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 # imgabs0 # formula, R1 and R2 each independently represent at least one selected from the group consisting of a halogen atom and an organic group having 1-12 carbon atoms, and n represents 1, 2, 3 or 4. The plurality of R1 and R2 may be the same group or different groups. And * represents a bonding site.

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 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 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 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 using an insulating material, etc., 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 the use environment such as temperature and humidity for forming a thin film used in laminating and forming a wiring layer.

[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 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 that a polycarbonate resin having a 1,1-bis(4-hydroxyphenyl)cyclododecane skeleton can be used as a binder resin for heat-resistant printing inks. It is described that the solvent solubility and strength required for printing inks are maintained in a well-balanced manner. However, there is no description or teaching of its dielectric properties or thermal expansion coefficient, etc. as an electronic substrate.

[0008] Patent Document 2 describes that a polycarbonate resin having a 1,1-bis(4-hydroxy-3-methylphenyl)cyclododecane skeleton can be used as a high surface hardness film or sheet used in packaging materials or optical films, etc. It should be noted that there is also no description or revelation of its dielectric properties or thermal expansion coefficient, etc. as an electronic substrate.

[0009] Patent Document 3 describes that a polycarbonate resin manufactured using a specific one or two bisphenols as raw materials can be used as a thermoplastic resin composition and molded article having excellent radio wave permeability in the microwave or millimeter wave band, and excellent heat resistance and flame retardancy, and 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 and 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 or extrusion molding. There is no description of the high solvent solubility or low solution viscosity characteristics, and thermal expansion for coating and forming of the present invention. In addition, there is no description of a polycarbonate resin into which a thermosetting group is introduced.

[0010] Prior art documents

[0011] Patent documents

[0012] Patent Document 1: Japanese Patent Application Laid-Open No. 2008-063501

[0013] Patent Document 2: Japanese Patent Application Laid-Open No. 2010-126594

[0014] Patent Document 3: International Publication No. WO2021 / 039970 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 properties.

[0017] Means for Solving the Problems

[0018] The present inventors have repeatedly conducted in-depth studies 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 capable of controlling the amount of terminal hydroxyl groups to a low level has been found.

[0019] That is, the gist of the present invention lies in the following [Constitution 1] to [Constitution 21].

[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, 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 1, 2, 3 or 4. A plurality of existing R 1 and R 2 may be the same group or different groups from each other. * represents a bonding site).

[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 site.

[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, X represents a single bond, -O-, -S-, -SO-, -SO2-, or an organic group having 1 or more and 20 or less carbon atoms. 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 existing R 1 and R 2 may be the same group or different groups from each other. * 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 1000 or more and 35000 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 0.0032 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 relative 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 Constitutions 1 to 8, wherein the resin has a crosslinked structure.

[0046] [Constitution 10]

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

[0048] [Constitution 11]

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

[0050] [Constitution 12]

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

[0052] [Constitution 13]

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

[0054] [Constitution 14]

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

[0056] [Constitution 15]

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

[0058] [Constitution 16]

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

[0060] [Chemical Formula 4]

[0061]

[0062] (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 1, 2, 3, or 4. A plurality of existing R 1 and R 2 may be the same group or different groups from each other. * represents a bonding site.)

[0063] [Constitution 17]

[0064] The resin according to Configuration 16, wherein the resin 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.

[0065]

Chemical Formula 5

[0066]

[0067] [Configuration 18]

[0068] A method for producing a resin, the resin having a structure represented by General Formula (UN1) and a terminal hydroxyl group content of 6000 mass ppm or less, the production method including: a step of subjecting a dicarbonate monomer or oligomer having a structure represented by General Formula (UN1) and a bisphenol compound to interfacial polycondensation reaction.

[0069]

Chemical Formula 6

[0070]

[0071] (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 1, 2, 3, or 4. A plurality of R 1 and R 2 may be the same group or different groups from each other. * represents a bonding site.)

[0072] [Configuration 19]

[0073] According to the method for producing a resin described in Configuration 18, the terminal hydroxyl group content of the resin having a structure represented by General Formula (UN1) is 530 mass ppm or less.

[0074]

Chemical Formula 7

[0075]

[0076] (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 1, 2, 3, or 4. A plurality of R 1 and R 2 may be the same group or different groups from each other. * represents a bonding site.)

[0077] According to one aspect of the present invention, an electronic substrate material having low dielectric properties 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 6, 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 6, Comparative Examples 1 and 2. Detailed implementation mode

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

[0081] [Resin]

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

[0083] The resin (polycarbonate resin) according to this embodiment mode 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), 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,

[0087] 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,

[0088] n represents 1, 2, 3 or 4.

[0089] A plurality of existing R 1 and R 2 may be the same group or different groups from each other.

[0090] In the case where 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.

[0091] * represents the bonding position.

[0092] As the halogen atom, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. can be cited.

[0093] 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.

[0094] 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.

[0095] 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.

[0096] 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.

[0097] It is considered that by having substituents such as R 1 and R 2 the molecular mobility of the carbonate group can be reduced by their steric hindrance, and this can reduce the dielectric loss tangent.

[0098] As the compound (monomer compound) having the structure represented by the general formula (UN1), 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 a ketone to dehydration condensation using an acid catalyst.

[0099] 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 the bonding position.

[0100]

Chemical formula 9

[0101]

[0102] From the viewpoint of dielectric properties, the polycarbonate resin according to the present embodiment preferably further has the structure represented by the following general formula (UN3).

