Electronic substrate material, resin, and method for producing resin

Abstract

An electronic substrate material contains a resin having a structure represented by general formula (UN1) and general formula (UN2) or a structure represented by general formula (UN1) and general formula (UN3). In the formula, * represents a bonding site. In the # imgabs0 # formula, R1 and R2 each independently represent a halogen atom, an organic group having 1-12 carbon atoms, or the like, and m represents 1 or the like. In the # imgabs1 # formula, X is an organic group having 6 to 12 carbon atoms, or the like, R3 is an organic group having 1 to 10 carbon atoms, and n is 1 or the like. In the formula # imgabs2, Y is a single bond or the like, R4 is an organic group having 1-10 carbon atoms, R5 is an organic group having 1-10 carbon atoms, and p is 1 or the like. When two p are both 1 and R4 and R5 are methyl groups, Y is an organic group having 4 or more carbon atoms.

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 travel 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 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 consists of two elements: conductor loss and dielectric loss. Among them, the dielectric loss is proportional to the square root of the relative dielectric constant (Dk) of the dielectric and the tangent of the dielectric loss angle (Df). Therefore, in order to reduce the transmission loss of an electronic substrate or the like using an insulating material, it is necessary to reduce the relative dielectric constant and the tangent of the dielectric loss angle of the material used as the insulating material. In addition, in order to reduce the conductor loss, there is a tendency to make the interface between the substrate and the metal wiring have a low roughness, and therefore, higher requirements are also placed on 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 thermal expansion coefficients 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 under use environments such as temperature or humidity for forming a thin film used in laminating and forming a wiring layer. As the insulating material, 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 for electronic substrates for various uses.

[0005] 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, and 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.

[0006] Patent Document 1 discloses that polycarbonate resins manufactured using specific one or two types of bisphenols as raw materials can be used as thermoplastic resin compositions and molded articles having excellent radio wave permeability in the microwave or millimeter wave band, as well as excellent heat resistance and flame retardancy, and communication device housings and communication devices with built-in microwave or millimeter wave antennas. It is similar to the present invention in terms of having low dielectric properties, high heat resistance, and reducing transmission loss. However, the communication device housing with a built-in 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 disclosure of the high solvent solubility, low solution viscosity characteristics, or thermal expansion for coating and forming of the present invention. In addition, there is no disclosure of polycarbonate resins into which thermosetting groups are introduced.

[0007] Patent Document 2 discloses a cover for a millimeter wave radar in which the tangent of the dielectric loss angle decreases and the millimeter wave permeability is improved by using a polycarbonate resin using a bisphenol having specific substituents as a raw material. It is similar to the purpose of the present invention in that it reduces the tangent of the dielectric loss angle. However, it is aimed at the use of a cover for a millimeter wave radar, which is different from the purpose of the present invention, and there is no disclosure of heat resistance, low thermal expansion, or thermosetting groups.

[0008] Patent Document 3 discloses a polycarbonate resin that has amine resistance and can be used as a molded article, film, or sheet for automotive interior parts. Although amine resistance is disclosed, there is no disclosure or teaching of its dielectric properties or coefficient of thermal expansion.

[0009] Prior Art Documents

[0010] Patent Documents

[0011] Patent Document 1: International Publication No. 2021 / 039970

[0012] Patent Document 2: Japanese Unexamined Patent Application Publication No. 2019-197048

[0013] Patent Document 3: Japanese Unexamined Patent Application Publication No. 2017-082131 Summary of the Invention

[0014] Problems to be Solved by the Invention

[0015] An object of the present invention is to provide an electronic substrate material having low dielectric characteristics.

[0016] Means for Solving the Problems

[0017] The present inventors repeatedly conducted in-depth studies and found that an electronic substrate material containing a resin having a specific structural unit has excellent low dielectric characteristics.

[0018] That is, the gist of the present invention lies in the following [Constitution 1] to [Constitution 17].[[]END]]

[0019] [Constitution 1]

[0020] An electronic substrate material comprising a resin having a structure represented by General Formula (UN1) and General Formula (UN2) or a structure represented by General Formula (UN1) and General Formula (UN3).

[0021] [Chemical Formula 1]

[0022]

[0023] (In the formula, Rand R 2 each independently represent at least one selected from the group consisting of a halogen atom and an organic group having 1 or more and 12 or less carbon atoms, and m represents 0, 1, 2, 3, or 4. When the sum of two m's is 2 or more, a plurality of R 1 and R 2 may be the same group or different groups from each other. * represents a bonding position.)

[0024] [Chemical Formula 2]

[0025]

[0026] (In the formula, X is an organic group having 6 or more and 12 or less carbon atoms or -C(CF3)2-, R 3 is an organic group having 1 or more and 10 or less carbon atoms, and when there are a plurality of R 3 , a plurality of R 3 may be the same group or different groups from each other, and n represents 0, 1, 2, 3, or 4. * represents a bonding position.)

[0027] [Chemical Formula 3]

[0028]

[0029] (In the formula,

[0030] Y is a single bond,

[0031] -O-,

[0032] -S-,

[0033] -SO-,

[0034] -SO2-,

[0035] or an organic group having 1 or more and 10 or less carbon atoms,

[0036] R 4 is an organic group having 1 or more and 10 or less carbon atoms,

[0037] R 5 is an organic group having 1 or more and 10 or less carbon atoms,

[0038] When there are multiple R 4 or R 5 respectively, the multiple Rs 4 can be the same group or different groups from each other, and the multiple Rs 5 can be the same group or different groups from each other. p represents 1, 2, 3, or 4. It should be noted that when both 2 ps are 1 and R 4 and R 5 are methyl groups, Y is an organic group having 4 or more carbon atoms. * represents the bonding position.)

[0039] [Constitution 2]

[0040] The electronic substrate material according to Constitution 1, wherein the resin has at least one set of structures selected from the structures represented by General Formula (UN1-1) and General Formula (UN2) or the structures represented by General Formula (UN1-1) and General Formula (UN3). * represents the bonding position.

[0041] [Chemical Formula 4]

[0042]

[0043] [Constitution 3]

[0044] The electronic substrate material according to Constitution 1 or Constitution 2, wherein the resin has a structure represented by any one of General Formula (UN1) and General Formula (UN1-1) in an amount of 10 mol% or more and 49 mol% or less; and at least one structure selected from the structures represented by General Formula (UN4) to General Formula (UN7) in an amount of 50 mol% or more. * represents the bonding position.

