Electronic substrate material, resin, and method for producing resin

Abstract

An electronic substrate material contains a resin having a structure represented by general formula (UN1) and general formula (UN2) or a structure represented by general formula (UN1) and general formula (UN3). In the formula, * represents a bonding site. # imgabs0 # (In the formula, R1 and R2 each independently represent an organic group having 1-12 carbon atoms or the like, and m represents 1 or the like. ) # imgabs1 # (In the formula, X is an organic group having 6-12 carbon atoms or the like, R3 is an organic group having 1-10 carbon atoms or the like, and n is 1 or the like. ) # imgabs2 # (In the formula, Y is a single bond, an organic group having 1 to 10 carbon atoms, or the like, R4 is an organic group having 1 to 10 carbon atoms, R5 is an organic group having 1 to 10 carbon atoms, and p is 1 or the like).

Description

Technical Field

[0001] The present invention relates to an electronic substrate material, a resin, and a method for manufacturing the resin. Background Art

[0002] Next-generation high-speed communication technologies such as 5G and 6G are characterized by "high speed and large capacity", "massive simultaneous connection", and "ultra-low latency", and have been introduced into various communication networks in the fields of electrical and electronic equipment, mobile transportation such as automobiles, and the medical field, bringing about economic and social changes. There are also various problems in improving the performance of electronic circuit boards or semiconductor packaging boards (hereinafter referred to as electronic substrates) used in these electronic devices such as communication devices. One of the major problems is that as the amount of information communication increases, the frequency used in communication is becoming higher. As a result, in the materials used in conventional electronic substrates, the proportion of the conversion of electrical signal energy into heat and loss, that is, the transmission loss, increases, resulting in energy loss or heat generation problems originating from the substrate.

[0003] The transmission loss consists of two elements: conductor loss and dielectric loss. Among them, the dielectric loss is proportional to the square root of the relative dielectric constant (Dk) of the dielectric and the tangent of the dielectric loss angle (Df). Therefore, in order to reduce the transmission loss of an electronic substrate or the like using an insulating material, it is necessary to reduce the relative dielectric constant and the tangent of the dielectric loss angle of the material used as the insulating material. In addition, in order to reduce the conductor loss, there is a tendency to make the interface between the substrate and the metal wiring have a low roughness, and therefore, higher requirements are also put forward for the adhesion to the metal foil or metal plating.

[0004] In addition, for electronic substrate materials, not only is it required to reduce the transmission loss, but also various required characteristics. For example, it can be cited: high heat resistance capable of withstanding high-temperature reflow soldering, low thermal expansion to suppress substrate warping caused by the difference in the thermal expansion rate between the copper circuit and the insulating layer. In addition, it can be cited: high solvent solubility and low solution viscosity characteristics or filler dispersibility for coating and forming an insulating material on the substrate. In addition, it can be cited: high solvent solubility, low viscosity characteristics, filler dispersibility for forming a thin film used in laminating and forming a wiring layer, or small changes in dielectric characteristics under use environments such as temperature or humidity.

[0005] As its insulating material, for electronic substrates for various uses, thermoplastic resins such as liquid crystal polymers, polyphenylene ethers, polyimides, or fluororesins, or thermosetting resins such as epoxy resins or maleimide resins have been improved and developed.

[0006] Among these resins, polycarbonate resins have been used as raw materials for molded articles in various industrial fields because of their excellent mechanical properties, thermal properties, electrical properties, transparency, etc. It should be noted that when used for the above-mentioned high-frequency electronic substrates, in the case of the dielectric properties of ordinary bisphenol A polycarbonate, the above-mentioned transmission loss deteriorates. In addition, the solubility in organic solvents or the solution stability is poor, and it is difficult to be used for the insulating coating liquid for fine wiring or the formation of a thin film insulating film. In addition, the dielectric properties of bisphenol Z-type polycarbonate used in applications such as coating and forming electrophotographic photoreceptors are also insufficient. Conventional polycarbonate resins cannot satisfy these requirements well in a well-balanced manner.

[0007] Patent Document 1 describes a conductive film that includes a substrate formed of a polycarbonate resin manufactured using one or two specific bisphenols as raw materials, which has low dielectric properties capable of forming an antenna with low transmission loss, flexibility, and good adhesion to the conductive film, and a conductive film. It is similar to the object of the present invention in terms of reducing the relative dielectric constant and the tangent of the dielectric loss angle. However, it is for the purpose of antenna applications, so it is different from the object of the present invention. In addition, the manufacturing method of the molded article is injection molding or extrusion molding, and the high solvent solubility or low solution viscosity characteristics for the coating molding of the present invention are not described. In addition, a polycarbonate resin into which a thermosetting group is introduced is not described.

[0008] Patent Document 2 describes that a polycarbonate resin manufactured using one or two specific bisphenols as raw materials can be used as a thermoplastic resin composition and a molded article having excellent radio wave permeability in the microwave or millimeter wave band, and excellent heat resistance and flame retardancy, as well as a housing for a communication device and a communication device having an antenna for microwave or millimeter wave. It is similar to the present invention in terms of having low dielectric properties, high heat resistance, and reducing transmission loss. However, the housing for a communication device with an in-built antenna is a box for accommodating a communication device, which is different from a wiring substrate and different from an electronic substrate. In addition, the use or its film, or the manufacturing method of the molded article is limited to injection molding or extrusion molding. The high solvent solubility, low solution viscosity characteristics, or thermal expansion for the coating molding of the present invention are not described. In addition, a polycarbonate resin into which a thermosetting group is introduced is not described.

[0009] Patent Document 3 describes a cover for a millimeter wave radar in which the tangent of the dielectric loss angle decreases and the millimeter wave permeability increases by using a polycarbonate resin with a bisphenol having a specific substituent as a raw material. It is similar to the object of the present invention in terms of reducing the tangent of the dielectric loss angle. However, it is for the purpose of a cover for a millimeter wave radar, which is different from the object of the present invention, and heat resistance, low thermal expansion, or a thermosetting group is not described.

[0010] Patent Document 4 describes a polycarbonate resin that has amine resistance and can be used as a molded article, film, or sheet for automotive interior parts. Although heat resistance is described, its dielectric properties or coefficient of thermal expansion are not described or taught.

[0011] Patent Document 5 describes a polycarbonate resin having a 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane skeleton, which provides molded articles, films, and sheets with good scratch resistance, heat resistance, and organic solvent resistance. Although heat resistance is described, its dielectric properties or coefficient of thermal expansion are not described or taught.

[0012] Prior Art Documents

[0013] Patent Documents

[0014] Patent Document 1: International Publication No. 2021 / 085051

[0015] Patent Document 2: International Publication No. 2021 / 039970

[0016] Patent Document 3: Japanese Unexamined Patent Application Publication No. 2019-197048

[0017] Patent Document 4: Japanese Unexamined Patent Application Publication No. 2017-082131

[0018] Patent Document 5: Japanese Unexamined Patent Application Publication No. 2017-019944 Summary of the Invention

[0019] Problems to be Solved by the Invention

[0020] An object of the present invention is to provide an electronic substrate material having low dielectric properties.

[0021] Means for Solving the Problems

[0022] The present inventors repeatedly conducted in-depth research and found that an electronic substrate material containing a resin having a specific structural unit has excellent low dielectric properties. In addition, a method for synthesizing a resin having a specific structural unit that can control the amount of terminal hydroxyl groups to a low level was found.

[0023] That is, the gist of the present invention lies in the following [Constitution 1] to [Constitution 19].

[0024] [Constitution 1]

[0025] An electronic substrate material comprising a resin having a structure represented by General Formula (UN1) and General Formula (UN2) or a structure represented by General Formula (UN1) and General Formula (UN3).

[0026] [Chemical Formula 1]

[0027]

[0028] (In the formula, R 1 and R 2 each independently represent at least one selected from the group consisting of a halogen atom and an organic group having 1 or more and 12 or less carbon atoms, and m represents 0, 1, 2, 3, or 4. When the total of two m's is 2 or more, a plurality of R 1 and R 2 may be the same group or different groups from each other. * represents a bonding site.)

[0029]

Chemical Formula 2

[0030]

[0031] (In the formula, X is an organic group having 6 or more and 12 or less carbon atoms or -C(CF3)2-, R 3 is an organic group having 1 or more and 10 or less carbon atoms. When there are a plurality of R 3 , the plurality of R 3 may be the same group or different groups from each other, and n represents 0, 1, 2, 3, or 4. * represents a bonding site.)

[0032]

Chemical Formula 3

[0033]

[0034] (In the formula,

[0035] Y is a single bond,

[0036] -O-,

[0037] -S-,

[0038] -SO-,

[0039] -SO2-,

[0040] or an organic group having 1 or more and 10 or less carbon atoms,

[0041] R 4 is an organic group having 1 or more and 10 or less carbon atoms,

[0042] R 5 is an organic group having 1 or more and 10 or less carbon atoms,

[0043] When there are a plurality of R 4 or R 5 respectively, the plurality of R 4 may be the same group or different groups from each other, and the plurality of R 5They can be the same group or different groups, and p represents 1, 2, 3 or 4. * represents the bonding site.)

[0044] [Constitution 2]

[0045] The electronic substrate material according to Constitution 1, wherein the resin has at least one group of structures selected from the structures represented by General Formula (UN1-1) or General Formula (UN1-2) and General Formula (UN2), and the structures represented by General Formula (UN1-1) or General Formula (UN1-2) and General Formula (UN3). * represents the bonding site.)

[0046] [Chemical Formula 4]

[0047]

[0048] [Constitution 3]

[0049] The electronic substrate material according to Constitution 1 or Constitution 2, wherein the resin further has a structure represented by any one of General Formula (UN1), General Formula (UN1-1) and General Formula (UN1-2) in an amount of 50 mol% or more and 90 mol% or less, and at least one structure selected from the structures represented by General Formula (UN4) and General Formula (UN5) in an amount of 10 mol% or more and 49 mol% or less. * represents the bonding site.)