[0103]

Chemical formula 10

[0104]

[0105] In the above general formula (UN3),

[0106] R 1 and R 2 As described above,

[0107] m is as described above,

[0108] * represents a bonding site.

[0109] 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 ketone to dehydration condensation using an acid catalyst.

[0110] 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).

[0111]

Chemical Formula 11

[0112]

[0113] In the above general formula (UN4),

[0114] X is a single bond or a linking group, and when X is a linking group, the linking group can be

[0115] -O-,

[0116] -S-,

[0117] -SO-,

[0118] -SO2- or an organic group having 1 or more and 20 or less carbon atoms.

[0119] Examples of the organic group having 1 or more and 20 or less carbon atoms include:

[0120] -CR 11 R 12 -,

[0121] a substituted or unsubstituted cycloalkylidene group having 5 or more and 20 or less carbon atoms,

[0122] a substituted or unsubstituted bicyclic hydrocarbon diyl group having 5 or more and 20 or less carbon atoms,

[0123] a substituted or unsubstituted tricyclic hydrocarbon diyl group having 5 or more and 20 or less carbon atoms,

[0124] An alkylene group having 2 to 12 carbon atoms, which may or may not be substituted, and

[0125] An arylene group having 6 to 12 carbon atoms, which may or may not be substituted, etc.

[0126] R 11 and R 12 each independently is selected from

[0127] a hydrogen atom,

[0128] an alkyl group having 1 to 12 carbon atoms, which may or may not be substituted, and

[0129] an aryl group having 6 to 12 carbon atoms, which may or may not be substituted

[0130] and is at least one selected from the group consisting of

[0131] R 11 and R 12 may be bonded to each other by the above alkyl group to form a ring represented by the following general formula (RIN1).

[0132]

Chemical Formula 12

[0133]

[0134] In the above general formula (RIN1),

[0135] R 3 is an alkyl group having 1 to 12 carbon atoms, which may or may not be substituted,

[0136] R 4 is selected from

[0137] a hydrogen atom,

[0138] an alkyl group having 1 to 12 carbon atoms, which may or may not be substituted,

[0139] an aryl group having 6 to 12 carbon atoms, which may or may not be substituted, and

[0140] a cycloalkyl group having 3 to 6 carbon atoms, which may or may not be substituted

[0141] and is at least one selected from the group consisting of

[0142] 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.

[0143] In addition, in the above general formula (UN4), * represents a bonding position.

[0144] As the compound (monomer compound) having the structure represented by the general formula (UN4), examples thereof include 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. These compounds can be obtained as commercially available products, or can be synthesized by subjecting the target phenol and ketone to dehydration condensation using an acid catalyst.

[0145] 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).

[0146]

Chemical formula 13

[0147]

[0148] In the above general formula (UN5),

[0149] R 1 and R 2 As described above,

[0150] m As described above,

[0151] * represents the bonding position.

[0152] As the compound (monomer compound) having the structure represented by the general formula (UN5), examples thereof include 2,2-dimethyl-4,4-biphenol, 2,2,6,6-tetramethyl-4,4-biphenol, and 2,2,3,3,6,6-hexamethyl-4,4-biphenol. These compounds can be obtained as commercially available products, or can be synthesized by subjecting the target phenol and ketone to dehydration condensation using an acid catalyst.

[0153] The polycarbonate resin according to the present embodiment may further have a structure represented by the following general formula (UN2).

[0154]

Chemical formula 14

[0155]

[0156] In the above general formula (UN2),

[0157] R 1 and R 2 As described above,

[0158] m As described above,

[0159] As described above,

[0160] * indicates a bonding site.

[0161] As the compound (monomer compound) having the structure represented by the derived general formula (UN2), 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.

[0162] 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).

[0163] 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) for measuring using a circular electric field along the specimen surface, 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.

[0164] In the polycarbonate resin according to the present 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 0.0032 or less, more preferably 0.003 or less, still 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 electric signal in the electronic substrate is reduced, and good performance is obtained. In addition, when using the resin according to the present embodiment 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.

[0165] In addition, preferably, when measuring the relative permittivity 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 permittivity is 0.03 or less, and the change amount of the tangent of the dielectric loss angle is 0.005 or less.

[0166] In the polycarbonate resin according to the present 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 50 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 50 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 means a unit sandwiched between two adjacent carbonate bonds constituting the main chain.

[0167] A polycarbonate resin having a reduced viscosity average molecular weight of 35,000 or less is easily soluble in a non-halogen-based solvent, has a low viscosity, and is easily handled in coating molding or is easily dispersed with a filler or other thermosetting material. Therefore, it has excellent versatility as an electronic substrate material.

[0168] From such a viewpoint, the polycarbonate resin according to the present embodiment preferably has a viscosity average molecular weight (Mv) of 1,000 or more and 35,000 or less, more preferably 1,000 or more and 25,000 or less, further preferably 1,000 or more and 22,000 or less, still further preferably 1,000 or more and 18,000 or less, and particularly preferably 1,000 or more and 16,000 or less.

[0169] In addition, since a low coefficient of thermal expansion is desired, the coefficient of thermal expansion of the polycarbonate resin according to the present embodiment from a temperature of 40°C to 100°C is preferably 100 ppm / K or less.

[0170] A thermosetting group (crosslinking group) may also be introduced into the structure of the polycarbonate resin according to the present embodiment. The resin containing the 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 the 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 article having an electronic substrate incorporated therein. At this time, by using a thermosetting resin having high heat resistance and elastic modulus, resin flow or deformation of the electronic substrate can be prevented.