[0045] [Chemical Formula 5]

[0046]

[0047] [Configuration 4]

[0048] The electronic substrate material according to any one of Configuration 1 to Configuration 3, wherein the viscosity-average molecular weight (Mv) of the resin is 1,000 or more and 35,000 or less.

[0049] [Configuration 5]

[0050] The electronic substrate material according to any one of Configuration 1 to Configuration 4, wherein the relative dielectric constant at a frequency of 10 GHz obtained by measurement according to the split cylinder resonator perturbation method is 2.63 or less.

[0051] [Configuration 6]

[0052] The electronic substrate material according to any one of Configuration 1 to Configuration 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.

[0053] [Configuration 7]

[0054] The electronic substrate material according to any one of Configuration 1 to Configuration 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 resin according to the split cylinder resonator perturbation method, the change amount of the relative dielectric constant is 0.05 or less, and the change amount of the tangent of the dielectric loss angle is 0.00101 or less.

[0055] [Configuration 8]

[0056] The electronic substrate material according to any one of Configuration 1 to Configuration 7, wherein the thermal expansion rate of the resin from a temperature of 40 °C to 100 °C is 100 ppm / K or less.

[0057] [Configuration 9]

[0058] The electronic substrate material according to any one of Configuration 1 to Configuration 8, wherein the resin has a crosslinked structure.

[0059] [Configuration 10]

[0060] The electronic substrate material according to Configuration 9, wherein the resin has a bond between polymer chains formed by a Diels-Alder reaction.

[0061] [Configuration 11]

[0062] The electronic substrate material according to any one of Configuration 1 to Configuration 10, wherein it further contains an inorganic filler.

[0063] [Constitution 12]

[0064] The electronic substrate material according to any one of Constitutions 1 to 11, further comprising a non-halogen-based solvent.

[0065] [Constitution 13]

[0066] A film comprising the electronic substrate material according to any one of Constitutions 1 to 12.

[0067] [Constitution 14]

[0068] A sheet comprising the electronic substrate material according to any one of Constitutions 1 to 12.

[0069] [Constitution 15]

[0070] An electronic substrate comprising the electronic substrate material according to any one of Constitutions 1 to 12.

[0071] [Constitution 16]

[0072] A resin having a structure represented by the general formula (UN8).

[0073] [Chemical Formula 6]

[0074]

[0075] (In the formula, the number of repeating units r is 1 or more and 5 or less, R 4 is an organic group having 1 or more and 10 or less carbon atoms, R 5 is an organic group having 1 or more and 10 or less carbon atoms, in R 4 or R 5 when there are a plurality of each, the plurality of R 4 may be the same group or different groups from each other, the plurality of R 5 may be the same group or different groups from each other, Z represents a single bond, -O-, -S-, -SO-, -SO2- or an organic group having 1 or more and 20 or less carbon atoms, q represents 0, 1, 2, 3 or 4. * represents a bonding site.)

[0076] [Constitution 17]

[0077] A method for producing a resin having a structure represented by the general formula (UN8), the production method including: a step of reacting a dicarbonate monomer or oligomer with a bisphenol compound by interfacial polycondensation.

[0078] [Chemical Formula 7]

[0079]

[0080] (In the formula, the number of repeating units r is 1 or more and 5 or less, and R 4 is an organic group having 1 or more and 10 or less carbon atoms, and R 5 is an organic group having 1 or more and 10 or less carbon atoms. When there are a plurality of R 4 or R 5 respectively, the plurality of R 4 may be the same group or different groups from each other, and the plurality of R 5 may be the same group or different groups from each other. Z represents a single bond, -O-, -S-, -SO-, -SO2-, or an organic group having 1 or more and 20 or less carbon atoms, and q represents 0, 1, 2, 3, or 4. * represents a bonding position.)

[0081] According to one aspect of the present invention, an electronic substrate material having low dielectric properties can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0082] Figure 1 is a graph showing the relationship between the temperature and the relative dielectric constant (Dk) of the specimens obtained in Examples 1 to 4 and Comparative Examples 1 to 3.

[0083] Figure 2 is a graph showing the relationship between the temperature and the dielectric loss tangent (Df) of the specimens obtained in Examples 1 to 4 and Comparative Examples 1 to 3. DETAILED DESCRIPTION

[0084] Hereinafter, the present invention will be described in detail.

[0085] [Resin]

[0086] The electronic substrate material according to the present embodiment contains the resin according to the present embodiment.

[0087] The resin (polycarbonate resin) according to the present embodiment is a resin having a structure represented by the general formula (UN1) and the general formula (UN2) or a structure represented by the general formula (UN1) and the general formula (UN3).

[0088] [Chemical Formula 8]

[0089]

[0090] In the above 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,

[0091] The organic group having 1 or more and 12 or less carbon atoms is at least 1 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.

[0092] When the total of two m's is 2 or more, a plurality of R's present 1 and R 2 may be the same group or different groups from each other.

[0093] In R 1 or R 2 when there are a plurality of each, the plurality of R's 1 may be the same group or different groups from each other, and the plurality of R's 2 may be the same group or different groups from each other.

[0094] n represents 0, 1, 2, 3 or 4.

[0095] * represents a bonding site.

[0096] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.

[0097] Examples of the alkyl group having 1 or more and 12 or less carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a cyclohexyl group, a trifluoromethyl group and the like.

[0098] Examples of the substituted or unsubstituted aryl group having 6 or more and 12 or less carbon atoms include a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 4-ethylphenyl group, a biphenyl group, a dichlorophenyl group, a naphthyl group, a methylnaphthyl group and the like.

[0099] Examples of the alkoxy group having 1 or more and 12 or less carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, various pentyloxy groups and various hexyloxy groups and the like.

[0100] Examples of the substituted or unsubstituted aryloxy group having 6 or more and 12 or less carbon atoms include a phenoxy group, a tolyloxy group, a naphthyloxy group and the like.

[0101]

Chemical Formula 9

[0102]

[0103] In the general formula (UN2),

[0104] X is an organic group having 6 or more and 12 or less carbon atoms or -C(CF3)2-,

[0105] R 3 is an organic group having 1 to 10 carbon atoms. When there are multiple Rs, 3 the multiple Rs 3 may be the same group or different groups from each other.

