Electronic substrate material, resin, and method for producing resin

Abstract

An electronic substrate material includes a resin having a structure represented by general formula (UN1). In the formula, X represents a single bond,-O-,-S-,-SO-,-SO2-, or an organic group having 1-20 carbon atoms. And * represents a bonding site. # imgabs0 #

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 called 5G and 6G have characteristics such as "high speed and large capacity", "large-scale simultaneous connection", and "ultra-low latency", and have been introduced into various communication networks in the fields of electrical and electronic devices, 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 package boards (hereinafter referred to as electronic substrates) used in these communication devices and other electronic 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 electrical signal energy converted into heat and lost, that is, the transmission loss, increases, resulting in energy loss or heat generation problems from the substrate.

[0003] The transmission loss is composed 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 there are 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 coefficient 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 or low viscosity characteristics, filler dispersibility, or small changes in dielectric characteristics in a use environment such as temperature or humidity for forming a thin film used in laminating and forming a wiring layer.

[0005] As the 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 formation of insulating coating liquids or thin film insulating films for fine wiring. 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 used in the present invention are not described. In addition, a polycarbonate resin having a thermosetting group introduced therein 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 the manufacturing method of its film or molded article is limited to injection molding and extrusion molding. The high solvent solubility, low solution viscosity characteristics, or thermal expansion for the coating molding used in the present invention are not described. In addition, a polycarbonate resin having a thermosetting group introduced therein is not described.

[0009] Patent Document 3 describes that a polycarbonate resin having a cyclohexyl group at the ortho position of bisphenol can be used as a film. However, since it is an invention of a film for the purpose of use in components and coating films of electronic and electrical equipment, it is different from the object of the present invention. In addition, this document does not describe dielectric properties or the coefficient of thermal expansion.

[0010] Prior Art Documents

[0011] Patent Documents

[0012] Patent Document 1: International Publication No. 2021 / 085051

[0013] Patent Document 2: International Publication No. 2021 / 039970

[0014] Patent Document 3: Japanese Patent Laid-Open No. 1-201329 SUMMARY OF THE INVENTION

[0015] Problems to be Solved by the Invention

[0016] An object of the present invention is to provide an electronic substrate material having low dielectric characteristics.

[0017] Means for Solving the Problems

[0018] The present inventors conducted intensive studies repeatedly and found that an electronic substrate material containing a resin having a specific structural unit has excellent low dielectric characteristics. In addition, a method for synthesizing a resin having a specific structural unit capable of controlling the amount of terminal hydroxyl groups to a low level was found.

[0019] That is, the gist of the present invention lies in the following [Constitution 1] to [Constitution 19].

[0020] [Constitution 1]

[0021] An electronic substrate material comprising a resin having a structure represented by the following general formula (UN1).

[0022] [Chemical Formula 1]

[0023]

[0024] (In the formula, X represents a single bond, -O-, -S-, -SO-, -SO2-, or an organic group having 1 or more and 20 or less carbon atoms. * represents a bonding position.)

[0025] [Constitution 2]

[0026] The electronic substrate material according to Constitution 1, wherein the resin has at least one structure selected from the group consisting of structures represented by general formula (UN1-1) and general formula (UN1-2). * represents a bonding position.

[0027] [Chemical Formula 2]

[0028]

[0029] [Constitution 3]

[0030] The electronic substrate material according to Constitution 1 or Constitution 2, wherein the resin further has at least one structure selected from the group consisting of structures represented by general formula (UN2), general formula (UN3), general formula (UN4), and general formula (UN5).

[0031] [Chemical Formula 3]

[0032]

[0033] (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 n represents 0, 1, 2, 3, or 4. When the sum of two n's is 2 or more, a plurality of R 1 and R 2 may be the same group or different groups from each other. X represents a single bond, -O-, -S-, -SO-, -SO2-, or an organic group having 1 or more and 20 or less carbon atoms. * represents a bonding site.)

[0034] [Constitution 4]

[0035] The electronic substrate material according to any one of Constitutions 1 to 3, wherein the viscosity-average molecular weight (Mv) of the above resin is 1,000 or more and 30,000 or less.

[0036] [Constitution 5]

[0037] The electronic substrate material according to any one of Constitutions 1 to 4, wherein the relative dielectric constant at a frequency of 10 GHz obtained by measurement according to the split cylinder resonator perturbation method is 2.6 or less.

[0038] [Constitution 6]

[0039] 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 obtained by measurement according to the split cylinder resonator perturbation method is 0.002 or less.

[0040] [Constitution 7]

[0041] The electronic substrate material according to any one of Constitutions 1 to 6, wherein when measuring the relative dielectric constant 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 above resin according to the split cylinder resonator perturbation method, the change amount of the dielectric constant is 0.03 or less, and the change amount of the tangent of the dielectric loss angle is 0.005 or less.

[0042] [Constitution 8]

[0043] The electronic substrate material according to any one of Constitutions 1 to 7, wherein the thermal expansion rate of the above resin from a temperature of 40°C to 100°C is 100 ppm / K or less.

[0044] [Constitution 9]

[0045] The electronic substrate material according to any one of Configurations 1 to 8, wherein the resin has a crosslinked structure.

[0046] [Configuration 10]

[0047] The electronic substrate material according to Configuration 9, wherein the resin has a bond between polymer chains formed by a Diels - Alder reaction.

[0048] [Configuration 11]

[0049] The electronic substrate material according to any one of Configurations 1 to 10, further comprising an inorganic filler.

[0050] [Configuration 12]

[0051] The electronic substrate material according to any one of Configurations 1 to 11, further comprising a non - halogen - based solvent.

[0052] [Configuration 13]

[0053] A film comprising the electronic substrate material according to any one of Configurations 1 to 12.

[0054] [Configuration 14]

[0055] A sheet comprising the electronic substrate material according to any one of Configurations 1 to 12.

[0056] [Configuration 15]

[0057] An electronic substrate comprising the electronic substrate material according to any one of Configurations 1 to 12.

[0058] [Configuration 16]

[0059] A resin having a structure represented by the general formula (UN1) and a terminal hydroxyl group amount of 6000 mass ppm or less.

[0060] [Chemical Formula 4]

[0061]

[0062] (In the formula, X represents a single bond, -O-, -S-, -SO-, -SO2- or an organic group having 1 or more and 20 or less carbon atoms. * represents a bonding position.)