[0171] As crosslinking groups for thermosetting resins, there are epoxy groups, allyl groups, maleimide groups, oxazole groups, cyclobutene groups, isocyanate groups, cyanate ester groups, etc.

[0172] For example, a conjugated diene structure or a conjugated diene group (hereinafter also simply referred to as "conjugated diene") capable of having bonding between polymer chains through a 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 ends of the polymer chains to bond the ends of the polymer chains to each other.

[0173]

Chemical Formula 15

[0174]

[0175] In the above general formula (UN6) and general formula (UN7),

[0176] R 5 each independently is

[0177] a single bond,

[0178] a linking group with other skeletons,

[0179] a hydrogen atom,

[0180] an aliphatic hydrocarbon group having 1 or more and 12 or less carbon atoms,

[0181] an aromatic hydrocarbon group having 6 or more and 12 or less ring - forming carbon atoms, or

[0182] an alkoxy group having 1 or more and 10 or less carbon atoms,

[0183] R 5 one or two of which are a single bond or a linking group with other skeletons,

[0184] As the linking group R 5 is a group that contains at least any one atom selected from the group consisting of carbon atoms, oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, phosphorus atoms, and boron atoms, and the bonding form between the atoms constituting the linking group is all composed of covalent bonds.

[0185] In addition, a cyclic structure (including an aromatic ring and a heterocyclic ring) formed by connecting multiple Rs 5 can also be formed.

[0186]

Chemical Formula 16

[0187]

[0188] In the above general formulas (UN8) to (UN10),

[0189] X 1 each independently is

[0190] -O-,

[0191] -(C=O)-O-,

[0192] -O-(C=O)-O- or

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

[0194] R 6 each independently is

[0195] an aliphatic hydrocarbon group having 1 or more and 10 or less carbon atoms,

[0196] an aromatic hydrocarbon group having 6 or more and 12 or less ring-constituting carbon atoms or

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

[0198] In addition, a cyclic structure (including an aromatic ring and a heterocyclic ring) formed by connecting a plurality of Rs 6 may also be formed.

[0199] R 7 each independently is

[0200] a hydrogen atom,

[0201] an aliphatic hydrocarbon group having 1 or more and 12 or less carbon atoms or

[0202] an aromatic hydrocarbon group having 6 or more and 12 or less carbon atoms,

[0203] n1 represents 0 or a natural number with the upper limit of the number of substituents.

[0204] * represents a bonding position.

[0205] As a crosslinking group of the thermosetting resin, for example, an allyl structure or an allyl group that can bond between polymer chains through an ene 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 formulas (UN11), (UN12), and (UN13). The allyl structure represented by the following general formula (UN11) has 2 allyl groups. The allyl structures represented by the following general formula (UN12) or (UN13) can perform an ene reaction between the ends of the polymer chains because an allyl group is introduced at the end of the polymer.

[0206]

Chemical Formula 17

[0207]

[0208] [Chemical Formula 18]

[0209]

[0210] In the above general formulas (UN11), (UN12), and (UN13),

[0211] X 2 is selected from the group consisting of

[0212] -O-,

[0213] -S-,

[0214] -SO-,

[0215] -SO2-,

[0216] -CR 11 R 12 -,

[0217] a substituted or unsubstituted cycloalkylene group having 5 or more and 20 or less carbon atoms,

[0218] a substituted or unsubstituted bicyclic hydrocarbon diyl group having 5 or more and 20 or less carbon atoms,

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

[0220] a substituted or unsubstituted alkylene group having 2 or more and 12 or less carbon atoms, and

[0221] a substituted or unsubstituted arylene group having 6 or more and 12 or less carbon atoms

[0222] and at least one selected from the group consisting of,

[0223] R 11 and R 12 as described above,

[0224] * represents a bonding position.

[0225] 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 use. 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 coefficient are exhibited.

[0226] The method for manufacturing the polycarbonate resin according to the present embodiment can employ conventional polymerization methods such as interfacial polycondensation or melt transesterification.

[0227] The interfacial polycondensation method is a method of obtaining a polycarbonate resin by forming a basic salt of a monomer such as a bisphenol compound in the presence of a non-reactive organic solvent and an aqueous basic 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.

[0228] The polycarbonate resin of the present embodiment preferably has a low terminal hydroxyl group content. The terminal hydroxyl group content indicates the hydroxyl groups derived from the residual bisphenol and the hydroxyl groups derived from 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 characteristics 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 characteristics and suppress characteristic unevenness, it is necessary to control the terminal hydroxyl group content.

[0229] 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 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 530 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.

[0230] 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, PTBP terminals (general formula (UN14)) and diethylamine terminals (general formula (UN15)) etc. can be cited. As the hydroxyl terminal structure, a 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-terminated 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.

[0231]

Chemical formula 19

[0232]

[0233] 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 by the interfacial polycondensation method, the amount of terminal hydroxyl groups sometimes cannot be sufficiently reduced.

[0234] When manufacturing a polycarbonate resin having a structure represented by the general formula (UN1) that exhibits low dielectric characteristics, if a bisphenol having these skeletons is used, due to its high acid dissociation constant, its solubility in an alkaline aqueous solution is poorer than that of a normal bisphenol, and it is only partially soluble in the alkaline aqueous solution at room temperature. Although even in this state, as the polymerization reaction proceeds and the bisphenol is consumed, the previously insoluble bisphenol newly dissolves, thereby also promoting the reaction, in this state, since only a component formed by the phenolate ionized of only one of the two hydroxyl groups of the bisphenol participates in the reaction, a hydroxyl group remains at the terminal of the obtained polymer.