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

[0107] * represents a bonding site.

[0108]

Chemical Formula 10

[0109]

[0110] In the general formula (UN3),

[0111] Y is a single bond,

[0112] -O-,

[0113] -S-,

[0114] -SO-,

[0115] -SO2- or

[0116] an organic group having 1 to 10 carbon atoms,

[0117] R 4 is an organic group having 1 to 10 carbon atoms,

[0118] R 5 is an organic group having 1 to 10 carbon atoms,

[0119] When there are multiple Rs in each of R 4 or R 5 the multiple Rs 4 may be the same group or different groups from each other, and the multiple Rs 5 may be the same group or different groups from each other.

[0120] p represents 1, 2, 3 or 4. It should be noted that when both of the two ps are 1 and R 4 and R 5 are methyl groups, Y is an organic group having 4 or more carbon atoms.

[0121] * represents a bonding site.

[0122] It is considered that by having substituents such as R 1 to R 5 the molecular mobility of the carbonate group can be decreased by their steric hindrance, and this can decrease the dielectric loss tangent.

[0123] As the compound (monomer compound) having the structure represented by the general formula (UN1), 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 appropriately obtained as commercially available products.

[0124] As the compound (monomer compound) having the structure represented by the general formula (UN2) or the general formula (UN3), for example, 2,2-bis(4-hydroxy-3-isopropylphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, etc. can be cited. These compounds can be obtained as commercially available products, or can be synthesized by subjecting the target phenol and ketone to dehydration condensation using an acid catalyst.

[0125] From the viewpoints of dielectric properties or low thermal expansion rate, etc., the polycarbonate resin according to the present embodiment preferably has the structure represented by the general formula (UN1-1). It should be noted that in the following formula, * represents the bonding position.

[0126]

Chemical Formula 11

[0127]

[0128] From the viewpoint of dielectric properties, the polycarbonate resin according to the present embodiment preferably further has the structures represented by the following general formula (UN4) to the general formula (UN7) in an amount of 50 mol% or more.

[0129]

Chemical Formula 12

[0130]

[0131] In the general formula (UN4) to the general formula (UN7),

[0132] * represents the bonding position.

[0133] As the compound (monomer compound) having the structures represented by the general formula (UN4) to the general formula (UN7), 2,2-bis(3'-cyclohexyl-4'-hydroxyphenyl)propane, 1,1-bis(3-cyclohexyl-4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxy-3-methylphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-hydroxy-3-methylphenyl)cyclododecane, 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.

[0134] From the viewpoint of dielectric properties, the polycarbonate resin according to the present embodiment preferably has the structure represented by the general formula (UN8).

[0135]

Chemical Formula 13

[0136]

[0137] In the general formula (UN8),

[0138] the repeating unit number r is 1 or more and 5 or less,

[0139] R 4 and R 5 As described above,

[0140] Z represents a single bond, -O-, -S-, -SO-, -SO2- or an organic group having 1 to 20 carbon atoms,

[0141] q represents 0, 1, 2, 3 or 4.

[0142] * represents a bonding site.

[0143] 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. For this incompleteness, no well-known quantitative explanation has been established. Therefore, conventionally, the electric field is considered to be the electric field passing through the entire specimen to calculate the relative dielectric constant. Therefore, although no electric field is applied at both ends of the sample, since the dielectric properties are calculated on the premise that an electric field is applied to the whole, the measured relative dielectric constant is low. On the other hand, in the case of the split cylinder resonator perturbation method (hereinafter referred to as the split cylinder method) using a circular electric field along the specimen surface for measurement, the error caused by the electric field shift at both ends of the specimen generated in the cavity resonance method does not occur. Therefore, compared with the cavity resonance method, the split cylinder method can output a value closer to the true value for dielectric properties.

[0144] In the polycarbonate resin according to this embodiment, the relative dielectric constant (Dk) measured using a split cylinder resonator at a frequency of 10 GHz at room temperature is preferably 2.63 or less, more preferably 2.55 or less, and particularly preferably 2.5 or less. In addition, the dielectric loss tangent (Df) measured using a split cylinder resonator at a frequency of 10 GHz at room temperature is preferably 0.003 or less, more preferably 0.002 or less, and particularly preferably 0.001 or less. By having the relative dielectric constant and the dielectric loss tangent 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 using the resin according to this 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 dielectric loss tangent is low at high temperatures.

[0145] In addition, preferably, when measuring the relative permittivity and the loss tangent 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 cylindrical resonator perturbation method, the change amount of the relative permittivity is 0.05 or less, and the change amount of the loss tangent is 0.005 or less.

[0146] When the polycarbonate resin according to the present embodiment sets all structural units to 100 mol%, the proportion of the general formula (UN1) is preferably 30 mol% or more and 49 mol% or less, more preferably 40 mol% or more and 49 mol% or less. If the proportion of the general formula (UN1) is above the above lower limit and 49 mol% or less, the dielectric properties or heat resistance are more excellent, and thus it is preferred. The proportion of the general formula (UN2) is preferably 40 mol% or more, more preferably 50 mol% or more, can be 55 mol% or more, can be 60 mol% or more, and preferably less than 70 mol%. If the proportion of the general formula (UN2) is 40 mol% or more, the dielectric properties or heat resistance are more excellent. In addition, the proportion of the general formula (UN2) can be 40 mol% or more and less than 70 mol%, and can be 50 mol% or more and less than 70 mol%. The proportion of the general formula (UN3) is preferably 40 mol% or more, more preferably 50 mol% or more, can be 55 mol% or more, can be 60 mol% or more, and preferably less than 70 mol%. If the proportion of the general formula (UN2) is 40 mol% or more, the dielectric properties or heat resistance are more excellent. In addition, the proportion of the general formula (UN2) can be 40 mol% or more and less than 70 mol%, and can be 50 mol% or more and less than 70 mol%. The structural unit in this specification refers to the unit sandwiched between two adjacent carbonate bonds constituting the main chain.

[0147] A polycarbonate resin having a reduced viscosity average molecular weight of 350,000 or less is easily soluble in a non-halogen-based solvent, has a low viscosity, and is easily handled in coating forming or is also easily dispersed with a filler or other thermosetting materials. Therefore, as an electronic substrate material, it has excellent versatility.