[0050] [Chemical Formula 5]

[0051]

[0052] [Constitution 4]

[0053] The electronic substrate material according to any one of Constitutions 1 to 3, wherein the viscosity-average molecular weight (Mv) of the resin is 1,000 or more and 25,000 or less.)

[0054] [Constitution 5]

[0055] The electronic substrate material according to any one of Constitutions 1 to 4, wherein the relative dielectric constant at a frequency of 10 GHz measured by the split cylinder resonator perturbation method is 2.6 or less.)

[0056] [Constitution 6]

[0057] The electronic substrate material according to any one of Constitutions 1 to 5, wherein the tangent of the dielectric loss angle at a frequency of 10 GHz measured by the split cylinder resonator perturbation method is 0.002 or less.)

[0058] [Constitution 7]

[0059] For the electronic substrate material according to any one of Configurations 1 to 6, when measuring the relative permittivity and the tangent of the dielectric loss angle from a temperature of 30°C to 150°C or from a temperature of 30°C to the glass transition temperature of the resin, the change amount of the permittivity is 0.05 or less, and the change amount of the tangent of the dielectric loss angle is 0.005 or less.

[0060] [Configuration 8]

[0061] For the electronic substrate material according to any one of Configurations 1 to 7, wherein the thermal expansion rate of the resin from a temperature of 40°C to 100°C is 100 ppm / K or less.

[0062] [Configuration 9]

[0063] For the electronic substrate material according to any one of Configurations 1 to 8, wherein the resin has a crosslinked structure.

[0064] [Configuration 10]

[0065] For the electronic substrate material according to Configuration 9, wherein the resin has a bond between polymer chains formed by a Diels - Alder reaction.

[0066] [Configuration 11]

[0067] For the electronic substrate material according to any one of Configurations 1 to 10, wherein it further contains an inorganic filler.

[0068] [Configuration 12]

[0069] For the electronic substrate material according to any one of Configurations 1 to 11, wherein it further contains a non - halogen - based solvent.

[0070] [Configuration 13]

[0071] A film, which contains the electronic substrate material according to any one of Configurations 1 to 12.

[0072] [Configuration 14]

[0073] A sheet, which contains the electronic substrate material according to any one of Configurations 1 to 12.

[0074] [Configuration 15]

[0075] An electronic substrate, which contains the electronic substrate material according to any one of Configurations 1 to 12.

[0076] [Configuration 16]

[0077] A resin, which has a structure represented by the general formula (UN1) and the amount of terminal hydroxyl groups is 6000 mass ppm or less.

[0078] [Chemical Formula 6]

[0079]

[0080] (In the formula, R 1 and R 2 each independently represent at least one selected from the group consisting of a halogen atom and an organic group having 1 or more and 12 or less carbon atoms, and m represents 0, 1, 2, 3, or 4. When the sum of two m's is 2 or more, the plurality of R 1 and R 2 may be the same group or different groups from each other. * represents a bonding site.)

[0081] [Constitution 17]

[0082] The resin according to Constitution 16, wherein it has at least one structure selected from the group consisting of the structures represented by General Formula (UN1-1) and General Formula (UN1-2). * represents a bonding site.

[0083] [Chemical Formula 7]

[0084]

[0085] [Constitution 18]

[0086] A method for producing a resin having a structure represented by General Formula (UN1), the production method including: a step of reacting a dichloroformate monomer or oligomer having a structure represented by General Formula (UN1) with a bisphenol compound by interfacial polycondensation.

[0087] [Chemical Formula 8]

[0088]

[0089] (In the formula, R 1 and R 2 each independently represent at least one selected from the group consisting of a halogen atom and an organic group having 1 or more and 12 or less carbon atoms, and m represents 0, 1, 2, 3, or 4. When the sum of two m's is 2 or more, the plurality of R 1 and R 2 may be the same group or different groups from each other. * represents a bonding site.)

[0090] [Constitution 19]

[0091] The method for producing a resin according to Constitution 18, wherein the amount of terminal hydroxyl groups in the polycarbonate resin having a structure represented by General Formula (UN1) is 6000 mass ppm or less.

[0092]

Chemical formula 9

[0093]

[0094] (Where R 1 and R 2 Each independently represents at least one selected from the group consisting of a halogen atom and an organic group having 1 to 12 carbon atoms, and m represents 0, 1, 2, 3 or 4. When the total of the two m's is 2 or more, the presence of multiple R 1 and R 2 They may be the same group or different groups. * indicates a bonding position.)

[0095] According to one aspect of the present invention, an electronic substrate material having low dielectric properties can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0096] Figure 1 This is a graph showing the relationship between temperature and relative dielectric constant (Dk) of the samples obtained in Examples 1 to 3 and Comparative Examples 1 and 2.

[0097] Figure 2 This is a graph showing the relationship between temperature and dielectric loss tangent (Df) of the samples obtained in Examples 1 to 3 and Comparative Examples 1 and 2. DETAILED DESCRIPTION

[0098] Hereinafter, the present invention will be described in detail.

[0099] [Resin]

[0100] The electronic substrate material according to this embodiment includes the resin according to this embodiment.

[0101] The resin (polycarbonate resin) according to the present embodiment is a resin having a structure represented by General Formula (UN1) and General Formula (UN2) or a structure represented by General Formula (UN1) and General Formula (UN3).

[0102]

Chemical Formula 10

[0103]

[0104] In the above general formula (UN1), R 1 and R 2 each independently represents at least one selected from the group consisting of a halogen atom and an organic group having 1 to 12 carbon atoms,

[0105] The organic group having 1 or more and 12 or less carbon atoms is at least one selected from the group consisting of an alkyl group having 1 or more and 12 or less carbon atoms, a substituted or unsubstituted aryl group having 6 or more and 12 or less carbon atoms, an alkoxy group having 1 or more and 12 or less carbon atoms, and a substituted or unsubstituted aryloxy group having 6 or more and 12 or less carbon atoms.

[0106] m represents 0, 1, 2, 3 or 4.

[0107] When the sum of two m's is 2 or more, the plurality of R's present 1 and R 2 may be the same group or different groups from each other.

[0108] In the case of R 1 or R 2 each being present in plurality, the plurality of R's 1 may be the same group or different groups from each other, and the plurality of R's 2 may be the same group or different groups from each other.

[0109] * represents a bonding site.

[0110] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0111] Examples of the alkyl group having 1 or more and 12 or less carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a cyclohexyl group, and a trifluoromethyl group.

[0112] Examples of the substituted or unsubstituted aryl group having 6 or more and 12 or less carbon atoms include a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 4-ethylphenyl group, a biphenyl group, a dichlorophenyl group, a naphthyl group, and a methylnaphthyl group.

[0113] Examples of the alkoxy group having 1 or more and 12 or less carbon atoms 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, and various hexyloxy groups.

[0114] Examples of the substituted or unsubstituted aryloxy group having 6 or more and 12 or less carbon atoms include a phenoxy group, a tolyloxy group, and a naphthyloxy group.

[0115]

Chemical Formula 11

[0116]

[0117] In the general formula (UN2),

[0118] X is an organic group having 6 or more and 12 or less carbon atoms or -C(CF3)2-.

[0119] R 3 is an organic group having 1 to 10 carbon atoms. When there are multiple Rs 3 the multiple Rs 3 may be the same group or different groups from each other.

[0120] n represents 0, 1, 2, 3 or 4.

[0121] * represents a bonding site.

[0122]

Chemical Formula 12

[0123]

[0124] In the general formula (UN3),

[0125] Y is a single bond,

[0126] -O-,

[0127] -S-,

[0128] -SO-,

[0129] -SO2- or

[0130] an organic group having 1 to 10 carbon atoms.

[0131] R 4 is an organic group having 1 to 10 carbon atoms.

[0132] R 5 is an organic group having 1 to 10 carbon atoms.

[0133] When there are multiple Rs in 4 or multiple Rs in 5 the multiple Rs 4 may be the same group or different groups from each other, and the multiple Rs 5 may be the same group or different groups from each other.

[0134] p represents 1, 2, 3 or 4.

[0135] * represents a bonding site.

[0136] It is considered that by having substituents such as R 1 to R 5 the molecular mobility of the carbonate group can be decreased by their steric hindrance, and this can decrease the dielectric loss tangent.

[0137] As the compound (monomeric compound) having a structure represented by the general formula (UN1), for example, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-hydroxy-3-methylphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-hydroxy-3,5-dimethylphenyl)-3,3,5-trimethylcyclohexane, etc. can be cited. These compounds can be obtained as commercial products, or can be synthesized by subjecting the target phenol and ketone to dehydration condensation using an acid catalyst.

[0138] As the compound (monomeric compound) having a structure represented by the general formula (UN2) or the general formula (UN3), for example, 2,2-bis(4-hydroxy-3-isopropylphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, etc. can be cited. These compounds can be obtained as commercial products, or can be synthesized by subjecting the target phenol and ketone to dehydration condensation using an acid catalyst.

[0139] From the viewpoints of dielectric properties or low thermal expansion rate, etc., the polycarbonate resin according to the present embodiment preferably has at least one structure selected from the group consisting of the structures represented by the general formula (UN1-1) and the general formula (UN1-2). It should be noted that in the following formula, * represents a bonding site.

[0140]

Chemical Formula 13

[0141]

[0142] From the viewpoint of dielectric properties, the polycarbonate resin according to the present embodiment preferably further has a structure represented by the following general formula (UN4) or the general formula (UN5) in an amount of 10 mol% or more and 49 mol% or less.

[0143]

Chemical Formula 14

[0144]

[0145] In the general formula (UN4) and the general formula (UN5),

[0146] * represents a bonding site.