[0235] Therefore, in order to reduce the amount of terminal hydroxyl groups, in-depth research has been carried out, and as a result, two methods have been found. The first method is to heat the alkaline aqueous solution of bisphenol to about 70 °C to temporarily form an alkaline salt of bisphenol and dissolve it, and then air-cool it to room temperature and carry out the reaction. In this method, by heating, the two terminals of bisphenol are phenolate ionized, thereby reducing the amount of terminal hydroxyl groups.

[0236] The second method is to react a dichloroformate monomer or oligomer represented by the general formula (1A) with bisphenol. By forming a dichloroformate oligomer of bisphenol having a 1,1-bis(4-hydroxyphenyl)cyclododecane skeleton, since it is not necessary to carry out phenolate ionization, it is not necessary to consider the above problems, and the amount of terminal hydroxyl groups can be reduced.

[0237]

Chemical formula 20

[0238]

[0239] In the general formula (1A),

[0240] R 1 and R 2 As described above,

[0241] n As described above,

[0242] 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.

[0243] The generated polycarbonate resin can be any one of a block copolymer, an alternating copolymer, a random copolymer, etc.

[0244] As preferably a monomer (n1A The reason for this (i.e., the molar ratio of the oligomer (1A) in the copolymerization reaction mixture is 1.0) is that the copolymerization ratio can be adjusted over a wide range. Particularly 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 controllable. In the case of a copolymerization target that is easily crystallized, a decrease in solubility can be prevented.

[0245] As a capping agent for generating chain ends in the interfacial polycondensation method, a monocarboxylic acid and its derivatives, or a monophenol can be used.

[0246] 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, perfluorododecyl p-hydroxybenzoate, p-(1H,1H-perfluorooctoxylated)phenol, and 2H,2H,9H-perfluorononanoic acid are used.

[0247] 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 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, 1 equivalent or more of the acid-binding agent can be used relative to 1 mole of the total hydroxyl groups of the diphenol as a raw material, and preferably 1 to 10 equivalents of the acid-binding agent can be used.

[0248] As a 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.

[0249] Here, an organic solvent that is "substantially immiscible with water" means an organic solvent that does not form a solution composed of a homogeneous layer (a solution in which neither a gel nor an insoluble substance is observed) when water and the organic solvent are mixed in a composition range of 1:9 to 9:1 under normal temperature and pressure conditions.

[0250] In addition, the fact that the organic solvent "can dissolve 5 mass% or more of the finally obtained polycarbonate copolymer" means the solubility of the polycarbonate copolymer when measured under the conditions of a temperature of 20 to 30°C and normal pressure.

[0251] In addition, the "finally obtained polycarbonate polymer" refers to the polymer obtained through the polymerization step in the manufacturing method of the polycarbonate polymer of the present embodiment, and is the polymer before crosslinking.

[0252] 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.

[0253] In addition, the catalyst used in the interfacial polycondensation is not particularly limited. 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.

[0254] In addition, a small amount of an antioxidant such as sodium sulfite or dithionite can be added to the reaction system as needed.

[0255] [Resin precursor composition]

[0256] The resin precursor composition according to the present embodiment refers to a composition containing a resin having the above crosslinking group and respective crosslinking agents.

[0257] 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.

[0258] For example, the following can be cited: bismaleimides such as 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, and polyphenylmethane bismaleimide; and a polycarbonate resin having a structure in which the molecular terminals are capped with the following compound.

[0259] [Chemical Formula 21]

[0260]

[0261] The above crosslinking agent can be appropriately set according to the content of the crosslinking groups of the conjugated diene structure and allyl structure in the polycarbonate resin, or according to the target physical properties or target uses.

[0262] [Coating Liquid Composition]

[0263] The coating liquid composition (varnish) according to the present embodiment contains the electronic substrate material according to the present embodiment. More specifically, it contains the polycarbonate resin or resin precursor composition according to the present embodiment and an organic solvent.

[0264] 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 the present embodiment, the drying speed after forming, the influence and danger (fire or health hazard) when remaining in the formed product.

[0265] Examples of the organic solvents 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)).

[0266] Among them, considering environmental or safety aspects, organic solvents other than halogenated hydrocarbons, that is, non-halogen solvents, are preferred.

[0267] 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, an appropriate 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.

[0268] [Electronic substrate]

[0269] Electronic substrates are roughly classified into the following semiconductor substrates and electronic circuit substrates.

[0270] (1) Semiconductor substrate material

[0271] 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 connecting different types of chips in parallel or stacked.

[0272] (2) Electronic circuit substrate

[0273] 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.

[0274] [Electronic substrate material]

[0275] The electronic substrate material according to this embodiment is used in a film, sheet, or coating liquid composition (varnish) 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.

[0276] The electronic substrate material according to this embodiment can be excellent in terms of low dielectric properties, 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.

[0277] [Film]

[0278] When the electronic substrate material according to this embodiment is used as a film, film formation can also be performed by thermoforming such as melt extrusion, or film formation can be performed by solution casting. When the thickness of the film 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 an inorganic filler such as silica being dispersed when forming the film. In addition, when using the electronic substrate material according to this embodiment having a crosslinked portion to perform film formation by solution casting, the degree of crosslinking can also be controlled and the elastic modulus of the film can be changed by containing a curing material and adjusting the heating temperature.

[0279] [Varnish]

[0280] The electronic substrate material according to this 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.