[0063] [Configuration 17]

[0064] The resin according to Configuration 16, having at least one structure selected from the group consisting of the structures represented by the general formulae (UN1 - 1) and (UN1 - 2). * represents a bonding position.

[0065]

Chemical Formula 5

[0066]

[0067] [Constitution 18]

[0068] A method for producing a resin having a structure represented by the general formula (UN1), the production method comprising: a step of reacting a dicarbonate monomer or oligomer having a structure represented by the general formula (UN1) with a bisphenol compound by interfacial polycondensation.

[0069]

Chemical Formula 6

[0070]

[0071] (In the formula, X represents a single bond, -O-, -S-, -SO-, -SO2- or an organic group having 1 or more and 20 or less carbon atoms. * represents the bonding position.)

[0072] [Constitution 19]

[0073] The method for producing a resin according to Constitution 18, wherein the amount of terminal hydroxyl groups in the resin having a structure represented by the general formula (UN1) is 6000 mass ppm or less.

[0074]

Chemical Formula 7

[0075]

[0076] (In the formula, X represents a single bond, -O-, -S-, -SO-, -SO2- or an organic group having 1 or more and 20 or less carbon atoms. * represents the bonding position.)

[0077] According to one aspect of the present invention, an electronic substrate material having low dielectric characteristics can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0078] Figure 1 It is a graph showing the relationship between the temperature and the relative dielectric constant (Dk) of the specimens obtained in Examples 1 to 4, 7, 8, Comparative Examples 1 and 2.

[0079] Figure 2 It is a graph showing the relationship between the temperature and the dielectric loss tangent (Df) of the specimens obtained in Examples 1 to 4, 7, 8, Comparative Examples 1 and 2. DETAILED DESCRIPTION OF THE INVENTION

[0080] Hereinafter, the present invention will be described in detail.

[0081] [Resin]

[0082] The electronic substrate material according to this embodiment contains the resin according to this embodiment.

[0083] The resin (polycarbonate resin) according to this embodiment is a resin having a structure represented by the following general formula (UN1).

[0084]

Chemical Formula 8

[0085]

[0086] In the above general formula (UN1),

[0087] X is a single bond or a linking group. When X is a linking group, the linking group is

[0088] -O-,

[0089] -S-,

[0090] -SO-,

[0091] -SO2- or

[0092] an organic group having 1 or more and 20 or less carbon atoms,

[0093] The organic group having 1 or more and 20 or less carbon atoms is selected from the group consisting of

[0094] -CR 11 R 12 -,

[0095] a substituted or unsubstituted cycloalkylene group having 5 or more and 20 or less carbon atoms,

[0096] a substituted or unsubstituted bicyclic hydrocarbon diyl group having 5 or more and 20 or less carbon atoms,

[0097] a substituted or unsubstituted tricyclic hydrocarbon diyl group having 5 or more and 20 or less carbon atoms,

[0098] a substituted or unsubstituted alkylene group having 2 or more and 12 or less carbon atoms, and

[0099] a substituted or unsubstituted arylene group having 6 or more and 12 or less carbon atoms

[0100] at least one selected from the group consisting of,

[0101] R 11 and R 12 are each independently selected from the group consisting of

[0102] a hydrogen atom,

[0103] a substituted or unsubstituted alkyl group having 1 or more and 12 or less carbon atoms, and

[0104] a substituted or unsubstituted aryl group having 6 or more and 12 or less carbon atoms

[0105] at least one in the group consisting of

[0106] R 11 and R 12 may be bonded to each other by the above alkyl groups to form a ring represented by the following general formula (RIN1),

[0107] * represents a bonding position.

[0108]

Chemical formula 9

[0109]

[0110] In the above general formula (RIN1),

[0111] R 3 is a substituted or unsubstituted alkyl group having 1 or more and 12 or less carbon atoms,

[0112] R 4 is selected from

[0113] a hydrogen atom,

[0114] a substituted or unsubstituted alkyl group having 1 or more and 12 or less carbon atoms,

[0115] a substituted or unsubstituted aryl group having 6 or more and 12 or less carbon atoms, and

[0116] a substituted or unsubstituted cycloalkyl group having 3 or more and 6 or less carbon atoms

[0117] at least one in the group consisting of

[0118] Multiple Rs may be attached to one ring 4 , in this case, multiple Rs 4 may be the same group or different groups from each other.

[0119] The polycarbonate resin according to this 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 position.

[0120] As a compound (monomer compound) having a structure represented by the general formula (UN1), for example, 1,1-bis(3-cyclohexyl-4-hydroxyphenyl)cyclohexane, 1,1-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 1,1-bis(3-cyclohexyl-4-hydroxyphenyl)cyclopentane, 1,1-bis(3-cyclohexyl-4-hydroxyphenyl)methane, 1,1-bis(3-cyclohexyl-4-hydroxyphenyl)ethane, 1,1-bis(3-cyclohexyl-4-hydroxyphenyl)-1-phenylethane, and 1,1-bis(3-cyclohexyl-4-hydroxyphenyl)adamantane can be mentioned. These compounds can be obtained as commercially available products, or can be synthesized by subjecting a target phenol and a ketone to dehydration condensation using an acid catalyst.

[0121]

Chemical Formula 10

[0122]

[0123] 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 (UN3).

[0124]

Chemical Formula 11

[0125]

[0126] In the above general formula (UN3), 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.

[0127] 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.

[0128] n represents 0, 1, 2, 3, or 4.

[0129] When the total of two n's is 2 or more, the plurality of R 1 and R 2 may be the same group or different groups from each other.

[0130] When there are a plurality of R 1 or R 2 each, the plurality of R 1 may be the same group or different groups from each other, and the plurality of R 2 may be the same group or different groups from each other.

[0131] * represents a bonding site.

[0132] As the halogen atom, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. can be cited.

[0133] As the alkyl group having 1 or more and 12 or less carbon atoms, for example, 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, a trifluoromethyl group, etc. can be cited.

[0134] As the substituted or unsubstituted aryl group having 6 or more and 12 or less carbon atoms, for example, 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, a methylnaphthyl group, etc. can be cited.

[0135] As the alkoxy group having 1 or more and 12 or less carbon atoms, for example, 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. can be cited.

[0136] As the substituted or unsubstituted aryloxy group having 6 or more and 12 or less carbon atoms, for example, a phenoxy group, a tolyloxy group, a naphthyloxy group, etc. can be cited.

