is represented by the following general formula (A11): (In the general formula (A11), R １ , R ２ , R ３ , R ４ , p, q and * each represent R in the general formula (A1). １ , R ２ , R ３ , R ４ , p, q and * are synonymous.) 34. The resin according to any one of claims 26 to 33, wherein p and q are 1.

35. The resin according to any one of claims 26 to 34, wherein the structural unit represented by the general formula (A1) is represented by the following general formula (A12): (In the general formula (A12), R １ , R ２ , R ３ , R ４ and * respectively represent R in the general formula (A1). １ , R ２ , R ３ , R ４ and * are synonymous.) 36. The resin according to any one of claims 26 to 35, wherein the structural unit represented by the general formula (D1) is represented by the following general formula (D2): (In the above general formula (D2), R １５１ ~R １５８ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 18 carbon atoms, a substituted or unsubstituted cycloalkyl group having 6 to 20 ring carbon atoms, a substituted or unsubstituted cycloalkoxy group having 6 to 20 ring carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 14 ring carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 14 ring carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms, a substituted or unsubstituted aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxy group; １ is (i) a single bond, or (ii) a substituted or unsubstituted alkylene group having 1 to 28 carbon atoms, a substituted or unsubstituted alkylidene group having 2 to 28 carbon atoms, a substituted or unsubstituted cycloalkylene group having 5 to 15 ring carbon atoms, a substituted or unsubstituted cycloalkylidene group having 3 to 26 ring carbon atoms, a substituted or unsubstituted arylene group having 6 to 20 ring carbon atoms, -S-, -SO-, -SO ２ (iii) a divalent group formed by linking two or more groups selected from the group (ii), * represents a bond.

37. The resin according to claim 36, １ is a substituted or unsubstituted cycloalkylidene group having 5 to 15 ring carbon atoms.

38. The resin according to claim 36 or 37, wherein R １５１ ~R １５８ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, or a substituted or unsubstituted cycloalkyl group having 6 to 20 ring carbon atoms.

39. The resin according to any one of claims 26 to 35, wherein the structural unit represented by the general formula (D1) is represented by the following general formula (D3): (In the above general formula (D3), X ２ (i) is a single bond, or (ii) is a substituted or unsubstituted divalent organic group having 7 to 12 carbon atoms, R １６１ ~R １６８ are each independently a hydrogen atom or a substituted or unsubstituted organic group having 1 to 10 carbon atoms, and * represents a bond.

40. A resin according to any one of claims 26 to 39, wherein the resin has a reduced viscosity of 0.80 dL / g or less, and wherein the reduced viscosity of the resin is the reduced viscosity at a temperature of 20°C of a solution having a concentration of 0.5 g / dL in methylene chloride as a solvent and the resin as a solute.

41. The resin according to any one of claims 26 to 40, comprising a repeating unit represented by the following general formula (PC-AB1) in which a structural unit represented by the general formula (A1) and a structural unit represented by the general formula (B1) are bonded together, and no chains are present between the repeating units represented by the general formula (PC-AB1) in the resin: (In the above general formula (PC-AB1), R １ , R ２ , R ３ , R ４ , m, n, p and q are each R in the general formula (A1). １ , R ２ , R ３ , R ４ , m, n, p and q are synonymous, and * represents a bond.

42. The resin according to any one of claims 26 to 38, wherein the resin is a polycarbonate resin.

43. A resin according to any one of claims 26 to 42, wherein the resin has a relative dielectric constant Dk of 2.70 or less.

44. A resin according to any one of claims 26 to 43, wherein the resin has a dielectric loss tangent Df of 0.00300 or less.

45. The resin according to any one of claims 26 to 44, wherein the resin has a viscosity average molecular weight Mv of 1,000 or more and 30,000 or less.

46. ​​A coating composition comprising the resin according to any one of claims 26 to 45 and a non-halogen-based solvent.

47. A film comprising the resin of any one of claims 26 to 45.

48. A sheet comprising a resin according to any one of claims 26 to 45.

49. An electronic substrate comprising the resin according to any one of claims 26 to 45.

50. A method for producing a resin according to any one of claims 26 to 45, comprising a polymerization step of polymerizing the resin using a compound represented by the following general formula (MA1), wherein the polymerization step is carried out in the absence of the compound represented by the following general formula (MA1) and phosgene: (In the above general formula (MA1), R １ , R ２ , R ３ , R ４ , m, n, p and q are each R in the general formula (A1). １ , R ２ , R ３ , R ４ , m, n, p and q are synonymous.

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