[0281] Suitable solvents are toluene, cyclohexanone, and MEK, etc.

[0282] [Sheet]

[0283] When the electronic substrate material according to this embodiment is used as a sheet, the sheet can be formed by immersing a substrate, etc. in the above varnish.

[0284] Examples

[0285] 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.

[0286] [Production Example: Preparation of Oligomer]

[0287] <Manufacturing Example 1: Synthesis of 1,1-bis(4-hydroxy-3-methylphenyl)cyclododecane oligomer (bischloroformate)>

[0288] 85.2 g (224 mmol) of 1,1-bis(4-hydroxy-3-methylphenyl)cyclododecane 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)cyclododecane 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 0.222 kg / L, and the average number of polymerization units was 1.03. Hereinafter, the obtained raw material is referred to as OCCDE-CF.

[0289] <Manufacturing Example 2: Synthesis of 1,1-bis(4-hydroxy-3,5-dimethylphenyl)cyclododecane oligomer (bischloroformate)>

[0290] 91.5 g (mmol) of 1,1-bis(4-hydroxy-3,5-dimethylphenyl)cyclododecane 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-3,5-dimethylphenyl)cyclododecane oligomer having a chloroformate group at the molecular terminal. The chloroformate concentration of the obtained solution was 0.78 mol / L, the solid content concentration was 0.216 kg / L, and the average number of polymerization units was 1.05. Hereinafter, the obtained raw material is referred to as TMBPCDE-CF.

[0291] [Synthesis Example 1]

[0292] (Manufacture of PC polymer)

[0293] In a reaction vessel equipped with a mechanical stirrer, stirring blades, and baffles, 225 mL of the OCCDE-CF prepared in Production Example 1 and 330 mL of dichloromethane were injected. p-tert-Butylphenol (hereinafter referred to as PTBP) (0.208 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 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: 185 mL of 1.5 N aqueous potassium hydroxide solution (18.2 g of potassium hydroxide) was prepared, and after cooling to below room temperature, 0.23 g of dithionite as an antioxidant and 26.2 g of OCTMC were added and completely dissolved) was added to this solution. While stirring, 29.5 mL of triethylamine aqueous solution (7 vol%) was added, and stirring was continued for 2 hours.

[0294] The resulting reaction mixture was diluted and washed with 0.72 L of dichloromethane and 0.04 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, whereby a PC polymer (PC-1) having the following structure was obtained.

[0295] (Identification of PC polymer)

[0296] 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. The result was 0.78 dL / g. It should be noted that for the structure and composition of the obtained PC-1, 1 analysis was carried out by 1H-NMR spectrum, and as a result, it was confirmed to be a PC polymer composed of the following repeating units and composition ratio.

[0297] [Chemical formula 22]

[0298]

[0299] The composition ratio (mol%) was OCCDE:OCTMC = 6:4.

[0300] [Synthesis Example 2]

[0301] (Manufacture of PC polymer)

[0302] In a reaction vessel equipped with a mechanical stirrer, stirring blades, and baffles, 225 mL of the OCCDE-CF prepared in Production Example 1 and 330 mL of dichloromethane were injected. PTBP (0.221 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 solution of 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane (hereinafter referred to as CHA) (Solution preparation method: 185 mL of 1.5N aqueous potassium hydroxide solution (18.2 g of potassium hydroxide) was prepared, and after cooling to below room temperature, 0.27 g of dithionite as an antioxidant and 30.4 g of CHA were added and completely dissolved to prepare) was added to this solution. While stirring, 29.5 mL of a triethylamine aqueous solution (7 vol%) was added, and stirring was continued for 2 hours.

[0303] The resulting reaction mixture was diluted and washed with 0.72 L of dichloromethane and 0.04 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, whereby a PC polymer (PC-2) having the following structure was obtained.

[0304] (Identification of PC polymer)

[0305] 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, and the result was 0.60 dL / g. It should be noted that for the structure and composition of the obtained PC-2, through 1 analysis by 1H-NMR spectrum, it was confirmed to be a PC polymer composed of the following repeating units and composition ratio.

[0306] [Chemical formula 23]

[0307]

[0308] The composition ratio (mol%) was OCCDE:CHA = 6:4.

[0309] [Synthesis Example 3]

[0310] (Manufacture of PC polymer)

[0311] In a reaction vessel equipped with a mechanical stirrer, stirring blades, and baffles, 225 mL of the OCCDE-CF prepared in Production Example 1 and 330 mL of dichloromethane were poured. PTBP (0.235 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 solution of 2-cyclohexyl-4-[1-(3-cyclohexyl-4-hydroxyphenyl)-1-phenylethyl]phenol (hereinafter referred to as CHAP) (Solution preparation method: 185 mL of 1.5 N aqueous potassium hydroxide solution (18.2 g of potassium hydroxide) was prepared, and after cooling to below room temperature, 0.308 g of dithionite as an antioxidant and 35.2 g of CHAP were added and completely dissolved) was added to this solution. While stirring, 29.5 mL of a triethylamine aqueous solution (7 vol%) was added, and stirring was continued for 2 hours.

[0312] The resulting reaction mixture was diluted and washed with 0.72 L of dichloromethane and 0.04 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.

[0313] (Identification of PC polymer)

[0314] 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, through 1 1H-NMR spectrum analysis, it was confirmed to be a PC polymer composed of the following repeating units and composition ratio.

[0315]

Chemical formula 24

[0316]

[0317] The composition ratio (mol%) was OCCDE:CHAP = 6:4.