[0147] As the compound (monomeric compound) having a structure represented by the general formula (UN4) or the general formula (UN5), 2,2-bis(3'-cyclohexyl-4'-hydroxyphenyl)propane, 1,1-bis(3-cyclohexyl-4-hydroxyphenyl)cyclohexane, etc. can be cited. These compounds can be obtained as commercial products, or can be synthesized by subjecting the target phenol and ketone to dehydration condensation using an acid catalyst.

[0148] Since these structures have a cyclohexyl group with a large volume as a substituent, there is a tendency for the relative dielectric constant or the dielectric loss tangent to decrease.

[0149] There are various methods for evaluating dielectric properties. As a frequently used method, there is the cavity resonator perturbation method (hereinafter referred to as the cavity resonance method) for evaluating dielectric properties using the electric field along the specimen. However, at both ends of the specimen, the electric field shifts outside the specimen. No well-known quantitative explanation has been established for this incompleteness. Therefore, conventionally, the electric field is considered to be the electric field passing through the entire specimen to calculate the relative dielectric constant. Therefore, although no electric field is applied at both ends of the sample, since the dielectric properties are calculated on the premise that an electric field is applied to the whole, the measured relative dielectric constant is low. On the other hand, in the case of the split cylinder resonator perturbation method (hereinafter referred to as the split cylinder method) using a circular electric field along the specimen surface for measurement, the error caused by the electric field shift at both ends of the specimen generated in the cavity resonance method does not occur. Therefore, compared with the cavity resonance method, the split cylinder method can output a value closer to the true value for dielectric properties.

[0150] In the polycarbonate resin according to this embodiment, the relative dielectric constant (Dk) measured using a split cylinder resonator at a frequency of 10 GHz at room temperature is preferably 2.6 or less, more preferably 2.55 or less, and particularly preferably 2.5 or less. In addition, the tangent of the dielectric loss angle (Df) measured using a split cylinder resonator at a frequency of 10 GHz at room temperature is preferably 0.003 or less, more preferably 0.002 or less, and particularly preferably 0.001 or less. By having the relative dielectric constant and the tangent of the dielectric loss angle below the above upper limits, the loss of the electrical signal in the electronic substrate is reduced, and good performance is obtained. In addition, when the resin according to this embodiment is used as an electronic substrate material, since the electronic substrate during use reaches a high temperature, it is also important that the relative dielectric constant or the tangent of the dielectric loss angle is low at high temperatures.

[0151] In addition, preferably, when measuring the relative dielectric constant and the tangent of the dielectric loss angle of the resin from a temperature of 30 °C to 150 °C or from a temperature of 30 °C to the glass transition temperature of the resin according to the split cylinder resonator perturbation method, the change amount of the relative dielectric constant is 0.05 or less, and the change amount of the tangent of the dielectric loss angle is 0.005 or less.

[0152] In the polycarbonate resin according to this embodiment, when all structural units are set to 100 mol%, the proportion of the general formula (UN1) is preferably 40 mol% or more, more preferably 50 mol% or more, still more preferably 55 mol% or more, and even more preferably 60 mol% or more. If the proportion of the general formula (UN1) is 40 mol% or more, the dielectric properties or heat resistance are more excellent. In addition, it may be 99 mol% or less, 90 mol% or less, or 80 mol% or less. It is preferably 40 mol% or more and 99 mol% or less, and more preferably 55 mol% or more and 90 mol% or less. The proportion of the general formula (UN2) is preferably 30 mol% or more and 49 mol% or less, and more preferably 40 mol% or more and 49 mol% or less. If the proportion of the general formula (UN2) is above the above lower limit and 49 mol% or less, the dielectric properties or heat resistance are more excellent, and thus it is preferred. The proportion of the general formula (UN3) is preferably 30 mol% or more and 49 mol% or less, and more preferably 40 mol% or more and 49 mol% or less. If the proportion of the general formula (UN3) is above the above lower limit and 49 mol% or less, the dielectric properties or heat resistance are more excellent, and thus it is preferred. The structural unit in this specification means a unit sandwiched between two adjacent carbonate bonds constituting the main chain.

[0153] The polycarbonate resin having a reduced viscosity average molecular weight of 25,000 or less is easily soluble in a non-halogen-based solvent and has a low viscosity, and is easily handled in coating forming or is also easily dispersed with a filler or other thermosetting materials. Therefore, it has excellent versatility as an electronic substrate material.

[0154] From such a viewpoint, the polycarbonate resin according to this embodiment preferably has a viscosity average molecular weight (Mv) of 1,000 or more and 25,000 or less, more preferably 1,000 or more and 22,000 or less, further preferably 1,000 or more and 20,000 or less, still further preferably 1,000 or more and 18,000 or less, and particularly preferably 1,000 or more and 17,000 or less.

[0155] In addition, since a low thermal expansion rate is desired, the polycarbonate resin according to this embodiment preferably has a thermal expansion rate of 100 ppm / K or less from a temperature of 40°C to 100°C.

[0156] A thermosetting group (crosslinking group) can also be introduced into the structure of the polycarbonate resin according to this embodiment. A resin containing such a crosslinked group structure, that is, a resin having a crosslinked structure, is called a thermosetting resin. By changing from thermoplastic to thermosetting, the heat resistance and elastic modulus can be improved. When used as an electronic substrate material, it reaches a high temperature during processing or reflow soldering, and reaches a high temperature when used in a molded product with an electronic substrate built in. At this time, by using a thermosetting resin with high heat resistance and elastic modulus, resin flow or deformation of the electronic substrate can be prevented.

[0157] Examples of the crosslinking group of the thermosetting resin include epoxy group, allyl group, maleimide, oxazole, cyclobutene, isocyanate, cyanate ester, and the like.

[0158] For example, a conjugated diene structure or a conjugated diene group (hereinafter also simply referred to as "conjugated diene") capable of having a bond between polymer chains through a Diels - Alder reaction can be cited. As the conjugated diene, at least one of the structures represented by the following general formula (UN6) and general formula (UN7) is preferably included. In addition, it can also be a Diels - Alder reaction in which a conjugated diene structure represented by the following general formula (UN8), general formula (UN9), and general formula (UN10) is introduced at the end of the polymer chain to bond the ends of the polymer chains to each other.

[0159]

Chemical formula 15

[0160]

[0161] In the above general formula (UN6) and general formula (UN7),

[0162] R 6 are each independently

[0163] a single bond,

[0164] a connecting group to another skeleton,

[0165] a hydrogen atom,

[0166] an aliphatic hydrocarbon group having 1 or more and 12 or less carbon atoms,

[0167] an aromatic hydrocarbon group having 6 or more and 12 or less carbon atoms in the ring or

[0168] an alkoxy group having 1 or more and 10 or less carbon atoms,

[0169] R 6 one or two of which are a single bond or a connecting group to another skeleton,

[0170] As the connecting group R 6Yes, it is a group containing at least any one atom selected from the group consisting of a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, and a boron atom, and the bonding forms of the atoms constituting the linking group are all covalent bonds.

[0171] In addition, multiple Rs can also be formed. 6 A cyclic structure (including an aromatic ring and a heterocyclic ring) formed by connection.

[0172]

Chemical Formula 16

[0173]

[0174] In the above general formulas (UN8) to (UN10),

[0175] X 1 Each independently is

[0176] -O-,

[0177] -(C=O)-O-,

[0178] -O-(C=O)-O- or

[0179] -O-(C=O)-,

[0180] R 7 Each independently is

[0181] An aliphatic hydrocarbon group having 1 or more and 10 or less carbon atoms,

[0182] An aromatic hydrocarbon group having 6 or more and 12 or less ring-forming carbon atoms or

[0183] An alkoxy group having 1 or more and 10 or less carbon atoms,

[0184] In addition, multiple Rs can also be formed. 7 A cyclic structure (including an aromatic ring and a heterocyclic ring) formed by connection.

[0185] R 8 Each independently is

[0186] A hydrogen atom,

[0187] An aliphatic hydrocarbon group having 1 or more and 12 or less carbon atoms or

[0188] An aromatic hydrocarbon group having 6 or more and 12 or less carbon atoms,

[0189] n1 represents 0 or a natural number with the upper limit of the replaceable quantity.

[0190] * represents the bonding position.

[0191] As a crosslinking group of a thermosetting resin, for example, an allyl structure or an allyl group capable of bonding between polymer chains through an olefin reaction can be cited. As the allyl structure, due to its high reactivity, it preferably contains at least any one of the structures represented by the following general formula (UN11), general formula (UN12), and general formula (UN13). The allyl structure represented by the following general formula (UN11) has two allyl groups. Since the allyl structure represented by the following general formula (UN12) or general formula (UN13) introduces an allyl group at the end of the polymer, the ends of the polymer chains can undergo an olefin reaction with each other.

[0192]

Chemical Formula 17

[0193]

[0194]

Chemical Formula 18

[0195]

[0196] In the above general formula (UN11) to general formula (UN13),

[0197] X 2 is selected from the group consisting of

[0198] -O-,

[0199] -S-,

[0200] -SO-,

[0201] -SO2-,

[0202] -CR 11 R 12 -,

[0203] a substituted or unsubstituted cycloalkylene group having 5 or more and 20 or less carbon atoms,

[0204] a substituted or unsubstituted bicyclic hydrocarbon diyl group having 5 or more and 20 or less carbon atoms,

[0205] a substituted or unsubstituted tricyclic hydrocarbon diyl group having 5 or more and 20 or less carbon atoms,

[0206] a substituted or unsubstituted alkylene group having 2 or more and 12 or less carbon atoms and

[0207] a substituted or unsubstituted arylene group having 6 or more and 12 or less carbon atoms

[0208] selected from the group consisting of at least 1,

[0209] R 11 and R 12 each independently is selected from the group consisting of

[0210] a hydrogen atom,

[0211] An alkyl group having 1 to 12 carbon atoms, which may be substituted or unsubstituted, and

[0212] an aryl group having 6 to 12 carbon atoms, which may be substituted or unsubstituted

[0213] at least one selected from the group consisting of

[0214] R 11 and R 12 may be bonded to each other to form a ring represented by the following general formula (RIN1),

[0215] * indicates the bonding position.