[0148] From such a viewpoint, the polycarbonate resin according to the present embodiment preferably has a reduced viscosity average molecular weight (Mv) of 1,000 or more and 35,000 or less, more preferably 1,000 or more and 31,000 or less, further preferably 1,000 or more and 25,000 or less, still further preferably 1,000 or more and 22,000 or less, still more preferably 1,000 or more and 20,000 or less, and particularly preferably 1,000 or more and 15,000 or less.

[0149] 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 40°C to 100°C is preferably 100 ppm / K or less.

[0150] A thermosetting group (crosslinking group) may also be introduced into the structure of the polycarbonate resin according to the present embodiment. A resin containing such a crosslinked group structure, that is, a resin having a crosslinked structure, is called a thermosetting resin. By changing from thermoplastic to thermosetting, heat resistance and elastic modulus can be improved. When used as an electronic substrate material, it reaches a high temperature during processing or reflow soldering, and reaches a high temperature when used in a molded product incorporating an electronic substrate. 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.

[0151] Examples of the crosslinking group of the thermosetting resin include epoxy group, allyl group, maleimide, oxazole, cyclobutene, isocyanate, cyanate ester, and the like.

[0152] For example, a conjugated diene structure or a conjugated diene group (hereinafter also simply referred to as "conjugated diene") capable of having a bond between polymer chains through a Diels-Alder reaction can be cited. As the conjugated diene, it is preferable to include at least one of the structures represented by the following general formula (UN9) and general formula (UN10). In addition, a Diels-Alder reaction in which a conjugated diene structure such as the following general formula (UN11), general formula (UN12), and general formula (UN13) is introduced at the end of the polymer chain to bond the ends of the polymer chains may also be used.

[0153]

Chemical formula 14

[0154]

[0155] In the above general formula (UN9) and general formula (UN10),

[0156] R 6 each independently represents

[0157] a single bond,

[0158] a linking group to another skeleton,

[0159] a hydrogen atom,

[0160] an aliphatic hydrocarbon group having 1 or more and 12 or less carbon atoms,

[0161] an aromatic hydrocarbon group having 6 or more and 12 or less ring carbon atoms, or

[0162] an alkoxy group having 1 or more and 10 or less carbon atoms,

[0163] R 6One or two of them are single bonds or linking groups to other skeletons.

[0164] R as the linking group 6 is a group containing at least any one atom selected from the group consisting of a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, and a boron atom, and the bonding forms of the atoms constituting the linking group are all covalent bonds.

[0165] In addition, multiple Rs can also form a cyclic structure (including an aromatic ring and a heterocyclic ring) connected together. 6

[0166]

Chemical Formula 15

[0167]

[0168] In the above general formulas (UN11) to (UN13),

[0169] X 1 are each independently

[0170] -O-,

[0171] -(C=O)-O-,

[0172] -O-(C=O)-O- or

[0173] -O-(C=O)-,

[0174] R 7 are each independently

[0175] an aliphatic hydrocarbon group having 1 or more and 10 or less carbon atoms,

[0176] an aromatic hydrocarbon group having 6 or more and 12 or less ring-constituting carbon atoms, or

[0177] an alkoxy group having 1 or more and 10 or less carbon atoms.

[0178] In addition, multiple R2s can also form a cyclic structure (including an aromatic ring and a heterocyclic ring) connected together.

[0179] R 8 are each independently

[0180] a hydrogen atom,

[0181] an aliphatic hydrocarbon group having 1 or more and 12 or less carbon atoms, or

[0182] an aromatic hydrocarbon group having 6 or more and 12 or less carbon atoms.

[0183] n1 represents 0 or a natural number with the upper limit of the substitutable quantity.

[0184] * represents the bonding position.

[0185] As a crosslinking group of the thermosetting resin, for example, an allyl structure or an allyl group having a bond between polymer chains through an ene reaction can be cited. Due to high reactivity, the allyl structure preferably contains at least any one of the structures represented by the following general formula (UN14), general formula (UN15), and general formula (UN16). The allyl structure represented by the following general formula (UN14) has two allyl groups. Since the allyl group is introduced at the end of the polymer in the allyl structure represented by the following general formula (UN15) or general formula (UN16), the ends of the polymer chains can undergo an ene reaction with each other.

[0186]

Chemical Formula 16

[0187]

[0188]

Chemical Formula 17

[0189]

[0190] In the above general formula (UN14) to general formula (UN16),

[0191] X 2 is selected from the group consisting of

[0192] -O-,

[0193] -S-,

[0194] -SO-,

[0195] -SO2-,

[0196] -CR 11 R 12 -,

[0197] a substituted or unsubstituted cycloalkylene group having 5 or more and 20 or less carbon atoms,

[0198] a substituted or unsubstituted bicyclic hydrocarbon diyl group having 5 or more and 20 or less carbon atoms,

[0199] a substituted or unsubstituted tricyclic hydrocarbon diyl group having 5 or more and 20 or less carbon atoms,

[0200] a substituted or unsubstituted alkylene group having 2 or more and 12 or less carbon atoms, and

[0201] a substituted or unsubstituted arylene group having 6 or more and 12 or less carbon atoms

[0202] and at least one selected from the group consisting of

[0203] R 11 and R 12 are each independently selected from the group consisting of

[0204] a hydrogen atom,

[0205] a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, and

[0206] a substituted or unsubstituted aryl group having 6 to 12 carbon atoms

[0207] at least one selected from the group consisting of,

[0208] R 11 and R 12 may be bonded to each other to form a ring represented by the following general formula (RIN1).

[0209] * represents a bonding position.

[0210]

Chemical Formula 18

[0211]

[0212] In the above general formula (RIN1),

[0213] R 9 is a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms,

[0214] R 10 is selected from the group consisting of

[0215] a hydrogen atom,

[0216] a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms,

[0217] a substituted or unsubstituted aryl group having 6 to 12 carbon atoms,

[0218] a substituted or unsubstituted cycloalkyl group having 3 to 6 carbon atoms

[0219] at least one selected from the group consisting of,

[0220] multiple Rs may be attached to one ring 10 , in which case, the multiple Rs 10 may be the same group or different groups from each other.

[0221] * represents a bonding position.

[0222] 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 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.

[0223] The manufacturing method of the polycarbonate resin according to this embodiment can employ conventional polymerization methods such as the interfacial polycondensation method or the melt transesterification method.