[0318] [Synthesis Example 4]

[0319] (Manufacture of PC polymer)

[0320] In a reaction vessel equipped with a mechanical stirrer, stirring blades, and baffles, 225 mL of the OCCDE-CF prepared in Production Example 1 and 330 mL of dichloromethane were injected. 0.230 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 solution of 1,1-bis(3-cyclohexyl-4-hydroxyphenyl)cyclohexane (hereinafter referred to as CHZ) (Solution preparation method: 185 mL of 1.5 N aqueous potassium hydroxide solution (18.2 g of potassium hydroxide) was prepared, and after cooling to below room temperature, 0.29 g of dithionite as an antioxidant and 33.5 g of CHZ were added and completely dissolved to prepare) was added to this solution. While stirring, 29.5 mL of a triethylamine aqueous solution (7 vol%) was added, and stirring was continued for 2 hours.

[0321] The obtained reaction mixture was diluted and washed with 0.72 L of dichloromethane and 0.04 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 obtained reprecipitate was filtered and dried, whereby a PC polymer (PC-4) having the following structure was obtained.

[0322] (Identification of PC polymer)

[0323] 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.

[0324] [Chemical formula 25]

[0325]

[0326] The composition ratio (mol%) was OCCDE:CHZ = 6:4.

[0327] [Synthesis Example 5]

[0328] (Manufacture of PC polymer)

[0329] In a reaction vessel equipped with a mechanical stirrer, stirring blades, and baffles, 225 mL of the OCCDE-CF prepared in Production Example 1 and 330 mL of dichloromethane were injected. PTBP (0.230 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 solution of 1,1-bis(4-hydroxy-3-methylphenyl) cyclododecane (hereinafter referred to as OCCDE) (Solution preparation method: 185 mL of 1.5N aqueous potassium hydroxide solution (18.2 g of potassium hydroxide) was prepared, 0.29 g of dithionite as an antioxidant and 33.5 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 in its entirety. While stirring, 29.5 mL of a triethylamine aqueous solution (7 vol%) was added, and stirring was continued for 2 hours.

[0330] The resulting reaction mixture was diluted and washed with 0.72 L of dichloromethane and 0.04 L of water. The lower layer was separated and further washed successively 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 resulting dichloromethane solution was added dropwise to methanol while stirring, and the resulting reprecipitate was filtered and dried, whereby a PC polymer (PC-5) having the following structure was obtained.

[0331] (Identification of PC polymer)

[0332] The PC polymer (PC-5) obtained by such operation 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 0.68 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.

[0333]

Chemical formula 26

[0334]

[0335] [Synthesis Example 6]

[0336] (Manufacture of PC polymer)

[0337] In a reaction vessel equipped with a mechanical stirrer, stirring blades, and baffles, 225 mL of the TMBPCDE-CF prepared in Production Example 2 and 330 mL of dichloromethane were injected. 0.152 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 CHZ solution (Solution preparation method: 185 mL of 1.5N aqueous potassium hydroxide solution (18.2 g of potassium hydroxide) was prepared, and after cooling to below room temperature, 0.29 g of dithionite as an antioxidant and 33.5 g of CHZ were added and completely dissolved to prepare it) was added to this solution. While stirring, 29.5 mL of a triethylamine aqueous solution (7 vol%) was added, and stirring was continued for 2 hours.

[0338] The resulting reaction mixture was diluted and washed with 0.72 L of dichloromethane and 0.04 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, whereby a PC polymer (PC-6) having the following structure was obtained.

[0339] (Identification of PC polymer)

[0340] The PC polymer (PC-6) 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 0.50 dL / g. It should be noted that for the structure and composition of the obtained PC-6, 1 analysis by 1H-NMR spectrum confirmed that it was a PC polymer composed of the following repeating units and composition ratio.

[0341] [Chemical Formula 27]

[0342]

[0343] The composition ratio (mol%) was TMBPCDE:CHZ = 6:4.

[0344] [Synthesis Example 7]

[0345] (Manufacture of PC polymer)

[0346] In a reaction vessel equipped with a mechanical stirrer, stirring blades, and baffles, 234 mL of the OCCDE-CF prepared in Production Example 1 and 264 mL of dichloromethane were injected. PTBP (0.702 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 1.5N aqueous potassium hydroxide solution (14.6 g of potassium hydroxide) was prepared, and after cooling to below room temperature, 0.19 g of dithionite as an antioxidant, 15.7 g of OCTMC, and 5.8 g of BIPANT were added and completely dissolved to prepare) were added in their entirety. While stirring, 31.5 mL of a triethylamine aqueous solution (7 vol%) was added, and stirring was continued for 2 hours.

[0347] 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 while stirring, and the resulting reprecipitate was filtered and dried, whereby a PC polymer (PC-7) having the following structure was obtained.

[0348] (Identification of PC polymer)

[0349] The PC polymer (PC-7) 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 0.41 dL / g. It should be noted that for the structure and composition of the obtained PC-7, 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.

[0350] [Chemical formula 28]

[0351]

[0352] The composition ratio (mol%) was OCCDE:OCTMC:BIPANT = 6:3:1.

[0353] <Preparation of coating liquid composition containing polycarbonate and production of resin film>

[0354] [Example 1]

[0355] 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.

[0356] [Example 2]

[0357] A resin film was obtained in the same manner as in Example 1, except that PC-2 was used instead of PC-1.

[0358] [Example 3]

[0359] A resin film was obtained in the same manner as in Example 1, except that PC-3 was used instead of PC-1.