[0216]

Chemical Formula 19

[0217]

[0218] In the above general formula (RIN1),

[0219] R 9 is an alkyl group having 1 to 12 carbon atoms, which may be substituted or unsubstituted,

[0220] R 10 is selected from the group consisting of

[0221] a hydrogen atom,

[0222] an alkyl group having 1 to 12 carbon atoms, which may be substituted or unsubstituted,

[0223] an aryl group having 6 to 12 carbon atoms, which may be substituted or unsubstituted,

[0224] a cycloalkyl group having 3 to 6 carbon atoms, which may be substituted or unsubstituted

[0225] at least one selected from the group consisting of

[0226] and may have a plurality of Rs attached to one ring 10 , and in this case, the plurality of Rs may be the same group or different groups from each other.

[0227] In addition, the content of the crosslinking groups of the conjugated diene structure and the allyl structure in the polycarbonate resin can be appropriately set according to the target physical properties or target uses. When considering the use as an electronic substrate material, when all the structural units are set to 100 mol%, when the proportion of the crosslinking groups is 10 mol% or more, the effects of significant improvement in heat resistance and decrease in thermal expansion rate are exhibited.

[0228] The manufacturing method of the polycarbonate resin according to the present embodiment can apply conventional polymerization methods such as interfacial polycondensation method or melt transesterification method.

[0229] The interfacial polycondensation method is a method of obtaining a polycarbonate resin by forming an alkaline salt of a monomer such as a bisphenol compound in the presence of a non-reactive organic solvent and an alkaline aqueous solution, and subjecting phosgene or a compound capable of forming a carbonate bond to polycondensation at the interface. In the melt transesterification method, for example, the transesterification reaction between a carbonate and a monomer such as a bisphenol or a diol compound is shown.

[0230] The polycarbonate resin of the present embodiment preferably has a low terminal hydroxyl group content. The terminal hydroxyl group content represents the hydroxyl groups derived from the residual bisphenol and the hydroxyl groups at the polymer terminals. If the terminal hydroxyl group content increases, according to the Clausius-Mossotti equation, the structure with high polarity increases the relative dielectric constant, so there is a tendency for the low dielectric property to deteriorate. In addition, the presence of high-polarity groups tends to increase the tangent of the dielectric loss angle. Therefore, in order to exhibit low dielectric properties and suppress property unevenness, it is necessary to control the terminal hydroxyl group content.

[0231] From such a viewpoint, the terminal hydroxyl group content of the polycarbonate resin according to the present embodiment is preferably 6000 mass ppm or less. The terminal hydroxyl group content can be 3000 mass ppm or less, can be 1000 mass ppm or less, can be 900 mass ppm or less, can be 800 mass ppm or less, can be 700 mass ppm or less, can be 600 mass ppm or less, can be 500 mass ppm or less, can be 400 mass ppm or less, can be 300 mass ppm or less, can be 215 mass ppm or less, can be 200 mass ppm or less, can be 100 mass ppm or less, can be 50 mass ppm or less.

[0232] As a method for calculating the terminal hydroxyl group content, first, the molar ratio of each structure (structural unit) of the polycarbonate is calculated using NMR. Each structure refers to the main structure, the sub-structure, the end-capping agent structure, and the hydroxyl-terminal structure. As the end-capping agent structure, the PTBP terminal (general formula (UN14)) and the diethylamine terminal (general formula (UN15)) etc. can be cited. As the hydroxyl-terminal structure, the hydroxyl-terminal structure derived from bisphenol (general formula (UN16)) etc. can be cited. In the present embodiment, since the interfacial polycondensation method is used, a part of the diethylamine-terminal polycarbonate derived from the catalyst triethylamine is also generated. The weight ratio is calculated based on the calculated molar ratio and the molecular weight of each structure, and the amount of hydroxyl groups in the weight of the entire polymer is calculated using mass ppm units.

[0233]

Chemical formula 20

[0234]

[0235] Existing manufacturing methods can be roughly classified into two types: interfacial polycondensation method and melt transesterification method. It is known that the interfacial polycondensation method is suitable for reducing the amount of terminal hydroxyl groups. However, even when manufacturing the polycarbonate resin according to the present embodiment using the interfacial polycondensation method, sometimes the amount of terminal hydroxyl groups cannot be sufficiently reduced.

[0236] Therefore, in-depth research has been conducted to reduce the amount of terminal hydroxyl groups, and as a result, two methods have been found. The first method is to control the ratio of bisphenol / carbonochloridate group. This bisphenol and carbonochloridate group represent the molar ratio.

[0237] Since this reaction is a condensation reaction, if there is a large difference in the ratio of the two reactive groups, the more abundant reactive group is likely to remain at the end of the polymer chain. Therefore, it is important to control the ratio of the reactive groups to each other. That is, in this reaction, it is necessary to control the ratio of carbonochloridate to bisphenol. By controlling this ratio, the amount of terminal hydroxyl groups as polar groups can be reduced. To determine the exact amount of carbonochloridate, most effectively, after synthesizing the oligomer from bisphenol and phosgene, the oligomer is separated and the concentration of the carbonochloridate group is accurately quantified. In the present embodiment, it has been found that by reacting an appropriate amount of bisphenol relative to the amount of carbonochloridate in the oligomer, the amount of terminal hydroxyl groups of the polymer can be controlled at an extremely low level.

[0238] The ratio of the carbonochloridate group to bisphenol needs to be appropriately set according to the characteristics resulting from the structural differences of the monomers used. The ratio range can be set to bisphenol / carbonochloridate = 0.5 to 1.1, preferably 0.6 to 1.0, and more preferably 0.7 to 0.9. If it is greater than 1.1, terminal hydroxyl groups are likely to remain. If it is less than 0.5, carbonochloridate is likely to remain.

[0239] In the case of bisphenol having a 1,1-bis(4-hydroxyphenyl)3,3,5-trimethylcyclohexane skeleton, since the hydrophilic environment around the phenolic hydroxyl group is alleviated by having substituents such as methyl at the position adjacent to the phenolic hydroxyl group, it has the characteristic of better solubility in dichloromethane as the reaction solvent than ordinary bisphenol. In the usual polymer growth reaction, the alkoxy group at the end of the polymer generated during the reaction is present at the interface, and thus a polymer is formed by reaction with the carbonochloridate in the dichloromethane layer. However, it has been found that if this bisphenol with good solubility in dichloromethane is used for the reaction, the alkoxy group at the end of the polymer becomes a hydroxyl group in trace amounts in the equilibrium reaction, and the resulting polymer dissolves in dichloromethane. Before the hydroxyl-terminated polymer transferred to the organic layer is alkoxylated again and undergoes a polymerization reaction, the reaction with the carbonochloridate as the active group of interest has already ended, and it is likely to remain as a hydroxyl-terminated polymer. To reduce this hydroxyl-terminated group, the above-mentioned control of the bisphenol / carbonochloridate ratio is also important.

[0240] The second method for reducing the amount of terminal hydroxyl groups is a method of reacting a dicarbonate monomer or oligomer represented by the general formula (1A) with bisphenol. By forming a dicarbonate oligomer from bisphenol having a 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane skeleton, since it is not necessary to use it in the form of bisphenol, the above-mentioned problem points do not need to be considered, and the amount of terminal hydroxyl groups can be reduced.

[0241]

Chemical Formula 21

[0242]

[0243] In the general formula (1A),

[0244] R 1 and R 2 As described above,

[0245] n is as described above,

[0246] n 1A represents the average number of polymerization units. In addition, the average number of polymerization units n 1A is 1.0 or more and 10 or less.

[0247] The resulting polycarbonate resin can be any one of block copolymers, alternating copolymers, and random copolymers, etc.

[0248] As the reason for preferably using a monomer (n 1A = 1.0), it is possible to adjust the copolymerization ratio over a wide range. Especially when the copolymerization molecular weight is low, if the number of polymerization units of the oligomer (1A) is high, the components to be copolymerized decrease. Or the molecular weight itself is also easy to control. In the case of a copolymerization object that is easily crystallized, a decrease in solubility can be prevented.

[0249] As a capping agent for generating chain ends in the interfacial polycondensation method, a monocarboxylic acid and its derivatives, and a monophenol can be used.

[0250] Preferably, for example, p-tert-butylphenol, p-phenylphenol, p-cumylphenol, p-perfluorononylphenol, p-(perfluorononylphenyl)phenol, p-(perfluorohexyl)phenol, p-perfluorotert-butylphenol, p-perfluorooctylphenol, 1-(p-hydroxybenzyl)perfluorodecane, p-[2-(1H,1H-perfluorotris(dodecyloxy))-1,1,1,3,3,3-hexafluoropropyl]phenol, 3,5-bis(perfluorohexyloxycarbonyl)phenol, p-perfluorododecyl hydroxybenzoate, p-(1H,1H-perfluorooctoxylated)phenol, and 2H,2H,9H-perfluorononanoic acid, etc. are used.

[0251] In interfacial polycondensation, as the acid-binding agent, examples include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and cesium hydroxide, alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide, alkali metal weak acid salts such as sodium carbonate and potassium carbonate, alkaline earth metal weak acid salts such as calcium acetate, and organic bases such as pyridine. Preferred acid-binding agents in interfacial polycondensation are alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and alkaline earth metal hydroxides such as calcium hydroxide. In addition, these acid-binding agents can also be used in the form of a mixture. The usage ratio of the acid-binding agent can be appropriately adjusted considering the stoichiometric ratio (equivalent) of the reaction. Specifically, relative to 1 mole of the total hydroxyl groups of the diphenol as the raw material, it is sufficient to use 1 equivalent or a more excessive amount of the acid-binding agent, and it is preferably sufficient to use 1 to 10 equivalents of the acid-binding agent.