[0224] In the interfacial polycondensation method, monomers such as bisphenol compounds form basic salts in the presence of a non-reactive organic solvent and an aqueous alkaline solution, and carbonyl chloride or a compound capable of forming a carbonate bond undergoes polycondensation at the interface to obtain a polycarbonate resin. In the melt transesterification method, for example, an ester exchange reaction between a carbonate and monomers such as bisphenol or a diol compound is shown.

[0225] The polycarbonate resin of this embodiment preferably has a low terminal hydroxyl group content. The terminal hydroxyl group content represents the hydroxyl groups derived from the remaining 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 properties to deteriorate. In addition, the high polar groups also tend to increase the tangent of the dielectric loss angle. Therefore, in order to exhibit low dielectric properties and suppress property non-uniformity, it is necessary to control the terminal hydroxyl group content.

[0226] Existing manufacturing methods are roughly classified into two types: the interfacial polycondensation method and the melt transesterification method. It is known that in order to reduce the terminal hydroxyl group content, the interfacial polycondensation method is suitable. The resin polymerized by the interfacial polycondensation method according to this embodiment has a low terminal hydroxyl group content, that is, it exhibits more excellent low dielectric properties, so it is preferred.

[0227] It is known that the bisphenol having a 4,4-biphenol skeleton structure, which is a monomer of the polycarbonate resin of this embodiment, has high crystallinity. On the other hand, the dicarbonate monomer or oligomer represented by the general formula (1A) derived by bisphenol dicarbonatation has low crystallinity. By reacting the pre-synthesized dicarbonate monomer or oligomer with low crystallinity and high solubility with bisphenol by interfacial polymerization, crystallization of the resin and a decrease in solubility can be prevented, and the terminal hydroxyl group content can be reduced.

[0228] [[Chemical formula 19]]

[0229]

[0230] In the general formula (1A),

[0231] R 4 and R 5 As described above,

[0232] Z is as described above,

[0233] q is as described above,

[0234] n 1A represents the average number of polymerization units. In addition, the average number of polymerization units n1A is 1.0 or more and 10 or less.

[0235] The polycarbonate resin produced can be any of block copolymers, alternating copolymers, random copolymers, etc.

[0236] The method for producing the resin according to this embodiment is preferably a method for producing a resin having the structure represented by the above general formula (UN8), and the production method includes: a step of reacting a dicarbonate monomer or oligomer with a bisphenol compound by interfacial polycondensation.

[0237] As the reason for preferably being a monomer (n 1A = 1.0), it is possible to adjust the copolymerization ratio over a wide range. Especially when the copolymerization molecular weight is low, if the number of polymerization units of the oligomer (1A) is high, the components to be copolymerized decrease. Or the molecular weight itself is also easily controlled.

[0238] 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.

[0239] 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, perfluorododecyl p-hydroxybenzoate, p-(1H,1H-perfluorooctoxylated)phenol, and 2H,2H,9H-perfluorononanoic acid, etc. are used.

[0240] 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 a mixture form. The use 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 excess amount of the acid-binding agent can be used relative to 1 mole of the total of the hydroxyl groups of the diphenol as a raw material, and preferably 1 to 10 equivalents of the acid-binding agent can be used.

[0241] As the solvent used in interfacial polymerization, an organic solvent that is substantially immiscible with water and can dissolve 5% by 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% by mass or more of the finally obtained polycarbonate copolymer.

[0242] Here, the 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.

[0243] In addition, the fact that the organic solvent "can dissolve 5% by 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.

[0244] 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.

[0245] 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.

[0246] In addition, as the catalyst used in interfacial polymerization, 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.

[0247] In addition, a small amount of an antioxidant such as sodium sulfite or dithionite can be added to the reaction system as needed.

[0248] [Resin precursor composition]

[0249] 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.

[0250] As the 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.

[0251] 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.

[0252] [Chemical Formula 20]

[0253]

[0254] 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.

[0255] [Coating Liquid Composition]

[0256] 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.

[0257] 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 rate after forming, the influence and danger (fire or health hazard) when remaining in the formed product.

[0258] 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)).

[0259] Among them, considering the environmental or safety aspects, an organic solvent other than halogenated hydrocarbons, that is, a non-halogen-based solvent, is preferred.

[0260] 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, 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.

[0261] [Electronic substrate]

[0262] Electronic substrates can be roughly classified into the following semiconductor substrates and electronic circuit substrates.

[0263] (1) Semiconductor substrate material

[0264] 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.

[0265] (2) An electronic circuit substrate 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.

[0266] [Electronic substrate material]

[0267] The electronic substrate material according to this embodiment is used in a film, sheet, or coating liquid composition (varnish) for forming the electronic substrate according to this embodiment. That is, the film, sheet, and varnish contain the electronic substrate material according to this embodiment.

[0268] 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.

[0269] [Film]

[0270] When using the electronic substrate material according to this embodiment as a film, film formation can also be performed by thermoforming such as melt extrusion, or 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 perform film formation by solution casting. In addition, for the purpose of reducing thermal expansion, etc., film formation can be performed in a state of being immersed in a glass fiber cloth or dispersed with an inorganic filler such as silica when forming the film. In addition, when using the electronic substrate material according to this embodiment having a crosslinked portion to perform film formation by solution casting, by containing a curing material and adjusting the heating temperature, the degree of crosslinking can also be controlled, and the elastic modulus of the film can be changed, etc.

[0271] [Varnish]

[0272] 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, etc. At this time, an inorganic filler such as silica can also be dispersed.

[0273] Suitable solvents are toluene, cyclohexanone, and MEK, etc.

[0274] [Sheet]

[0275] When using the electronic substrate material according to this embodiment as a sheet, the sheet can be made by immersing a substrate, etc. in the above varnish.

[0276] Examples

[0277] 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.

[0278] [Production Example: Preparation of Oligomer]

[0279] <Manufacturing Example 1: Synthesis of 2,2-bis(3'-cyclohexyl-4'-hydroxyphenyl)propane oligomer (bischloroformate)>

[0280] 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.

[0281] <Manufacturing Example 2: Synthesis of 1,1-bis(3-cyclohexyl-4-hydroxyphenyl)cyclohexane oligomer (bischloroformate)>

[0282] 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.

[0283] [Manufacturing Example: Preparation of Oligomer]

[0284] <Manufacturing Example 3: Synthesis of 1,1-bis(4-hydroxy-3-methylphenyl)cyclododecane oligomer (bischloroformate)>

[0285] 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 will be referred to as OCCDE-CF.