[0137] By having substituents such as R 1 and R 2 the molecular mobility of the carbonate group can be decreased by their steric hindrance. This decreases the dielectric loss tangent, and thus is preferred. In addition, in order to decrease the relative dielectric constant, low density and low polarity are required. By having substituents such as R 1 and R 2 it is difficult for polymer chains to stack with each other, and thus the density is decreased, or in the case where the substituent is a low-polarity group, the concentration of the carbonate group as the polar group of the polycarbonate is decreased, and the whole polymer is low-polarized. Therefore, for low dielectric constant, the more low-polar and large-volume substituents are, the more preferred.

[0138] As the compound (monomer compound) having the structure represented by the derived general formula (UN3), 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 commercially available products, or can be synthesized by subjecting the target phenol and a ketone to dehydration condensation using an acid catalyst.

[0139] 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).

[0140]

Chemical formula 12

[0141]

[0142] In the above general formula (UN4),

[0143] R 1 and R 2 As described above,

[0144] n is as described above,

[0145] * represents a bonding site.

[0146] As the compound (monomeric compound) having the structure represented by the derived general formula (UN4), for example, 1,1-bis(4-hydroxyphenyl)cyclododecane, 1,1-bis(4-hydroxy-3-methylphenyl)cyclododecane, 1,1-bis(4-hydroxy-3,5-dimethylphenyl)cyclododecane, 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.

[0147] 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 (UN5).

[0148]

Chemical Formula 13

[0149]

[0150] In the above general formula (UN5),

[0151] R 1 and R 2 As described above,

[0152] n is as described above,

[0153] * represents a bonding site.

[0154] As the compound having the structure represented by the general formula (UN5), for example, 2,2-dimethyl-4,4-biphenol, 2,2,6,6-tetramethyl-4,4-biphenol, 2,2,3,3,6,6-hexamethyl-4,4-biphenol, 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.

[0155] The polycarbonate resin according to the present embodiment may further have a structure represented by the following general formula (UN2).

[0156]

Chemical Formula 14

[0157]

[0158] In the above general formula (UN2),

[0159] R 1 and R 2 As described above,

[0160] n As described above,

[0161] X As described above,

[0162] * indicates a bonding site.

[0163] As compounds (monomer compounds) having the structure represented by the derived general formula (UN2), for example, 2,2-bis(4-hydroxy-3-isopropylphenyl)propane and 1,1-bis(4-hydroxyphenyl)cyclohexane can be mentioned. 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.

[0164] The polycarbonate resin according to the present embodiment preferably further has at least one structure selected from the group consisting of the structures represented by the above general formula (UN2), the above general formula (UN3), the above general formula (UN4), and the above general formula (UN5).

[0165] There are various methods for evaluating dielectric properties. As a frequently used method, there is a cavity resonator perturbation method (hereinafter referred to as the cavity resonance method) for evaluating dielectric properties using an 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 calculate the relative dielectric constant by the electric field passing through the entire specimen. 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 that occurs 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.

[0166] In the polycarbonate resin according to this embodiment, the relative dielectric constant (Dk) measured at a frequency of 10 GHz at room temperature using a split cylinder resonator 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 at a frequency of 10 GHz at room temperature using a split cylinder resonator 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 achieved. In addition, when the resin according to this embodiment is used as an electronic substrate material, since the electronic substrate reaches a high temperature during use, it is also important that the relative dielectric constant or the tangent of the dielectric loss angle is low at high temperatures.

[0167] 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 dielectric constant is 0.03 or less, and the change amount of the tangent of the dielectric loss angle is 0.005 or less.

[0168] 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 structural unit in this specification refers to the unit sandwiched between two adjacent carbonate bonds constituting the main chain.

[0169] A polycarbonate resin having a reduced viscosity average molecular weight of 30,000 or less is easily soluble in a non-halogen-based solvent, has a low viscosity, and is easy to handle in coating molding or is also easy to disperse with a filler or other thermosetting materials. Therefore, it has excellent versatility as an electronic substrate material.

[0170] 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 30,000 or less, preferably 1,000 or more and 26,000 or less, more preferably 1,000 or more and 22,000 or less, further preferably 1,000 or more and 19,000 or less, still more preferably 1,000 or more and 18,000 or less, and particularly preferably 1,000 or more and 17,500 or less.

[0171] In addition, due to the low desired coefficient of thermal expansion, the coefficient of thermal expansion of the polycarbonate resin according to this embodiment from 40°C to 100°C is preferably 100 ppm / K or less.

[0172] A thermosetting group (crosslinking group) may also be introduced into the structure of the polycarbonate resin according to this embodiment. The resin containing this crosslinked group structure, that is, the resin having a crosslinked structure, is called a thermosetting resin. By changing from thermoplastic to thermosetting, the heat resistance and elastic modulus can be increased. 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.

[0173] Examples of the crosslinking group of the thermosetting resin include epoxy group, allyl group, maleimide, oxazole, cyclobutene, isocyanate, cyanate ester, etc.

[0174] For example, a conjugated diene structure or a conjugated diene group (hereinafter also simply referred to as "conjugated diene") that can have a bond between polymer chains through the Diels-Alder reaction can be cited. As the conjugated diene, it preferably contains at least one of the structures represented by the following general formula (UN6) and general formula (UN7). In addition, it can also be a Diels-Alder reaction in which a conjugated diene structure such as 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.

[0175]

Chemical formula 15

[0176]

[0177] In the above general formula (UN6) and general formula (UN7),

[0178] R 5 each independently is

[0179] a single bond,

[0180] a connecting group to other skeletons,

[0181] a hydrogen atom,

[0182] an aliphatic hydrocarbon group having 1 or more and 12 or less carbon atoms,

[0183] an aromatic hydrocarbon group having 6 or more and 12 or less ring-forming carbon atoms, or

[0184] an alkoxy group having 1 or more and 10 or less carbon atoms,

[0185] R 5One or two of them are single bonds or linking groups to other skeletons.

[0186] R as the linking group 5 is a group that contains 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.

[0187] In addition, multiple Rs can also form 5 a cyclic structure (including an aromatic ring and a heterocyclic ring) formed by connection.