[0252] As the solvent used in interfacial polycondensation, it is preferred to use an organic solvent that is substantially immiscible with water and can dissolve 5 mass% or more of the finally obtained polycarbonate copolymer. The organic solvent is preferably an organic solvent that is substantially immiscible with water and can dissolve 5 mass% or more of the finally obtained polycarbonate copolymer.

[0253] Here, the organic solvent that is "substantially immiscible with water" means that under normal temperature and pressure conditions, when water and the organic solvent are mixed in a composition range of 1:9 to 9:1, a solution composed of a homogeneous layer (a solution in which neither a gel nor insoluble matter is observed) cannot be obtained.

[0254] In addition, the fact that the organic solvent "can dissolve 5 mass% or more of the finally obtained polycarbonate copolymer" refers to the solubility of the polycarbonate copolymer measured under the conditions of a temperature of 20 to 30 °C and normal pressure.

[0255] In addition, the "finally obtained polycarbonate polymer" refers to the polymer obtained through the polymerization process in the manufacturing method of the polycarbonate polymer of this embodiment, and is the polymer before crosslinking.

[0256] Examples of such organic solvents include aromatic hydrocarbons such as toluene, ketones such as cyclohexanone, and halogenated hydrocarbons such as dichloromethane. Among them, dichloromethane is preferred because of its high solubility.

[0257] In addition, as the catalyst used in interfacial polycondensation, there is no particular limitation. For example, preferred are tertiary amines such as trimethylamine, triethylamine, tributylamine, N,N-dimethylcyclohexylamine, pyridine, N,N-diethylaniline, and N,N-dimethylaniline, quaternary ammonium salts such as trimethylbenzylammonium chloride, triethylbenzylammonium chloride, tributylbenzylammonium chloride, trioctylmethylammonium chloride, tetrabutylammonium chloride, and tetrabutylammonium bromide, and quaternary phosphonium salts such as tetrabutylphosphonium chloride and tetrabutylphosphonium bromide.

[0258] In addition, a small amount of antioxidants such as sodium sulfite or dithionite can be added to the reaction system as needed.

[0259] [Resin precursor composition]

[0260] The resin precursor composition according to this embodiment refers to a composition of a resin having the above crosslinking groups and their respective crosslinking agents.

[0261] As the crosslinking agent, for example, in the case of the Diels-Alder reaction or the ene reaction, due to its high reactivity, a crosslinking agent having a maleimide skeleton is preferably used. For example, 4,4-diphenylmethane bismaleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, 4-diphenyl ether bismaleimide, 4,4-diphenylsulfone bismaleimide, 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene, a diphenylmethane-4,4-bismaleimide polymer having 4,4-methylenedianiline, N,N-(2,2-diethyl-6,6-dimethylenediphenylene)bismaleimide, N,N-(4-methyl-m-phenylene)bismaleimide, N,N-m-phenylene dimaleimide, N,N-m-phenylene bismaleimide, polyphenylmethane bismaleimide and other bismaleimides, and a polycarbonate resin having a structure in which the molecular terminals are blocked with the following compounds.

[0262] [Chemical formula 22]

[0263]

[0264] The above crosslinking agent can be appropriately set according to the content of the conjugated diene structure and the crosslinking group of the allyl structure in the polycarbonate resin or according to the target physical properties or target uses.

[0265] [Coating liquid composition]

[0266] The coating liquid composition (varnish) according to this embodiment contains the electronic substrate material according to this embodiment. More specifically, it contains the polycarbonate resin or resin precursor composition according to this embodiment and an organic solvent.

[0267] As the organic solvent of the coating liquid composition, it can be appropriately selected in consideration of the solubility of materials such as the polycarbonate resin or resin precursor composition according to this embodiment, the drying rate after forming, the influence and danger (fire or health hazard) when remaining in the formed article.

[0268] As the organic solvent according to this embodiment, 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)) can be cited.

[0269] Among them, considering the environmental or safety aspects, organic solvents other than halogenated hydrocarbons, that is, non-halogen-based solvents, are preferred.

[0270] The concentration of the polycarbonate resin or resin precursor composition according to this embodiment in the coating liquid composition according to this embodiment only needs to be a concentration that forms an appropriate viscosity suitable for the usage method of the coating liquid composition, and is preferably 0.1% by mass or more and 40% by mass or less, more preferably 1% by mass or more and 35% by mass or less, and further preferably 5% by mass or more and 30% by mass or less. If it is 40% by mass or less, the viscosity will not increase excessively and the coatability is good. As long as it is above the above lower limit, a moderate viscosity can be ensured and a homogeneous film can be obtained. In addition, a concentration suitable for shortening the drying time after coating or easily forming the target film thickness is formed.

[0271] [Electronic substrate]

[0272] Electronic substrates are roughly classified into the following semiconductor substrates and electronic circuit substrates.

[0273] (1) Semiconductor substrate material

[0274] It is a wiring layer that undertakes the input and output of electrical signals of chips such as logic ICs, memories, and sensors, and is a substrate for forming FC-CSP (flip chip-chip scale package), FC-BGA (flip chip-ball grid array), FO-WLP (fan-out package), or a connection layer when connecting different types of chips in parallel or stacked.

[0275] (2) Electronic circuit substrate

[0276] It is a substrate on which a wiring layer for connecting multiple electronic components such as semiconductors or capacitors is formed. As types, there are multilayer substrates (rigid or flexible) with stacked wirings, etc.

[0277] [Electronic substrate material]

[0278] The electronic substrate material according to the present embodiment is used in a film, sheet, or coating liquid composition (varnish) to form the electronic substrate according to the present embodiment. That is, the film, sheet, and varnish contain the electronic substrate material according to the present embodiment.

[0279] The electronic substrate material according to the present embodiment can be excellent in terms of low dielectric characteristics, low thermal expansion rate, and high heat resistance. The electronic substrate material according to the present embodiment can provide a composition for a coating liquid having high solvent solubility or low solution viscosity characteristics for coating and forming. The electronic substrate material according to the present embodiment can provide a thermosetting resin obtained by introducing a thermosetting group for improving heat resistance and elastic modulus.

[0280] [Film]

[0281] When using the electronic substrate material according to the present embodiment as a film, film formation can also be performed by thermoforming such as melt extrusion, or by solution casting. When the film thickness used is thin, in the case of several μm to several tens of μm, it is suitable to perform film formation by solution casting. In addition, for the purpose of reducing thermal expansion, etc., film formation can be performed in a state of being immersed in a glass fiber cloth or dispersed with an inorganic filler such as silica when forming the film. In addition, when using the electronic substrate material according to the present embodiment having a crosslinked portion to perform film formation by solution casting, by containing a curing material and adjusting the heating temperature, the degree of crosslinking can also be controlled, and the elastic modulus of the film can be changed, etc.

[0282] [Varnish]

[0283] The electronic substrate material according to the present embodiment can be directly coated on a core material formed of polyimide or epoxy resin, etc. in a solution state. At this time, an inorganic filler such as silica can also be dispersed.

[0284] As solvents, toluene, cyclohexanone, and MEK, etc. are suitable.

[0285] [Sheet]

[0286] When using the electronic substrate material according to the present embodiment as a sheet, the sheet can be made by immersing a substrate, etc. in the above-mentioned varnish.

[0287] Examples

[0288] Next, the present invention will be further described in detail by way of examples and comparative examples. The present invention is not limited to these examples, and various modifications and applications can be made without departing from the spirit of the present invention.

[0289] [Production Example: Preparation of Oligomer]

[0290] <Production Example 1: Synthesis of 1,1-bis(4-hydroxy-3-methylphenyl)-3,3,5-trimethylcyclohexane Oligomer (Bis(chloroformate))>

[0291] 75.8 g (224 mmol) of 1,1-bis(4-hydroxy-3-methylphenyl)-3,3,5-trimethylcyclohexane was suspended in 1080 mL of dichloromethane, and 66.0 g (667 mmol) of phosgene was added thereto and dissolved. A solution prepared by dissolving 44.0 g (435 mmol) of triethylamine in 120 mL of dichloromethane was added dropwise thereto in the temperature range of 5°C to 15°C. Next, after stirring for 30 minutes, dichloromethane was distilled off to a specific concentration. 210 mL of pure water, 1.2 g of concentrated hydrochloric acid, and 450 mg of dithionite were added to the residue for washing. Thereafter, washing was repeated 5 times with 210 mL of pure water to obtain a dichloromethane solution of 1,1-bis(4-hydroxy-3-methylphenyl)-3,3,5-trimethylcyclohexane oligomer having a chloroformate group at the molecular terminal. The chloroformate concentration of the obtained solution was 0.92 mol / L, the solid content concentration was 0.220 kg / L, and the average number of polymerization units was 1.04. Hereinafter, the obtained raw material will be referred to as OCTMC-CF.

[0292] <Production Example 2: Synthesis of 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane Oligomer (Bis(chloroformate))>

[0293] 82.1 g (224 mmol) of 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane was suspended in 1080 mL of dichloromethane, and 66.0 g (667 mmol) of phosgene was added thereto and dissolved. A solution prepared by dissolving 44.0 g (435 mmol) of triethylamine in 120 mL of dichloromethane was added dropwise thereto in the temperature range of 5 °C to 15 °C. Next, after stirring for 30 minutes, dichloromethane was distilled off to a specific concentration. 210 mL of pure water, 1.2 g of concentrated hydrochloric acid, and 450 mg of dithionite were added to the residue for washing. Thereafter, washing was repeated 5 times with 210 mL of pure water to obtain a dichloromethane solution of 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane oligomer having a chloroformate group at the molecular terminal. The chloroformate concentration of the obtained solution was 0.86 mol / L, the solid content concentration was 0.225 kg / L, and the average number of polymerization units was 1.08. Hereinafter, the obtained raw material is referred to as TMBPTMC-CF.