[0360] [Example 4]

[0361] A resin film was obtained in the same manner as in Example 1, except that PC-4 was used instead of PC-1.

[0362] [Example 5]

[0363] A resin film was obtained in the same manner as in Example 1, except that PC-5 was used instead of PC-1.

[0364] [Example 6]

[0365] A resin film was obtained in the same manner as in Example 1, except that PC-6 was used instead of PC-1.

[0366] [Example 7]

[0367] A resin film was obtained in the same manner as in Example 1, except that PC-7 was used instead of PC-1.

[0368] [Example 8]

[0369] 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.

[0370] [Comparative Example 1]

[0371] Using the carbonate ester of 1,1-bis(4-hydroxyphenyl)propane and the carbonate ester of 1,1-bis(4-hydroxyphenyl)propane in place of the carbonate esters of OCTMC and OCCDE, and carrying out the same operations as in Synthesis Example 1 and Example 1, a polycarbonate resin and a resin film having the following structure were obtained.

[0372] [Chemical Formula 29]

[0373]

[0374] [Comparative Example 2]

[0375] Using the carbonate ester of 1,1-bis(4-hydroxyphenyl)cyclohexane and the carbonate ester of 1,1-bis(4-hydroxyphenyl)cyclohexane in place of the carbonate esters of OCTMC and OCCDE, and carrying out the same operations as in Synthesis Example 1 and Example 1, a polycarbonate resin and a resin film having the following structure were obtained.

[0376] [Chemical Formula 30]

[0377]

[0378] [Example 9]

[0379] In the solution preparation method of Synthesis Example 5, a method without heating was used (185 mL of 1.5 N aqueous potassium hydroxide solution (18.2 g of potassium hydroxide) was prepared, and after cooling to room temperature or below, 0.29 g of dithionite as an antioxidant and 33.5 g of OCCDE were added to prepare it), and the same operations as in Synthesis Example 1 and Example 1 were carried out, and a polycarbonate resin and a resin film having the following structure were obtained.

[0380] [Chemical Formula 31]

[0381]

[0382] [Example 10]

[0383] Using a polycarbonate resin having a viscosity-average molecular weight (Mv) of 16,000 obtained by using the same polymerization method as in Synthesis Example 2 and adjusting the amount of the end-capping agent PTBP, and carrying out the same operations as in Example 1, a resin film was obtained.

[0384] [Example 11]

[0385] A polycarbonate resin having a viscosity-average molecular weight (Mv) of 2,300 was obtained by using the same polymerization method as in Synthesis Example 1 and only changing the amount of the end-capping agent PTBP to 3.12 g. It should be noted that it was difficult to form into a film shape and the dielectric properties could not be measured.

[0386] Each physical property of the polycarbonate resin was evaluated by the following method.

[0387] <Evaluation of viscosity-average molecular weight>

[0388] 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, use Mv calculated by the following formula as the viscosity-average molecular weight. The device used for the measurement is a kinematic viscosity measurement device (VMR-052 USPC manufactured by Clutch Co., Ltd.), and an Ubbelohde modified type (410-UIB type) viscometer is used. The obtained results are shown in Table 1.

[0389] η sp / C = [η] × (1 + 0.28 × η sp )

[0390] According to the Schnell formula,

[0391] 〔η〕 = 1.23 × 10 -5 Mv 0.83

[0392] Perform deformation,

[0393] Mv = ([η] / 1.23 × 10 -5 ) 1 / 0.83

[0394] 〔η〕: Intrinsic viscosity

[0395] C: Specimen concentration (g / L)

[0396] <Evaluation of relative dielectric constant and dielectric loss tangent>

[0397] Cut a square film with a length of 60 mm and a width of 60 mm from the resin film, and after conditioning for 24 hours at room temperature of 22 ± 1 °C and humidity of 33 ± 5%, use a split cylinder resonator (manufactured by EMlabs) and a network analyzer (manufactured by Keysight Technologies) to measure the relative dielectric constant (Dk) and dielectric loss tangent (Df) at a frequency of 10 GHz. 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 dielectric constant 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 (change amount) between these values are shown in Table 3.

[0398] <Evaluation of solution viscosity>

[0399] 0.27 g (5 mass%) of the resin films obtained in Examples 2 and 10 and 5.2 g of toluene were placed in a sample tube, stirred at room temperature, and the solution viscosity was measured using a tuning fork vibration viscometer SV-10 (manufactured by A&D Company). The SV display value [mPa·s×g / cm 3 shows viscosity × density and relatively represents the viscosity of the liquid. The results obtained are shown in Table 2.

[0400] <Evaluation of glass transition temperature and coefficient of thermal expansion>

[0401] A strip-shaped 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 results obtained are shown in Table 1.

[0402] Measurement mode: Tensile Temperature condition: -30°C to 320°C (heating rate 5°C / min)

[0403] Data processing method: The coefficient of thermal expansion (CTE) was calculated at 40°C to 100°C, and the glass transition temperature (Tg) was the temperature at the inflection point

[0404] <Evaluation of solubility in a non-halogenated solvent (toluene)>

[0405] 0.1 g (3 mass%) of the resin film and 3.2 g of toluene were placed in a sample tube, stirred at room temperature, and the appearance of the solution after one day was visually confirmed. The results obtained are shown in Table 1.

[0406] A: No insoluble components, transparent

[0407] B: Although there are no insoluble components, turbidity can be visually confirmed

[0408] F: There are insoluble components

[0409] <Evaluation of the amount of terminal hydroxyl groups>

[0410] 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 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.