[0286] [Production Example: Preparation of Oligomer]

[0287] <Production Example 4: Synthesis of 1,1-bis(4-hydroxy-3-methylphenyl)-3,3,5-trimethylcyclohexane Oligomer (Bis Chloroformate)>

[0288] 75.8 g (224 mmol) of 1,1-bis(4-hydroxy-3-methylphenyl)-3,3,5-trimethylcyclohexane was suspended in 1080 mL of dichloromethane, and 66.0 g (667 mmol) of phosgene was added thereto and dissolved. A solution prepared by dissolving 44.0 g (435 mmol) of triethylamine in 120 mL of dichloromethane was added dropwise thereto in the temperature range of 5°C to 15°C. Next, after stirring for 30 minutes, dichloromethane was distilled off to a specific concentration. 210 mL of pure water, 1.2 g of concentrated hydrochloric acid, and 450 mg of dithionite were added to the residue for washing. Thereafter, washing was repeated 5 times with 210 mL of pure water to obtain a dichloromethane solution of 1,1-bis(4-hydroxy-3-methylphenyl)-3,3,5-trimethylcyclohexane oligomer having a chloroformate group at the molecular terminal. The chloroformate concentration of the obtained solution was 0.92 mol / L, the solid content concentration was 0.220 kg / L, and the average number of polymerization units was 1.04. Hereinafter, the obtained raw material will be referred to as OCTMC-CF.

[0289] [Synthesis Example 1]

[0290] (Manufacture of PC Polymer)

[0291] 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. p-tert-Butylphenol (hereinafter referred to as PTBP) (0.185 g) as a capping agent was added thereto, and stirring was carried out under a nitrogen atmosphere to ensure thorough mixing. After cooling until the temperature inside the reactor reached 10 °C, the entire amount of the prepared 3,3’,5,5’-tetramethyl-4,4’-dihydroxybiphenyl (hereinafter referred to as TMBP) solution (solution preparation method: 148 mL of 1.5 N aqueous potassium hydroxide solution (14.2 g of potassium hydroxide) was prepared, and after cooling to below room temperature, 0.13 g of dithionite as an antioxidant and 14.6 g of TMBP were added and completely dissolved) 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.

[0292] 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-1) having the following structure was obtained.

[0293] (Identification of PC polymer)

[0294] 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 0.72 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.

[0295] [Chemical formula 21]

[0296]

[0297] The composition ratio (mol%) was CHA:TMBP = 6:4.

[0298] [Synthesis Example 2]

[0299] (Manufacture of PC polymer)

[0300] In a reaction vessel equipped with a mechanical stirrer, stirring blades, and baffles, 233 mL of CHZ-CF prepared in Production Example 2 and 265 mL of dichloromethane were injected. PTBP (0.182 g) as a capping agent was added thereto, and stirring was carried out under a nitrogen atmosphere to achieve sufficient mixing. After cooling until the temperature inside the reactor reached 10 °C, the entire amount of the prepared TMBP 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, 0.12 g of dithionite as an antioxidant and 13.2 g of TMBP were added and completely dissolved) was added to this solution. While stirring, 1.4 mL of triethylamine aqueous solution (7 vol%) was added, and stirring was continued for 90 minutes.

[0301] 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-2) having the following structure was obtained.

[0302] (Identification of PC polymer)

[0303] 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 0.58 dL / g. It should be noted that for the structure and composition of the obtained PC-2, analysis by 1 1H-NMR spectrum confirmed that it was a PC polymer composed of the following repeating units and composition ratio.

[0304] [Chemical Formula 22]

[0305]

[0306] The composition ratio (mol%) was CHZ:TMBP = 6:4.

[0307] [Synthesis Example 3]

[0308] (Manufacture of PC polymer)

[0309] In a reaction vessel equipped with a mechanical stirrer, stirring blades, and baffles, 234 mL of the OCCDE-CF prepared in Production Example 3 and 264 mL of dichloromethane were poured. 0.149 g of PTBP as a capping agent was added thereto, and stirring was carried out under a nitrogen atmosphere to ensure thorough mixing. After cooling until the temperature inside the reactor reached 10 °C, the entire amount of the prepared TMBP solution (Solution preparation method: 148 mL of a 1.5 N aqueous potassium hydroxide solution (14.6 g of potassium hydroxide) was prepared, and after cooling to below room temperature, 0.13 g of dithionite as an antioxidant and 15.0 g of TMBP were added and completely dissolved to prepare) was added to this solution, and 23.6 mL of an aqueous triethylamine solution (7 vol%) was added while stirring, and stirring was continued for 2 hours.

[0310] 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 resulting dichloromethane solution was added dropwise to methanol with stirring, and the resulting reprecipitate was filtered and dried, whereby a PC polymer (PC-3) having the following structure was obtained.

[0311] (Identification of PC polymer)

[0312] 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, and the result was 0.51 dL / g. It should be noted that for the structure and composition of the obtained PC-3, 1 analysis was performed 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.

[0313] [Chemical formula 23]

[0314]

[0315] The composition ratio (mol%) was OCCDE:TMBP = 6:4.

[0316] [Synthesis Example 4]

[0317] (Manufacture of PC polymer)

[0318] In a reaction vessel equipped with a mechanical stirrer, stirring blades, and baffles, 236 mL of the OCTMC-CF prepared in Production Example 4 and 263 mL of dichloromethane were injected. PTBP (0.151 g) as a capping agent was added thereto, and stirring was carried out under a nitrogen atmosphere to ensure thorough mixing. After cooling until the temperature inside the reactor reached 10°C, the entire amount of the prepared TMBP solution (solution preparation method: 148 mL of a 1.6N aqueous potassium hydroxide solution (15.7 g of potassium hydroxide) was prepared, and after cooling to below room temperature, 0.14 g of dithionite as an antioxidant and 16.2 g of TMBP were added and completely dissolved to prepare it) was added to this solution, and 1.7 mL of a triethylamine aqueous solution (7 vol%) was added while stirring, and stirring was continued for 90 minutes.

[0319] 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-4) having the following structure was obtained.

[0320] (Identification of PC Polymer)

[0321] 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 was carried out 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.

[0322] [Chemical Formula 24]

[0323]

[0324] The composition ratio (mol%) was OCTMC:TMBP = 6:4.