[0294] [Synthesis Example 1]

[0295] (Manufacture of PC Polymer)

[0296] In a reaction vessel equipped with a mechanical stirrer, stirring blades, and baffles, 182 mL of OCTMC-CF prepared in Production Example 1 and 263 mL of dichloromethane were poured. p-tert-Butylphenol (hereinafter referred to as PTBP) (0.176 g) as a capping agent was added thereto and stirred well for mixing. After cooling until the temperature in the reactor reached 10 °C, the entire amount of the prepared solution of 2,2-bis(3'-cyclohexyl-4'-hydroxyphenyl)propane (hereinafter referred to as CHA) (Solution preparation method: 148 mL (15.7 g of potassium hydroxide) of 1.63 N aqueous potassium hydroxide solution was prepared, cooled to below room temperature, and then 0.22 g of dithionite as an antioxidant and 22.6 g of CHA were added and completely dissolved) was added to this solution, and 1.7 mL of an aqueous triethylamine solution (7 vol%) was added while stirring, and stirring was continued for 2 hours.

[0297] The obtained reaction mixture was diluted and washed with 0.83 L of dichloromethane and 0.08 L of water. 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. The obtained dichloromethane solution was added dropwise to methanol with stirring, and the obtained reprecipitate was filtered and dried to obtain a PC polymer (PC-1) having the following structure.

[0298] (Identification of PC Polymer)

[0299] The PC polymer (PC-1) obtained by such operation was dissolved in dichloromethane to prepare a solution with a concentration of 0.5 g / dL, and the specific viscosity [ηsp / C] at 20 °C was measured. The result was 0.42 dL / g. It should be noted that for the structure and composition of the obtained PC-1, through 1 1H-NMR spectrum analysis, the result was confirmed to be a PC polymer composed of the following repeating units and composition ratio.

[0300] [Chemical formula 23]

[0301]

[0302] The composition ratio (mol%) was OCTMC:CHA = 6:4.

[0303] [Synthesis example 2]

[0304] (Manufacture of PC polymer)

[0305] In a reaction vessel equipped with a mechanical stirrer, stirring blades, and baffles, 182 mL of OCTMC-CF from Production Example 1 and 263 mL of dichloromethane were injected. PTBP (0.189 g) as a capping agent was added thereto, and stirring was performed to mix well. After cooling until the temperature in the reactor reached 10 °C, the entire amount of the prepared solution of 1,1-bis(3-cyclohexyl-4-hydroxyphenyl)cyclohexane (hereinafter referred to as CHZ) (solution preparation method: 148 mL of 1.63 N aqueous potassium hydroxide solution (15.7 g of potassium hydroxide) was prepared, and after cooling to below room temperature, 0.25 g of dithionite as an antioxidant and 22.6 g of CHA were added and completely dissolved) was added to the solution. While stirring, 1.7 mL of triethylamine aqueous solution (7 vol%) was added, and stirring was continued for 2 hours.

[0306] The obtained reaction mixture was diluted and washed with 0.83 L of dichloromethane and 0.08 L of water. The lower layer was separated, and it was 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. The obtained dichloromethane solution was added dropwise to methanol with stirring, and the obtained reprecipitate was filtered and dried, whereby a PC polymer (PC-2) having the following structure was obtained.

[0307] (Identification of PC polymer)

[0308] The PC polymer (PC-2) obtained by such operation was dissolved in dichloromethane to prepare a solution with a concentration of 0.5 g / dL, and the specific viscosity [ηsp / C] at 20 °C was measured. The result was 0.50 dL / g. It should be noted that for the structure and composition of the obtained PC-2, through1 The PC polymer was analyzed by 1H-NMR spectroscopy, and the result was confirmed to be a PC polymer composed of the following repeating units and composition ratio.

[0309] [Chemical formula 24]

[0310]

[0311] The composition ratio (mol%) was OCTMC:CHZ = 6:4.

[0312] [Synthesis Example 3]

[0313] (Manufacture of PC polymer)

[0314] In a reaction vessel equipped with a mechanical stirrer, stirring blades, and baffles, 178 mL of TMBPTMC-CF from Production Example 2 and 267 mL of dichloromethane were injected. PTBP (0.183 g) as a capping agent was added thereto, and stirring was carried out to mix well. After cooling until the temperature in the reactor reached 10 °C, the entire amount of the prepared CHZ solution (solution preparation method: 148 mL of 1.49 N aqueous potassium hydroxide solution (14.4 g of potassium hydroxide) was prepared, and after cooling to below room temperature, 0.23 g of dithionite as an antioxidant and 26.5 g of CHZ were added and completely dissolved) was added to this solution, and 1.6 mL of triethylamine aqueous solution (7 vol%) was added while stirring, and stirring was continued for 2 hours.

[0315] The obtained reaction mixture was diluted and washed with 0.83 L of dichloromethane and 0.08 L of water. The lower layer was separated, and it was 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. The obtained dichloromethane solution was added dropwise to methanol with stirring, and the obtained reprecipitate was filtered and dried, whereby a PC polymer (PC-3) having the following structure was obtained.

[0316] (Identification of PC polymer)

[0317] The PC polymer (PC-3) obtained by such operations was dissolved in dichloromethane to prepare a solution with a concentration of 0.5 g / dL, and the specific viscosity at 20 °C [ηsp / C] was measured. The result was 0.43 dL / g. It should be noted that for the structure and composition of the obtained PC-3, by 1 1H-NMR spectroscopy was analyzed, and the result was confirmed to be a PC polymer composed of the following repeating units and composition ratio.

[0318] [Chemical formula 25]

[0319]

[0320] The composition ratio (mol%) is TMBPTMC:CHZ = 6:4.

[0321] [Synthesis Example 4]

[0322] (Manufacture of PC polymer)

[0323] In a reaction vessel equipped with a mechanical stirrer, stirring blades, and baffles, OCTMC-CF (236 mL) and dichloromethane (263 mL) from Production Example 1 were injected. PTBP (0.777 g) as a capping agent was added thereto, and stirring was carried out to mix well. After cooling until the temperature inside the reactor reached 10 °C, the prepared CHZ and 9-(4-hydroxybenzyl)-10-(4-hydroxyphenyl)anthracene (hereinafter referred to as BIPANT) solution (solution preparation method: 148 mL of 1.6N aqueous potassium hydroxide solution (15.7 g of potassium hydroxide) was prepared, and after cooling to below room temperature, 0.25 g of dithionite as an antioxidant, 21.7 g of CHZ, and 6.3 g of BIPANT were added and completely dissolved to prepare) was added in its entirety. While stirring, 34.0 mL of triethylamine aqueous solution (7 vol%) was added, and stirring was continued for 2 hours.

[0324] The obtained reaction mixture was diluted and washed with 0.83 L of dichloromethane and 0.08 L of water. The lower layer was separated, and it was further washed once with 0.23 L of water, once with 0.23 L of 0.03N hydrochloric acid, and three times with 0.23 L of water. The obtained dichloromethane solution was added dropwise to methanol with stirring, and the obtained reprecipitate was filtered and dried, whereby a PC polymer (PC-4) having the following structure was obtained.

[0325] (Identification of PC polymer)

[0326] The PC polymer (PC-4) obtained by such operations was dissolved in dichloromethane to prepare a solution with a concentration of 0.5 g / dL, and the specific viscosity at 20 °C [ηsp / C] was measured. The result was 0.51 dL / g. It should be noted that for the structure and composition of the obtained PC-4, through 1 1H-NMR spectrum analysis, it was confirmed to be a PC polymer composed of the following repeating units and composition ratio.

[0327] [Chemical Formula 26]

[0328]

[0329] The composition ratio (mol%) is OCTMC:CHZ:BIPANT = 6:3:1.

[0330] [Synthesis Example 5]

[0331] (Manufacture of PC Polymer)

[0332] In a reaction vessel equipped with a mechanical stirrer, stirring blades, and baffles, 236 mL of OCTMC-CF from Production Example 1 and 263 mL of dichloromethane were injected. 0.718 g of PTBP as a capping agent was added thereto, and stirring was performed to achieve thorough mixing. After cooling until the temperature inside the reactor reached 10 °C, the entire amount of the prepared solution of 1,1-bis(4-hydroxy-3-methylphenyl)-3,3,5-trimethylcyclohexane (hereinafter referred to as OCTMC) and BIPANT (Solution preparation method: 148 mL of 1.6N aqueous potassium hydroxide solution (15.7 g of potassium hydroxide) was prepared, cooled to below room temperature, and then 0.20 g of dithionite as an antioxidant, 17.0 g of OCTMC, and 6.3 g of BIPANT were added and completely dissolved to prepare the solution) was added to this solution. While stirring, 34.0 mL of triethylamine aqueous solution (7 vol%) was added, and stirring was continued for 2 hours.

[0333] The resulting reaction mixture was diluted and washed with 0.83 L of dichloromethane and 0.08 L of water. The lower layer was separated, and it was further washed once with 0.23 L of water, once with 0.23 L of 0.03N hydrochloric acid, and three times with 0.23 L of water. The obtained dichloromethane solution was added dropwise to methanol with stirring, and the resulting reprecipitate was filtered and dried, thereby obtaining a PC polymer (PC-5) having the following structure.

[0334] (Identification of PC Polymer)

[0335] The PC polymer (PC-5) obtained by such operations was dissolved in dichloromethane to prepare a solution with a concentration of 0.5 g / dL, and the specific viscosity at 20 °C [ηsp / C] was measured. The result was 0.42 dL / g. It should be noted that for the structure and composition of the obtained PC-5, through 1 1H-NMR spectrum analysis, it was confirmed to be a PC polymer composed of the following repeating units and composition ratio.