[0188] [Chemical Formula 16]

[0189]

[0190] In the above general formulas (UN8) to (UN10),

[0191] X 1 are each independently

[0192] -O-,

[0193] -(C=O)-O-,

[0194] -O-(C=O)-O- or

[0195] -O-(C=O)-,

[0196] R 6 are each independently

[0197] an aliphatic hydrocarbon group having 1 or more and 10 or less carbon atoms,

[0198] an aromatic hydrocarbon group having 6 or more and 12 or less ring-forming carbon atoms, or

[0199] an alkoxy group having 1 or more and 10 or less carbon atoms,

[0200] In addition, multiple Rs can also form 6 a cyclic structure (including an aromatic ring and a heterocyclic ring) formed by connection.

[0201] R 7 are each independently

[0202] a hydrogen atom,

[0203] an aliphatic hydrocarbon group having 1 or more and 12 or less carbon atoms or

[0204] an aromatic hydrocarbon group having 6 or more and 12 or less carbon atoms,

[0205] n1 represents 0 or a natural number with the upper limit of the substitutable quantity.

[0206] * indicates a bonding site.

[0207] As the crosslinking group of the thermosetting resin of the present invention, for example, an allyl structure or an allyl group that can bond between polymer chains through an ene reaction can be cited. Due to the high reactivity of the allyl structure, it is preferably to contain 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 2 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 ene reaction with each other.

[0208]

Chemical Formula 17

[0209]

[0210]

Chemical Formula 18

[0211]

[0212] In the above general formula (UN11), general formula (UN12), and general formula (UN13),

[0213] X 2 is selected from the group consisting of

[0214] -O-,

[0215] -S-,

[0216] -SO-,

[0217] -SO2-,

[0218] -CR 11 R 12 -,

[0219] a substituted or unsubstituted cycloalkylene group having 5 or more and 20 or less carbon atoms,

[0220] a substituted or unsubstituted bicyclic hydrocarbon diyl group having 5 or more and 20 or less carbon atoms,

[0221] a substituted or unsubstituted tricyclic hydrocarbon diyl group having 5 or more and 20 or less carbon atoms,

[0222] a substituted or unsubstituted alkylene group having 2 or more and 12 or less carbon atoms, and

[0223] a substituted or unsubstituted arylene group having 6 or more and 12 or less carbon atoms

[0224] selected from the group consisting of at least 1,

[0225] R 11 and R12 As described above,

[0226] * indicates a bonding site.

[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. Considering the use as an electronic substrate material, when all structural units are set to 100 mol%, when the proportion of the crosslinking groups is 10 mol% or more, the effects of improved heat resistance and decreased thermal expansion rate are significantly exhibited.

[0228] The manufacturing method of the polycarbonate resin according to the present embodiment can employ conventional polymerization methods such as the interfacial polycondensation method or the 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, an ester exchange 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 relatively high dielectric constant is increased by the highly polar structure, so there is a tendency for the low dielectric characteristics to deteriorate. In addition, the high polar groups tend to increase the dielectric loss tangent. Therefore, in order to exhibit low dielectric characteristics and suppress characteristic 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. This 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 208 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 amount of terminal hydroxyl groups, first, the molar ratio of each structure (structural unit) of the polycarbonate is calculated using NMR. Each structure refers to the main structure, the secondary 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)) can be cited, etc. As the hydroxyl-terminal structure, the hydroxyl-terminal structure derived from bisphenol (general formula (UN16)) can be cited, etc. 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 19]]

[0234]

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

[0236] Therefore, in order to reduce the amount of terminal hydroxyl groups, in-depth research was conducted, and as a result, two methods were discovered. The first method is to control the ratio of bisphenol / carbonochloridate group. This bisphenol and the 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. In order 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 invention, it was found that by reacting an appropriate amount of bisphenol with respect 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, and if it is less than 0.5, carbonochloridate is likely to remain.

[0239] In the case of bisphenol having a cyclohexyl group in the ortho position, a part of the bisphenol has a substituent at a position adjacent to the phenolic hydroxyl group, whereby the hydrophilic environment around the phenolic hydroxyl group is alleviated, and thus it has the characteristic of better solubility in dichloromethane as a reaction solvent than ordinary bisphenol. In a usual polymer growth reaction, the alkoxy group at the polymer terminal generated during the reaction exists at the interface, and thus a polymer is formed by reaction with the chloroformate in the dichloromethane layer. However, it was found that if this bisphenol with good solubility in dichloromethane is used for the reaction, the alkoxy group at the polymer terminal slightly becomes a hydroxyl group in the equilibrium reaction, and the resulting polymer dissolves in dichloromethane. Before the hydroxyl-terminated polymer transferred to the organic layer is alkoxylated again to carry out the polymerization reaction, the reaction with the chloroformate as the target active group is already completed, and it easily remains as a hydroxyl-terminated polymer. In order to reduce this hydroxyl terminal, the control of the above-mentioned bisphenol / chloroformate ratio is also important.

[0240] The second method for reducing the amount of terminal hydroxyl groups is a method of reacting a dichloroformate monomer or oligomer represented by the general formula (1A) with bisphenol. By forming a dichloroformate oligomer from bisphenol having a cyclohexyl group in the ortho position, since it is not necessary to use it in the form of bisphenol, the above-mentioned problems do not need to be considered, and the amount of terminal hydroxyl groups can be reduced.

[0241]

Chemical Formula 20

[0242]

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

[0244] 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.

[0245] The resulting polycarbonate resin can be any one of a block copolymer, an alternating copolymer, and a random copolymer, etc.

[0246] As the reason for preferably using a monomer (n 1A = 1.0), it is possible to adjust the copolymerization ratio in 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 easily controlled. In the case of a copolymerization target that is easily crystallized, a decrease in solubility can be prevented.

[0247] When producing a polycarbonate resin of general formula (UN1) exhibiting low dielectric properties and having a bisphenol with a cyclohexyl group in the ortho position, if a bisphenol having these skeletons is used, due to its high acid dissociation constant, its solubility in an alkaline aqueous solution is worse than that of a normal bisphenol, and it is only partially soluble in the alkaline aqueous solution at room temperature. In this state, although the bisphenol is also consumed as the polymerization reaction proceeds, the previously insoluble bisphenol newly dissolves, thereby promoting the reaction. However, in this state, since only one of the two hydroxyl groups of the bisphenol undergoes phenolate ionization and the resulting component participates in the reaction, a large amount of hydroxyl groups remain at the ends of the obtained polymer. Regarding this problem, by converting the bisphenol having a cyclohexyl group in the ortho position into a bis(chloroformate) oligomer, since it is not necessary to use it in the form of a bisphenol, it is not necessary to consider the above-mentioned problem points, and the amount of terminal hydroxyl groups can also be reduced.