[0325] [Synthesis Example 5]

[0326] (Manufacture of PC Polymer)

[0327] 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. 0.514 g of PTBP as a capping agent was added thereto, and stirring was carried out to achieve sufficient mixing. After cooling until the temperature in the reactor reached 10 °C, the prepared solution of TMBP and 9-(4-hydroxybenzyl)-10-(4-hydroxyphenyl)anthracene (hereinafter referred to as BIPANT) (Solution preparation method: 148 mL of 1.5 N aqueous potassium hydroxide solution (14.2 g of potassium hydroxide) was prepared, and after cooling to below room temperature, 0.15 g of dithionite as an antioxidant, 11.0 g of TMBP, and 5.7 g of BIPANT were added and completely dissolved to prepare) was added in its entirety, and 1.5 mL of triethylamine aqueous solution (7 vol%) was added while stirring, followed by continuous stirring for 90 minutes.

[0328] The obtained reaction mixture was diluted and washed with 0.83 L of dichloromethane and 0.08 L of water. The lower layer was separated, and it was further washed once with 0.23 L of water, once with 0.23 L of 0.03 N hydrochloric acid, and three times with 0.23 L of water. The obtained dichloromethane solution was added dropwise to methanol with stirring, and the obtained reprecipitate was filtered and dried, whereby a PC polymer (PC-5) having the following structure was obtained.

[0329] (Identification of PC polymer)

[0330] 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, and the result was 0.37 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.

[0331] [Chemical formula 25]

[0332]

[0333] The composition ratio (mol%) was CHA:TMBP:BIPANT = 6:3:1.

[0334] <Preparation of coating liquid composition containing polycarbonate and production of resin film>

[0335] [Example 1]

[0336] 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.

[0337] [Example 2]

[0338] A resin film was obtained in the same manner as in Example 1, except that PC-2 was used instead of PC-1.

[0339] [Example 3]

[0340] A resin film was obtained in the same manner as in Example 1, except that PC-3 was used instead of PC-1.

[0341] [Example 4]

[0342] A resin film was obtained in the same manner as in Example 1, except that PC-4 was used instead of PC-1.

[0343] [Example 5]

[0344] A resin film was obtained in the same manner as in Example 1, except that PC-5 was used instead of PC-1.

[0345] [Example 6]

[0346] 1.5 g (15% by mass) of PC-3 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.

[0347] [Example 7]

[0348] Using a polycarbonate resin with a viscosity-average molecular weight (Mv) of 17100 obtained by the same polymerization method as in Synthesis Example 1 and adjusting the amount of the end-capping agent PTBP, the same operations as in Example 1 were carried out to obtain a resin film.

[0349] [Example 8]

[0350] Using the same polymerization method as in Synthesis Example 2, the amount of the end-capping agent PTBP was only changed to 2.73 g, and a polycarbonate resin having a viscosity-average molecular weight (Mv) of 1800 and the following structure was obtained. It should be noted that it was difficult to form into a film shape and the dielectric properties could not be measured.

[0351] [Chemical Formula 26]

[0352]

[0353] [Comparative Example 1]

[0354] Instead of the chloroformate bodies of TMBP and CHA, 1,1-bis(4-hydroxyphenyl)propane and the chloroformate body 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, and a polycarbonate resin and a resin film having the following structure were obtained.

[0355] [Chemical Formula 27]

[0356]

[0357] [Comparative Example 2]

[0358] Instead of the chloroformate bodies of TMBP and CHA, 1,1-bis(4-hydroxyphenyl)cyclohexane and the chloroformate body 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, and a polycarbonate resin and a resin film having the following structure were obtained.

[0359] [Chemical Formula 28]

[0360]

[0361] [Comparative Example 3]

[0362] Instead of the chloroformate bodies of TMBP and CHA, TMBP and the chloroformate body of 1,1-bis(3-methyl-4-hydroxyphenyl)propane were used, and the same operations as in Synthesis Example 1 and Example 1 were carried out except for this, and a polycarbonate resin and a resin film having the following structure were obtained.

[0363] [Chemical Formula 29]

[0364]

[0365] The physical properties of the polycarbonate resin were evaluated by the following methods.

[0366] <Viscosity-average molecular weight evaluation>

[0367] Dissolve 0.2 g of polycarbonate resin in 40 mL of dichloromethane, and measure the specific viscosity (ηsp) of the solution at 20 °C. Then, take Mv calculated by the following formula as the viscosity-average molecular weight. The apparatus used for the measurement is a kinematic viscosity measurement apparatus (VMR-052 USPC manufactured by Reiko Co., Ltd.), and an Ubbelohde modified type (410-UIB type) viscometer is used. The results obtained are shown in Table 1.

[0368] η sp / C = [η] × (1 + 0.28 × η sp )

[0369] According to the Schnell formula,

[0370] [η] = 1.23 × 10 -5 Mv 0.83

[0371] Perform deformation,

[0372] Mv = ([η] / 1.23 × 10 -5 ) 1 / 0.83

[0373] [η]: Intrinsic viscosity

[0374] C: Specimen concentration (g / L)

[0375] <Evaluation of relative permittivity and dielectric loss tangent>

[0376] Cut a square film with a length of 60 mm and a width of 60 mm from the resin film. 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 permittivity (Dk) and dielectric loss tangent (Df) at a frequency of 10 GHz. The results obtained are shown in Table 1. For the measurement of the temperature dependence of dielectric properties, also use an ESPEC SH-662 small environmental test chamber to change the temperature, and measure the relative permittivity and dielectric loss tangent at a frequency of 10 GHz. The results obtained are shown in Figure 1 and Figure 2 . In addition, the maximum and minimum values of Dk and Df between 30 °C and 150 °C, and the difference between these values are shown in Table 3.

[0377] <Evaluation of solution viscosity>

[0378] In a sample tube, 0.27 g (5 mass%) of the resin films obtained in Examples 2 and 9 and 5.2 g of toluene were put in, and after stirring at room temperature, 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.

[0379] <Evaluation of glass transition temperature and coefficient of thermal expansion>

[0380] 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.

[0381] Measurement mode: Tensile Temperature condition: -30°C to 320°C (heating rate 5°C / min)

[0382] 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

[0383] <Evaluation of solubility in a non-halogen-based solvent (toluene)>

[0384] In a sample tube, 0.1 g (3 mass%) of the resin film and 3.2 g of toluene were put in, and after stirring at room temperature, the appearance of the solution after one day was visually confirmed. The results obtained are shown in Table 1.