[0336] [Chemical Formula 27]

[0337]

[0338] The composition ratio (mol%) was OCTMC:BIPANT = 9:1.

[0339] [Synthesis Example 6]

[0340] (Manufacture of PC Polymer)

[0341] In a reaction vessel equipped with a mechanical stirrer, stirring blades, and baffles, 178 mL of the TMBPTMC-CF prepared in Production Example 2 and 263 mL of dichloromethane were poured in. PTBP (0.718 g) as a capping agent was added thereto, and stirring was carried out to achieve sufficient mixing. After cooling until the temperature inside the reactor reached 10°C, the entire amount of the prepared 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (hereinafter referred to as TMBPTMC) (solution preparation method: 148 mL of 1.6 N aqueous potassium hydroxide solution (15.7 g of potassium hydroxide) was prepared, and after cooling to below room temperature, 0.20 g of dithionite as an antioxidant and 17.0 g of TMBPTMC were added and completely dissolved to prepare) was added to this solution, and 34.0 mL of an aqueous triethylamine solution (7 vol%) was added while stirring, and stirring was continued for 2 hours.

[0342] The obtained reaction mixture was diluted and washed with 0.83 L of dichloromethane and 0.08 L of water. The lower layer was separated, and it was 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. The obtained dichloromethane solution was added dropwise to methanol with stirring, and the obtained reprecipitate was filtered and dried, whereby a PC polymer (PC-6) having the following structure was obtained.

[0343] (Identification of PC polymer)

[0344] Since a part of the PC polymer (PC-6) obtained by such operation was insoluble in dichloromethane, the reduced viscosity [ηsp / C] at 20°C could not be measured. It should be noted that for the structure and composition of the obtained PC-6, analysis was carried out by 1 1H-NMR spectrum, and as a result, it was confirmed to be a PC polymer composed of the following repeating units and composition ratios.

[0345] [Chemical formula 28]

[0346]

[0347] <Preparation of coating liquid composition containing polycarbonate and production of resin film>

[0348] [Example 1]

[0349] 1.1 g of PC-1 was measured into a sample tube with a screw cap and dissolved in 6 mL of tetrahydrofuran to obtain a coating liquid composition. The obtained coating liquid composition was cast into a film on a glass plate using an applicator with a gap of 500 μm. After air-drying for 1 hour, it was dried under reduced pressure at a temperature of 50°C for 8 hours and then at a temperature of 100°C for 8 hours using a vacuum dryer to remove the solvent and obtain a resin film with a thickness of 50 to 100 μm.

[0350] [Example 2]

[0351] A resin film was obtained in the same manner as in Example 1, except that PC-2 was used instead of PC-1.

[0352] [Example 3]

[0353] A resin film was obtained in the same manner as in Example 1, except that PC-3 was used instead of PC-1.

[0354] [Example 4]

[0355] A resin film was obtained in the same manner as in Example 1, except that PC-4 was used instead of PC-1.

[0356] [Example 5]

[0357] A resin film was obtained in the same manner as in Example 1, except that PC-5 was used instead of PC-1.

[0358] [Example 6]

[0359] 1.5 g (15% by mass) of PC-1 and 3 g (30% by mass) of spherical silica (ADMAFINE SC2500-SQ manufactured by Admatechs) were measured into a sample tube with a screw cap and dissolved in 6.3 mL (55% by mass) of toluene to obtain a coating liquid composition. The obtained coating liquid composition was cast into a film on a glass plate using an applicator with a gap of 600 μm. After air-drying for 1 hour, it was dried under reduced pressure at a temperature of 50°C for 8 hours and then at a temperature of 130°C for 8 hours using a vacuum dryer to remove the solvent and obtain a resin film.

[0360] [Example 7]

[0361] A resin film was obtained in the same manner as in Example 1, except that PC-6 was used instead of PC-1.

[0362] [Example 8]

[0363] Using the same polymerization method as in Synthesis Example 2, a polycarbonate resin having the following structure with a viscosity-average molecular weight (Mv) of 2300 was obtained by changing only the amount of the end-capping agent PTBP to 2.84 g. It should be noted that it was difficult to form into a film shape and the dielectric properties could not be measured.

[0364] [Chemical Formula 29]

[0365]

[0366] [Example 9]

[0367] Instead of the chloroformate bodies of CHA and OCTMC, the chloroformate bodies of OCTMC and 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane were used, adjusted to bisphenol / chloroformate = 0.8, and the same operations as in Synthesis Example 1 and Example 1 were carried out otherwise, to obtain a polycarbonate resin and a resin film having the following structure.

[0368] [Chemical Formula 30]

[0369]

[0370] [Example 10]

[0371] Instead of the chloroformate bodies of CHA and OCTMC, the chloroformate bodies of OCTMC and 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane were used, adjusted to bisphenol / chloroformate = 1, and the same operations as in Synthesis Example 1 and Example 1 were carried out otherwise, to obtain a polycarbonate resin and a resin film having the following structure.

[0372] [Chemical Formula 31]

[0373]

[0374] [Comparative Example 1]

[0375] Instead of the chloroformate bodies of CHA and OCTMC, the chloroformate bodies of 1,1-bis(4-hydroxyphenyl)propane and 1,1-bis(4-hydroxyphenyl)propane were used, and the same operations as in Synthesis Example 1 and Example 1 were carried out otherwise, to obtain a polycarbonate resin and a resin film having the following structure.

[0376] [Chemical Formula 32]

[0377]

[0378] [Comparative Example 2]

[0379] Instead of using chloroformate bodies of CHA and OCTMC, 1,1-bis(4-hydroxyphenyl)cyclohexane and chloroformate bodies of 1,1-bis(4-hydroxyphenyl)cyclohexane were used, and the same operations as in Synthesis Example 1 and Example 1 were carried out except for this, to obtain a polycarbonate resin and a resin film having the following structure.

[0380] [[Chemical Formula 33]]

[0381]

[0382] The physical properties of the polycarbonate resin were evaluated by the following methods.

[0383] <Evaluation of Viscosity-Average Molecular Weight>

[0384] Dissolve 0.2 g of the polycarbonate resin in 40 mL of dichloromethane, and measure the specific viscosity (ηsp) of the solution at 20 °C. Then, take Mv calculated by the following formula as the viscosity-average molecular weight. The apparatus used for the measurement is a kinematic viscosity measuring apparatus (VMR-052 USPC manufactured by Reika Co., Ltd.), and an Ubbelohde modified type (410-UIB type) viscometer is used. The results obtained are shown in Table 1.

[0385] ηsp / C = [η] × (1 + 0.28 × ηsp)

[0386] According to the Schnell formula,

[0387] [η] = 1.23×10 -5 Mv 0.83

[0388] Perform deformation,

[0389] Mv = ([η] / 1.23×10 -5 ) 1 / 0.83

[0390] [η]: Intrinsic viscosity

[0391] C: Specimen concentration (g / L)

[0392] <Evaluation of Relative Dielectric Constant and Dielectric Loss Tangent>

[0393] A square film with a length of 60 mm and a width of 60 mm was cut from the resin film. After conditioning for 24 hours at 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). The results obtained are shown in Table 1. For the measurement of the temperature dependence of dielectric properties, the temperature was also changed using an ESPEC SH-662 small environmental tester, and the relative dielectric constant and dielectric loss tangent were measured at a frequency of 10 GHz. The results obtained are shown in Figure 1 and Figure 2 . In addition, the maximum and minimum values of Dk and Df between 30 °C and 150 °C and the difference between these values are shown in Table 2.

[0394] <Evaluation of glass transition temperature and coefficient of thermal expansion>

[0395] A long strip film with a length of 40 mm and a width of 4 mm was cut from the resin film and measured using a TMA (Hitachi High-Technologies Science, TMA7100). The results obtained are shown in Table 1.

[0396] Measurement mode: Tensile Temperature condition: -30 °C to 320 °C (heating rate 5 °C / min)

[0397] Data processing method: Coefficient of thermal expansion (CTE) is calculated at 40 °C to 100 °C, and the glass transition temperature (Tg) uses the temperature at the inflection point

[0398] <Evaluation of solubility in non-halogenated solvent (toluene)>

[0399] 0.1 g (3 mass%) of the resin film and 3.2 g of toluene were put into a sample tube. After stirring at room temperature, the appearance of the solution after one day was visually confirmed. The results obtained are shown in Table 1.

[0400] A: No insoluble components, transparent

[0401] B: Although there are no insoluble components, turbidity can be visually confirmed

[0402] F: There are insoluble components

[0403] <Evaluation of the amount of terminal hydroxyl groups>

[0404] As a method for calculating the amount of terminal hydroxyl groups, first, the molar ratio of each structure of the polycarbonate was calculated using deuterated dichloromethane and 1H-NMR (manufactured by JEOL REASONANCE Co., Ltd.) at 400 MHz. The preparation method of the evaluated solution was to add 0.74 mL of deuterated dichloromethane to 10 ± 0.5 mg of the resin and stir. The weight ratio was calculated based on the calculated molar ratio and the molecular weight of each structure, and the amount of hydroxyl groups in the weight of the entire polymer was calculated using the unit of mass ppm. In the case where the peak of hydroxyl groups was not detected, it was set as "peak not detected". The results obtained are shown in Table 1.

[0405] <Crosslinking evaluation of resin film>

[0406] 1.4 g of the resin of Example 4 (functional group concentration: 0.245 mmol / g) and 98 mg of 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane (hereinafter referred to as MI-BisA, functional group concentration: 3.51 mmol / g) as a curing material were measured into a sample tube with a screw cap and dissolved in 8 mL of toluene to obtain a coating liquid composition. The obtained coating liquid composition was cast into a film on a glass plate using an applicator with a gap of 600 μm. After air drying for 1 hour, it was dried under reduced pressure at a temperature of 50 °C in a vacuum dryer for 16 hours to remove the solvent and obtain a resin film. Next, the obtained resin film was heated at a temperature of 170 °C for 2 hours using a vacuum dryer. At the same time, the resin film of Example 2 was separately heated at a temperature of 170 °C for 2 hours using a vacuum dryer. After air cooling to room temperature, 5 mL of dichloromethane was added respectively, and the appearance was observed. The results obtained are shown in Table 3.