[0248] 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.

[0249] 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(perfluorohexoxycarbonyl)phenol, p-perfluorododecyl hydroxybenzoate, p-(1H,1H-perfluorooctoxylated)phenol, and 2H,2H,9H-perfluorononanoic acid are used.

[0250] When performing interfacial polycondensation, as an acid-binding agent, for example, 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 can be cited. Preferred acid-binding agents for performing 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 in consideration of the stoichiometric ratio (equivalent) of the reaction. Specifically, with respect to a total of 1 mole of the hydroxyl groups of the diphenol as a 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.

[0251] As the solvent used in interfacial polycondensation, an organic solvent that is substantially immiscible with water and can dissolve 5 mass% or more of the finally obtained polycarbonate copolymer is preferably used. 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.

[0252] Here, the organic solvent that is "substantially immiscible with water" means an organic solvent that, under normal temperature and pressure conditions, does not form a solution composed of a homogeneous layer (a solution in which neither a gel nor insoluble matter is observed) when water and the organic solvent are mixed in a composition range of 1:9 to 9:1.

[0253] 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.

[0254] 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 the present embodiment, and is the polymer before crosslinking.

[0255] 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.

[0256] 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.

[0257] In addition, a small amount of an antioxidant such as sodium sulfite or dithionite can be added to the reaction system as needed.

[0258] [Resin precursor composition]

[0259] The resin precursor composition according to the present embodiment refers to a composition of a resin having the above crosslinking group and respective crosslinking agents.

[0260] As a crosslinking agent, for example, in the case of a Diels-Alder reaction or an ene reaction, due to its high reactivity, a crosslinking agent having a maleimide skeleton is preferably used. For example, the following can be mentioned: 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-diphenyl sulfone 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 bismaleimide compounds, and a polycarbonate resin having a structure in which the molecular terminals are blocked with the following compound.

[0261] [Chemical Formula 21]

[0262]

[0263] 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 use.

[0264] [Coating Liquid Composition]

[0265] 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.

[0266] 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 product.

[0267] Examples of the organic solvent involved in 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)), etc.

[0268] Among them, considering environmental or safety aspects, an organic solvent other than halogenated hydrocarbons, that is, a non-halogen-based solvent, is preferred.

[0269] The concentration of the polycarbonate resin or resin precursor composition involved in the coating liquid composition of 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 coating property 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.

[0270] [Electronic substrate]

[0271] Electronic substrates can be roughly classified into the following semiconductor substrates and electronic circuit substrates.

[0272] (1) Semiconductor substrate material

[0273] 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 a connection layer when connecting FC-CSP (flip chip-chip scale package), FC-BGA (flip chip-ball grid array), FO-WLP (fan-out package), or when connecting different types of chips in parallel or stacked.

[0274] (2) Electronic circuit substrate

[0275] 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.

[0276] [Electronic substrate material]

[0277] The electronic substrate material according to this embodiment is used in a film, sheet, or coating liquid composition (varnish) in order to form the electronic substrate according to this embodiment. That is, the film, sheet, and varnish contain the electronic substrate material according to this embodiment.

[0278] The electronic substrate material according to this embodiment can be excellent in terms of low dielectric characteristics, low thermal expansion rate, and high heat resistance. The electronic substrate material according to this 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 this embodiment can provide a thermosetting resin obtained by introducing a thermosetting group for improving heat resistance and elastic modulus.

[0279] [Film]

[0280] When using the electronic substrate material according to this embodiment as a film, it can also be formed into a film by thermoforming such as melt extrusion, or formed into a film by solution casting. In the case where the film thickness used is thin, in the range of several μm to several tens of μm, it is suitable to form the film by solution casting. In addition, for the purpose of reducing thermal expansion and the like, it can be formed into a film while being immersed in a glass fiber cloth or in a state where an inorganic filler such as silica is dispersed during film formation. In addition, when using the electronic substrate material according to this embodiment having a crosslinked portion to form a film 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.

[0281] [Varnish]

[0282] The electronic substrate material according to this embodiment can be directly coated in a solution state on a core material formed of polyimide, epoxy resin, or the like. At this time, an inorganic filler such as silica can also be dispersed.

[0283] Suitable solvents are toluene, cyclohexanone, and MEK, etc.

[0284] [Sheet]

[0285] When using the electronic substrate material according to this embodiment as a sheet, the sheet can be formed by immersing a substrate or the like in the above varnish.

[0286] Examples

[0287] 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 idea of the present invention.

[0288] [Production Example: Preparation of Oligomer]

[0289] <Manufacturing Example 1: Synthesis of 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane oligomer (bischloroformate)>

[0290] 87.9 g (224 mmol) of 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane 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 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane oligomer having a chloroformate group at the molecular terminal. The chloroformate concentration of the obtained solution was 0.84 mol / L, the solid content concentration was 0.223 kg / L, and the average number of polymerization units was 1.03. Hereinafter, the obtained raw material is referred to as CHA-CF.

[0291] <Manufacturing Example 2: Synthesis of 1,1-bis(3-cyclohexyl-4-hydroxyphenyl)cyclohexane oligomer (bischloroformate)>

[0292] 96.9 g (224 mmol) of 1,1-bis(3-cyclohexyl-4-hydroxyphenyl)cyclohexane 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 2,2-bis(3'-cyclohexyl-4'-hydroxyphenyl)propane oligomer having a chloroformate group at the molecular terminal. The chloroformate concentration of the obtained solution was 0.75 mol / L, the solid content concentration was 0.221 kg / L, and the average number of polymerization units was 1.07. Hereinafter, the obtained raw material is referred to as CHZ-CF.