[0385] A: No insoluble components, transparent

[0386] B: Although there are no insoluble components, turbidity can be visually confirmed

[0387] F: There are insoluble components

[0388] <Crosslinking evaluation of the resin film>

[0389] 1.4 g of the resin of Example 5 (functional group concentration: 0.263 mmol / g) and 105 mg of 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane (hereinafter referred to as MI-BisA, functional group concentration: 3.51 mmol / g) as a curing material were measured into a sample tube with a screw cap and dissolved in 8 mL of toluene to obtain a coating liquid composition. The obtained coating liquid composition was cast into a film on a glass plate using an applicator with a gap of 600 μm. After air drying for 1 hour, it was dried under reduced pressure at a temperature of 50°C in a vacuum dryer for 16 hours to remove the solvent and obtain a resin film. Next, the obtained resin film was heated at a temperature of 170°C for 2 hours using a vacuum dryer. At the same time, the resin film of Example 1 was separately heated at a temperature of 170°C for 2 hours using a vacuum dryer. After air cooling to room temperature, 5 mL of dichloromethane was added respectively, and the appearance was observed. The results obtained are shown in Table 4.

[0390] F (dissolved): Visually, there is no insoluble component.

[0391] A (insoluble): It did not swell or slightly swelled and maintained the film shape.

[0392] <Evaluation of solution fluidity>

[0393] 20 mg of the resins obtained in Example 2 and Example 8 were respectively added to a microtube with an inner diameter of 1 cm and a height of 5 cm, and 30 mg of toluene was added to prepare a 40 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 results obtained are shown in Table 1.

[0394] A: The time taken for the solution to reach the cap of the microtube is within 3 seconds.

[0395] B: The time taken for the solution to reach the cap of the microtube is more than 3 seconds.

[0396]

Table 1

[0397]

[0398] [Research]

[0399] Examples 1 to 4 copolymerized with TMBP have lower dielectric properties compared to the polymers of Comparative Examples 1 and 2. In addition, the solubility in toluene as a non-halogenated solvent is also excellent. In addition, when Example 4 is compared with Comparative Example 3, they are equivalent in terms of low dielectric properties, but the glass transition temperature of Example 4 is more excellent.

[0400] According to Example 5, it is possible to introduce a crosslinking group into the TMBP copolymer.

[0401] According to Example 6, it is possible to fabricate a film containing spherical silica and resin. At this time, due to the influence of silica with a high relative dielectric constant, the Dk is worse than that when only resin is used. Therefore, it is important to have a resin with lower dielectric properties.

[0402] By reducing the molecular weight of the resin with low dielectric properties (Example 2) (Example 8), it is possible to endow the coating solution with the characteristic that it exhibits fluidity even when dissolved at a high concentration.

[0403]

Table 2

[0404]

[0405] [Research]

[0406] Table 2 shows the influence of the difference in molecular weight on the dielectric properties and solution viscosity in resins with the same copolymer backbone.

[0407] Based on the dielectric properties of Example 1 and Example 7, it can be seen that even when the viscosity-average molecular weight changes, the dielectric properties do not change significantly.

[0408] Based on the solution viscosities of Example 1 and Example 7, it can be seen that the solution viscosity of Example 7 with a smaller viscosity-average molecular weight is lower. Therefore, it can be known that the solution viscosity changes depending on the viscosity-average molecular weight.

[0409]

Table 3

[0410]

[0411] [Research]

[0412] According to Figure 1 and Table 3, it can be seen that Dk has almost no temperature dependence.

[0413] 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.

[0414] Comparing Examples 1 to 4 with Comparative Examples 1 and 2, it can be seen that when TMBP is included, the increase ratio of Df with respect to the temperature rise decreases.

[0415]

Table 4

[0416]

[0417] [Research]

[0418] Since the resin film of Example 1 was completely soluble in dichloromethane, it was understood 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 was understood that a crosslinking reaction had taken place.

Claims

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

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

3. The electronic substrate material according to claim 1 or 2, wherein the resin has: a structure represented by any one of general formula (UN1) and general formula (UN1-1) in an amount of 10 mol% or more and 49 mol% or less; and, at least one structure selected from the structures represented by general formula (UN4) to general formula (UN7) in an amount of 50 mol% or more, in general formula (UN4) to general formula (UN7), * represents a bonding site.

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 35000 or less.

5. The electronic substrate material according to any one of claims 1 to 4, the dielectric constant at a frequency of 10 GHz measured by the split cylinder resonator perturbation method is 2.63 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, 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 resin by the split cylinder resonator perturbation method, the change amount of the relative dielectric constant is 0.05 or less, and the change amount of the tangent of the dielectric loss angle is 0.00101 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 comprises an inorganic filler.

12. The electronic substrate material according to any one of claims 1 to 11, wherein it further comprises 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 (UN8), In the general formula (UN8), the number of repeating units r is 1 or more and 5 or less, and R 4 is an organic group having 1 or more and 10 or less carbon atoms, and R 5 is an organic group having 1 or more and 10 or less carbon atoms. When there are multiple R 4 or R 5 respectively, the multiple Rs 4 are optionally the same group or different groups from each other, and the multiple Rs 5 are optionally the same group or different groups from each other. Z represents a single bond, -O-, -S-, -SO-, -SO2- or an organic group having 1 or more and 20 or less carbon atoms, q represents 0, 1, 2, 3 or 4, and * represents a bonding position.

17. A method for producing a resin having a structure represented by the general formula (UN8), The manufacturing method includes: a step of reacting a dicarbonate monomer or oligomer with a bisphenol compound by interfacial polycondensation, In the general formula (UN8), the number of repeating units r is 1 or more and 5 or less, and R 4 is an organic group having 1 or more and 10 or less carbon atoms, and R 5 is an organic group having 1 or more and 10 or less carbon atoms. When there are multiple R 4 or R 5 respectively, the multiple Rs 4 are optionally the same group or different groups from each other, and the multiple Rs 5 are optionally the same group or different groups from each other. Z represents a single bond, -O-, -S-, -SO-, -SO2- or an organic group having 1 or more and 20 or less carbon atoms, q represents 0, 1, 2, 3 or 4, and * represents a bonding position.

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