[0411] <Crosslinking Evaluation of Resin Film>

[0412] 1.4 g of the resin of Example 7 (functional group concentration: 0.229 mmol / g) and 92 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, 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. Then, the obtained resin film was heated at a temperature of 220 °C for 2 hours using a vacuum dryer. At the same time, the resin film of Example 1 was heated alone at a temperature of 220 °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 obtained results are shown in Table 4.

[0413] F (dissolved): Visually, there is no insoluble component.

[0414] A (insoluble): It did not swell or slightly swelled and maintained the film shape.

[0415] <Evaluation of Solution Fluidity>

[0416] 20 mg of the resins obtained in Example 1 and Example 11 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 mass% toluene solution. After that, it was stirred for 1 hour using an oscillator, and the state when tilted 180 degrees was visually observed. The obtained results are shown in Table 1.

[0417] A: The time taken for the solution to reach the cap of the microtube is within 3 seconds.

[0418] B: The time taken for the solution to reach the cap of the microtube is more than 3 seconds. The time taken for the solution to reach the cap of the microtube is within 3 seconds.

[0419] [Table 1]

[0420]

[0421] [Research]

[0422] Examples 1 to 6 obtained by copolymerizing OCCDE or TMBPCDE have lower dielectric properties compared to the homopolymers of Comparative Examples 1 and 2. In addition, the solubility in toluene as a non-halogenated solvent is also excellent.

[0423] According to Example 5 and Example 9, in Example 5 where the alkaline aqueous solution of OCCDE was heated, the amount of terminal hydroxyl groups decreased compared to Example 9 where no heating treatment was performed. Therefore, in order to reduce the amount of terminal hydroxyl groups, methods such as performing a heating treatment or using OCCDE as a dicarbonate are effective.

[0424] According to Example 7, it is possible to introduce a crosslinking group into the OCCDE copolymer.

[0425] According to Example 8, it is possible to produce a film containing spherical silica and a resin. At this time, due to the influence of silica with a high relative dielectric constant, Dk is worse than when only using the resin, so it is important to have a resin with lower dielectric properties.

[0426] By reducing the molecular weight of the resin with low dielectric properties (Example 1) (Example 11), it is possible to impart the characteristic that even when dissolved at a high concentration, the coating solution exhibits fluidity.

[0427] [Table 2]

[0428]

[0429] [Research]

[0430] Table 2 shows the effects of the difference in molecular weight on the dielectric properties and solution viscosity in resins with the same copolymer backbone.

[0431] Based on the dielectric properties of Example 2 and Example 10, even when the viscosity-average molecular weight changes, the dielectric properties do not change significantly.

[0432] Based on the solution viscosities of Example 2 and Example 10, the solution viscosity of Example 10 with a lower viscosity-average molecular weight is lower. Therefore, it can be seen that the solution viscosity varies depending on the viscosity-average molecular weight.

[0433] [Table 3]

[0434]

[0435] [Research]

[0436] According to Figure 1 and Table 3, Dk has almost no temperature dependence.

[0437] 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 increases, the resin is prone to molecular motion.

[0438] Comparing Examples 1 to 6 with Comparative Examples 1 and 2, it can be seen that when OCCDE or TMBPCDE is included, the increase ratio of Df with respect to the temperature rise decreases.

[0439]

Table 4

[0440]

[0441] [Research]

[0442] Since the resin film of Example 1 was completely soluble in dichloromethane, it was found that no crosslinking reaction occurred even upon heating. Since the resin film formed by mixing the resin of Example 7 with MI-BisA was insoluble in dichloromethane, it was found that a crosslinking reaction occurred.

Claims

1. An electronic substrate material comprising a resin having a structure represented by the general formula (UN1). 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, n represents 1, 2, 3 or 4, and a plurality of R 1 and R 2 are optionally the same group or different groups from each other, and * represents a bonding position.

2. The electronic substrate material according to claim 1, wherein the resin 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). 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 structures represented by the general formula (UN2), the general formula (UN3), the general formula (UN4), and the general formula (UN5). In General Formulas (UN2) to (UN5), X represents a single bond, -O-, -S-, -SO-, -SO2-, or an organic group having 1 to 20 carbon atoms, 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, m represents 0, 1, 2, 3, or 4, and when the sum of two m's is 2 or more, the multiple R 1 and R 2 are optionally the same group or different groups from each other, and * represents a bonding position.

4. The electronic substrate material according to any one of claims 1 to 3, wherein the viscosity-average molecular weight Mv of the resin is 1000 or more and 35000 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 obtained by measurement according to 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 obtained by measurement according to the split cylinder resonator perturbation method is 0.0032 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 according to the split cylinder resonator perturbation method, the change amount of the relative 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 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 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 the amount of terminal hydroxyl groups 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, n represents 1, 2, 3 or 4, and 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, which 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). * represents a bonding site.

18. A method for manufacturing a resin, the resin having a structure represented by the general formula (UN1) and having an amount of terminal hydroxyl groups of 6000 mass ppm or less, the manufacturing method comprising: 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 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, n represents 1, 2, 3 or 4, and a plurality of R 1 and R 2 are optionally the same group or different groups from each other, and * represents a bonding position.

19. The manufacturing method of the resin according to claim 18, wherein the amount of terminal hydroxyl groups of the resin having the structure represented by the general formula (UN1) is 530 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, n represents 1, 2, 3 or 4, and a plurality of R 1 and R 2 are each optionally the same group or different groups, and * represents a bonding site.

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