[0293] [Synthesis Example 1]

[0294] (Manufacture of PC polymer)

[0295] In a reaction vessel equipped with a mechanical stirrer, stirring blades, and baffles, 233 mL of the CHA-CF prepared in Production Example 1 and 265 mL of dichloromethane were injected. p-tert-Butylphenol (hereinafter referred to as PTBP) (0.192 g) as a capping agent was added thereto, and stirring was performed to achieve sufficient 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)cyclododecane (hereinafter referred to as OCCDE) (Solution preparation method: Prepare 148 mL of a 1.5 N aqueous potassium hydroxide solution (14.2 g of potassium hydroxide), add 0.20 g of dithionite as an antioxidant and 22.9 g of OCCDE, heat to 70 °C to completely dissolve it. Then, air-cool to room temperature.)) was added to this solution, and 1.5 mL of a triethylamine aqueous solution (7 vol%) was added while stirring, and stirring was continued for 90 minutes.

[0296] 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 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 resulting reprecipitate was filtered and dried, thereby obtaining a PC polymer (PC-1) having the following structure.

[0297] (Identification of PC polymer)

[0298] The PC polymer (PC-1) 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, and the result was 0.61 dL / g. It should be noted that for the structure and composition of the obtained PC-1, 1 analysis by 1H-NMR spectrum confirmed that it was a PC polymer composed of the following repeating units and composition ratio.

[0299] [Chemical formula 22]

[0300]

[0301] The composition ratio (mol%) was CHA:OCCDE = 6:4.

[0302] [Synthesis Example 2]

[0303] (Manufacture of PC polymer)

[0304] In a reaction vessel equipped with a mechanical stirrer, stirring blades, and baffles, 233 mL of CHA-CF prepared in Production Example 1 and 265 mL of dichloromethane were injected. 0.207 g of PTBP 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 solution of 1,1-bis(4-hydroxy-3-methylphenyl)-3,3,5-trimethylcyclohexane (hereinafter referred to as OCTMC) (Solution preparation method: 148 mL of 1.5N aqueous potassium hydroxide solution (14.2 g of potassium hydroxide) was prepared, and after cooling to below room temperature, 0.18 g of dithionite as an antioxidant and 20.4 g of OCTMC were added and completely dissolved to prepare) was added to this solution. While stirring, 1.5 mL of triethylamine aqueous solution (7 vol%) was added, and stirring was continued for 90 minutes.

[0305] 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-2) having the following structure was obtained.

[0306] (Identification of PC polymer)

[0307] The PC polymer (PC-2) 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 0.47 dL / g. It should be noted that for the structure and composition of the obtained PC-2, through 1 1H-NMR spectrum analysis, it was confirmed to be a PC polymer composed of the following repeating units and composition ratio.

[0308] [Chemical formula 23]

[0309]

[0310] The composition ratio (mol%) was CHA:OCTMC = 6:4.

[0311] [Synthesis Example 3]

[0312] (Manufacture of PC polymer)

[0313] In a reaction vessel equipped with a mechanical stirrer, stirring blades, and baffles, 235 mL of the CHZ-CF prepared in Production Example 2 and 263 mL of dichloromethane were injected. 0.210 g of PTBP as a capping agent was added thereto, and stirring was carried out to ensure thorough mixing. After cooling until the temperature inside the reactor reached 10°C, the entire amount of the prepared OCCDE solution (Solution preparation method: 148 mL of a 1.3 N aqueous potassium hydroxide solution (12.8 g of potassium hydroxide) was prepared, 0.18 g of dithionite as an antioxidant and 20.7 g of OCCDE were added, and the mixture was heated to 70°C to completely dissolve it. Then, it was air-cooled to room temperature.)) was added to this solution, and 1.4 mL of a triethylamine aqueous solution (7 vol%) was added while stirring, and stirring was continued for 90 minutes.

[0314] 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 0.03 N hydrochloric acid, and three times with 0.23 L of water. The obtained dichloromethane solution was added dropwise to methanol while stirring, and the resulting reprecipitate was filtered and dried, whereby a PC polymer (PC-3) having the following structure was obtained.

[0315] (Identification of PC polymer)

[0316] 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 0.61 dL / g. It should be noted that for the structure and composition of the obtained PC-3, 1 analysis was performed by 1H-NMR spectroscopy, and as a result, it was confirmed to be a PC polymer composed of the following repeating units and composition ratio.

[0317] [Chemical formula 24]

[0318]

[0319] The composition ratio (mol%) was CHZ:OCCDE = 6:4.

[0320] [Synthesis Example 4]

[0321] (Manufacture of PC polymer)

[0322] In a reaction vessel equipped with a mechanical stirrer, stirring blades, and baffles, 235 mL of CHZ-CF prepared in Production Example 2 and 263 mL of dichloromethane were injected. PTBP (0.201 g) as a capping agent was added thereto, and stirring was carried out to ensure thorough mixing. After cooling until the temperature inside the reactor reached 10 °C, the entire amount of the prepared OCCDE solution (solution preparation method: 148 mL of 1.3 N aqueous potassium hydroxide solution (12.8 g of potassium hydroxide) was prepared, and after cooling to below room temperature, 0.18 g of dithionite as an antioxidant and 18.4 g of OCTMC were added and completely dissolved to prepare) was added to this solution, and 1.4 mL of triethylamine aqueous solution (7 vol%) was added while stirring, and stirring was continued for 90 minutes.

[0323] 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 0.03 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 resulting reprecipitate was filtered and dried, whereby a PC polymer (PC-4) having the following structure was obtained.

[0324] (Identification of PC polymer)

[0325] 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, and the result was 0.49 dL / g. It should be noted that for the structure and composition of the obtained PC-4, 1 analysis by 1H-NMR spectrum confirmed that it was a PC polymer composed of the following repeating units and composition ratio.

[0326] [Chemical formula 25]

[0327]

[0328] The composition ratio (mol%) was CHZ:OCTMC = 6:4.

[0329] [Synthesis Example 5]

[0330] (Manufacture of PC polymer)

[0331] In a reaction vessel equipped with a mechanical stirrer, stirring blades, and baffles, 233 mL of the CHA-CF prepared in Production Example 1 and 265 mL of dichloromethane were injected. PTBP (0.418 g) as a capping agent was added thereto, and stirring was carried out to ensure thorough mixing. After cooling until the temperature inside the reactor reached 10 °C, the prepared OCTMC and a solution of 9-(4-hydroxybenzyl)-10-(4-hydroxyphenyl)anthracene (hereinafter referred to as BIPANT) (Solution preparation method: 148 mL of a 1.5 N aqueous potassium hydroxide solution (14.2 g of potassium hydroxide) was prepared, and after cooling to below room temperature, 0.18 g of dithionite as an antioxidant, 15.3 g of OCTMC, and 5.7 g of BIPANT were added and completely dissolved to prepare) were added in their entirety to this solution. While stirring, 1.5 mL of a triethylamine aqueous solution (7 vol%) was added, and stirring was continued for 90 minutes.