[0407] F (dissolved): Visually, there is no insoluble component.

[0408] A (insoluble): It did not swell or slightly swelled and maintained the film shape.

[0409] <Evaluation of solution fluidity>

[0410] 20 mg of the resins obtained in Example 2 and Example 8 were respectively added to a microtube with an inner diameter of 1 cm and a height of 5 cm, and 30 mg of toluene was added to prepare a 40 wt% toluene solution. After that, it was stirred using an oscillator for 1 hour, and the state when tilted 180 degrees was visually observed. The results obtained are shown in Table 1.

[0411] A: The time taken for the solution to reach the cap of the microtube is within 3 seconds.

[0412] B: The time taken for the solution to reach the cap of the microtube is more than 3 seconds.

[0413] <Evaluation method for GPC measurement>

[0414] Using the following measuring apparatus and measuring conditions, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the resin of Example 7 were calculated.

[0415] Measuring apparatus: "HLC-8420 GPC" manufactured by Tosoh Corporation

[0416] Column: Guard column "TSKgel guardcolumn HXL-H", separation column "TSKgel GMHXL" × 2 pieces + "TSKgel G2000HXL" × 1 piece (all manufactured by Tosoh Corporation)

[0417] Detector: RI (differential refractive index) detector

[0418] Data processing: "GPC workstation EcoSEC Elite-WS" manufactured by Tosoh Corporation

[0419] Measuring conditions: Column temperature 40°C, developing solvent tetrahydrofuran, flow rate 1.0 mL / min

[0420] Standard PS: A-500, A-1000, A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40, F-80, F-128, F-450

[0421] Sample concentration: 1 mg / mL-THF (filtered through a microfilter)

[0422] Injection volume: 100 μL

[0423]

Table 1

[0424]

[0425] [Research]

[0426] Examples 1 to 3 copolymerized with OCTMC or TMBPTMC have lower dielectric properties compared to the homopolymers of Comparative Examples 1 and 2. In addition, the solubility in toluene, which is a non-halogenated solvent, is also excellent.

[0427] From Examples 4 and 5, it can be seen that a crosslinking group can be introduced into the OCTMC copolymer.

[0428] From Example 6, it can be seen that a film containing spherical silica and resin can be produced. At this time, due to the influence of silica with a high relative dielectric constant, Dk is worse than that of using only the resin. Therefore, it is important to have a resin with lower dielectric properties.

[0429] As can be seen from Examples 9 to 10, by setting the bisphenol / chloroformate to an appropriate value, the amount of terminal hydroxyl groups can be reduced. Moreover, the reduction in the amount of terminal hydroxyl groups contributes to the decrease in Df.

[0430] By reducing the molecular weight of the resin with low dielectric properties (Example 2) (Example 8), it is possible to impart the characteristic that even when dissolved at a high concentration, the coating solution exhibits fluidity.

[0431]

Table 2

[0432]

[0433] [Research]

[0434] According to Figure 1 and Table 2, Dk has almost no temperature dependence.

[0435] On the other hand, according to Figure 2 and Table 2, Df has a tendency to increase with temperature. It is considered that this is because as the temperature rises, molecular motion of the resin is likely to occur.

[0436] Comparing Examples 1 to 3 with Comparative Examples 1 and 2, it can be seen that when OCTMC or TMBPTMC is included, the increase ratio of Df with respect to the temperature rise decreases.

[0437]

Table 3

[0438]

[0439] [Research]

[0440] Since the resin film of Example 2 was completely soluble in dichloromethane, it can be seen that no crosslinking reaction occurred even upon heating. Since the resin film formed by mixing the resin of Example 4 with MI-BisA was insoluble in dichloromethane, it can be seen that a crosslinking reaction occurred.

Claims

1. An electronic substrate material comprising a resin having a structure represented by general formula (UN1) and general formula (UN2) or a structure represented by general formula (UN1) and general formula (UN3), In the general formula (UN1), R 1 and R 2 each independently represents at least one selected from the group consisting of a halogen atom and an organic group having 1 or more and 12 or less carbon atoms, m represents 0, 1, 2, 3, or 4, and when the total of two m's is 2 or more, the plurality of R 1 and R 2 are optionally the same group or different groups from each other, and * represents a bonding position. In the general formula (UN2), X is an organic group having 6 or more and 12 or less carbon atoms or -C(CF3)2-, and R 3 is an organic group having 1 or more and 10 or less carbon atoms. When there are multiple Rs 3 , the multiple Rs 3 are each independently optionally the same or different groups, n represents 0, 1, 2, 3 or 4, and * represents the bonding position. In general formula (UN3), Y is a single bond, -O-、 -S-、 -SO-, -SO2-, or an organic group having 1 or more and 10 or less carbon atoms, R 4 is an organic group having 1 or more and 10 or less carbon atoms, R 5 is an organic group having 1 or more and 10 or less carbon atoms, At R 4 or R 5 In the case where there are multiple of each, multiple Rs 4 are optionally the same group or different groups from each other, and multiple Rs 5 are optionally the same group or different groups from each other, p represents 1, 2, 3 or 4, and * represents the bonding position.

2. The electronic substrate material according to claim 1, wherein the resin has a structure selected from at least one of the following groups; a structure represented by general formula (UN1-1) or general formula (UN1-2) and general formula (UN2); and, a structure represented by general formula (UN1-1) or general formula (UN1-2) and general formula (UN3), In general formula (UN1-1) and general formula (UN1-2), * represents a bonding position.

3. The electronic substrate material according to claim 1 or 2, wherein the resin has: a structure represented by any one of general formula (UN1), general formula (UN1-1) and general formula (UN1-2) in an amount of 50 mol% or more and 90 mol% or less; and at least one structure selected from the structures represented by general formula (UN4) and general formula (UN5) in an amount of 10 mol% or more and 49 mol% or less, In general formula (UN4) and general formula (UN5), * represents a bonding position.

4. The electronic substrate material according to any one of claims 1 to 3, wherein the resin has a viscosity-average molecular weight Mv of 1000 or more and 25000 or less.

5. The electronic substrate material according to any one of claims 1 to 4, wherein the relative dielectric constant at a frequency of 10 GHz measured by the split cylinder resonator perturbation method is 2.6 or less.

6. The electronic substrate material according to any one of claims 1 to 5, wherein the dielectric loss tangent at a frequency of 10 GHz measured by the split cylinder resonator perturbation method is 0.002 or less.

7. The electronic substrate material according to any one of claims 1 to 6, wherein when measuring the relative dielectric constant and the dielectric loss tangent from a temperature of 30°C to 150°C or from a temperature of 30°C to the glass transition temperature of the resin by the split cylinder resonator perturbation method, the change amount of the dielectric constant is 0.05 or less and the change amount of the dielectric loss tangent is 0.005 or less.

8. The electronic substrate material according to any one of claims 1 to 7, wherein the thermal expansion rate of the resin from a temperature of 40°C to 100°C is 100 ppm / K or less.

9. The electronic substrate material according to any one of claims 1 to 8, wherein the resin has a crosslinked structure.

10. The electronic substrate material according to claim 9, wherein the resin has a bond between polymer chains formed by a Diels-Alder reaction.

11. The electronic substrate material according to any one of claims 1 to 10, wherein it contains an inorganic filler.

12. The electronic substrate material according to any one of claims 1 to 11, wherein it contains a non-halogen-based solvent.

13. A film comprising the electronic substrate material according to any one of claims 1 to 12.

14. A sheet comprising the electronic substrate material according to any one of claims 1 to 12.

15. An electronic substrate comprising the electronic substrate material according to any one of claims 1 to 12.

16. A resin having a structure represented by the general formula (UN1) and having a terminal hydroxyl group content of 6000 mass ppm or less. In the general formula (UN1), R 1 and R 2 each independently represent at least one selected from the group consisting of a halogen atom and an organic group having 1 or more and 12 or less carbon atoms, m represents 0, 1, 2, 3, or 4, and when the total of two m's is 2 or more, a plurality of R 1 and R 2 are optionally the same group or different groups from each other, and * represents a bonding position.

17. The resin according to claim 16, wherein it has at least one structure selected from the group consisting of the structure represented by the general formula (UN1-1) and the structure represented by the general formula (UN1-2). In the general formula (UN1-1) and the general formula (UN1-2), * represents a bonding site.

18. A method for producing a resin having a structure represented by the general formula (UN1). The manufacturing method includes: A step of reacting a dichloroformate monomer or oligomer having a structure represented by the general formula (UN1) with a bisphenol compound by interfacial polycondensation. In the general formula (UN1), R 1 and R 2 each independently represents at least one selected from the group consisting of a halogen atom and an organic group having 1 or more and 12 or less carbon atoms, m represents 0, 1, 2, 3, or 4, and when the total of two m's is 2 or more, the plurality of R 1 and R 2 are optionally the same group or different groups from each other, and * represents a bonding site.

19. The method for producing a resin according to claim 18, wherein the terminal hydroxyl group content of the polycarbonate resin having a structure represented by the general formula (UN1) is 6000 mass ppm or less. In general formula (UN1), R 1 and R 2 each independently represent at least one selected from the group consisting of a halogen atom and an organic group having 1 or more and 12 or less carbon atoms, m represents 0, 1, 2, 3 or 4, and when the sum of two m's is 2 or more, a plurality of R 1 and R 2 are optionally the same group or different groups from each other, and * represents a bonding site.

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