[0332] 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 0.03 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 resulting reprecipitate was filtered and dried, whereby a PC polymer (PC-5) having the following structure was obtained.

[0333] (Identification of PC polymer)

[0334] 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 0.52 dL / g. It should be noted that for the structure and composition of the obtained PC-5, 1 analysis by 1H-NMR spectrum confirmed that it was a PC polymer composed of the following repeating units and composition ratio.

[0335] [Chemical formula 26]

[0336]

[0337] The composition ratio (mol%) was CHA:OCTMC:BIPANT = 6:3:1.

[0338] <Preparation of coating liquid composition containing polycarbonate and production of resin film>

[0339] [Example 1]

[0340] 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 50 °C for 8 hours and then at 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.

[0341] [Example 2]

[0342] A resin film was obtained in the same manner as in Example 1, except that PC-2 was used instead of PC-1.

[0343] [Example 3]

[0344] A resin film was obtained in the same manner as in Example 1, except that PC-3 was used instead of PC-1.

[0345] [Example 4]

[0346] A resin film was obtained in the same manner as in Example 1, except that PC-4 was used instead of PC-1.

[0347] [Example 5]

[0348] A resin film was obtained in the same manner as in Example 1, except that PC-5 was used instead of PC-1.

[0349] [Example 6]

[0350] 1.5 g (15% by mass) of PC-2 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 50 °C for 8 hours and then at 130 °C for 8 hours using a vacuum dryer to remove the solvent and obtain a resin film.

[0351] [Example 7]

[0352] The same operations as in Synthesis Example 1 and Example 1 were carried out, except that the chloroformate of CHA and CHA was used instead of the chloroformate of OCCDE and CHA, to obtain a polycarbonate resin and a resin film having the following structure.

[0353] [Chemical Formula 27]

[0354]

[0355] [Example 8]

[0356] Instead of the chloroformate bodies of OCCDE and CHA, the chloroformate bodies of CHZ and CHZ 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.

[0357] [Chemical Formula 28]

[0358]

[0359] [Example 10]

[0360] Using the same polymerization method as in Synthesis Example 4, only the amount of the end-capping agent PTBP was changed to 3.02 g to obtain a polycarbonate resin having a viscosity-average molecular weight (Mv) of 1800 and having the following structure. It should be noted that it was difficult to form it into a film shape and the dielectric properties could not be measured.

[0361] [Chemical Formula 29]

[0362]

[0363] [Example 11]

[0364] Instead of the chloroformate bodies of OCCDE and CHA, the chloroformate bodies of CHA and 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane were used, adjusted to bisphenol / chloroformate = 0.74, 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.

[0365] [Chemical Formula 30]

[0366]

[0367] [Example 12]

[0368] Instead of the chloroformate bodies of OCCDE and CHA, the chloroformate bodies of CHA and 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane were used, adjusted to bisphenol / chloroformate = 0.86, 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.

[0369] [Chemical Formula 31]

[0370]

[0371] [Comparative Example 1]

[0372] Instead of using the chloroformate of OCCDE and CHA, 1,1-bis(4-hydroxyphenyl)propane and the chloroformate of 1,1-bis(4-hydroxyphenyl)propane 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.

[0373]

Chemical Formula 32

[0374]

[0375] [Comparative Example 2]

[0376] Instead of using the chloroformate of OCCDE and CHA, 1,1-bis(4-hydroxyphenyl)cyclohexane and the chloroformate 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.

[0377]

Chemical Formula 33

[0378]

[0379] [Example 9]

[0380] A polycarbonate resin having a viscosity-average molecular weight (Mv) of 17,500 obtained by using the same polymerization method as in Synthesis Example 1 and adjusting the amount of the end-capping agent PTBP was used, and the same operations as in Example 1 were carried out except for this, to obtain a resin film.

[0381] Each physical property of the polycarbonate resin was evaluated by the following method.

[0382] <Evaluation of viscosity-average molecular weight>

[0383] 0.2 g of the polycarbonate resin was dissolved in 40 mL of dichloromethane, and the specific viscosity (ηsp) of the solution at 20 °C was measured. Then, the Mv calculated by the following formula was used as the viscosity-average molecular weight. The apparatus used for the measurement was a kinematic viscosity measuring apparatus (VMR-052 USPC manufactured by Reika Co., Ltd.), and an Ubbelohde modified type (410-UIB type) viscometer was used. The results obtained are shown in Table 1.

[0384] η sp / C = [η] × (1 + 0.28 × η sp )

[0385] According to the Schnell formula,

[0386] 〔η〕 = 1.23 × 10 -5 Mv 0.83

[0387] was deformed,

[0388] Mv = ([η] / 1.23×10 -5 ) 1 / 0.83

[0389] [η]: Intrinsic viscosity

[0390] C: Specimen concentration (g / L)

[0391] <Evaluation of relative permittivity and dielectric loss tangent>

[0392] 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 permittivity (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 obtained results 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 test chamber, and the relative permittivity and dielectric loss tangent were measured at a frequency of 10 GHz. The obtained results 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 3.

[0393] <Evaluation of solution viscosity>

[0394] 0.27 g (5 mass%) of the resin film obtained in Examples 1 and 9 and 5.2 g of toluene were placed in a sample tube. After stirring at room temperature, the solution viscosity was measured using a tuning fork vibration viscometer SV-10 (manufactured by A&D). The SV display value [mPa·s×g / cm 3 shows viscosity × density and relatively represents the viscosity of the liquid. The obtained results are shown in Table 2.

[0395] <Evaluation of glass transition temperature and thermal expansion coefficient>

[0396] 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 TMA (Hitachi High-Technologies Science, TMA7100). The obtained results are shown in Table 1.

[0397] Measurement mode: Tensile Temperature condition: -30°C to 320°C (heating rate 5°C / min)

[0398] Data processing method: Thermal expansion coefficient (CTE) is calculated at 40°C to 100°C, and the glass transition temperature (Tg) uses the temperature at the inflection point

[0399] <Solubility Evaluation in a Non-Halogen Solvent (Toluene)>

[0400] Into a sample tube, 0.1 g (3% by mass) of the resin film and 3.2 g of toluene were introduced. After stirring at room temperature, the appearance of the solution after one day was visually confirmed. The results obtained are shown in Table 1.

[0401] A: No insoluble components, transparent

[0402] B: Although there are no insoluble components, turbidity can be visually confirmed.

[0403] F: There are insoluble components

[0404] <Evaluation of the Amount of Terminal Hydroxyl Groups>

[0405] As a calculation method for the amount of terminal hydroxyl groups, first, the molar ratio of each structure of the polycarbonate was calculated using deuterated dichloromethane and 400 MHz 1H-NMR (manufactured by JEOL REASONANCE CO., LTD.). The preparation method of the solution to be evaluated 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.

[0406] <Crosslinking Evaluation of the Resin Film>

[0407] 1.4 g of the resin of Example 5 (functional group concentration: 0.236 mmol / g) and 94 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 160 °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 160 °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 4.

[0408] F (dissolved): Visually, there are no insoluble components.

[0409] A (insoluble): Not swollen or slightly swollen and maintaining the film shape.

[0410] <Evaluation of solution fluidity>

[0411] 20 mg of the resins obtained in Example 4 and Example 10 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 toluene solution with a concentration of 40% by mass. Then, it was stirred with an oscillator for 1 hour, and the state when tilted 180 degrees was visually observed. The results obtained are shown in Table 1.

[0412] A: The time taken for the solution to reach the lid of the microtube is within 3 seconds.

[0413] B: The time taken for the solution to reach the lid of the microtube is more than 3 seconds.

[0414] [Table 1]

[0415]

[0416] [Research]

[0417] Examples 1 to 4 copolymerized with CHA or CHZ have relatively low dielectric properties compared to the homopolymers of Comparative Examples 1 and 2. In addition, the solubility in toluene, which is a non-halogen-based solvent, is also excellent.

[0418] According to Example 5, it is possible to introduce a crosslinking group into the CHA copolymer.

[0419] According to Example 6, it is possible to produce a film containing spherical silica and resin. At this time, due to the influence of silica with a relatively high relative permittivity, Dk is worse than that of using only the resin. Therefore, it is important to have a resin with lower dielectric properties.

[0420] The homopolymers of Examples 7 and 8 of CHA or CHZ have relatively low dielectric properties compared to the homopolymers of Comparative Examples 1 and 2.

[0421] According to Examples 11 to 12, by setting the bisphenol / carbonochloridate to an appropriate value, the amount of terminal hydroxyl groups can be reduced. In addition, the reduction of the amount of terminal hydroxyl groups contributes to the decrease of Dk.

[0422] By reducing the molecular weight of the resin with low dielectric properties (Example 4) (Example 10), it is possible to impart the characteristic that the coating solution exhibits fluidity even when dissolved at a high concentration.

[0423] [Table 2]

[0424]

[0425] [Research]

[0426] Table 2 shows the effects of the difference in molecular weight on the dielectric properties and solution viscosity in resins with the same copolymerization backbone.

[0427] From the dielectric properties of Example 1 and Example 9, it can be seen that even if the viscosity-average molecular weight changes, the dielectric properties do not change significantly.

[0428] From the solution viscosities of Example 1 and Example 9, it can be seen that the solution viscosity of Example 9 with a lower viscosity-average molecular weight is lower. Therefore, it can be known that the solution viscosity changes depending on the viscosity-average molecular weight.

[0429]

Table 3

[0430]

[0431] [Research]

[0432] According to Figure 1 and Table 3, Dk has almost no temperature dependence.

[0433] On the other hand, according to Figure 2 and Table 3, Df has a tendency to increase as the temperature rises. It is considered that this is because as the temperature rises, molecular motion in the resin becomes easier.

[0434] When comparing the polycarbonate containing cyclohexyl in the ortho position with Comparative Examples 1 and 2, it can be seen that when CHA or CHZ is included, the increasing ratio of Df with respect to the temperature rise decreases.

[0435]

Table 4

[0436]

[0437] [Research]

[0438] 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 5 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 the general formula (UN1), In the general formula (UN1), X represents a single bond, -O-, -S-, -SO-, -SO2-, or an organic group having 1 to 20 carbon atoms, and * represents a bonding site.

2. The electronic substrate material according to claim 1, wherein the resin 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.

3. The electronic substrate material according to claim 1 or 2, wherein the resin further has at least one structure selected from the group consisting of the structure represented by the general formula (UN2), the structure represented by the general formula (UN3), the structure represented by the general formula (UN4), and the structure represented by the general formula (UN5), In general formulas (UN2) to (UN5), 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, n represents 0, 1, 2, 3 or 4, and when the sum of two n's is 2 or more, a plurality of R 1 and R 2 are optionally the same group or different groups from each other, X represents a single bond, -O-, -S-, -SO-, -SO2- or an organic group having 1 or more and 20 or less carbon atoms, and * 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 30000 or less.

5. The electronic substrate material according to any one of claims 1 to 4, 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, 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.

7. The electronic substrate material according to any one of claims 1 to 6, when measuring the relative dielectric constant 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 by the split cylinder resonator perturbation method, the change amount of the dielectric constant is 0.03 or less, and the change amount of the tangent of the dielectric loss angle 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 bonding 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 further contains an inorganic filler.

12. The electronic substrate material according to any one of claims 1 to 11, wherein it further 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 a terminal hydroxyl group amount of 6000 mass ppm or less, In general formula (UN1), X represents a single bond, -O-, -S-, -SO-, -SO2-, or an organic group having 1 to 20 carbon atoms, and * represents a bonding site.

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

18. A method for producing a resin having the structure represented by general formula (UN1). The manufacturing method includes: A step of reacting a dicarbonate monomer or oligomer having the structure represented by general formula (UN1) with a bisphenol compound by interfacial polycondensation. In general formula (UN1), X represents a single bond, -O-, -S-, -SO-, -SO2-, or an organic group having 1 to 20 carbon atoms, and * represents a bonding site.

19. The method for producing a resin according to claim 18, wherein the amount of terminal hydroxyl groups in the resin having the structure represented by general formula (UN1) is 6000 mass ppm or less. In general formula (UN1), X represents a single bond, -O-, -S-, -SO-, -SO2-, or an organic group having 1 to 20 carbon atoms, and * represents a bonding site.

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